Self-cleaning and surface chemical reactions during hafnium dioxide atomic layer deposition on indium arsenide.

PubMed

Timm, Rainer; Head, Ashley R; Yngman, Sofie; Knutsson, Johan V; Hjort, Martin; McKibbin, Sarah R; Troian, Andrea; Persson, Olof; Urpelainen, Samuli; Knudsen, Jan; Schnadt, Joachim; Mikkelsen, Anders

2018-04-12

Atomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy. We find that the widely used ligand exchange model of the ALD process for the removal of native oxide on the semiconductor and the simultaneous formation of the first hafnium dioxide layer must be significantly revised. Our study provides substantial evidence that the efficiency of the self-cleaning process and the quality of the resulting semiconductor-oxide interface can be controlled by the molecular adsorption process of the ALD precursors, rather than the subsequent oxide formation.

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2017-01-01

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549

Improve oxidation resistance at high temperature by nanocrystalline surface layer

NASA Astrophysics Data System (ADS)

Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

2015-08-01

An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content.

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

PubMed

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

2014-06-01

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

Strong and reversible modulation of carbon nanotube-silicon heterojunction solar cells by an interfacial oxide layer.

PubMed

Jia, Yi; Cao, Anyuan; Kang, Feiyu; Li, Peixu; Gui, Xuchun; Zhang, Luhui; Shi, Enzheng; Wei, Jinquan; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai

2012-06-21

Deposition of nanostructures such as carbon nanotubes on Si wafers to make heterojunction structures is a promising route toward high efficiency solar cells with reduced cost. Here, we show a significant enhancement in the cell characteristics and power conversion efficiency by growing a silicon oxide layer at the interface between the nanotube film and Si substrate. The cell efficiency increases steadily from 0.5% without interfacial oxide to 8.8% with an optimal oxide thickness of about 1 nm. This systematic study reveals that formation of an oxide layer switches charge transport from thermionic emission to a mixture of thermionic emission and tunneling and improves overall diode properties, which are critical factors for tailoring the cell behavior. By controlled formation and removal of interfacial oxide, we demonstrate oscillation of the cell parameters between two extreme states, where the cell efficiency can be reversibly altered by a factor of 500. Our results suggest that the oxide layer plays an important role in Si-based photovoltaics, and it might be utilized to tune the cell performance in various nanostructure-Si heterojunction structures.

Oxidation and alpha-case formation in Ti–6Al–2Sn–4Zr–2Mo alloy

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

Gaddam, Raghuveer, E-mail: raghuveer.gaddam@ltu.se; Sefer, Birhan; Pederson, Robert

2015-01-15

Isothermal heat treatments in ambient air were performed on wrought Ti–6Al–2Sn–4Zr–2Mo (Ti-6242) material at 500, 593 and 700°C for times up to 500 h. In the presence of oxygen at elevated temperatures simultaneous reactions occurred in Ti-6242 alloy, which resulted in the formation of an oxide scale and a layer with higher oxygen concentration (termed as alpha-case). Total weight gain analysis showed that there was a transition in the oxidation kinetics. At 500°C, the oxidation kinetics obeyed a cubic relationship up to 200 h and thereafter changed to parabolic at prolonged exposure times. At 593°C, it followed a parabolic relationship.more » After heat treatment at 700°C, the oxidation obeyed a parabolic relationship up to 200 h and thereafter changed to linear at prolonged exposure times. The observed transition is believed to be due to the differences observed in the oxide scale. The activation energy for parabolic oxidation was estimated to be 157 kJ/mol. In addition, alpha-case layer was evaluated using optical microscope, electron probe micro-analyser and microhardness tester. The thickness of the alpha-case layer was found to be a function of temperature and time, increasing proportionally, and following a parabolic relationship. The activation energy for the formation of alpha-case layer was estimated to be 153 kJ/mol. - Highlights: • Transition in oxidation kinetics was observed in Ti–6Al–2Sn–4Zr–2Mo alloy in the temperature range 500–700°C. • The activation energy for parabolic oxidation and for alpha-case formation is about 157 kJ/mol and 153 kJ/mol. • Thickness of alpha-case layer estimated by optical microscopy and electron probe microanalysis is comparable.« less

Investigations into the structure of PEO-layers for understanding of layer formation

NASA Astrophysics Data System (ADS)

Friedemann, A. E. R.; Thiel, K.; Haßlinger, U.; Ritter, M.; Gesing, Th. M.; Plagemann, P.

2018-06-01

Plasma electrolytic oxidation (PEO) is a type of high-voltage anodic oxidation process capable of producing a thick oxide layer with a wide variety of structural and chemical properties influenced by the electrolytic system. This process enables the combined adjustment of various characteristics, i.e. the morphology and chemical composition. The procedure facilitates the possibility of generating an individual structure as well as forming a crystalline surface in a single step. A highly porous surface with a high crystalline content consisting of titanium dioxide phases is ensured through the process of plasma electrolytic oxidizing pure titanium. In the present study plasma electrolytic oxidized TiO2-layers were investigated regarding their crystallinity through the layer thickness. The layers were prepared with a high applied voltage of 280 V to obtain a PEO-layer with highly crystalline anatase and rutile amounts. Raman spectroscopy and electron backscatter diffraction (EBSD) were selected to clarify the structure of the oxide layer with regard to its crystallinity and phase composition. The composition of the TiO2-phases is more or less irregularly distributed as a result of the higher energy input on the uppermost side of the layer. Scanning transmission electron microscopy (STEM) provided a deeper understanding of the structure and the effects of plasma discharges on the layer. It was observed that the plasma discharges have a strong influence on crystallite formation on top of the oxide layer and also at the boundary layer to the titanium substrate. Therefore, small crystallites of TiO2 could be detected in these regions. In addition, it was shown that amorphous TiO2 phases are formed around the characteristic pore structures, which allows the conclusion to be drawn that a rapid cooling from the gas phase had to take place in these areas.

In-situ formation of multiphase deposited thermal barrier coatings

DOEpatents

Subramanian, Ramesh

2004-01-13

A multiphase ceramic thermal barrier coating is provided. The coating is adapted for use in high temperature applications in excess of about 1200.degree. C., for coating superalloy components of a combustion turbine engine. The coating comprises a ceramic single or two oxide base layer disposed on the substrate surface; and a ceramic oxide reaction product material disposed on the base layer, the reaction product comprising the reaction product of the base layer with a ceramic single or two oxide overlay layer.

Steam based conversion coating on AA6060 alloy: Effect of sodium silicate chemistry and corrosion performance

NASA Astrophysics Data System (ADS)

Din, Rameez Ud; Bordo, Kirill; Tabrizian, Naja; Jellesen, Morten Stendahl; Ambat, Rajan

2017-11-01

Surface treatment of aluminium alloy AA6060 using an industrially applicable pilot steam jet system with and without silicate chemistry has been investigated. Treatment using steam alone and steam with silicate, resulted in an oxide layer formation with thickness ∼425 nm and ∼160 nm, respectively. Moreover, the use of sodium silicate resulted in the formation of distinct microstructure and incorporation of silicate into the oxide film. These oxide films reduced the anodic activity 4 times, while the corrosion protection by silicate containing oxide was the function of its concentration. Further, in acid salt spray and filiform corrosion tests, oxide layer containing silicate exhibited two times higher corrosion resistance.

Polymer/graphite oxide composites as high-performance materials for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Tien, Chien-Pin; Teng, Hsisheng

A single graphene sheet represents a carbon material with the highest surface area available to accommodating molecules or ions for physical and chemical interactions. Here we demonstrate in an electric double layer capacitor the outstanding performance of graphite oxide for providing a platform for double layer formation. Graphite oxide is generally the intermediate compound for obtaining separated graphene sheets. Instead of reduction with hydrazine, we incorporate graphite oxide with a poly(ethylene oxide)-based polymer and anchor the graphene oxide sheets with poly(propylene oxide) diamines. This polymer/graphite oxide composite shows in a "dry" gel-electrolyte system a double layer capacitance as high as 130 F g -1. The polymer incorporation developed here can significantly diversify the application of graphene-based materials in energy storage devices.

Biquadratic coupling through nano-oxide layers in pinned layers of IrMn-based spin valves

NASA Astrophysics Data System (ADS)

Lai, Chih-Huang; Lu, K. H.

2003-05-01

We have investigated the coupling between top and bottom pinned layers through various nano-oxide layers (NOLs) in IrMn-based spin valves. The NOLs were formed by using oxygen-plasma oxidation or natural oxidation on 1 nm metallic layers. By inserting naturally oxidized Co-NOLs in the pinned layer, strong ferromagnetic coupling through NOLs and high specularity at the NOL interface were achieved. In contrast, when the plasma-oxidized Co-NOLs were inserted, ferromagnetic coupling through NOLs disappeared, plausibly due to the formation of nonferromagnetic oxides, which led to a low magnetoresistance (MR). Insertion of naturally oxidized Ni80Fe20-NOLs showed the same results as that of naturally oxidized Co-NOLs. On the other hand, biquadratic coupling between top and bottom pinned-Co90Fe10 layers was observed by inserting plasma-oxidized Ni80Fe20-NOLs. The highest MR was obtained when the field was applied along the direction perpendicular to the field-annealing direction. Similar biquadratic coupling was also found with naturally oxidized or plasma-oxidized Fe-NOLs. We suggest that the biquadratic coupling between pinned Co90Fe10 layers through NOLs results from the coupling between Fe (or Co90Fe10) and Fe+3 oxides

Formation of CCP-NOL in CPP-GMR spin valve structure for the enhancement of magnetoresistance

NASA Astrophysics Data System (ADS)

Kang, Y. M.; Isogami, S.; Tsunoda, M.; Takahashi, M.; Yoo, S. I.

2007-03-01

For the MR enhancement in current perpendicular to plane-giant magetoresistance spin valve (CPP-GMR SV), a current-confined path—nano-oxide layer (CCP-NOL)—AlO x was formed on the Cu spacer of half SV structure. In order to form effective current-confining paths, an ultra-thin AlO x layer was deposited on a Cu spacer layer by O 2 reactive sputtering of Al with infra-red (IR) heat treatment on the substrate, and that enable to form an island-structured insulating AlO x layer having holes between AlO x islands. By controlling PO 2 and substrate temperature in the NOL deposition, AlO x layer formation without an oxidizing bottom layer could be achieved.

Design for Oxidation Resistance

NASA Technical Reports Server (NTRS)

Smialek, James L.; Schaeffer, Jon C.; Barrett, Charles A.

1997-01-01

Alloys intended for use in high-temperature environment rely on the formation of a continuous, compact, slow-growing oxide layer for oxidation and hot corrosion resistance. To be protective, this oxide layer must be chemically, thermodynamically stable. Successful alloy design for oxidative environment is best achieved by developing alloys that are capable of forming adherent scales of either alumina (Al2O3), chromia (Cr2O3), or silica (SiO2). In this article, emphasis has been placed on the issue related to high-temperature oxidation of superalloys used in gas turbine engine application. Despite the complexity of these alloys, optimal performance has been associated with protective alumina scale formation. As will be described below, both compositional makeup and protective coatings play key role in providing oxidation protection. Other high-temperature materials described include nickel and titanium aluminide intermetallics, refractory metal, and ceramics.

Two-step growth mechanism of supported Co3O4-based sea-urchin like hierarchical nanostructures

NASA Astrophysics Data System (ADS)

Maurizio, Chiara; Edla, Raju; Michieli, Niccolo'; Orlandi, Michele; Trapananti, Angela; Mattei, Giovanni; Miotello, Antonio

2018-05-01

Supported 3D hierarchical nanostructures of transition metal oxides exhibit enhanced photocatalytic performances and long-term stability under working conditions. The growth mechanisms crucially determine their intimate structure, that is a key element to optimize their properties. We report on the formation mechanism of supported Co3O4 hierarchical sea urchin-like nanostructured catalyst, starting from Co-O-B layers deposited by Pulsed Laser Deposition (PLD). The particles deposited on the layer surface, that constitute the seeds for the urchin formation, have been investigated after separation from the underneath deposited layer, by X-ray diffraction, X-ray absorption spectroscopy and scanning electron microscopy. The comparison with PLD deposited layers without O and/or B indicates a crucial role of B for the urchin formation that (i) limits Co oxidation during the deposition process and (ii) induces a chemical reduction of Co, especially in the particle core, in the first step of air annealing (2 h, 500 °C). After 2 h heating Co oxidation proceeds and Co atoms outdiffuse from the Co fcc particle core likely through fast diffusion channel present in the shell and form Co3O4 nano-needles. The growth of nano-needles from the layer beneath the particles is prevented by a faster Co oxidation and a minimum fraction of metallic Co. This investigation shows how diffusion mechanisms and chemical effects can be effectively coupled to obtain hierarchical structures of transition metal oxides.

Formation of ZnO at zinc oxidation by near- and supercritical water under the constant electric field

NASA Astrophysics Data System (ADS)

Shishkin, A. V.; Sokol, M. Ya.; Shatrova, A. V.; Fedyaeva, O. N.; Vostrikov, A. A.

2014-12-01

The work has detected an influence of a constant electric field (up to E = 300 kV/m) on the structure of a nanocrystalline layer of zinc oxide, formed on the surface of a planar zinc anode in water under supercritical (673 K and 23 MPa) and near-critical (673 K and 17. 5 MPa) conditions. The effect of an increase of zinc oxidation rate with an increase in E is observed under supercritical conditions and is absent at near-critical ones. Increase in the field strength leads to the formation of a looser structure in the inner part of the zinc oxide layer.

Low-damage direct patterning of silicon oxide mask by mechanical processing

PubMed Central

2014-01-01

To realize the nanofabrication of silicon surfaces using atomic force microscopy (AFM), we investigated the etching of mechanically processed oxide masks using potassium hydroxide (KOH) solution. The dependence of the KOH solution etching rate on the load and scanning density of the mechanical pre-processing was evaluated. Particular load ranges were found to increase the etching rate, and the silicon etching rate also increased with removal of the natural oxide layer by diamond tip sliding. In contrast, the local oxide pattern formed (due to mechanochemical reaction of the silicon) by tip sliding at higher load was found to have higher etching resistance than that of unprocessed areas. The profile changes caused by the etching of the mechanically pre-processed areas with the KOH solution were also investigated. First, protuberances were processed by diamond tip sliding at lower and higher stresses than that of the shearing strength. Mechanical processing at low load and scanning density to remove the natural oxide layer was then performed. The KOH solution selectively etched the low load and scanning density processed area first and then etched the unprocessed silicon area. In contrast, the protuberances pre-processed at higher load were hardly etched. The etching resistance of plastic deformed layers was decreased, and their etching rate was increased because of surface damage induced by the pre-processing. These results show that etching depth can be controlled by controlling the etching time through natural oxide layer removal and mechanochemical oxide layer formation. These oxide layer removal and formation processes can be exploited to realize low-damage mask patterns. PMID:24948891

Method of coating an iron-based article

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

Magdefrau, Neal; Beals, James T.; Sun, Ellen Y.

A method of coating an iron-based article includes a first heating step of heating a substrate that includes an iron-based material in the presence of an aluminum source material and halide diffusion activator. The heating is conducted in a substantially non-oxidizing environment, to cause the formation of an aluminum-rich layer in the iron-based material. In a second heating step, the substrate that has the aluminum-rich layer is heated in an oxidizing environment to oxidize the aluminum in the aluminum-rich layer.

Control of the Structure of Diffusion Layer in Carbon Steels Under Nitriding with Preliminary Deposition of Copper Oxide Catalytic Films

NASA Astrophysics Data System (ADS)

Petrova, L. G.; Aleksandrov, V. A.; Malakhov, A. Yu.

2017-07-01

The effect of thin films of copper oxide deposited before nitriding on the phase composition and the kinetics of growth of diffusion layers in carbon steels is considered. The process of formation of an oxide film involves chemical reduction of pure copper on the surface of steel specimens from a salt solution and subsequent oxidation under air heating. The oxide film exerts a catalytic action in nitriding of low- and medium-carbon steels, which consists in accelerated growth of the diffusion layer, the nitride zone in the first turn. The kinetics of the nitriding process and the phase composition of the layer are controlled by the thickness of the copper oxide precursor, i.e., the deposited copper film.

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

Dumpala, Ravikumar; Nano Functional Materials Technology Centre, Department of Physics, Indian Institute of Technology Madras, Chennai 600036; Kumar, N.

Tribo-layer formation and frictional characteristics of the SiC ball were studied with the sliding test against nanocrystalline diamond coating under atmospheric test conditions. Unsteady friction coefficients in the range of 0.04 to 0.1 were observed during the tribo-test. Friction and wear characteristics were found to be influenced by the formation of cohesive tribo-layer (thickness ∼ 1.3 μm) in the wear track of nanocrystalline diamond coating. Hardness of the tribo-layer was measured using nanoindentation technique and low hardness of ∼ 1.2 GPa was observed. The presence of silicon and oxygen in the tribo-layer was noticed by the energy dispersive spectroscopy mappingmore » and the chemical states of the silicon were analyzed using X-ray photoelectron spectroscopy. Large amount of oxygen content in the tribo-layer indicated tribo-oxidation wear mechanism. - Highlights: • Sliding wear and friction characteristics of SiC were studied against NCD coating. • Silicon oxide tribo-layer formation was observed in the NCD coating wear track. • Low hardness 1.2 GPa of tribo-layer was measured using nanoindentation technique. • Chemical states of silicon were analyzed using X-ray photoelectron spectroscopy.« less

Metal assisted photochemical etching of 4H silicon carbide

NASA Astrophysics Data System (ADS)

Leitgeb, Markus; Zellner, Christopher; Schneider, Michael; Schwab, Stefan; Hutter, Herbert; Schmid, Ulrich

2017-11-01

Metal assisted photochemical etching (MAPCE) of 4H-silicon carbide (SiC) in Na2S2O8/HF and H2O2/HF aqueous solutions is investigated with platinum as metallic cathode. The formation process of the resulting porous layer is studied with respect to etching time, concentration and type of oxidizing agent. From the experiments it is concluded that the porous layer formation is due to electron hole pairs generated in the semiconductor, which stem from UV light irradiation. The generated holes are consumed during the oxidation of 4H-SiC and the formed oxide is dissolved by HF. To maintain charge balance, the oxidizing agent has to take up electrons at the Pt/etching solution interface. Total dissolution of the porous layers is achieved when the oxidizing agent concentration decreases during MAPCE. In combination with standard photolithography, the definition of porous regions is possible. Furthermore chemical micromachining of 4 H-SiC at room temperature is possible.

Steam assisted oxide growth on aluminium alloys using oxidative chemistries: Part I Microstructural investigation

NASA Astrophysics Data System (ADS)

Din, Rameez Ud; Piotrowska, Kamila; Gudla, Visweswara Chakravarthy; Jellesen, Morten Stendahl; Ambat, Rajan

2015-11-01

The surface treatment of aluminium alloys under steam containing KMnO4 and HNO3 resulted in the formation of an oxide layer having a thickness of up to 825 nm. The use of KMnO4 and HNO3 in the steam resulted in incorporation of the respective chemical species into the oxide layer. Steam treatment with solution containing HNO3 caused dissolution of Cu and Si from the intermetallic particles in the aluminium substrate. The growth rate of oxide layer was observed to be a function of MnO4- and NO3- ions present in the aqueous solution. The NO3- ions exhibit higher affinity towards the intermetallic particles resulting in poor coverage by the steam generated oxide layer compared to the coating formed using MnO4- ions. Further, increase in the concentration of NO3- ions in the solution retards precipitation of the steam generated aluminium hydroxide layer.

Conversion coatings prepared or treated with calcium hydroxide solutions

NASA Technical Reports Server (NTRS)

Maxey, Jason (Inventor); Nelson, Carl (Inventor); Eylem, Cahit (Inventor); Minevski, Zoran (Inventor); Clarke, Eric (Inventor)

2002-01-01

A conversion coating process that forms a stable and corrosion-resistant oxide layer on metal or metal oxide substrates or layers. Particularly, the conversion coating process involves contacting the metal or metal oxide substrate or layer with the aqueous calcium hydroxide solutions in order to convert the surface of the substrate to a stable metal oxide layer or coating. According to the present invention, the calcium hydroxide solution is prepared by removing carbon dioxide from water or an aqueous solution before introducing the calcium hydroxide. In this manner, formation of calcium carbonate particles is avoided and the porosity of the conversion coating produced by the calcium hydroxide solution is reduced to below about 1%.

Oxidation behaviors of porous Haynes 214 alloy at high temperatures

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

Wang, Yan, E-mail: wangyan@csu.edu.cn; Liu, Yong, E-mail: yonliu@csu.edu.cn; Tang, Huiping, E-mail: hptang@c-nin.com

The oxidation behaviors of porous Haynes 214 alloy at temperatures from 850 to 1000 °C were investigated. The porous alloys before and after the oxidation were examined by optical microscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) analyses, and X-ray photoelectron spectroscopy (XPS). The oxidation kinetics of the porous alloy approximately follows a parabolic rate law and exhibits two stages controlled by different oxidation courses. Complex oxide scales composed of Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4} and Al{sub 2}O{sub 3} are formed on the oxidized porous alloys, and the formation of Cr{sub 2}O{sub 3} onmore » its outer layer is promoted with the oxidation proceeding. The rough surface as well as the micropores in the microstructures of the porous alloy caused by the manufacturing process provides fast diffusion paths for oxygen so as to affect the formation of the oxide layers. Both the maximum pore size and the permeability of the porous alloys decrease with the increase of oxidation temperature and exposure time, which may limit its applications. - Highlights: • Two-stage oxidation kinetics controlled by different oxidation courses is showed. • Oxide scale mainly consists of Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4} and Al{sub 2}O{sub 3}. • Rough surface and micropores lead to the formation of uneven oxide structure. • Content of Cr{sub 2}O{sub 3} in the outer layer of the scale increases with time at 1000 °C. • Maximum pore size and permeability decrease with increasing temperature and time.« less

Photochemically assisted fast abiotic oxidation of manganese and formation of δ-MnO 2 nanosheets in nitrate solution

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

Jung, Haesung; Chadha, Tandeep S.; Kim, Doyoon

This study introduces a new and previously unconsidered fast abiotic formation of Mn(IV) oxides. We report photochemically assisted fast abiotic oxidation of Mn 2+ (aq) to Mn(IV) (s) by superoxide radicals generated from nitrate photolysis. This photochemical pathway generates randomly stacked layered birnessite (δ-MnO 2) nanosheets.

Effects of iron content in Ni-Cr-xFe alloys and immersion time on the oxide films formed in a simulated PWR water environment

NASA Astrophysics Data System (ADS)

Ru, Xiangkun; Lu, Zhanpeng; Chen, Junjie; Han, Guangdong; Zhang, Jinlong; Hu, Pengfei; Liang, Xue

2017-12-01

The iron content in Ni-Cr-xFe (x = 0-9 at.%) alloys strongly affected the properties of oxide films after 978 h of immersion in the simulated PWR primary water environment at 310 °C. Increasing the iron content in the alloys increased the amount of iron-bearing polyhedral spinel oxide particles in the outer oxide layer and increased the local oxidation penetrations into the alloy matrix from the chromium-rich inner oxide layer. The effects of iron content in the alloys on the oxide film properties after 500 h of immersion were less significant than those after 978 h. Iron content increased, and chromium content decreased, in the outer oxide layer with increasing iron content in the alloys. Increasing the immersion time facilitated the formation of the local oxidation penetrations along the matrix/film interface and the nickel-bearing spinel oxides in the outer oxide layer.

Effect of water vapor on evolution of a thick Pt-layer modified oxide on the NiCoCrAl alloy at high temperature

NASA Astrophysics Data System (ADS)

Song, Peng; He, Xuan; Xiong, Xiping; Ma, Hongqing; Song, Qunling; Lü, Jianguo; Lu, Jiansheng

2018-03-01

To investigate the effect of water vapor on the novel Pt-containing oxide growth behavior, Pt-addition within the oxide layer on the surface of NiCoCrAl coating and furnace cycle tests were carried out at 1050 °C in air and air plus water vapor. The thick Pt-containing oxide layer on NiCoCrAl exhibits a different oxidation growth behavior compared to the conventional Pt-diffusion metallic coatings. The Pt-containing oxide after oxidation in air plus water vapor showed a much thicker oxide layer compare to the ones without Pt addition, and also presented a much better coating adhesion. During the oxidation process in air, Pt promotes the spinel (NiCr2O4) formation. However, the Cr2O3 formed in air with water vapor and fixed Pt within the complex oxide layer. The water vapor promoted the Ni and Co outer-diffusion, and combined with Pt to form CoPt compounds on the surface of the NiCoCrAl coating system.

Dynamic oxidation behavior of TD-NiCr alloy with different surface pretreatments

NASA Technical Reports Server (NTRS)

Young, C. T.; Tenney, D. R.; Herring, H. W.

1975-01-01

Oxidation tests of TD-NiCr alloy with different surface pretreatments were conducted in a Mach-5 arc-jet at 1200 C and 0.002 lb/sec flowing air environment. The mechanisms responsible for the observed oxidation behavior are examined. The presence of atomic oxygen in the air stream plays a significant role in determining the oxidation characteristic of the alloy. The rate of Cr2O3 vaporization by formation of volatile CrO3 is greatly enhanced by the flowing conditions. The typical microstructure of oxides formed in the dynamic tests consists of an external layer of NiO with a porous mushroom-type morphology, an intermediate layer of NiO and Cr2O3 oxide mixture, and a continuous inner layer of Cr2O3 in contact with the Cr-depleted alloy substrate. Three basic processes underlying the formation of mushroom-type NiO are identified and discussed. The oxidation rate is determined by the rate of vaporization of NiO. Surface pretreatment has a significant effect on the oxidation behavior of the alloy in the early stage of oxidation, but becomes less important as exposure time increases. Mechanical polishing induces surface recrystallization, but promotes the concurrence of external growth of NiO and internal oxidation of the alloy in the dynamic atmosphere.

Formation of a Ge-rich Si1-x Ge x (x > 0.9) fin epitaxial layer condensed by dry oxidation

NASA Astrophysics Data System (ADS)

Jang, Hyunchul; Kim, Byongju; Koo, Sangmo; Ko, Dae-Hong

2017-11-01

We have selectively grown an epitaxial Si0.35Ge0.65 fin layer in a 65 nm oxide trench pattern array and formed a Ge-rich Si1-x Ge x (x > 0.9) fin layer with condensed Ge using dry oxidation. During oxidation of the SiGe fin structure, we found that the compressive strain of the condensed SiGe layer was increased by about 1.3% while Ge was efficiently condensed due to a two-dimensional oxidation reaction. In this paper, we discussed in detail the diffusion during the two-dimensional condensation reaction as well as the asymmetric biaxial strain of the SiGe fin before and after oxidation using a reciprocal space mapping measurement. The application of dry oxidation on selectively grown SiGe fin layer can be an effective method for increasing hole mobility of SiGe fin with increased Ge content and self-induced compressive strain.

Method for improving the performance of oxidizable ceramic materials in oxidizing environments

NASA Technical Reports Server (NTRS)

Nagaraj, Bangalore A. (Inventor)

2002-01-01

Improved adhesion of thermal barrier coatings to nonmetallic substrates using a dense layer of ceramic on an underlying nonmetallic substrate that includes at least one oxidizable component. The improved adhesion occurs because the application of the dense ceramic layer forms a diffusion barrier for oxygen. This diffusion barrier prevents the oxidizable component of the substrate from decomposing. The present invention applies ceramic by a process that deposits a relatively thick and dense ceramic layer on the underlying substrate. The formation of the dense layer of ceramic avoids the problem of void formation associated with ceramic formation by most prior art thermal decomposition processes. The formation of voids has been associated with premature spalling of thermal barrier layers and other protective layers applied to substrates.

Biogenic precipitation of manganese oxides and enrichment of heavy metals at acidic soil pH

NASA Astrophysics Data System (ADS)

Mayanna, Sathish; Peacock, Caroline L.; Schäffner, Franziska; Grawunder, Anja; Merten, Dirk; Kothe, Erika; Büchel, Georg

2014-05-01

The precipitation of biogenic Mn oxides at acidic pH is rarely reported and poorly understood, compared to biogenic Mn oxide precipitation at near neutral conditions. Here we identified and investigated the precipitation of biogenic Mn oxides in acidic soil, and studied their role in the retention of heavy metals, at the former uranium mining site of Ronneburg, Germany. The site is characterized by acidic pH, low carbon content and high heavy metal loads including rare earth elements. Specifically, the Mn oxides were present in layers identified by detailed soil profiling and within these layers pH varied from 4.7 to 5.1, Eh varied from 640 to 660 mV and there were enriched total metal contents for Ba, Ni, Co, Cd and Zn in addition to high Mn levels. Using electron microprobe analysis, synchrotron X-ray diffraction and X-ray absorption spectroscopy, we identified poorly crystalline birnessite (δ-MnO2) as the dominant Mn oxide in the Mn layers, present as coatings covering and cementing quartz grains. With geochemical modelling we found that the environmental conditions at the site were not favourable for chemical oxidation of Mn(II), and thus we performed 16S rDNA sequencing to isolate the bacterial strains present in the Mn layers. Bacterial phyla present in the Mn layers belonged to Firmicutes, Actinobacteria and Proteobacteria, and from these phyla we isolated six strains of Mn(II) oxidizing bacteria and confirmed their ability to oxidise Mn(II) in the laboratory. The biogenic Mn oxide layers act as a sink for metals and the bioavailability of these metals was much lower in the Mn layers than in adjacent layers, reflecting their preferential sorption to the biogenic Mn oxide. In this presentation we will report our findings, concluding that the formation of natural biogenic poorly crystalline birnessite can occur at acidic pH, resulting in the formation of a biogeochemical barrier which, in turn, can control the mobility and bioavailability of heavy metals in acidic soil environments.

Intermixing and thermal oxidation of ZrO2 thin films grown on a-Si, SiN, and SiO2 by metallic and oxidic mode magnetron sputtering

NASA Astrophysics Data System (ADS)

Coloma Ribera, R.; van de Kruijs, R. W. E.; Sturm, J. M.; Yakshin, A. E.; Bijkerk, F.

2017-03-01

The initial growth of DC sputtered ZrO2 on top of a-Si, SiN, and SiO2 layers has been studied by in vacuo high-sensitivity low energy ion scattering for two gas deposition conditions with different oxygen contents (high-O and low-O conditions). This unique surface sensitive technique allowed the determination of surface composition and thicknesses required to close the ZrO2 layer on all three substrates for both conditions. The ZrO2 layer closes similarly on all substrates due to more favorable enthalpies of formation for ZrO2 and ZrSiO4, resulting in passivation of the Si from the substrate. However, this layer closes at about half of the thickness (˜1.7 nm) for low-O conditions due to less oxidative conditions and less energetic particles arriving at the sample, which leads to less intermixing via silicate formation. In contrast, for high-O conditions, there is more ZrSiO4 and/or SiOx formation, giving more intermixing (˜3.4 nm). In vacuo X-ray photoelectron spectroscopy (XPS) measurements revealed similar stoichiometric ZrO2 layers deposited by both conditions and a higher interaction of the ZrO2 layer with the underlying a-Si for high-O conditions. In addition, oxygen diffusion through low-O ZrO2 films on a-Si has been investigated by ex situ angular-resolved XPS of samples annealed in atmospheric oxygen. For temperatures below 400 °C, no additional oxidation of the underlying a-Si was observed. This, together with the amorphous nature and smoothness of these samples, makes ZrO2 a good candidate as an oxidation protective layer on top of a-Si.

The influence of coating solution and calcination condition on the durability of Ir1-xSnxO2/Ti anodes for oxygen evolution

NASA Astrophysics Data System (ADS)

Kato, Zenta; Kashima, Ryo; Tatsumi, Kohei; Fukuyama, Shinnosuke; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2016-12-01

For oxygen formation without forming chlorine in seawater electrolysis for hydrogen production we have been using the anode consisting of three layers of MnO2-type multiple oxide catalyst, intermediate layer and titanium substrate. The intermediate layer was used for prevention of oxidation of the titanium substrate during anodic polarization for oxygen evolution and was prepared by calcination of butanol solutions of H2IrCl6 and SnCl4 coated on titanium. The protectiveness of Ir1-xSnxO2 layer formed was directly examined using Ir1-xSnxO2/Ti anodes in H2SO4 solution changing the preparation conditions of the layer. When the sum of Ir4+ and Sn4+ was 0.1 M, the highest protectiveness was observed at 0.06 M Sn4+. Although an increase in calcination temperature led to the formation of Ir1-x-ySnxTiyO2 triple oxide with a slightly lower catalytic activity for oxygen evolution, the anode calcined at 450 °C showed the highest protectiveness.

Observation of Electron-Beam-Induced Phase Evolution Mimicking the Effect of the Charge–Discharge Cycle in Li-Rich Layered Cathode Materials Used for Li Ion Batteries

DOE PAGES

Lu, Ping; Yan, Pengfei; Romero, Eric; ...

2015-01-27

Capacity loss, and voltage decrease upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[Li xMn yTM 1-x-y]O 2, TM = Ni, Co or Fe) have recently been attributed to the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li 0.2Ni 0.2Mn 0.6]O 2 (LNMO) particles, which are identical to those reported due to the charge-discharge cycle butmore » are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by electron dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LNMO is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. The observation through this study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.« less

Formation of nitrile species on Ag nanostructures supported on a-Al2O3: a new corrosion route for silver exposed to the atmosphere.

PubMed

Peláez, R J; Espinós, J P; Afonso, C N

2017-04-28

The aging of supported Ag nanostructures upon storage in ambient conditions (air and room temperature) for 20 months has been studied. The samples are produced on glass substrates by pulsed laser deposition (PLD); first a 15 nm thick buffer layer of amorphous aluminum oxide (a-Al 2 O 3 ) is deposited, followed by PLD of Ag. The amount of deposited Ag ranges from that leading to a discontinuous layer up to an almost-percolated layer with a thickness of <6 nm. Some regions of the as-grown silver layers are converted, by laser induced dewetting, into round isolated nanoparticles (NPs) with diameters of up to ∼25 nm. The plasmonic, structural and chemical properties of both as-grown and laser exposed regions upon aging have been followed using extinction spectroscopy, scanning electron microscopy and x-ray photoelectron spectroscopy, respectively. The results show that the discontinuous as-grown regions are optically and chemically unstable and that the metal becomes oxidized faster, the smaller the amount of Ag. The corrosion leads to the formation of nitrile species due to the reaction between NO x species from the atmosphere adsorbed at the surface of Ag, and hydrocarbons adsorbed in defects at the surface of the a-Al 2 O 3 layer during the deposition of the Ag nanostructures by PLD that migrate to the surface of the metal with time. The nitrile formation thus results in the main oxidation mechanism and inhibits almost completely the formation of sulphate/sulphide. Finally, the optical changes upon aging offer an easy-to-use tool for following the aging process. They are dominated by an enhanced absorption in the UV side of the spectrum and a blue-shift of the surface plasmon resonance that are, respectively, related to the formation of a dielectric overlayer on the Ag nanostructure and changes in the dimensions/features of the nanostructures, both due to the oxidation process.

Effect of Nonionic Surfactant Additive in PEDOT:PSS on PFO Emission Layer in Organic-Inorganic Hybrid Light-Emitting Diode.

PubMed

Cho, Seong Rae; Porte, Yoann; Kim, Yun Cheol; Myoung, Jae-Min

2018-03-21

Poly(9,9-dioctylfluorene) (PFO) has attracted significant interests owing to its versatility in electronic devices. However, changes in its optical properties caused by its various phases and the formation of oxidation defects limit the application of PFO in light-emitting diodes (LEDs). We investigated the effects of the addition of Triton X-100 (hereinafter shortened as TX) in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to induce interlayer diffusion between PEDOT:PSS and PFO to enhance the stability of the PFO phase and suppress its oxidation. Photoluminescence (PL) measurement on PFO/TX-mixed PEDOT:PSS layers revealed that, upon increasing the concentration of TX in the PEDOT:PSS layer, the β phase of PFO could be suppressed in favor of the glassy phase and the wide PL emission centered at 535 nm caused by ketone defects formed by oxidation was decreased considerably. LEDs were then fabricated using PFO as an emission layer, TX-mixed PEDOT:PSS as hole-transport layer, and zinc oxide (ZnO) nanorods as electron-transport layer. As the TX concentration reached 3 wt %, the devices exhibited dramatic increases in current densities, which were attributed to the enhanced hole injection due to TX addition, along with a shift in the dominant emission wavelength from a green electroluminescence (EL) emission centered at 518 nm to a blue EL emission centered at 448 nm. The addition of TX in PEDOT:PSS induced a better hole injection in the PFO layer, and through interlayer diffusion, stabilized the glassy phase of PFO and limited the formation of oxidation defects.

Oxidation behavior of thermal barrier coating systems with Al interlayer under isothermal loading

NASA Astrophysics Data System (ADS)

Ali, I.; Sokołowski, P.; Grund, T.; Pawłowski, L.; Lampke, T.

2018-06-01

In the present study, the phenomena related to the Thermally Grown Oxides (TGO) in atmospheric plasma sprayed Thermal Barrier Coatings (TBCs) are discussed. CoNiCrAlY bond coatings were sprayed on Inconel 600 substrates. Subsequently, thin Al layers were deposited by DC-Magnetron sputtering. Finally, yttria-stabilized zirconia (YSZ) top coatings were deposited to form a three-layered TBC system. The thus produced aluminum interlayer containing thermal barrier coatings (Al-TBC) were subjected to isothermal exposure with different holding times at 1150 °C and compared with reference TBCs of the same kind, but without Al interlayers (R-TBC). The oxide film formation in the interface between bond coating (BC) and top coating (TC) was investigated by scanning electron microscope (SEM) after 100 and 300 h of high temperature isothermal exposure. The growth of this oxide film as a function of the isothermal exposure time was studied. As a result, the designed Al-TBC system exhibited better oxidation resistance in the BC/TC interface than the two-layered R-TBC system. This was lead back to the Al enrichment, which slows down the formation rate of transition metal oxides during thermal loading.

Recent Progress and Required Developments in Atmospheric Corrosion of Galvanised Steel and Zinc

PubMed Central

Cole, Ivan S.

2017-01-01

This paper reviews the progress in atmospheric corrosion of zinc since 2009. It firstly summarises the state of the art in 2009, then outlines progress since 2009, and then looks at the significance of this progress and the areas the need more research. Within this framework, it looks at climate effects, oxide formation, oxide properties, pitting, laboratory duplication of atmospheric corrosion, and modelling. The major findings are that there have been major advances in the fields understanding of the structure of corrosion patina, in particular their layered structure and the presence of compact layers, local corrosion attacks have been found to be a significant process in atmospheric corrosion and experiments under droplets are leading to new understanding of the criticality of drop size in regulating atmospheric corrosion processes. Further research is indicating that zinc oxide within corrosion products may promote the oxygen reduction reaction (ORR) and that, in porous oxides, the ORR would control pore chemistry and may promote oxide densification. There is a strong need for more research to understand more deeply the formation and properties of these layered oxides as well as additional research to refine and quantify our emerging understanding of corrosion under droplets. PMID:29120373

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.

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.

Comparison and characterization of different tunnel layers, suitable for passivated contact formation

NASA Astrophysics Data System (ADS)

Ling, Zhi Peng; Xin, Zheng; Ke, Cangming; Jammaal Buatis, Kitz; Duttagupta, Shubham; Lee, Jae Sung; Lai, Archon; Hsu, Adam; Rostan, Johannes; Stangl, Rolf

2017-08-01

Passivated contacts for solar cells can be realized using a variety of differently formed ultra-thin tunnel oxide layers. Assessing their interface properties is important for optimization purposes. In this work, we demonstrate the ability to measure the interface defect density distribution D it(E) and the fixed interface charge density Q f for ultra-thin passivation layers operating within the tunnel regime (<2 nm). Various promising tunnel layer candidates [i.e., wet chemically formed SiO x , UV photo-oxidized SiO x , and atomic layer deposited (ALD) AlO x ] are investigated for their potential application forming electron or hole selective tunnel layer passivated contacts. In particular, ALD AlO x is identified as a promising tunnel layer candidate for hole-extracting passivated contact formation, stemming from its high (negative) fixed interface charge density in the order of -6 × 1012 cm-2. This is an order of magnitude higher compared to wet chemically or UV photo-oxidized formed silicon oxide tunnel layers, while keeping the density of interface defect states D it at a similar level (in the order of ˜2 × 1012 cm-2 eV-1). This leads to additional field effect passivation and therefore to significantly higher measured effective carrier lifetimes (˜2 orders of magnitude). A surface recombination velocity of ˜40 cm/s has been achieved for a 1.5 nm thin ALD AlO x tunnel layer prior to capping by an additional hole transport material, like p-doped poly-Si or PEDOT:PSS.

Enhanced electrochemical performance of Li-rich layered cathode materials via chemical activation of Li2MnO3 component and formation of spinel/carbon coating layer

NASA Astrophysics Data System (ADS)

Pang, Shengli; Xu, Kaijie; Wang, Yonggang; Shen, Xiangqian; Wang, Wenzhi; Su, Yanjing; Zhu, Meng; Xi, Xiaoming

2017-10-01

Li-rich layered oxides are promising cathode materials for advanced Li-ion batteries because of their high specific capacity and operating potential. In this work, the Li-rich layered oxide Li1·2Mn0·54Ni0·13Co0·13O2 (LMNC), is modified via a carbonization-reduction process (yielding the corresponding reduced compound denoted LMNC-R). Compared to the pristine oxide, LMNC-R delivers significantly enhanced initial discharge capacity/columbic efficiency, remarkably improved rate performance with an accelerated Li+ diffusion rate, and significantly increased capacity/voltage retention. The specific energy density and energy retention after 100 cycles increase from 378.2 Wh kg-1 and 47.7% for LMNC to 572.0 Wh kg-1 and 71.3%, respectively, for LMNC-R. The enhancement in the electrochemical performance of LMNC-R can be attributed to the synchronous formation of the oxygen non-stoichiometric Li2MnO3-δ component and to the carbon/spinel double coating layer in the material that resulted from the post-treatment process. Thus, the carbonization-reduction modification process can be used to tailor the structural evolution procedure and to suppress the metal ion dissolution of the Li-rich layered oxide during cycling.

High-temperature oxidation behavior and mechanism of a new type of wrought Ni-Fe-Cr-Al superalloy up to 1300 C

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

Huang, J.; Fang, H.; Fu, X.

The oxidation behavior of a new type of wrought Ni-Fe-Cr-Al superalloys has been investigated systematically in the temperature range of 1,100 to 1,300 C. Results are compared with those of alloy 214, Inconel 600, and GH 3030. It is shown that the oxidation resistance of the new superalloys is excellent and much better than that of the comparison alloys. Scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and X-ray diffraction (XRD) experiments reveal that the excellent oxidation resistance of the new superalloy is due to the formation of a dense, stable and continuous Al{sub 2}O{sub 3} and Cr{sub 2}O{sub 3}more » oxide layer at high temperatures. Differential thermal analysis (DTA) shows that the formation of Cr{sub 2}O{sub 3} and Al{sub 2}O{sub 3} oxide layers on the new superalloy reaches a maximum at 1,060 and 1,356 C, respectively. The Cr{sub 2}O{sub 3} layer peels off easily, and the single dense Al{sub 2}O{sub 3} layer remains, giving good oxidation resistance at temperatures higher than 1,150 C. In addition, the new superalloy possesses high mechanical strength at high temperatures. On-site tests showed that the new superalloy has ideal oxidation resistance and can be used at high temperatures up to 1,300 C in various oxidizing and corrosion atmospheres, such as those containing SO{sub 2}, CO{sub 2} etc., for long periods.« less

Structural changes in the nano-oxide layer with annealing in specular spin valves

NASA Astrophysics Data System (ADS)

Jang, S. H.; Kim, Y. W.; Kang, T.; Kim, H. J.; Kim, K. Y.

2003-05-01

We investigated microstructural changes in a nano-oxide layer (NOL) with annealing in specular spin valves (SVs) by cross-sectional transmission electron microscopy and x-ray photoelectron spectroscopy analysis. In the SV annealed at high temperature of 400 °C, an increase in thickness and a local breakdown of the NOL were observed. This local coarsening of the NOL is closely related to the formation of Mn oxides in the oxide-rich part of the NOL through Mn diffusion. Thus, the chemical structure of the NOL changes to the structure with Mn oxide-rich content after annealing.

Corrosion characteristics of Ni-base superalloys in high temperature steam with and without hydrogen

NASA Astrophysics Data System (ADS)

Kim, Donghoon; Kim, Daejong; Lee, Ho Jung; Jang, Changheui; Yoon, Duk Joo

2013-10-01

The hot steam corrosion behavior of Alloy 617 and Haynes 230 were evaluated in corrosion tests performed at 900 °C in steam and steam + 20 vol.% H2 environments. Corrosion rates of Alloy 617 was faster than that of Haynes 230 at 900 °C in steam and steam + 20 vol.% H2 environments. When hydrogen was added to steam, the corrosion rate was accelerated because added hydrogen increased the concentration of Cr interstitial defects in the oxide layer. Isolated nodular MnTiO3 oxides were formed on the MnCr2O4/Cr2O3 oxide layer and sub-layer Cr2O3 was formed in steam and steam + 20 vol.% H2 for Alloy 617. On the other hand, a MnCr2O4 layer was formed on top of the Cr2O3 oxide layer for Haynes 230. The extensive sub-layer Cr2O3 formation resulted from the oxygen or hydroxide inward diffusion in such environments. When hydrogen was added, the initial surface oxide morphology was changed from a convex shape to platelets because of the accelerated diffusion of cations under the oxide layer.

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

Lu, Ping; Yan, Pengfei; Romero, Eric

Capacity loss, and voltage decrease upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[Li xMn yTM 1-x-y]O 2, TM = Ni, Co or Fe) have recently been attributed to the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li 0.2Ni 0.2Mn 0.6]O 2 (LNMO) particles, which are identical to those reported due to the charge-discharge cycle butmore » are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by electron dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LNMO is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. The observation through this study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.« less

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

Lu, Ping; Yan, Pengfei; Romero, Eric

Capacity loss, and voltage fade upon electrochemical charge-discharge cycling observed in lithium-rich layered cathode oxides (Li[LixMnyTM1-x-y]O2 , TM = Ni, Co or Fe) have recently been identified to be correlated to the gradual phase transformation, featuring the formation of a surface reconstructed layer (SRL) that evolves from a thin (<2 nm), defect spinel layer upon the first charge, to a relatively thick (~5 nm), spinel or rock-salt layer upon continuous charge-discharge cycling. Here we report observations of a SRL and structural evolution of the SRL on the Li[Li0.2Ni0.2Mn0.6]O2 (LMR) particles, which are identical to those reported due to the charge-dischargemore » cycle but are a result of electron-beam irradiation during scanning transmission electron microscopy (STEM) imaging. Sensitivity of the lithium-rich layered oxides to high-energy electrons leads to the formation of thin, defect spinel layer on surfaces of the particles when exposed to a 200 kV electron beam for as little as 30 seconds under normal high-resolution STEM imaging conditions. Further electron irradiation produces a thicker layer of the spinel phase, ultimately producing a rock-salt layer at a higher electron exposure. Atomic-scale chemical mapping by energy dispersive X-ray spectroscopy in STEM indicates the electron-beam-induced SRL formation on LMR is accomplished by migration of the transition metal ions to the Li sites without breaking down the lattice. This study provides an insight for understanding the mechanism of forming the SRL and also possibly a mean to study structural evolution in the Li-rich layered oxides without involving the electrochemistry.« less

Growth of micrometric oxide layers for the study of metallic surfaces decontamination by laser

NASA Astrophysics Data System (ADS)

Carvalho, Luisa; Pacquentin, Wilfried; Tabarant, Michel; Maskrot, Hicham; Semerok, Alexandre

2017-09-01

The nuclear industry produces a wide range of radioactive waste in term of level of hazard, contaminants and material. For metallic equipment like steam generators, the radioactivity is mainly located in the oxide surface. In order to study and develop techniques for dismantling and for decontamination in a safe way, it is important to have access to oxide layers with a representative distribution of non-radioactive contaminants. We propose a method of formation of oxide layer on stainless steel 304L with europium (Eu) as contaminant marker. In this method, an Eu-solution is sprayed on the stainless steel samples. The specimen are firstly treated with a pulsed nanosecond laser and secondly the steel samples are exposed to a 600°C furnace for various durations in order to grow an oxide layer. The oxide structure and in-depth distribution of Eu in the oxide layer are analysed by scanning electron microscopy coupled with energy dispersive X-ray microanalyzer, and by glow discharge optical emission or mass spectrometry. The oxide layers were grown to thicknesses in the range of 200 nm to 4.5 μm regarding to the laser treatment parameters and the heating duration. These contaminated oxides have a `duplex structure' with a mean weight percentage of 0.5% of europium in the volume of the oxide layer. It appears that europium implementation prevents the oxide growth by furnace but has no impact on laser heating. These oxide layers are used to study the decontamination of metallic surfaces such as stainless steel 304L using a nanosecond pulsed laser.

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

Bolotov, V. V.; Knyazev, E. V.; Ponomareva, I. V.

The oxidation of mesoporous silicon in a double-layer “macroporous silicon–mesoporous silicon” structure is studied. The morphology and dielectric properties of the buried insulating layer are investigated using electron microscopy, ellipsometry, and electrical measurements. Specific defects (so-called spikes) are revealed between the oxidized macropore walls in macroporous silicon and the oxidation crossing fronts in mesoporous silicon. It is found that, at an initial porosity of mesoporous silicon of 60%, three-stage thermal oxidation leads to the formation of buried silicon-dioxide layers with an electric-field breakdown strength of E{sub br} ~ 10{sup 4}–10{sup 5} V/cm. Multilayered “porous silicon-on-insulator” structures are shown to bemore » promising for integrated chemical micro- and nanosensors.« less

Surface treatment to form a dispersed Y2O3 layer on Zircaloy-4 tubes

NASA Astrophysics Data System (ADS)

Jung, Yang-Il; Kim, Hyun-Gil; Guim, Hwan-Uk; Lim, Yoon-Soo; Park, Jung-Hwan; Park, Dong-Jun; Yang, Jae-Ho

2018-01-01

Zircaloy-4 is a traditional zirconium-based alloy developed for application in nuclear fuel cladding tubes. The surfaces of Zircaloy-4 tubes were treated using a laser beam to increase their mechanical strength. Laser beam scanning of a tube coated with yttrium oxide (Y2O3) resulted in the formation of a dispersed oxide layer in the tube's surface region. Y2O3 particles penetrated the Zircaloy-4 during the laser treatment and were distributed uniformly in the surface region. The thickness of the dispersed oxide layer varied from 50 to 140 μm depending on the laser beam trajectory. The laser treatment also modified the texture of the tube. The preferred basal orientation along the normal to the tube surface disappeared, and a random structure appeared after laser processing. The most obvious result was an increase in the mechanical strength. The tensile strength of Zircaloy-4 increased by 10-20% with the formation of the dispersed oxide layer. The compressive yield stress also increased, by more than 15%. Brittle fracture was observed in the surface-treated samples during tensile and compressive deformation at room temperature; however, the fracture behavior was changed in ductile at elevated temperatures.

Electron affinity of cubic boron nitride terminated with vanadium oxide

NASA Astrophysics Data System (ADS)

Yang, Yu; Sun, Tianyin; Shammas, Joseph; Kaur, Manpuneet; Hao, Mei; Nemanich, Robert J.

2015-10-01

A thermally stable negative electron affinity (NEA) for a cubic boron nitride (c-BN) surface with vanadium-oxide-termination is achieved, and its electronic structure was analyzed with in-situ photoelectron spectroscopy. The c-BN films were prepared by electron cyclotron resonance plasma-enhanced chemical vapor deposition employing BF3 and N2 as precursors. Vanadium layers of ˜0.1 and 0.5 nm thickness were deposited on the c-BN surface in an electron beam deposition system. Oxidation of the metal layer was achieved by an oxygen plasma treatment. After 650 °C thermal annealing, the vanadium oxide on the c-BN surface was determined to be VO2, and the surfaces were found to be thermally stable, exhibiting an NEA. In comparison, the oxygen-terminated c-BN surface, where B2O3 was detected, showed a positive electron affinity of ˜1.2 eV. The B2O3 evidently acts as a negatively charged layer introducing a surface dipole directed into the c-BN. Through the interaction of VO2 with the B2O3 layer, a B-O-V layer structure would contribute a dipole between the O and V layers with the positive side facing vacuum. The lower enthalpy of formation for B2O3 is favorable for the formation of the B-O-V layer structure, which provides a thermally stable surface dipole and an NEA surface.

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.

Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel.

PubMed

Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

2016-01-07

Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially 'clean' strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2(•-) radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO(-)) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems, especially once the influence of both the atomic-scale structure and the presence of oxide are mechanistically better understood.

Formation of thin walled ceramic solid oxide fuel cells

DOEpatents

Claar, Terry D.; Busch, Donald E.; Picciolo, John J.

1989-01-01

To reduce thermal stress and improve bonding in a high temperature monolithic solid oxide fuel cell (SOFC), intermediate layers are provided between the SOFC's electrodes and electrolyte which are of different compositions. The intermediate layers are comprised of a blend of some of the materials used in the electrode and electrolyte compositions. Particle size is controlled to reduce problems involving differential shrinkage rates of the various layers when the entire structure is fired at a single temperature, while pore formers are provided in the electrolyte layers to be removed during firing for the formation of desired pores in the electrode layers. Each layer includes a binder in the form of a thermosetting acrylic which during initial processing is cured to provide a self-supporting structure with the ceramic components in the green state. A self-supporting corrugated structure is thus formed prior to firing, which the organic components of the binder and plasticizer removed during firing to provide a high strength, high temperature resistant ceramic structure of low weight and density.

Surface functionalization of magnetic nanoparticles formed by self-associating hydrophobized oxidized dextrans

NASA Astrophysics Data System (ADS)

Farber, Shimon; Ickowicz, Diana E.; Melnik, Kristie; Yudovin-Farber, Ira; Recko, Daniel; Rampersaud, Arfaan; Domb, Abraham J.

2014-06-01

Magnetic iron oxide nanoparticles surface covered with oleic acid layer followed by a second layer of hydrophobized oxidized dextran aldehyde were prepared and tested for physico-chemical properties and ligand- and cell-specific binding. It was demonstrated that oleic acid-iron oxide nanoparticles coated with an additional layer of hydrophobized oxidized dextran were dispersible in buffer solutions and possess surface aldehyde active groups available for further binding of ligands or markers via imine or amine bond formation. Hydrophobized dextrans were synthesized by periodate oxidation and conjugation of various alkanamines to oxidized dextran by imination. Physico-chemical properties, as separation using magnetic field, magnetite concentration, and particle diameter, of the prepared magnetic samples are reported. The biotin-binding protein, neutravidin, was coupled to the particle surface by a simple reductive amination procedure. The particles were used for specific cell separation with high specificity.

Native oxide formation on pentagonal copper nanowires: A TEM study

NASA Astrophysics Data System (ADS)

Hajimammadov, Rashad; Mohl, Melinda; Kordas, Krisztian

2018-06-01

Hydrothermally synthesized copper nanowires were allowed to oxidize in air at room temperature and 30% constant humidity for the period of 22 days. The growth of native oxide layer was followed up by high-resolution transmission electron microscopy and diffraction to reveal and understand the kinetics of the oxidation process. Copper oxides appear in the form of differently oriented crystalline phases around the metallic core as a shell-like layer (Cu2O) and as nanoscopic islands (CuO) on the top of that. Time dependent oxide thickness data suggests that oxidation follows the field-assisted growth model at the beginning of the process, as practically immediately an oxide layer of ∼2.8 nm thickness develops on the surface. However, after this initial rapid growth, the local field attenuates and the classical parabolic diffusion limited growth plays the main role in the oxidation. Because of the single crystal facets on the side surface of penta-twinned Cu nanowires, the oxidation rate in the diffusion limited regime is lower than in polycrystalline films.

Oxidation of SUS-316 stainless steel for fast breeder reactor fuel cladding under oxygen pressure controlled by Ni/NiO oxygen buffer

NASA Astrophysics Data System (ADS)

Saito, Minoru; Furuya, Hirotaka; Sugisaki, Masayasu

1985-09-01

Oxidation of SUS-316 stainless steel for a fast breeder reactor fuel cladding was examined in the temperature range of 843-1010 K under the oxygen pressure of 1017 t - 10 t-13 Pa hy use of an experimental technique of a Ni/NiO oxygen buffer. The formation of the duplex oxide layer, i.e. an outer Fe 3O 4 layer and an inner (Fe, Cr, Ni)-spinel layer, was observed and the oxidation kinetics was found to obey the parabolic rate law. The oxygen pressure and temperature dependence of the parabolic rate constant kp( PO2, T) was determined as follows: kp( PO2, T)/ kg2 · m-1 · s-1 = 0.170( PO2/ Pa) 0.141exp[-114 × 10 3/( RT/ J)]. On the basis of the oxidation kinetics and the metallographic information, the outward diffusion of Fe in the outer oxide layer was assigned to be the rate-determining process.

Apatite grown in niobium by two-step plasma electrolytic oxidation.

PubMed

Pereira, Bruno Leandro; Lepienski, Carlos Maurício; Mazzaro, Irineu; Kuromoto, Neide Kazue

2017-08-01

Plasma electrolytic oxidation (PEO) of niobium plates were done electrochemically in two steps with electrolytes containing phosphorous and calcium being observed the formation of crystalline apatite. All samples were submitted to a first step of PEO using an electrolyte containing phosphate ions. The second oxidization step was made using three different electrolytes. Some samples were oxidized by PEO in electrolyte containing calcium, while in other samples it was used two mixtures of phosphoric acid and calcium acetate monohydrate solutions. Three different surface layers were obtained. The morphology and chemical composition of the films were analyzed by scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS) respectively. It was observed that all samples submitted to two-step oxidation shown porous surface and a calcium and phosphorus rich layer. Average surface roughness (Ra) was measured by a profilometer remaining in the sub-micrometric range. The contact angle by sessile drop technique, using 1μL of distilled water was performed with an optical goniometer. It was verified a higher hydrophilicity in all surfaces compared to the polished niobium. Orthorhombic Nb 2 O 5 was identified by XRD in the oxide layer. Crystalline apatite was identified by XRD in surfaces after the second oxidation made with the Ca-rich electrolyte and a mixture of an electrolyte richer in Ca compared to P. These results indicate that a two-step oxidized niobium surface present great features for applications in the osseointegration processes: favorable chemical composition that increase the biocompatibility, the formation of crystalline niobium pentoxide (orthorhombic), high hydrophilicity and formation of crystalline calcium phosphate (apatite) under adequate electrolyte composition. Copyright © 2016 Elsevier B.V. All rights reserved.

Linkage of iron elution and dissolved oxygen consumption with removal of organic pollutants by nanoscale zero-valent iron: Effects of pH on iron dissolution and formation of iron oxide/hydroxide layer.

PubMed

Fujioka, Nanae; Suzuki, Moe; Kurosu, Shunji; Kawase, Yoshinori

2016-02-01

The iron elution and dissolved oxygen (DO) consumption in organic pollutant removal by nanoscale zero-valent iron (nZVI) was examined in the range of solution pH from 3.0 to 9.0. Their behaviors were linked with the removal of organic pollutant through the dissolution of iron and the formation of iron oxide/hydroxide layer affected strongly by solution pH and DO. As an example of organic pollutants, azo-dye Orange II was chosen in this study. The chemical composition analyses before and after reaction confirmed the corrosion of nZVI into ions, the formation of iron oxide/hydroxide layer on nZVI surface and the adsorption of the pollutant and its intermediates. The complete decolorization of Orange II with nZVI was accomplished very quickly. On the other hand, the total organic carbon (TOC) removal was considerably slow and the maximum TOC removal was around 40% obtained at pH 9.0. The reductive cleavage of azo-bond by emitted electrons more readily took place as compared with the cleavage of aromatic rings of Orange II leading to the degradation to smaller molecules and subsequently the mineralization. A reaction kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach was developed to elucidate mechanisms for organic pollutant removal controlled by the formation of iron oxide/hydroxide layer, the progress of which could be characterized by considering the dynamic concentration changes in Fe(2+) and DO. The dynamic profiles of Orange II removal linked with Fe(2+) and DO could be reasonably simulated in the range of pH from 3.0 to 9.0. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electric-Field Control of Oxygen Vacancies and Magnetic Phase Transition in a Cobaltite/Manganite Bilayer

NASA Astrophysics Data System (ADS)

Cui, B.; Song, C.; Li, F.; Zhong, X. Y.; Wang, Z. C.; Werner, P.; Gu, Y. D.; Wu, H. Q.; Saleem, M. S.; Parkin, S. S. P.; Pan, F.

2017-10-01

Manipulation of oxygen vacancies (VO ) in single oxide layers by varying the electric field can result in significant modulation of the ground state. However, in many oxide multilayers with strong application potentials, e.g., ferroelectric tunnel junctions and solid-oxide fuel cells, understanding VO behavior in various layers under an applied electric field remains a challenge, owing to complex VO transport between different layers. By sweeping the external voltage, a reversible manipulation of VO and a corresponding fixed magnetic phase transition sequence in cobaltite/manganite (SrCoO3 -x/La0.45Sr0.55MnO3 -y ) heterostructures are reported. The magnetic phase transition sequence confirms that the priority of electric-field-induced VO formation or annihilation in the complex bilayer system is mainly determined by the VO formation energies and Gibbs free-energy differences, which is supported by theoretical analysis. We not only realize a reversible manipulation of the magnetic phase transition in an oxide bilayer but also provide insight into the electric-field control of VO engineering in heterostructures.

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.

Effect of hot water and heat treatment on the apatite-forming ability of titania films formed on titanium metal via anodic oxidation in acetic acid solutions.

PubMed

Cui, Xinyu; Kim, Hyun-Min; Kawashita, Masakazu; Wang, Longbao; Xiong, Tianying; Kokubo, Tadashi; Nakamura, Takashi

2008-04-01

Titanium and its alloys have been widely used for orthopedic implants because of their good biocompatibility. We have previously shown that the crystalline titania layers formed on the surface of titanium metal via anodic oxidation can induce apatite formation in simulated body fluid, whereas amorphous titania layers do not possess apatite-forming ability. In this study, hot water and heat treatments were applied to transform the titania layers from an amorphous structure into a crystalline structure after titanium metal had been anodized in acetic acid solution. The apatite-forming ability of titania layers subjected to the above treatments in simulated body fluid was investigated. The XRD and SEM results indicated hot water and/or heat treatment could greatly transform the crystal structure of titania layers from an amorphous structure into anatase, or a mixture of anatase and rutile. The abundance of Ti-OH groups formed by hot water treatment could contribute to apatite formation on the surface of titanium metals, and subsequent heat treatment would enhance the bond strength between the apatite layers and the titanium substrates. Thus, bioactive titanium metals could be prepared via anodic oxidation and subsequent hot water and heat treatment that would be suitable for applications under load-bearing conditions.

Oxyhydroxide of metallic nanowires in a molecular H2O and H2O2 environment and their effects on mechanical properties.

PubMed

Aral, Gurcan; Islam, Md Mahbubul; Wang, Yun-Jiang; Ogata, Shigenobu; Duin, Adri C T van

2018-06-14

To avoid unexpected environmental mechanical failure, there is a strong need to fully understand the details of the oxidation process and intrinsic mechanical properties of reactive metallic iron (Fe) nanowires (NWs) under various aqueous reactive environmental conditions. Herein, we employed ReaxFF reactive molecular dynamics (MD) simulations to elucidate the oxidation of Fe NWs exposed to molecular water (H2O) and hydrogen peroxide (H2O2) environment, and the influence of the oxide shell layer on the tensile mechanical deformation properties of Fe NWs. Our structural analysis shows that oxidation of Fe NWs occurs with the formation of different iron oxide and hydroxide phases in the aqueous molecular H2O and H2O2 oxidizing environments. We observe that the resulting microstructure due to pre-oxide shell layer formation reduces the mechanical stress via increasing the initial defect sites in the vicinity of the oxide region to facilitate the onset of plastic deformation during tensile loading. Specifically, the oxide layer of Fe NWs formed in the H2O2 environment has a relatively significant effect on the deterioration of the mechanical properties of Fe NWs. The weakening of the yield stress and Young modulus of H2O2 oxidized Fe NWs indicates the important role of local oxide microstructures on mechanical deformation properties of individual Fe NWs. Notably, deformation twinning is found as the primary mechanical plastic deformation mechanism of all Fe NWs, but it is initially observed at low strain and stress level for the oxidized Fe NWs.

Influence of temperature on oxidation mechanisms of fiber-textured AlTiTaN coatings.

PubMed

Khetan, Vishal; Valle, Nathalie; Duday, David; Michotte, Claude; Delplancke-Ogletree, Marie-Paule; Choquet, Patrick

2014-03-26

The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.

Role of Al in Zn bath on the formation of the inhibition layer during hot-dip galvanizing for a 1.2Si-1.5Mn transformation-induced plasticity steel

NASA Astrophysics Data System (ADS)

Wang, Kuang-Kuo; Hsu, Chiung-Wen; Chang, Liuwen; Gan, Dershin; Yang, Kuo-Cheng

2013-11-01

This study investigated the interaction between the Al in the Zn bath and the surface oxides formed by selective oxidation on a 1.2Si-1.5Mn TRIP steel during hot-dip galvanizing. XPS and TEM were employed for characterization. The results indicated that the amorphous xMnO·SiO2 oxide could react with Al to form a Si-Mn-Al-containing oxide. The crystalline MnSiO3 and Mn2SiO4 oxides could be largely reduced by Al to form holes in the oxide film. Consequently, the steel covered by a layer of mixed xMnO·SiO2 and MnSiO3 could form a continuous Fe2Al5 inhibition layer and showed the highest galvanizability among the three samples examined.

Formation and anisotropic magnetoresistance of Co/Pt nano-contacts through aluminum oxide barrier

NASA Astrophysics Data System (ADS)

Al-Mahdawi, Muftah; Sahashi, Masashi

2014-01-01

We report on the observation of anisotropic magnetoresistance (AMR) in vertical asymmetric nano-contacts (NCs) made through AlOx nano-oxide layer (NOL) formed by ion-assisted oxidation method in the film stack of Co/AlOx-NOL/Pt. Analysis of NC formation was based on in situ conductive atomic force microscopy and transmission electron microscopy. Depending on the purity of NCs from Al contamination, we observed up to 29% AMR ratio at room temperature.

Cobalt germanide nanostructure formation and memory characteristic enhancement in silicon oxide films

NASA Astrophysics Data System (ADS)

Joo, Beom Soo; Kim, Hyunseung; Jang, Seunghun; Han, Dongwoo; Han, Moonsup

2018-08-01

We investigated nano-floating gate memory having a charge trap layer (CTL) composed of cobalt germanide nanostructure (ns-CoGe). A tunneling oxide layer; a CTL containing Co, Ge, and Si; and a blocking oxide layer were sequentially deposited on a p-type silicon substrate by RF magnetron sputtering and low-pressure chemical vapor deposition. We optimized the CTL formation conditions by rapid thermal annealing at a somewhat low temperature (about 830 °C) by considering the differences in Gibbs free energy and chemical enthalpy among the components. To characterize the charge storage properties, capacitance-voltage (C-V) measurements were performed. Further, we used X-ray photoelectron spectroscopy for chemical analysis of the CTL. In this work, we not only report that the C-V measurement shows a remarkable opening of the memory window for the ns-CoGe compared with those of nanostructures composed of Co or Ge alone, but also clarify that the improvement in the memory characteristics originates in the nanostructure formation, which consists mainly of Co-Ge bonds. We expect ns-CoGe to be a strong candidate for fabrication of next-generation memory devices.

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

NASA Technical Reports Server (NTRS)

Huang, C. J.; Yeager, E.; Ogrady, W. E.

1975-01-01

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

High temperature oxidation of alumina forming cast austenitic stainless steels within an environment of pure steam

NASA Astrophysics Data System (ADS)

Prenzlow, Elmer A.

Steam cracking of hydrocarbons in the petrochemical industry is a multibillion dollar industry. The processes performed in these plants create byproducts that negatively affect the integrity of stainless steel piping through high temperature corrosion. Alloys used presently in industry rely on the formation of chromium oxide (chromia) as a protective layer between the bulk metal pipe and chemical byproducts. However, chromia can become susceptible to attack from aggressive species such as carbon, water vapor, and sulfur compounds, thus creating a need for a better protection method. A new series of austenitic stainless steels have been developed in recent years that, rather than forming chromia, create a protective layer of aluminum oxide (alumina) under oxidative conditions. These alloys have high nickel content for the stabilization of the austenitic phase, and a more thermodynamically stable oxide layer relative to the traditional chromia formers. Consequently, alumina forming alloys have been proposed as replacements for chromia forming alloys in the petrochemical industry. General oxidation testing has been performed on alumina forming alloys under dry and 10% water vapor conditions. However, oxidation conditions in industry resemble a 100% steam environment. Therefore, test methods to mimic such conditions are needed so that alloys can be tested and developed further for these applications. Four alloys with aluminum contents ranging from 2.6 to 3.9 wt% were cut from centrifugally cast pipes and subjected to oxidation in an environment of pure steam for up to 30 hours, at temperatures of 800 °C and 950 °C. Samples were analyzed using Raman, SEM, and EDS and showed a continuous alumina layer free of cracks. The alumina layer thickness increased with time. Additionally, larger thicknesses were observed in samples oxidized at 950 °C from those of 800 °C. Thickness measurements were used to calculate parabolic and non-parabolic oxidation rate constants. Samples were compared using calculated parabolic and modified parabolic rates of oxidation. Plots for the prediction of oxide layer thickness were generated both for the Wagner model of parabolic oxidation, and an experimentally determined modification to said model. Oxide scale thickness as formed in pure steam was shown to be related to the aluminum content of the alloy and the temperature and time of exposure. Further testing of alumina forming stainless steels in other concentrations of steam would allow for the determination of steam's effect on alumina formation kinetics. In addition, tests at additional temperatures between 800 and 950 °C would allow for the calculation of activation energies and full understanding of the oxide layer. Finally, the analysis of alumina layer thickness effects on coking performance in a petrochemical application would allow for the potential transition of these alloys into the commercial market.

Oxidation characteristics of Ti-25Al-10Nb-3V-1Mo intermetallic alloy

NASA Technical Reports Server (NTRS)

Wallace, Terryl A.; Clark, Ronald K.; Sankaran, Sankara N.; Wiedemann, Karl E.

1990-01-01

Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x ray diffraction techniques, electron microprobe analysis, and energy dispersive x ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.

Photovoltaic devices comprising zinc stannate buffer layer and method for making

DOEpatents

Wu, Xuanzhi; Sheldon, Peter; Coutts, Timothy J.

2001-01-01

A photovoltaic device has a buffer layer zinc stannate Zn.sub.2 SnO.sub.4 disposed between the semiconductor junction structure and the transparent conducting oxide (TCO) layer to prevent formation of localized junctions with the TCO through a thin window semiconductor layer, to prevent shunting through etched grain boundaries of semiconductors, and to relieve stresses and improve adhesion between these layers.

Surface-interface exploration of Mg deposited on Si(100) and oxidation effect on interfacial layer

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

Sarpi, B.; Daineche, R.; Girardeaux, C.

Using scanning tunneling microscopy and spectroscopy, Auger electron spectroscopy, and low energy electron diffraction, we have studied the growth of Mg deposited on Si(100)-(2 × 1). Coverage from 0.05 monolayer (ML) to 3 ML was investigated at room temperature. The growth mode of the magnesium is a two steps process. At very low coverage, there is formation of an amorphous ultrathin silicide layer with a band gap of 0.74 eV, followed by a layer-by-layer growth of Mg on top of this silicide layer. Topographic images reveal that each metallic Mg layer is formed by 2D islands coalescence process on top of the silicidemore » interfacial layer. During oxidation of the Mg monolayer, the interfacial silicide layer acts as diffusion barrier for the oxygen atoms with a decomposition of the silicide film to a magnesium oxide as function of O{sub 2} exposure.« less

Surface Oxidation of the High-Strength Steels Electrodeposited with Cu or Fe and the Resultant Defect Formation in Their Coating during the Following Galvanizing and Galvannealing Processes

NASA Astrophysics Data System (ADS)

Choi, Yun-Il; Beom, Won-Jin; Park, Chan-Jin; Paik, Doojin; Hong, Moon-Hi

2010-12-01

This study examined the surface oxidation of high-strength steels electrodeposited with Cu or Fe and the resultant defect formation in their coating during the following galvanizing and galvannealing processes. The high-strength steels were coated with an Cu or Fe layer by the electroplating method. Then, the coated steels were annealed in a reducing atmosphere, dipped in a molten zinc, and finally transformed into galvannealed steels through the galvannealing process. The formation of Si and Mn oxides on the surface of the high-strength steel was effectively suppressed, and the density of surface defects on the galvanized steel was significantly reduced by the pre-electrodeposition of Cu and Fe. This effect was more prominent for the steels electrodeposited at higher cathodic current densities. The finer electrodeposit layer formed at higher cathodic current density on the steels enabled the suppression of partial surface oxidation by Mn or Si and better wetting of Zn on the surface of the steels in the following galvanizing process. Furthermore, the pre-electrodeposited steels exhibited a smoother surface without surface cracks after the galvannealing process compared with the untreated steel. The diffusion of Fe and Zn in the Zn coating layer in the pre-electrodeposited steels appears to occur more uniformly during the galvannealing process due to the low density of surface defects induced by oxides.

Passivation of uranium towards air corrosion by N 2+ and C + ion implantation

NASA Astrophysics Data System (ADS)

Arkush, R.; Mintz, M. H.; Shamir, N.

2000-10-01

The passivation of uranium surfaces against air corrosion, by ion implantation processes was studied, using surface analysis methods. Implanting 45 keV N +2 and C + ions produces thin modified surface layers with gradual gradients of the corresponding compounds (i.e., nitrides and carbides, respectively), which avoid the formation of discontinuous interfaces typical to coatings. Such gradual interfaces impart excellent mechanical stability and adhesion to the modified layers, in spite of the large misfit between the metal substrate and the implantation on induced compounds. It turns out that these layers provide an almost absolute protection against air corrosion. A rapid initial stage of oxidation of the modified surface layers takes place, forming very thin protective oxidation zones (1-4 nm thick), which practically stop further air oxidation for years. The mechanism of the initial oxidation stage of the modified layers seems to vary with the type of surface (i.e., either nitrides or carbides). However, in any case the protection ability of the formed oxidation products is excellent, probably due to the close match between these compounds and the underlying nitrides or carbides.

Study the formation of porous surface layer for a new biomedical titanium alloy

NASA Astrophysics Data System (ADS)

Talib Mohammed, Mohsin; Diwan, Abass Ali; Ali, Osamah Ihsan

2018-03-01

In the present work, chemical treatment using hydrogen peroxide (H2O2) oxidation and subsequent thermal treatment was applied to create a uniform porous layer over the surface of a new metastable β-Ti alloy. The results revealed that this oxidation treatment can create a stable ultrafine porous film over the oxidized surface. This promoted the electrochemical characteristics of H2O2-treated Ti-Zr-Nb (TZN) alloy system, presenting nobler corrosion behavior in simulated body fluid (SBF) comparing with untreated sample.

Selective oxidation of cube textured Ni and Ni-Cr substrate for the formation of cube textured NiO as a component buffer layer for REBa 2Cu 3O 7+ x (REBCO) coated conductors

NASA Astrophysics Data System (ADS)

Lockman, Z.; Goldacker, W.; Nast, R.; deBoer, B.; MacManus-Driscoll, J. L.

2002-08-01

Thermal oxidation of cube textured, pure Ni and Ni-Cr tapes was undertaken under different oxidation conditions to form cube textured NiO for the use as a first component of buffer layer for the coated conductor. Cube textured NiO was formed on pure Ni after oxidising for more than 130 min in O 2 at 1250 °C. The oxide thickness was >30 μm. Much shorter oxidation times (20-40 min, NiO thickness of ∼5 μm) and lower temperature (1050 °C) were required to form a similar texture on Ni-Cr foils. In addition, NiO formed on Ni-13%Cr was more highly textured than Ni-10%Cr. A Cr 2O 3 inner layer and NiO outer layer was formed on the Ni-Cr alloys.

Evaluation of passive oxide layer formation-biocompatibility relationship in NiTi shape memory alloys: geometry and body location dependency.

PubMed

Toker, S M; Canadinc, D; Maier, H J; Birer, O

2014-03-01

A systematic set of ex-situ experiments were carried out on Nickel-Titanium (NiTi) shape memory alloy (SMA) in order to identify the dependence of its biocompatibility on sample geometry and body location. NiTi samples with three different geometries were immersed into three different fluids simulating different body parts. The changes observed in alloy surface and chemical content of fluids upon immersion experiments designed for four different time periods were analyzed in terms of ion release, oxide layer formation, and chemical composition of the surface layer. The results indicate that both sample geometry and immersion fluid significantly affect the alloy biocompatibility, as evidenced by the passive oxide layer formation on the alloy surface and ion release from the samples. Upon a 30 day immersion period, all three types of NiTi samples exhibited lower ion release than the critical value for clinic applications. However; a significant amount of ion release was detected in the case of gastric fluid, warranting a thorough investigation prior to utility of NiTi in gastrointestinal treatments involving long-time contact with tissue. Furthermore, certain geometries appear to be safer than the others for each fluid, providing a new set of guidelines to follow while designing implants making use of NiTi SMAs to be employed in treatments targeting specific body parts. Copyright © 2013 Elsevier B.V. All rights reserved.

How salt lakes affect atmospheric new particle formation: A case study in Western Australia.

PubMed

Kamilli, K A; Ofner, J; Krause, T; Sattler, T; Schmitt-Kopplin, P; Eitenberger, E; Friedbacher, G; Lendl, B; Lohninger, H; Schöler, H F; Held, A

2016-12-15

New particle formation was studied above salt lakes in-situ using a mobile aerosol chamber set up above the salt crust and organic-enriched layers of seven different salt lakes in Western Australia. This unique setup made it possible to explore the influence of salt lake emissions on atmospheric new particle formation, and to identify interactions of aqueous-phase and gas-phase chemistry. New particle formation was typically observed at enhanced air temperatures and enhanced solar irradiance. Volatile organic compounds were released from the salt lake surfaces, probably from a soil layer enriched in organic compounds from decomposed leaf litter, and accumulated in the chamber air. After oxidation of these organic precursor gases, the reaction products contributed to new particle formation with observed growth rates from 2.7 to 25.4nmh -1 . The presence of ferrous and ferric iron and a drop of pH values in the salt lake water just before new particle formation events indicated that organic compounds were also oxidized in the aqueous phase, affecting the new particle formation process in the atmosphere. The contribution of aqueous-phase chemistry to new particle formation is assumed, as a mixture of hundreds of oxidized organic compounds was characterized with several analytical techniques. This chemically diverse composition of the organic aerosol fraction contained sulfur- and nitrogen-containing organic compounds, and halogenated organic compounds. Coarse mode particles were analyzed using electron microscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy. Ultra-high resolution mass spectrometry was applied to analyze filter samples. A targeted mass spectral analysis revealed the formation of organosulfates from monoterpene precursors and two known tracers for secondary organic aerosol formation from atmospheric oxidation of 1,8-cineole, which indicates that a complex interplay of aqueous-phase and gas-phase oxidation of monoterpenes contributes to new particle formation in the investigated salt lake environment. Copyright © 2016. Published by Elsevier B.V.

Ethanol gas sensing performance of high-dimensional fuzz metal oxide nanostructure

NASA Astrophysics Data System (ADS)

Ibano, Kenzo; Kimura, Yoshihiro; Sugahara, Tohru; Lee, Heun Tae; Ueda, Yoshio

2018-04-01

Gas sensing ability of the He plasma induced fiber-like nanostructure, so-called fuzz structure, was firstly examined. A thin Mo layer deposited on a quartz surface was irradiated by He plasma to form the fuzz structure and oxidized by annealing in a quartz furnace. Electric conductivity of the fuzz Mo oxide layer was then measured through the Au electrodes deposited on the layer. Changes in electric conductivity by C2H5OH gas flow were examined as a function of temperature from 200 to 400 °C. Improved sensitivities were observed for the specimens after a fuzz nanostructure formation. However, the sensor developed in this study showed lower sensitivities than previously reported MoO3 nano-rod sensor, further optimization of oxidation is needed to improve the sensitivity.

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

Bandriyana,, E-mail: bandri@batan.go.id; Ismoyo, Agus Hadi; Dimyati, A.

Surface treatment by implantation with nitrogen-ion was performed on the commercial feritic high strength steel AISI 410 which is termed for high temperature applications. The aim of this research was focused on the surface modification to improve its high temperature oxidation property in the early stages. Ion implantation was carried out at acceleration energy of 100 KeV and ion current 10 mA for 30, 60 and 90 minutes. The samples were subjected to the high temperature oxidation test by means of thermogravimetry in a magnetic suspension balance (MSB) at 500 °C for 5 hours. The scanning electron microscopy (SEM), X-ray diffractionmore » spectrometry (XRD) and Vickers Hardness measurement were used for sample characterization. The formation of ferro-nitride phase after implantation did not occur, however a thin layer considered to contain nitrogen interstitials was detected. The oxidation of both samples before and after implantation followed parabolic kinetics indicating inward growth of oxide scale characteristically due to diffusion of oxygen anions towards matrix surface. After oxidation test relativelly stable oxide scales were observed. Oxidation rates decreased proportionally with the increasing of implantation time due to the formation of oxide layer which is considered to be effectiv inhibitor for the oxygen diffusion.« less

The influence of hydrogenation and oxygen vacancies on molybdenum oxides work function and gap states for application in organic optoelectronics.

PubMed

Vasilopoulou, Maria; Douvas, Antonios M; Georgiadou, Dimitra G; Palilis, Leonidas C; Kennou, Stella; Sygellou, Labrini; Soultati, Anastasia; Kostis, Ioannis; Papadimitropoulos, Giorgos; Davazoglou, Dimitris; Argitis, Panagiotis

2012-10-03

Molybdenum oxide is used as a low-resistance anode interfacial layer in applications such as organic light emitting diodes and organic photovoltaics. However, little is known about the correlation between its stoichiometry and electronic properties, such as work function and occupied gap states. In addition, despite the fact that the knowledge of the exact oxide stoichiometry is of paramount importance, few studies have appeared in the literature discussing how this stoichiometry can be controlled to permit the desirable modification of the oxide's electronic structure. This work aims to investigate the beneficial role of hydrogenation (the incorporation of hydrogen within the oxide lattice) versus oxygen vacancy formation in tuning the electronic structure of molybdenum oxides while maintaining their high work function. A large improvement in the operational characteristics of both polymer light emitting devices and bulk heterojunction solar cells incorporating hydrogenated Mo oxides as hole injection/extraction layers was achieved as a result of favorable energy level alignment at the metal oxide/organic interface and enhanced charge transport through the formation of a large density of gap states near the Fermi level.

In situ atomic-scale imaging of the metal/oxide interfacial transformation

DOE PAGES

Zou, Lianfeng; Li, Jonathan; Zakharov, Dmitri; ...

2017-08-21

Directly probing structure dynamics at metal/oxide interfaces has been a major challenge due to their buried nature.Using environmental transmission electron microscopy,here we report observations of the in-place formation of Cu 2O/Cu interfaces via the oxidation of Cu, and subsequently probe the atomic mechanisms by which interfacial transformation and grain rotation occur at the interfaces during reduction in an H 2 gas environment. The Cu 2O→Cu transformation is observed to occur initially along the Cu 2O/Cu interface in a layer-by-layer manner.The accumulation of oxygen vacancies at the Cu 2O/Cu interface drives the collapse of the Cu 2O lattice near the interfacemore » region, which results in a tilted Cu 2O/Cu interface with concomitant Cu 2O island rotation. Lastly, these results provide unprecedented microscopic detail regarding the redox reactions of supported oxides,which differs fundamentally from the reduction of bulk or isolated oxides that requires the formation of new interfaces between the parent oxide and the reduced phase.« less

The oxidation behavior of a model molybdenum/tungsten-containing alloy in air alone and in air with trace levels of NaCl(g)

NASA Technical Reports Server (NTRS)

Smeggil, J. G.; Bornstein, N. S.

1983-01-01

Thermogravimetric, metallographic, and X-ray studies of a model alloy, Ni-(17 a/o)Al-(10 a/o)Mo+W, oxidized in dry air at 600-1200 C and in air with 10 ppm NaCl gas at 900 C, are reported. The alloy was melted under Ar and pretreated in flowing H2 for 24 h at 1300 C. Polished 1.3 x 1.3 x 0.2-cm specimens were washed and degreased prior to oxidation in a quartz tube within a furnace for up to 120 hr. The oxidation activation energy of the alloy is determined to be about 30 kcal/mole. The specimens oxidized at 900 C and hotter exhibited oxidized and nitrided phases covered by complex NiMoO4, NiWO4, and NiAl2O4 scales and a porous, nonprotective outer layer of NiO. The oxidation behavior is found to be determined by the formation and growth of the scale, especially the (Mo,W)O2 component. Al2O3 scale layers were not formed, and further runs with pure O2 or Ar-(20 percent)O2 ruled out an explanation of this phenomenon based on aluminum nitride formation. The oxidation was accelerated by the addition of NaCl gas, a finding attributed to the reaction of NaCl with external locally protective Al2O3 scales and with the internal(Mo, W)O2 layers.

Effect of Phosphate on the Oxidation of Hydroxysulfate Green Rust

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

Benali, Omar; Abdelmoula, Mustapha; Genin, Jean-Marie R.

During Hydroxysulfate green rust GR(SO{sub 4}{sup 2}) oxidation, lepidocrocite and goethite were formed. The oxidation of GR(SO{sub 4}{sup 2-}) in the presence of phosphate ions, also involved the formation of poorly crystallized lepidocrocite but not that of goethite. The dissolution of lepidocrocite is inhibited by adsorption of phosphate ions as confirmed by X-ray photoelectron spectroscopy. The formation of the poorly crystallized protective layer against corrosion is effectively due to the phosphate ions which adsorb on the surface of lepidocrocite, and prevents it to turn into a well crystallized oxide.

Cu-rGO subsurface layer creation on copper substrate and its resistance to oxidation

NASA Astrophysics Data System (ADS)

Pietrzak, Katarzyna; Strojny-Nędza, Agata; Olesińska, Wiesława; Bańkowska, Anna; Gładki, Andrzej

2017-11-01

On the basis of a specially designed experiment, this paper presents a model, which is an attempt to explain the mechanism of formatting and creating oxidation resistance of Cu-rGO subsurface layers. Practically zero chemical affinity of copper to carbon is a fundamental difficulty in creating composite structures of Cu-C, properties which are theoretically possible to estimate. In order to bind the thermally reduced graphene oxide with copper surface, the effect of structural rebuilding of the copper oxide, in the process of annealing in a nitrogen atmosphere, have been used. On intentionally oxidized and anoxic copper substrates the dispersed graphene oxide (GO) and thermally reduced graphene oxide (rGO) were loaded. Annealing processes after the binding effects of both graphene oxide forms to Cu substrates were tested. The methods for high-resolution electron microscopy were found subsurface rGO-Cu layer having a substantially greater resistance to oxidation than pure copper. The mechanism for the effective resistance to oxidation of the Cu-rGO has been presented in a hypothetical form.

Volatility of Common Protective Oxides in High-Temperature Water Vapor: Current Understanding and Unanswered Questions

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.

2004-01-01

Many structural materials rely on the formation of chromia, silica or alumina as a protective layer when exposed in high temperature oxidizing environments. The presence of these oxide layers provides a protective diffusion barrier which slows down further oxidation. In atmospheres containing water vapor, however, reactions to form volatile hydroxide species occur which remove the surface oxide, thus, lowering the protective capability of the oxide scale. This paper summarizes the current understanding of volatility of chromia, silica and alumina in water vapor containing combustion environments. In addition unanswered questions in each system are discussed. Th current paper represents an update on the considerable information learned in the past five years for these systems.

Obtention of low oxidation states of copper from Cu 2+-Al 3+ layered double hydroxides containing organic sulfonates in the interlayer

NASA Astrophysics Data System (ADS)

Trujillano, Raquel; Holgado, María Jesús; Rives, Vicente

2009-03-01

A series of hydrotalcite-type compounds containing Cu(II) and Al(III) in the layers, and carbonate or different alkylsulfonates in the interlayer, have been prepared and studied. Calcination of these solids gives rise to formation of metallic copper and Cu 2+ and Cu + oxides or sulfates, depending on the calcination temperature and on the precise nature of the interlayer alkylsulfonate.

Low-temperature reduction of Ge oxide by Si and SiH4 in low-pressure H2 and Ar environment

NASA Astrophysics Data System (ADS)

Minami, Kaichiro; Moriya, Atsushi; Yuasa, Kazuhiro; Maeda, Kiyohiko; Yamada, Masayuki; Kunii, Yasuo; Niwano, Michio; Murota, Junichi

2015-08-01

Introduction of Ge into ULSIs has become increasingly attractive because of the higher carrier mobility of Ge. Since Ge native oxide is formed easily in cleanroom air, the control of formation and reduction of the Ge oxide is requested for the introduction of Ge layers into Si process. Here, the reactions between gas phase Ge oxide and Si substrate and between the Ge oxide on Ge epitaxial layer and SiH4 are investigated. The native-oxidized Ge amount is obtained by calculating from chemically shifted peak intensity of Ge 3d measured by X-ray photoelectron spectroscopy. By the adsorption of the Ge oxide on Si(1 0 0) surface, pure Ge and Si oxide are formed on the Si surface even at 350 °C and the formed Ge amount tends to correspond to the oxidized Si amount, independently of the heat-treatment environment of H2 and Ar under the condition that Si oxide is not reduced by H2. By SiH4 treatment, the amount of the oxidized Ge on the Ge layer decreases drastically even at 350 °C and Si oxide is formed on the Ge layer. From these results, it is suggested that the Ge oxide is reduced even at 350 °C by Si or SiH4, and the Si oxide and the pure Ge are formed.

Structure of oxides prepared by decomposition of layered double Mg–Al and Ni–Al hydroxides

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

Cherepanova, Svetlana V.; Novosibirsk State University, Novosibirsk; Leont’eva, Natalya N., E-mail: n_n_leonteva@list.ru

2015-05-15

Abstracts: Thermal decomposition of Mg–Al and Ni–Al layered double hydroxides LDH at temperatures lower than 800 °C leads to the formation of oxides with different structures. Mg–Al oxide has a very defective structure and consists of octahedral layers as in periclase MgO and mixed octahedral–tetrahedral layers as in spinel MgAl{sub 2}O{sub 4}. Mixed Ni–Al oxide has a sandwich-like structure, consisting of a core with Al-doped NiO-like structure and some surface layers with spinel NiAl{sub 2}O{sub 4} structure epitaxial connected with the core. Suggested models were verified by simulation of X-ray diffraction patterns using DIFFaX code, as well as HRTEM, IR-,more » UV-spectroscopies, and XPS. - Graphical abstract: In the Mg–Al layered double hydroxide Al{sup 3+} ions migrate into interlayers during decomposition. The Mg–Al oxide represents sequence of octahedral and octahedral–tetrahedral spinel layers with vacancies. The Ni–Al oxide has a sandwich-like structure with NiO-like core and surface spinel layers as a result of migration of Al{sup 3+} ions on the surface. The models explain the presence and absence of “memory effect” for the Mg–Al and Ni–Al oxides, respectively. - Highlights: • We study products of Mg(Ni)–Al LDH decomposition by calcination at 500(400)–800 °C. • In Mg–Al/Ni–Al LDH Al ions migrate into interlayers/on the surface during decomposition. • Mg–Al oxide represents sequence of periclase- and spinel-like layers with vacancies. • Ni–Al oxide has a sandwich-like structure with NiO-like core and surface spinel layers. • The models explain the presence/absence of “memory effect” for Mg–Al/Ni–Al oxides.« less

Mechanisms of nitrous oxide (N2 O) formation and reduction in denitrifying biofilms.

PubMed

Sabba, Fabrizio; Picioreanu, Cristian; Nerenberg, Robert

2017-12-01

Nitrous oxide (N 2 O) is a potent greenhouse gas that can be formed in wastewater treatment processes by ammonium oxidizing and denitrifying microorganisms. While N 2 O emissions from suspended growth systems have been extensively studied, and some recent studies have addressed emissions from nitrifying biofilms, much less is known about N 2 O emissions from denitrifying biofilm processes. This research used modeling to evaluate the mechanisms of N 2 O formation and reduction in denitrifying biofilms. The kinetic model included formation and consumption of key denitrification species, including nitrate (NO3-), nitrite (NO2-), nitric oxide (NO), and N 2 O. The model showed that, in presence of excess of electron donor, denitrifying biofilms have two distinct layers of activity: an outer layer where there is net production of N 2 O and an inner layer where there is net consumption. The presence of oxygen (O 2 ) had an important effect on N 2 O emission from suspended growth systems, but a smaller effect on biofilm systems. The effects of NO3- and O 2 differed significantly based on the biofilm thickness. Overall, the effects of biofilm thickness and bulk substrate concentrations on N 2 O emissions are complex and not always intuitive. A key mechanism for denitrifying biofilms is the diffusion of N 2 O and other intermediates from one zone of the biofilm to another. This leads to zones of N 2 O formation or consumption transformations that would not exist in suspended growth systems. © 2017 Wiley Periodicals, Inc.

Self-aligned periodic Ni nano dots embedded in nano-oxide layer

NASA Astrophysics Data System (ADS)

Doi, M.; Izumi, M.; Kawasaki, S.; Miyake, K.; Sahashi, M.

The Ni nano constriction dots embedded in the Ta-nano-oxide layer (NOL) was prepared by the ion beam sputtering (IBS) method. After the various conditions of the oxidations, the structural analyses of the NOL were performed by RHEED, AES and in situ STM/AFM observations. From the current image of the conductive AFM for NOL, the periodically aligned metallic dots with the size around 5-10 nm were successfully observed. The mechanism of the formation of the self-organized aligned Ni nano constriction dots is discussed from the standpoint of the grain size, the crystal orientation, the preferred oxidation of Ta at the diffused interface.

Peculiarities of structure formation of layered metal-oxide system Ti-Ta-(Ti,Ta)xOy during electro-spark alloying and thermally stimulated modification

NASA Astrophysics Data System (ADS)

Fomina, Marina A.; Koshuro, Vladimir A.; Fomin, Aleksandr A.; Rodionov, Igor V.; Skaptsov, Aleksandr A.; Zakharevich, Andrey M.; Aman, Alexander; Oseev, Aleksandr; Hirsch, Soeren; Majcherek, Soeren

2016-04-01

The study focuses on high-performance combined electro-spark alloying of titanium and titanium alloy (VT1-0, VT16) surface and porous matrix structure oxidation. The metal-oxide coatings morphology is the result of melt drop transfer, heat treatment, and oxidation. The study establishes the influence of technological regimes of alloying and oxidation on morphological heterogeneity of biocompatible layered metal-oxide system Ti-Ta-(Ti,Ta)xOy. It was found that during electro-spark alloying the concentration of tantalum on the titanium surface ranges from 0.1 to 3.2 at.%. Morphology of the deposited splats is represented by uniformly grown crystals of titanium and tantalum oxides, which increase from nano- to submicron size.

Characterization of oxide scales grown on alloy 310S stainless steel after long term exposure to supercritical water at 500 °C

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

Behnamian, Yashar, E-mail: behnamia@ualberta.ca

The oxide scale grown of static capsules made of alloy 310S stainless steel was investigated by exposure to the supercritical water at 500 °C 25 MPa for various exposure times up to 20,000 h. Characterization techniques such as X-ray diffraction, scanning/transmission electron microscopy, energy dispersive spectroscopy, and fast Fourier transformation were employed on the oxide scales. The elemental and phase analyses indicated that long term exposure to the SCW resulted in the formation of scales identified as Fe{sub 3}O{sub 4} (outer layer), Fe-Cr spinel (inner layer), Cr{sub 2}O{sub 3} (transition layer) on the substrate, and Ni-enrichment (chrome depleted region) inmore » the alloy 310S. It was found that the layer thickness and weight gain vs. exposure time followed parabolic law. The oxidation mechanism and scales grown on the alloy 310S stainless steel exposed to SCW are discussed. - Highlights: •Oxidation of alloy 310S stainless steel exposed to SCW (500 °C/25 MPa) •The layer thickness and weight gain vs. exposure time followed parabolic law. •Oxide layers including Fe{sub 3}O{sub 4} (outer), Fe-Cr spinel (inner) and Cr{sub 2}O{sub 3} (transition) •Ni element is segregated by the selective oxidation of Cr.« less

Controlling the defects and transition layer in SiO2 films grown on 4H-SiC via direct plasma-assisted oxidation

PubMed Central

Kim, Dae-Kyoung; Jeong, Kwang-Sik; Kang, Yu-Seon; Kang, Hang-Kyu; Cho, Sang W.; Kim, Sang-Ok; Suh, Dongchan; Kim, Sunjung; Cho, Mann-Ho

2016-01-01

The structural stability and electrical performance of SiO2 grown on SiC via direct plasma-assisted oxidation were investigated. To investigate the changes in the electronic structure and electrical characteristics caused by the interfacial reaction between the SiO2 film (thickness ~5 nm) and SiC, X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), density functional theory (DFT) calculations, and electrical measurements were performed. The SiO2 films grown via direct plasma-assisted oxidation at room temperature for 300s exhibited significantly decreased concentrations of silicon oxycarbides (SiOxCy) in the transition layer compared to that of conventionally grown (i.e., thermally grown) SiO2 films. Moreover, the plasma-assisted SiO2 films exhibited enhanced electrical characteristics, such as reduced frequency dispersion, hysteresis, and interface trap density (Dit ≈ 1011 cm−2 · eV−1). In particular, stress induced leakage current (SILC) characteristics showed that the generation of defect states can be dramatically suppressed in metal oxide semiconductor (MOS) structures with plasma-assisted oxide layer due to the formation of stable Si-O bonds and the reduced concentrations of SiOxCy species defect states in the transition layer. That is, energetically stable interfacial states of high quality SiO2 on SiC can be obtained by the controlling the formation of SiOxCy through the highly reactive direct plasma-assisted oxidation process. PMID:27721493

Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

PubMed

Seiler, Steffen; Halbig, Christian E; Grote, Fabian; Rietsch, Philipp; Börrnert, Felix; Kaiser, Ute; Meyer, Bernd; Eigler, Siegfried

2018-02-26

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

USGS Publications Warehouse

Bargar, J.R.; Fuller, C.C.; Marcus, M.A.; Brearley, A.J.; Perez De la Rosa, M.; Webb, S.M.; Caldwell, W.A.

2009-01-01

The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption- and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick ?? 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-?? basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn-Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mn oxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments. ?? 2008 Elsevier Ltd.

Comparative study of the oxidation of NiAl(100) by molecular oxygen and water vapor using ambient-pressure X-ray photoelectron spectroscopy

DOE PAGES

Liu, Qianqian; Qin, Hailang; Boscoboinik, Jorge Anibal; ...

2016-10-11

The oxidation behavior of NiAl(100) by molecular oxygen and water vapor under a near-ambient pressure of 0.2 Torr is monitored using ambient-pressure X-ray photoelectron spectroscopy. O 2 exposure leads to the selective oxidation of Al at temperatures ranging from 40 to 500 °C. By contrast, H 2O exposure results in the selective oxidation of Al at 40 and 200 °C, and increasing the oxidation temperature above 300 °C leads to simultaneous formation of both Al and Ni oxides. Furthermore, these results demonstrate that the O 2 oxidation forms a nearly stoichiometric Al 2O 3 structure that provides improved protection tomore » the metallic substrate by barring the outward diffusion of metals. By contrast, the H 2O oxidation results in the formation of a defective oxide layer that allows outward diffusion of Ni at elevated temperatures for simultaneous NiO formation.« less

Modification of molybdenum surface by low-energy oxygen implantation at room temperature

NASA Astrophysics Data System (ADS)

Kavre Piltaver, Ivna; Jelovica Badovinac, Ivana; Peter, Robert; Saric, Iva; Petravic, Mladen

2017-12-01

We have studied the initial stages of oxide formation on molybdenum surfaces under 1 keV O2+ ion bombardment at room temperature (RT), using x-ray photoelectron spectroscopy around Mo 3d or O 1s core-levels and the valence band photoemission. The results are compared with the oxidation mechanism of thermally oxidized Mo at RT. The thermal oxidation reveals the formation of a very thin MoO2 layer that prevents any further adsorption of oxygen at higher oxygen doses. Oxygen implantation is more efficient in creating thicker oxide films with the simultaneous formation of several oxide compounds. The oxidation rates of MoO2 and Mo2O5 follow the parabolic growth rate consistent with the mass transport driven by diffusion of either neutral or singly and doubly charged oxygen interstitials. The oxidation of MoO3, which occurs at a later oxidation stage, follows the logarithmic rate driven by the diffusion of cations in an electric field.

Comparative study of the oxidation of NiAl(100) by molecular oxygen and water vapor using ambient-pressure X-ray photoelectron spectroscopy

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

Liu, Qianqian; Qin, Hailang; Boscoboinik, Jorge Anibal

The oxidation behavior of NiAl(100) by molecular oxygen and water vapor under a near-ambient pressure of 0.2 Torr is monitored using ambient-pressure X-ray photoelectron spectroscopy. O 2 exposure leads to the selective oxidation of Al at temperatures ranging from 40 to 500 °C. By contrast, H 2O exposure results in the selective oxidation of Al at 40 and 200 °C, and increasing the oxidation temperature above 300 °C leads to simultaneous formation of both Al and Ni oxides. Furthermore, these results demonstrate that the O 2 oxidation forms a nearly stoichiometric Al 2O 3 structure that provides improved protection tomore » the metallic substrate by barring the outward diffusion of metals. By contrast, the H 2O oxidation results in the formation of a defective oxide layer that allows outward diffusion of Ni at elevated temperatures for simultaneous NiO formation.« less

Micro-mechanisms of Surface Defects Induced on Aluminum Alloys during Plastic Deformation at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Gali, Olufisayo A.

Near-surface deformed layers developed on aluminum alloys significantly influence the corrosion and tribological behavior as well as reduce the surface quality of the rolled aluminum. The evolution of the near-surface microstructures induced on magnesium containing aluminum alloys during thermomechanical processing has been investigated with the aim generating an understanding of the influence of individual forming parameters on its evolution and examine the microstructure of the roll coating induced on the mating steel roll through material transfer during rolling. The micro-mechanisms related to the various features of near-surface microstructure developed during tribological conditions of the simulated hot rolling process were identified. Thermomechanical processing experiments were performed with the aid of hot rolling (operating temperature: 550 to 460 °C, 4, 10 and 20 rolling pass schedules) and hot forming (operating temperature: 350 to 545 °C, strain rate: 4 x 10-2 s-1) tribo-simulators. The surface, near-surface features and material transfer induced during the elevated temperature plastic deformation were examined and characterized employing optical interferometry, SEM/EDS, FIB and TEM. Near-surface features characterized on the rolled aluminum alloys included; cracks, fractured intermetallic particles, aluminum nano-particles, oxide decorated grain boundaries, rolled-in oxides, shingles and blisters. These features were related to various individual rolling parameters which included, the work roll roughness, which induced the formation of shingles, rolling marks and were responsible for the redistribution of surface oxide and the enhancements of the depth of the near-surface damage. The enhanced stresses and strains experienced during rolling were related to the formation and propagation of cracks, the nanocrystalline structure of the near-surface layers and aluminum nano-particles. The mechanism of the evolution of the near-surface microstructure were determined to include grain boundary sliding which induced the cracks at the surface and subsurface of the alloy, magnesium diffusion to free surfaces, crack propagation from shear stresses and the shear strains inducing the nanocrystalline grain structure, the formation of shingles by the shear deformation of micro-wedges induced by the work roll grooves, and the deformation of this oxide covered micro-wedges inducing the rolled-in oxides. Magnesium diffusion to free surfaces was identified as inducing crack healing due to the formation of MgO within cracks and was responsible for the oxide decorated grain boundaries. An examination of the roll coating revealed a complex layered microstructure that was induced through tribo-chemical and mechanical entrapment mechanisms. The microstructure of the roll coating suggested that the work roll material and the rolled aluminum alloy were essential in determining its composition and structure. Subsequent hot forming processes revealed the rich oxide-layer of the near-surface microstructure was beneficial for reducing the coefficient of friction during tribological contact with the steel die. Damage to the microstructure include cracks induced from grain boundary sliding of near-surface grains and the formation of oxide fibres within cracks of the near-surface deformed layers.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

First Principles Calculations on the Diffusion of Cu, Ag and Au Atoms or Aggregates on the Bulk and Surface of Titania

DTIC Science & Technology

2011-04-01

filament. The filament may be composed of the metal electrode which is transported into the insulator or due to the formation of sub-oxides. During the...possibility that ionic transport and red-ox processes are at the basis of the resistive switching. The idea is that the oxidation of the active metal...oxide layer and subsequent discard at the inert metal counter-electrode. This mechanism should lead to the formation of metal dendrimers inside the

α-Tocopherol/Gallic Acid Cooperation in the Protection of Galactolipids Against Ozone-Induced Oxidation.

PubMed

Rudolphi-Skórska, Elżbieta; Filek, Maria; Zembala, Maria

2016-04-01

The protective ability of α-tocopherol (TOH) and gallic acid (GA) acting simultaneously at the moment of oxidizer application was evaluated by determination of galactolipid layers' oxidation degree. Addition of GA resulted in a significant decrease of ozone-derived radicals shifting the threshold of lipid sensitivity by an amount approximately corresponding to the GA intake in bulk reaction with ozone. TOH presence in lipid layers results in a change of the role of GA which additionally may be involved in the reduction of tocopheroxyl radical formed during oxidation. This leads to a decrease in effectiveness of GA in diminishing the amount of ozone radicals. Such an effect was not observed for mixed layers containing galactolipid and pre-oxidized tocopherol where the ozone threshold level was associated with a stoichiometry of GA + O3 reaction. It was concluded that probably subsequent transformations of tocopheroxyl radical to less reactive forms prevent its reaction with GA the entire quantity of which is used for radicals scavenging. This result shows the role of time parameter in systems where substrates are engaged in various reactions taking place simultaneously. The inactivation of 1,1-diphenyl-2-picrylhydrazyl radical by studied antioxidants in homogeneous system confirmed observations made on the basis of lipid layer properties indicating their antagonistic action (at least at studied conditions). Formation of layers in post-oxidation situation did not depend whether tocopherol was oxidized during oxidation of lipid/tocopherol mixture or was introduced as pre-oxidized. This may be interpreted as indication that products of tocopherol oxidation may stabilize lipid layers.

Annealing Effects on the Formation of Copper Oxide Thin Films

NASA Astrophysics Data System (ADS)

Marzuki, Marina; Zamzuri Mohamad Zain, Mohd; Zarul Hisham, Nurazhra; Zainon, Nooraizedfiza; Harun, Azmi; Nani Ahmad, Rozie

2018-03-01

This study approached the simple method of developing CuO thin films by thermal oxidation on pure Cu sheets. The effects of annealing temperature on the formation of CuO layers have been investigated. The oxide layers have been fabricated by annealing of Cu sheets for 5 hours at different temperatures of 980 ~ 1010 °C. The morphologies and optical properties of annealed Cu sheets were studied by using SEM and UV-Vis spectrophotometer respectively. It is revealed that the annealing temperature influence the grain growth and the grain size increases as the temperature increase. The highest grain size was observed on sample annealed at 1000 °C with average area per grain size of 0.023 mm2. Theoretically, larger grain size provides less barriers for electron mobility and increase the efficiency of solar devices. The optical absorption spectra of the oxide films was also measured. Interference pattern was noted at wavelength about 900 nm corresponding to the formation of CuO film. The interference noise observed could be due to the coarse surface and the presence of powdery oxide deposits that causes the scattering loses from the surface. CuO film obtained by this method may be further studied and exploited as low cost photovoltaic device.

Metal-oxide-semiconductor devices using Ga2O3 dielectrics on n-type GaN

NASA Astrophysics Data System (ADS)

Lee, Ching-Ting; Chen, Hong-Wei; Lee, Hsin-Ying

2003-06-01

Using a photoelectrochemical method involving a He-Cd laser, Ga2O3 oxide layers were directly grown on n-type GaN. We demonstrated the performance of the resultant metal-oxide-semiconductor devices based on the grown Ga2O3 layer. An extremely low reverse leakage current of 200 pA was achieved when devices operated at -20 V. Furthermore, high forward and reverse breakdown electric fields of 2.80 MV/cm and 5.70 MV/cm, respectively, were obtained. Using a photoassisted current-voltage method, a low interface state density of 2.53×1011 cm-2 eV-1 was estimated. The varactor devices permit formation of inversion layers, so that they may be applied for the fabrication of metal-oxide-semiconductor field-effect transistors.

Homogeneous double-layer amorphous Si-doped indium oxide thin-film transistors for control of turn-on voltage

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

Kizu, Takio, E-mail: KIZU.Takio@nims.go.jp, E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Tsukagoshi, Kazuhito, E-mail: KIZU.Takio@nims.go.jp, E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Aikawa, Shinya

We fabricated homogeneous double-layer amorphous Si-doped indium oxide (ISO) thin-film transistors (TFTs) with an insulating ISO cap layer on top of a semiconducting ISO bottom channel layer. The homogeneously stacked ISO TFT exhibited high mobility (19.6 cm{sup 2}/V s) and normally-off characteristics after annealing in air. It exhibited normally-off characteristics because the ISO insulator suppressed oxygen desorption, which suppressed the formation of oxygen vacancies (V{sub O}) in the semiconducting ISO. Furthermore, we investigated the recovery of the double-layer ISO TFT, after a large negative shift in turn-on voltage caused by hydrogen annealing, by treating it with annealing in ozone. The recoverymore » in turn-on voltage indicates that the dense V{sub O} in the semiconducting ISO can be partially filled through the insulator ISO. Controlling molecule penetration in the homogeneous double layer is useful for adjusting the properties of TFTs in advanced oxide electronics.« less

Epitaxial growth of YBa2Cu3O7 - delta films on oxidized silicon with yttria- and zirconia-based buffer layers

NASA Astrophysics Data System (ADS)

Pechen, E. V.; Schoenberger, R.; Brunner, B.; Ritzinger, S.; Renk, K. F.; Sidorov, M. V.; Oktyabrsky, S. R.

1993-09-01

A study of epitaxial growth of YBa2Cu3O7-δ films on oxidized Si with yttria- and zirconia-based buffer layers is reported. Using substrates with either SiO2 free or naturally oxidized (100) surfaces of Si it was found that a thin SiO2 layer on top of the Si favors high-quality superconducting film formation. Compared to yttria-stabilized ZrO2 (YSZ) single layers, YSZY2O3 double and YSZ/Y2O3YSZ triple layers allows the deposition of thin YBa2Cu3O7-δ films with improved properties including reduced aging effects. In epitaxial YBa2Cu3O7-δ films grown on the double buffer layers a critical temperature Tc(R=0)=89.5 K and critical current densities of 3.5×106 A/cm2 at 77 K and 1×107 A/cm2 at 66 K were reached.

Buried Oxide Densification for Low Power, Low Voltage CMOS Applications

NASA Technical Reports Server (NTRS)

Allen, L. P.; Anc, M. J.; Dolan, B.; Jiao, J.; Guss, B.; Seraphin, S.; Liu, S. T.; Jenkins, W.

1998-01-01

Special technology and circuit architecture are of growing interest for implementation of circuits which operate at low supply voltages and consume low power levels without sacrificing performance[1]. Use of thin buried oxide SOI substrates is a primary approach to simultaneously achieve these goals. A significant aspect regarding SIMOX SOI for low voltage, low power applications is the reliability and performance of the thin buried oxide. In addition, when subjected to high total dose irradiation, the silicon islands within the BOX layer of SIMOX can store charges and significantly effect the back channel threshold voltages of devices. Thus, elimination of the islands within the buried oxide (BOX) layer is preferred in order to prevent leakage through these conductive islands and charge build-up within the buried oxide layer. A differential (2-step) ramp rate as applied to full and 100 nm BOX SIMOX was previously reported to play a significant role in the stoichiometry and island formation within the buried layer[2]. This paper focus is on the properties of a thin (120nm) buried oxide as a function of the anneal ramp rate and the temperature of anneal. In this research, we have found an improvement in the buried oxide stoichiometry with the use of a slower, singular ramp rate for specified thin buried oxides, with slower ramp rates and higher temperatures of anneal suggested for reducing the presence of Si islands within the BOX layer.

Spectroscopic and electrochemical characterization of interfacial biomimetic assemblies on electrochemically generated gold oxide surfaces.

PubMed

Krysiński, Paweł; Blanchard, G J

2005-04-01

We report on the formation of a gold oxide layer and the reaction of this oxide with an acid chloride to form a stable, relatively complete monolayer bound through an ester-like bond to the gold oxide surface. We have used cyclic voltammetry, FTIR and optical ellipsometry to characterize this novel monolayer structure. The exposed functional groups of this monolayer can participate in subsequent surface reactions, opening the door to the use of oxide-based surface attachment chemistry on metallic substrates. This chemistry will allow for the formation of films tailored to contain both hydrophobic and hydrophilic regions, stacked at predetermined distances from the substrate that may serve as biomembrane mimetic assemblies.

Monitoring plasma treatment of thin films by surface plasmon resonance

NASA Astrophysics Data System (ADS)

Laha, Ranjit; Manivannan, A.; Kasiviswanathan, S.

2014-03-01

We report the surface plasmon resonance (SPR) measurements during plasma treatment of thin films by an indigenously designed setup. From the measurements on Al (6.3 nm)/Ag (38 nm) bi-layer at a pressure of 0.02 mbar, the SPR position was found to be shifted by ˜20° after a plasma treatment of ˜7 h. The formation of oxide layers during plasma oxidation was confirmed by glancing angle x-ray diffraction (GXRD) measurements. Combined analysis of GXRD and SPR data confirmed that while top Al layer enables controlling plasma oxidation of Ag, the setup enables monitoring the same. The setup designed is a first of its kind for in situ SPR studies where creation of low pressure is a prerequisite.

Monitoring plasma treatment of thin films by surface plasmon resonance.

PubMed

Laha, Ranjit; Manivannan, A; Kasiviswanathan, S

2014-03-01

We report the surface plasmon resonance (SPR) measurements during plasma treatment of thin films by an indigenously designed setup. From the measurements on Al (6.3 nm)/Ag (38 nm) bi-layer at a pressure of 0.02 mbar, the SPR position was found to be shifted by ~20° after a plasma treatment of ~7 h. The formation of oxide layers during plasma oxidation was confirmed by glancing angle x-ray diffraction (GXRD) measurements. Combined analysis of GXRD and SPR data confirmed that while top Al layer enables controlling plasma oxidation of Ag, the setup enables monitoring the same. The setup designed is a first of its kind for in situ SPR studies where creation of low pressure is a prerequisite.

X-ray Crystal Truncation Rod Studies of Surface Oxidation and Reduction on Pt(111)

DOE PAGES

Liu, Yihua; Barbour, Andi; Komanicky, Vladimir; ...

2016-02-26

Here, we present X-ray crystal truncation rods measurements of Pt(111) surface under electrochemical conditions. Analyses of crystal truncation rods reveal that surface oxide formation buckles the top surface layer of platinum to two different heights at the potential (0.95 V vs RHE) below the so-called place-exchange potential. While the anti-Bragg intensity, sensitive to the top surface layer, drops in response to the anodic charge transfers, its responses to the cathodic charge transfers are significantly delayed. Implications to the surface oxidation and reduction behaviors are discussed.

The Effect of Bi on the Selective Oxide Formation on CMnSi TRIP Steel

NASA Astrophysics Data System (ADS)

Oh, Jonghan; Cho, Lawrence; Kim, Myungsoo; Kang, Kichul; De Cooman, Bruno C.

2016-11-01

The effect of Bi addition on the selective oxidation and the galvanizability of CMnSi transformation-induced plasticity (TRIP) steels was studied by hot dip galvanizing laboratory simulations. Bi-added TRIP steels were intercritically annealed at 1093 K (820 °C) and galvanized in a 0.22 wt pct Al-containing Zn bath. The oxide morphology was investigated by scanning electron microscopy, transmission electron microscopy, and 3D atom probe tomography. Bi formed a Bi-enriched surface layer during the intercritical annealing. A decrease of the oxygen permeability was observed with increasing Bi addition. The internal oxidation was suppressed in Bi-added CMnSi TRIP steel. The surface oxide morphology was changed from a continuous layer morphology to a more lens-shaped morphology. The galvanizability of the Bi-added TRIP steel was improved by the combination of the change of the oxide morphology and the dissolution of the Bi-enriched surface layer during immersion of the strip in the Zn bath.

Isothermal Oxidation of Magnetite to Hematite in Air and Cyclic Reduction/Oxidation Under Carbon Looping Combustion Conditions

NASA Astrophysics Data System (ADS)

Simmonds, Tegan; Hayes, Peter C.

2017-12-01

In the carbon looping combustion process the oxygen carrier is regenerated through oxidation in air; this process has been simulated by the oxidation of dense synthetic magnetite for selected temperatures and times. The oxidation of magnetite in air is shown to occur through the formation of dense hematite layers on the particle surface. This dense hematite forms through lath type shear transformations or solid-state diffusion through the product layer. Cyclic reduction in CO-CO2/oxidation in air of hematite single crystals has been carried out under controlled laboratory conditions at 1173 K (900 °C). It has been shown that the initial reduction step is critical to determining the product microstructure, which consists of gas pore dendrites in the magnetite matrix with blocky hematite formed on the pore surfaces. The progressive growth of the magnetite layer with the application of subsequent cycles appears to continue until no original hematite remains, after which physical disintegration of the particles takes place.

Facile Phase Control of Multivalent Vanadium Oxide Thin Films (V2O5 and VO2) by Atomic Layer Deposition and Postdeposition Annealing.

PubMed

Song, Gwang Yeom; Oh, Chadol; Sinha, Soumyadeep; Son, Junwoo; Heo, Jaeyeong

2017-07-19

Atomic layer deposition was adopted to deposit VO x thin films using vanadyl tri-isopropoxide {VO[O(C 3 H 7 )] 3 , VTIP} and water (H 2 O) at 135 °C. The self-limiting and purge-time-dependent growth behaviors were studied by ex situ ellipsometry to determine the saturated growth conditions for atomic-layer-deposited VO x . The as-deposited films were found to be amorphous. The structural, chemical, and optical properties of the crystalline thin films with controlled phase formation were investigated after postdeposition annealing at various atmospheres and temperatures. Reducing and oxidizing atmospheres enabled the formation of pure VO 2 and V 2 O 5 phases, respectively. The possible band structures of the crystalline VO 2 and V 2 O 5 thin films were established. Furthermore, an electrochemical response and a voltage-induced insulator-to-metal transition in the vertical metal-vanadium oxide-metal device structure were observed for V 2 O 5 and VO 2 films, respectively.

Efficient phosphate sequestration for water purification by unique sandwich-like MXene/magnetic iron oxide nanocomposites

NASA Astrophysics Data System (ADS)

Zhang, Qingrui; Teng, Jie; Zou, Guodong; Peng, Qiuming; Du, Qing; Jiao, Tifeng; Xiang, Jianyong

2016-03-01

Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene.Rationally tailored intercalation for two-dimensional (2D) layered MXene materials has aroused extraordinary enthusiasm for broadening their applications. Herein, a novel sandwiched structural 2D MXene-iron oxide (MXI) material, prepared by selectively exfoliating an Al layer followed by magnetic ferric oxide intercalation, exhibits remarkable applicability to trace phosphate sequestration in the environmental remediation realm. Compared with commercial adsorbents, the resultant MXI nanocomposite exhibits a fast separation in 120 s together with the superior treatment capacities of 2100 kg and 2400 kg per kg in simulated and real phosphate wastewater applications, respectively. Such efficient sequestration is ascribed to the formation of a unique nano-ferric oxide morphology. The ultrafine nano-Fe2O3 particles can intercalate into the interior layers of MXene, widening the layer distance, and stimulating the available overlapping activated layers; while the efficient phosphate removal can be achieved by the strong complexation onto the embedded magnetic nano-Fe3O4 with a unique sandwich-structure as well as the stimulated Ti-O terminal within MXene. Apart from the fact that this approach suggests a complementary means for environmental remediation, it opens a new trajectory to achieve the functionalization of MXene. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr09303a

Post-Treatment-Free Solution-Processed Reduced Phosphomolybdic Acid Containing Molybdenum Oxide Units for Efficient Hole-Injection Layers in Organic Light-Emitting Devices.

PubMed

Ohisa, Satoru; Endo, Kohei; Kasuga, Kosuke; Suzuki, Michinori; Chiba, Takayuki; Pu, Yong-Jin; Kido, Junji

2018-02-19

We report the development of solution-processed reduced phosphomolybdic acid (rPMA) containing molybdenum oxide units for post-treatment-free hole-injection layers (HILs) in organic light-emitting devices (OLEDs). The physical and chemical properties of rPMA, including its structure, solubility in several solvents, film surface roughness, work function, and valence states, were investigated. The formation of gap states just below the Fermi level of rPMA was observed. Without any post-treatment after the formation of rPMA films, OLEDs employing rPMA as an HIL exhibited a very low driving voltage and a high luminous efficiency. The low driving voltage was attributed to the energy level alignment between the gap states formed by reduction and the HOMO level of the hole-transport layer material N,N'-bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine.

Induced nano-scale self-formed metal-oxide interlayer in amorphous silicon tin oxide thin film transistors.

PubMed

Liu, Xianzhe; Xu, Hua; Ning, Honglong; Lu, Kuankuan; Zhang, Hongke; Zhang, Xiaochen; Yao, Rihui; Fang, Zhiqiang; Lu, Xubing; Peng, Junbiao

2018-03-07

Amorphous Silicon-Tin-Oxide thin film transistors (a-STO TFTs) with Mo source/drain electrodes were fabricated. The introduction of a ~8 nm MoO x interlayer between Mo electrodes and a-STO improved the electron injection in a-STO TFT. Mo adjacent to the a-STO semiconductor mainly gets oxygen atoms from the oxygen-rich surface of a-STO film to form MoO x interlayer. The self-formed MoO x interlayer acting as an efficient interface modification layer could conduce to the stepwise internal transport barrier formation while blocking Mo atoms diffuse into a-STO layer, which would contribute to the formation of ohmic contact between Mo and a-STO film. It can effectively improve device performance, reduce cost and save energy for the realization of large-area display with high resolution in future.

About structural phase state of coating based on zirconium oxide formed by microplasma oxidation method

NASA Astrophysics Data System (ADS)

Gubaidulina, Tatiana A.; Sergeev, Viktor P.; Kuzmin, Oleg S.; Fedorischeva, Marina V.; Kalashnikov, Mark P.

2017-12-01

The oxide-ceramic coating based of zirconium oxide is formed by the method of microplasma oxidation. The producing modes of the oxide layers on E110 zirconium alloy are under testing. It was found that using microplasma treatment of E110 zirconium in aluminosilicate electrolyte makes possible the formation of porous oxide-ceramic coatings based on zirconium alloyed by aluminum and niobium. The study is focused on the modes how to form heat-shielding coatings with controlled porosity and minimal amount of microcracks. The structural-phase state of the coating is studied by X-ray diffraction analysis and scanning electron microscopy (SEM). It was found that the ratio of the monoclinic and tetragonal phases changes with the change occurring in the coating formation modes.

Synthesis, integration, and characterization of metal oxide films as alternative gate dielectric materials

NASA Astrophysics Data System (ADS)

Lin, You-Sheng

ZrO2 and HfO2 were investigated in this study to replace SiO2 as the potential gate dielectric materials in metal-oxide-semiconductor field effect transistors. ZrO2 and HfO2 films were deposited on p-type Si (100) wafers by an atomic layer chemical vapor deposition (ALCVD) process using zirconium (IV) t-butoxide and hafnium (IV) t-butoxide as the metal precursors, respectively. Oxygen was used alternatively with these metal alkoxide precursors into the reactor with purging and evacuation in between. The as-deposited ZrO2 and HfO2 films were stoichiometric and uniform based on X-ray photoemission spectroscopy and ellipsometry measurements. X-ray diffraction analysis indicated that the deposited films were amorphous, however, the high-resolution transmission electron microscopy showed an interfacial layer formation on the silicon substrate. Time-of-flight secondary ion mass spectrometry and medium energy ion scattering analysis showed significant intermixing between metal oxides and Si, indicating the formation of metal silicates, which were confirmed by their chemical etching resistance in HF solutions. The thermal stability of ZrO2 and HfO2 thin films on silicon was examined by monitoring their decomposition temperatures in ultra-high vacuum, using in-situ synchrotron radiation ultra-violet photoemission spectroscopy. The as-deposited ZrO2 and HfO2 thin films were thermally stable up to 880°C and 950°C in vacuum, respectively. The highest achieveable dielectric constants of as-deposited ZrO 2 and HfO2 were 21 and 24, respectively, which were slightly lower than the reported dielectric constants of bulk ZrO2 and HfO 2. These slight reductions in dielectric constants were attributed to the formation of the interfacial metal silicate layers. Very small hysteresis and interface state density were observed for both metal oxide films. Their leakage currents were a few orders of magnitude lower than that of SiO 2 at the same equivalent oxide thickness. NMOSFETs were also fabricated with the as-deposited metal oxide films, and reasonable ID-V D and IG-VG results were obtained. The electron mobilities were high from devices built using a plasma etching process to pattern the metal oxide films. However, they can be degraded if an HF wet etching process was used due to the large contact resistences. Upon oxygen annealing, the formation of SiOx at the interface improved the thermal stability of the as-deposited metal oxide films, however, lower overall dielectric constant and higher leakage current were observed. Upon ammonia annealing, the formation of SiOxNy improved not only the thermal stability but also reduced the leakage current. However, the overall dielectric constant of the film was still reduced due to the formation of the additional interfacial layer.

Surface texture of single-crystal silicon oxidized under a thin V{sub 2}O{sub 5} layer

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

Nikitin, S. E., E-mail: nikitin@mail.ioffe.ru; Verbitskiy, V. N.; Nashchekin, A. V.

The process of surface texturing of single-crystal silicon oxidized under a V{sub 2}O{sub 5} layer is studied. Intense silicon oxidation at the Si–V{sub 2}O{sub 5} interface begins at a temperature of 903 K which is 200 K below than upon silicon thermal oxidation in an oxygen atmosphere. A silicon dioxide layer 30–50 nm thick with SiO{sub 2} inclusions in silicon depth up to 400 nm is formed at the V{sub 2}O{sub 5}–Si interface. The diffusion coefficient of atomic oxygen through the silicon-dioxide layer at 903 K is determined (D ≥ 2 × 10{sup –15} cm{sup 2} s{sup –1}). A modelmore » of low-temperature silicon oxidation, based on atomic oxygen diffusion from V{sub 2}O{sub 5} through the SiO{sub 2} layer to silicon, and SiO{sub x} precipitate formation in silicon is proposed. After removing the V{sub 2}O{sub 5} and silicon-dioxide layers, texture is formed on the silicon surface, which intensely scatters light in the wavelength range of 300–550 nm and is important in the texturing of the front and rear surfaces of solar cells.« less

Timing of Neogene Manganese Deposit Formation in the Paleo-Japan Sea, northeast Japan

NASA Astrophysics Data System (ADS)

Ito, T.; Orihashi, Y.; Yanagisawa, Y.; Sakai, S.; Motoyama, I.; Kamikuri, S. I.; Komuro, K.; Suzuki, K.

2017-12-01

The generation ages of the two Neogene manganese deposits in northeast Japan were determined by diatom and radiolarian biostratigraphic analyses and zircon U-Pb dating. The manganese deposits analyzed were from the Kitaichi and Maruyama mines in the Fukaura district, northeast Japan. Manganese oxide layers of 0.5 m (Kitaichi) and 1.5 m (Maruyama) in thickness were predominantly composed of todorokite and occur conformably within volcanogenic sediments, which stratigraphically had correlated to middle Miocene in previous studies. The ages of the manganese oxide layers were 12.4 Ma. There was no time gap between the Kitaichi and the Maruyama manganese oxide layers, between the manganese oxide layer and the underlying tuffaceous sandstone in the Kitaichi mine, or within the manganese oxide layer of ca. 1.5 m thickness in the Maruyama mine. On the other hand, the overlying tuffaceous sandstone was dated at 4.5 Ma. The results suggest that the manganese oxide layers were formed immediately after the deposition of the tuffaceous sandstone at 12.4 Ma and that the restricted supply of volcanogenic and/or other detrital matter had kept for a long time (ca. 7 m.y.). The timing of the manganese deposit generation, 12.4 Ma, is identical to the age of the base of the Onnagawa Stage on the Nishikurosawa Stage in the Neogene stratotype section on the Japan Sea side, northeast Japan. And this is equivalent to the age of the start of diatom blooming. Paleogeographically, the manganese oxide deposition happened in a shallower area on a paleo-hill or a small island surrounded by stagnant mid to deep basins with diatom and organically carbon-rich, laminated, and fine-grained mud. It is highly probable that upwelling of mid to deep water rich in both dissolved manganese and nutrients is the trigger for the manganese deposit generation in shallower areas and the deposition of diatomaceous sediments in mid and deep basins. Eustatic regression might be the reason for the short-term formation of manganese deposits in shallower areas compared to continuous sedimentation ( several million years) of diatomaceous and organic carbon-rich mud in the surrounding mid to deep basins.

Selective-area catalyst-free MBE growth of GaN nanowires using a patterned oxide layer.

PubMed

Schumann, T; Gotschke, T; Limbach, F; Stoica, T; Calarco, R

2011-03-04

GaN nanowires (NWs) were grown selectively in holes of a patterned silicon oxide mask, by rf-plasma-assisted molecular beam epitaxy (PAMBE), without any metal catalyst. The oxide was deposited on a thin AlN buffer layer previously grown on a Si(111) substrate. Regular arrays of holes in the oxide layer were obtained using standard e-beam lithography. The selectivity of growth has been studied varying the substrate temperature, gallium beam equivalent pressure and patterning layout. Adjusting the growth parameters, GaN NWs can be selectively grown in the holes of the patterned oxide with complete suppression of the parasitic growth in between the holes. The occupation probability of a hole with a single or multiple NWs depends strongly on its diameter. The selectively grown GaN NWs have one common crystallographic orientation with respect to the Si(111) substrate via the AlN buffer layer, as proven by x-ray diffraction (XRD) measurements. Based on the experimental data, we present a schematic model of the GaN NW formation in which a GaN pedestal is initially grown in the hole.

Method and apparatus for detecting the presence and thickness of carbon and oxide layers on EUV reflective surfaces

DOEpatents

Malinowski, Michael E.

2005-01-25

The characteristics of radiation that is reflected from carbon deposits and oxidation formations on highly reflective surfaces such as Mo/Si mirrors can be quantified and employed to detect and measure the presence of such impurities on optics. Specifically, it has been shown that carbon deposits on a Mo/Si multilayer mirror decreases the intensity of reflected HeNe laser (632.8 nm) light. In contrast, oxide layers formed on the mirror should cause an increase in HeNe power reflection. Both static measurements and real-time monitoring of carbon and oxide surface impurities on optical elements in lithography tools should be achievable.

Interfacial characterization in carbon nanotube reinforced aluminum matrix composites

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

Housaer, F., E-mail: francois.housaer@ed.univ-lille1.fr; Beclin, F., E-mail: franck.beclin@univ-lille1.fr; Touzin, M., E-mail: matthieu.touzin@univ-lille1.fr

2015-12-15

In this work, the effects of the sintering parameters, such as temperature and the techniques used (HP and SPS), on CNT/Al composite interfaces are studied. The major role of the native aluminum oxide (Al{sub 2}O{sub 3}) layer covering the aluminum grains is highlighted. It is shown that, for a sintering temperature below 620 °C, the amorphous Al{sub 2}O{sub 3} layer prevents the reaction between aluminum and carbon. For greater sintering temperatures, the breaking of the oxide layer due to its crystallization leads to the formation of aluminum carbide (Al{sub 4}C{sub 3}) by reaction between aluminum and the CNT. The Al{submore » 4}C{sub 3} crystals grow perpendicularly to the matrix grain boundaries by thermally activated diffusion of the carbon atoms coming from the CNT. It is also demonstrated that, by limiting the sintering time, which is the case in SPS, it is possible to limit the growth of the Al{sub 4}C{sub 3} crystals and thus to preserve the CNT. - Highlights: • The high reactivity between CNT and Al matrix, resulting Al{sub 4}C{sub 3} formation during the sintering process is highlighted. • We demonstrate, thanks to in-situ TEM observations, that Al{sub 4}C{sub 3} crystals grow into aluminum grains by carbon diffusion. • The native aluminum oxide around the aluminum particles prevents the diffusion of carbon into the aluminum grains. • We show that the protective layer can be broken because of its crystallization, leading to the formation of Al{sub 4}C{sub 3}. • SPS, by limiting the sintering duration, is an interesting way for preparing CNT/Al composites without carbide formation.« less

Formation of silicon carbide by laser ablation in graphene oxide-N-methyl-2-pyrrolidone suspension on silicon surface

NASA Astrophysics Data System (ADS)

Jaleh, Babak; Ghasemi, Samaneh; Torkamany, Mohammad Javad; Salehzadeh, Sadegh; Maleki, Farahnaz

2018-01-01

Laser ablation of a silicon wafer in graphene oxide-N-methyl-2-pyrrolidone (GO-NMP) suspension was carried out with a pulsed Nd:YAG laser (pulse duration = 250 ns, wavelength = 1064 nm). The surface of silicon wafer before and after laser ablation was studied using optical microscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The results showed that the ablation of silicon surface in liquid by pulsed laser was done by the process of melt expulsion under the influence of the confined plasma-induced pressure or shock wave trapped between the silicon wafer and the liquid. The X-ray diffraction‌ (XRD) pattern of Si wafer after laser ablation showed that 4H-SiC layer is formed on its surface. The formation of the above layer was also confirmed by Raman spectroscopy, and X-ray photoelectron spectroscopy‌ (XPS), as well as EDX was utilized. The reflectance of samples decreased with increasing pulse energy. Therefore, the morphological alteration and the formation of SiC layer at high energy increase absorption intensity in the UV‌-vis regions. Theoretical calculations confirm that the formation of silicon carbide from graphene oxide and silicon wafer is considerably endothermic. Development of new methods for increasing the reflectance without causing harmful effects is still an important issue for crystalline Si solar cells. By using the method described in this paper, the optical properties of solar cells can be improved.

Methane Decomposition and Carbon Growth on Y2O3, Yttria-Stabilized Zirconia, and ZrO2

PubMed Central

2014-01-01

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents. PMID:24587591

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

DOE PAGES

Mu, Linqin; Lin, Ruoqian; Xu, Rong; ...

2018-04-18

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

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

Mu, Linqin; Lin, Ruoqian; Xu, Rong

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Surface Structure Formation in Direct Chill (DC) Casting of Al Alloys

NASA Astrophysics Data System (ADS)

Bayat, Nazlin; Carlberg, Torbjörn

2014-05-01

The aim of this study is to increase the understanding of the surface zone formation during direct chill (DC) casting of aluminum billets produced by the air slip technology. The depth of the shell zone, with compositions deviating from the bulk, is of large importance for the subsequent extrusion productivity and quality of final products. The surface microstructures of 6060 and 6005 aluminum alloys in three different surface appearances—defect free, wavy surface, and spot defects—were studied. The surface microstructures and outer appearance, segregation depth, and phase formation were investigated for the mentioned cases. The results were discussed and explained based on the exudation of liquid metal through the mushy zone and the fact that the exudated liquid is contained within a surface oxide skin. Outward solidification in the surface layer was quantitatively analyzed, and the oxide skin movements explained meniscus line formation. Phases forming at different positions in the segregation zone were analyzed and coupled to a cellular solidification in the exudated layer.

Nucleation of graphene layers on magnetic oxides: Co 3O 4(111) and Cr 2O 3(0001) from theory and experiment

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

Beatty, John; Cheng, Tao; Cao, Yuan

We report directly grown strongly adherent graphene on Co 3O 4(111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co 3O 4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co 3O 4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ~0.08 electrons/carbon atom transferred to the oxide from the first graphene layer,more » in agreement with DFT. In contrast, for Cr 2O 3 DFT finds no strong bonding to the surface and C MBE on Cr 2O 3(0001) yields only graphite formation at 700 K, with C desorption above 800 K. As a result, strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.« less

Nucleation of graphene layers on magnetic oxides: Co 3O 4(111) and Cr 2O 3(0001) from theory and experiment

DOE PAGES

Beatty, John; Cheng, Tao; Cao, Yuan; ...

2016-12-14

We report directly grown strongly adherent graphene on Co 3O 4(111) by carbon molecular beam epitaxy (C MBE) at 850 K and density functional theory (DFT) findings that the first graphene layer is reconstructed to fit the Co 3O 4 surface, while subsequent layers retain normal graphene structure. This adherence to the Co 3O 4 structure results from partial bonding of half the carbons to top oxygens of the substrate. This structure is validated by X-ray photoelectron spectroscopy and low-energy electron diffraction studies, showing layer-by-layer graphene growth with ~0.08 electrons/carbon atom transferred to the oxide from the first graphene layer,more » in agreement with DFT. In contrast, for Cr 2O 3 DFT finds no strong bonding to the surface and C MBE on Cr 2O 3(0001) yields only graphite formation at 700 K, with C desorption above 800 K. As a result, strong graphene-to-oxide charge transfer aids nucleation of graphene on incommensurate oxide substrates and may have implications for spintronics.« less

Environmental Effects in Niobium Base Alloys and Other Selected Intermetallic Compounds

DTIC Science & Technology

1991-04-30

formation of this surface layer requires that the oxide be more stable than the lowest oxide of the base metal. Figure 2 indicates the free energies of...such requirements for temperatures beyond 10500C are aluminum and silicon. Both of these elements form oxides with large, negative free energies of...Nb-Si, and Ta-Si systems. In attempting to develop alloys in which aluminum or silicon is selectively oxidized, the standard free energies of oxides

Influence of anodizing conditions on generation of internal cracks in anodic porous tin oxide films grown in NaOH electrolyte

NASA Astrophysics Data System (ADS)

Zaraska, Leszek; Gawlak, Karolina; Gurgul, Magdalena; Dziurka, Magdalena; Nowak, Marlena; Gilek, Dominika; Sulka, Grzegorz D.

2018-05-01

Nanoporous tin oxide layers were synthesized via simple one-step anodic oxidation of a low-purity Sn foil (98.8%) in sodium hydroxide electrolyte. The process of pore formation at the early stage of anodization was discussed on the basis of concepts of oxygen bubble mould effect and viscous flow of oxide. The effect of anodizing conditions on the generation of internal cracks and fractures within the anodic film was investigated in detail. It was confirmed that crack-free tin oxide films can be obtained if the anodization is carried out at the potential of 4 V independently of the electrolyte concentration. On the other hand, the porous anodic film with a totally stacked internal morphology is obtained at the potential of 5 V in 0.1 M NaOH electrolyte. The generation of internal cracks and voids can be attributed to a much lower surface porosity and local trapping of O2 inside the pores of the oxide layer. However, increasing electrolyte concentration allows for obtaining less cracked porous films due to effective and uniform liberation of oxygen bubbles from the channels through completely open pore mouths. Furthermore, it was confirmed that uniformity of the anodic tin oxide layers can be significantly improved by vigorous electrolyte stirring. Finally, we observed that the addition of ethanol to the electrolyte can reduce anodic current density and the oxide growth rate. In consequence, less cracked anodic film can be formed even at the potential of 6 V. The generation of oxygen at the pore bottoms, together with the open pore mouths were found to be critical factors responsible for the anodic formation of crack-free porous tin oxide films.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, J.D.

1995-03-07

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of ``standard`` polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers apparatus

DOEpatents

Affinito, John D.

1996-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, John D.

1995-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

High-efficiency exfoliation of large-area mono-layer graphene oxide with controlled dimension.

PubMed

Park, Won Kyu; Yoon, Yeojoon; Song, Young Hyun; Choi, Su Yeon; Kim, Seungdu; Do, Youngjin; Lee, Junghyun; Park, Hyesung; Yoon, Dae Ho; Yang, Woo Seok

2017-11-27

In this work, we introduce a novel and facile method of exfoliating large-area, single-layer graphene oxide using a shearing stress. The shearing stress reactor consists of two concentric cylinders, where the inner cylinder rotates at controlled speed while the outer cylinder is kept stationary. We found that the formation of Taylor vortex flow with shearing stress can effectively exfoliate the graphite oxide, resulting in large-area single- or few-layer graphene oxide (GO) platelets with high yields (>90%) within 60 min of reaction time. Moreover, the lateral size of exfoliated GO sheets was readily tunable by simply controlling the rotational speed of the reactor and reaction time. Our approach for high-efficiency exfoliation of GO with controlled dimension may find its utility in numerous industrial applications including energy storage, conducting composite, electronic device, and supporting frameworks of catalyst.

Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals

PubMed Central

Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

2015-01-01

In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV). PMID:26039669

Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals.

PubMed

Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

2015-06-03

In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV).

Gas-driven microturbine

DOEpatents

Sniegowski, Jeffrey J.; Rodgers, Murray S.; McWhorter, Paul J.; Aeschliman, Daniel P.; Miller, William M.

2002-01-01

A microturbine fabricated by a three-level semiconductor batch-fabrication process based on polysilicon surface-micromachining. The microturbine comprises microelectromechanical elements formed from three polysilicon multi-layer surfaces applied to a silicon substrate. Interleaving sacrificial oxide layers provides electrical and physical isolation, and selective etching of both the sacrificial layers and the polysilicon layers allows formation of individual mechanical and electrical elements as well as the required space for necessary movement of rotating turbine parts and linear elements.

Investigation of the oxidation behavior of dispersion stabilized alloys when exposed to a dynamic high temperature environment

NASA Technical Reports Server (NTRS)

Tenney, D. R.

1974-01-01

The oxidation behavior of TD-NiCr and TD-NiCrAlY alloys have been studied at 2000 and 2200 F in static and high speed flowing air environments. The TD-NiCrAlY alloys preoxidized to produce an Al2O3 scale on the surface showed good oxidation resistance in both types of environments. The TD-NiCr alloy which had a Cr2O3 oxide scale after preoxidation was found to oxidize more than an order of magnitude faster under the dynamic test conditions than at comparable static test conditions. Although Cr2O3 normally provides good oxidation protection, it was rapidly lost due to formation of volatile CrO3 when exposed to the high speed air stream. The preferred oxide arrangement for the dynamic test consisted of an external layer of NiO with a porous mushroom type morphology, an intermediate duplex layer of NiO and Cr2O3, and a continuous inner layer of Cr2O3 in contact with the alloy substrate. An oxidation model has been developed to explain the observed microstructure and overall oxidation behavior of all alloys.

Moving hydrocarbons through portions of tar sands formations with a fluid

DOEpatents

Stegemeier, George Leo; Mudunuri, Ramesh Raju; Vinegar, Harold J.; Karanikas, John Michael; Jaiswal, Namit; Mo, Weijian

2010-05-18

A method for treating a tar sands formation is disclosed. The method includes heating a first portion of a hydrocarbon layer in the formation from one or more heaters located in the first portion. The heat is controlled to increase a fluid injectivity of the first portion. A drive fluid and/or an oxidizing fluid is injected and/or created in the first portion to cause at least some hydrocarbons to move from a second portion of the hydrocarbon layer to a third portion of the hydrocarbon layer. The second portion is between the first portion and the third portion. The first, second, and third portions are horizontally displaced from each other. The third portion is heated from one or more heaters located in the third portion. Hydrocarbons are produced from the third portion of the formation. The hydrocarbons include at least some hydrocarbons from the second portion of the formation.

Determination of sulfuric acid concentration for anti-cavitation characteristics of Al alloy by two step anodizing process to forming nano porous.

PubMed

Lee, Seung-Jun; Kim, Seong-Kweon; Jeong, Jae-Yong; Kim, Seong-Jong

2014-12-01

Al alloy is a highly active metal but forms a protective oxide film having high corrosion resistance in atmosphere environment. However, the oxide film is not suitable for practical use, since the thickness of the film is not uniform and it is severly altered with formation conditions. This study focused on developing an aluminum anodizing layer having hardness, corrosion resistance and abrasion resistance equivalent to a commercial grade protective layer. Aluminum anodizing layer was produced by two-step aluminum anodizing oxide (AAO) process with different sulfuric acid concentrations, and the cavitation characteristics of the anodized coating layer was investigated. In hardness measurement, the anodized coating layer produced with 15 vol.% of sulfuric acid condition had the highest value of hardness but exhibited poor cavitation resistance due to being more brittle than those with other conditions. The 10 vol.% of sulfuric acid condition was thus considered to be the optimum condition as it had the lowest weight loss and damage depth.

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Golden, D. C.

2004-01-01

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Apparatus for sensing patterns of electrical field variations across a surface

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

Warren, William L.; Devine, Roderick A. B.

An array of nonvolatile field effect transistors used to sense electric potential variations. The transistors owe their nonvolatility to the movement of protons within the oxide layer that occurs only in response to an externally applied electric potential between the gate on one side of the oxide and the source/drain on the other side. The position of the protons within the oxide layer either creates or destroys a conducting channel in the adjacent source/channel/drain layer below it, the current in the channel being measured as the state of the nonvolatile memory. The protons can also be moved by potentials createdmore » by other instrumentalities, such as charges on fingerprints or styluses above the gates, pressure on a piezoelectric layer above the gates, light shining upon a photoconductive layer above the gates. The invention allows sensing of fingerprints, handwriting, and optical images, which are converted into digitized images thereof in a nonvolatile format.« less

Optimization of Oxidation Temperature for Commercially Pure Titanium to Achieve Improved Corrosion Resistance

NASA Astrophysics Data System (ADS)

Bansal, Rajesh; Singh, J. K.; Singh, Vakil; Singh, D. D. N.; Das, Parimal

2017-03-01

Thermal oxidation of commercially pure titanium (cp-Ti) was carried out at different temperatures, ranging from 200 to 900 °C to achieve optimum corrosion resistance of the thermally treated surface in simulated body fluid. Scanning electron microscopy, x-ray diffraction, Raman spectroscopy and electrochemical impedance spectroscopy techniques were used to characterize the oxides and assess their protective properties exposed in the test electrolyte. Maximum resistance toward corrosion was observed for samples oxidized at 500 °C. This was attributed to the formation of a composite layer of oxides at this temperature comprising Ti2O3 (titanium sesquioxide), anatase and rutile phases of TiO2 on the surface of cp-Ti. Formation of an intact and pore-free oxide-substrate interface also improved its corrosion resistance.

Structures of Cu surfaces developing in benzotriazole solutions: Effect of pH

NASA Astrophysics Data System (ADS)

Kondoh, Eiichi; Kawakami, Tatsuya; Watanabe, Mitsuhiro; Jin, Linhua; Hamada, Satomi; Shima, Shohei; Hiyama, Hirokuni

2017-07-01

The effect of pH on layer formation onto clean Cu surfaces in benzotriazole (BTA) aqueous solutions was studied by in situ spectroscopic ellipsometry. The effect of H2O2 addition was also investigated. Time changes in the ellipsometric parameters Ψ and Δ, which correspond to the structural changes of the layers on Cu, were discussed. In acidic solutions, a BTA or a Cu-BTA complex layer grows directly on Cu. The out-diffusion of Cu is suppressed at the Cu layer interface. When H2O2 was mixed, the Cu surface is eroded in acidic solutions. In alkaline solutions, the BTA layer grows on the oxidized Cu layer, or no growth occurs, depending on the composition of the solutions. In neutral solutions, the Cu-BTA complex layer forms on Cu, and the uncovered part is oxidized in the presence of H2O2.

Dynamics of ultrathin V-oxide layers on Rh(111) in catalytic oxidation of ammonia and CO.

PubMed

von Boehn, B; Preiss, A; Imbihl, R

2016-07-20

Catalytic oxidation of ammonia and CO has been studied in the 10(-4) mbar range using a catalyst prepared by depositing ultra-thin vanadium oxide layers on Rh(111) (θV ≈ 0.2 MLE). Using photoemission electron microscopy (PEEM) as a spatially resolving method, we observe that upon heating in an atmosphere of NH3 and O2 the spatial homogeneity of the VOx layer is removed at 800 K and a pattern consisting of macroscopic stripes develops; at elevated temperatures this pattern transforms into a pattern of circular VOx islands. Under reaction conditions the neighboring VOx islands become attracted by each other and coalesce. Similar processes of pattern formation and island coalescence are observed in catalytic CO oxidation. Reoxidation of the reduced VOx catalyst proceeds via surface diffusion of oxygen adsorbed onto Rh(111). A pattern consisting of macroscopic circular VOx islands can also be obtained by heating a Rh(111)/VOx catalyst in pure O2.

Stability of Y-Ti-O nanoparticles during laser deposition of oxide dispersion strengthened steel powder

NASA Astrophysics Data System (ADS)

Euh, Kwangjun; Arkhurst, Barton; Kim, Il Hyun; Kim, Hyun-Gil; Kim, Jeoung Han

2017-11-01

This study investigated the feasibility of a direct energy deposition process for fabrication of oxide dispersion strengthened steel cladding. The effect of the laser working power and scan speed on the microstructural stability of oxide nanoparticles in the deposition layer was examined. Y-Ti-O type oxide nanoparticles with a mean diameter of 45 nm were successfully dispersed by the laser deposition process. The laser working power significantly affected nanoparticle size and number density. A high laser power with a low scan speed seriously induced particle coarsening and agglomeration. Compared with bulk oxide dispersion strengthened steel, the hardness of the laser deposition layer was much lower because of a relatively coarse particle and grain size. Formation mechanism of nanoparticles during laser deposition was discussed.

Double layer of platinum electrodes: Non-monotonic surface charging phenomena and negative double layer capacitance

NASA Astrophysics Data System (ADS)

Huang, Jun; Zhou, Tao; Zhang, Jianbo; Eikerling, Michael

2018-01-01

In this study, a refined double layer model of platinum electrodes accounting for chemisorbed oxygen species, oriented interfacial water molecules, and ion size effects in solution is presented. It results in a non-monotonic surface charging relation and a peculiar capacitance vs. potential curve with a maximum and possibly negative values in the potential regime of oxide-formation.

The asymptotic structure of nonpremixed methane-air flames with oxidizer leakage of order unity

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

Seshadri, K.; Ilincic, N.

1995-04-01

The asymptotic structure of nonpremixed methane-air flames is analyzed using a reduced three-step mechanism. The three global steps of this reduced mechanism are similar to those used in a previous analysis. The rates of the three steps are related to the rates of the elementary reactions appearing in the C{sub 1}-mechanism for oxidation of methane. The present asymptotic analysis differs from the previous analysis in that oxygen is presumed to leak from the reaction zone to the leading order. Chemical reactions are presumed to occur in three asymptotically thin layers: the fuel-consumption layer, the nonequilibrium layer for the water-gas shiftmore » reaction and the oxidation layer. The structure of the fuel-consumption layer is presumed to be identical to that analyzed previously and in this layer the fuel reacts with the radicals to form primarily CO and H{sub 2} and some CO{sub 2} and H{sub 2}O In the oxidation layer the CO and H{sub 2} formed in the fuel-consumption layer are oxidized to CO{sub 2} and H{sub 2}O. The present analysis of the oxidation layer is simpler than the previous analysis because the variation in the values of the concentration of oxygen can be neglected to the leading order and this is a better representation of the flame structure in the vicinity of the critical conditions of extinction. The predictions of the critical conditions of extinction of the present model are compared with the predictions of previous models. It is anticipated that the present simple model can be easily extended to more complex problems such as pollutant formation in flames or chemical inhibition of flames.« less

Formation of anodic layers on InAs (111)III. Study of the chemical composition

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

Valisheva, N. A., E-mail: valisheva@thermo.isp.nsc.ru; Tereshchenko, O. E.; Prosvirin, I. P.

2012-04-15

The chemical composition of {approx}20-nm-thick anodic layers grown on InAs (111)III in alkaline and acid electrolytes containing or not containing NH{sub 4}F is studied by X-ray photoelectron spectroscopy. It is shown that the composition of fluorinated layers is controlled by the relation between the concentrations of fluorine and hydroxide ions in the electrolyte and by diffusion processes in the growing layer. Fluorine accumulates at the (anodic layer)/InAs interface. Oxidation of InAs in an acid electrolyte with a low oxygen content and a high NH{sub 4}F content brings about the formation of anodic layers with a high content of fluorine andmore » elemental arsenic and the formation of an oxygen-free InF{sub x}/InAs interface. Fluorinated layers grown in an alkaline electrolyte with a high content of O{sup 2-} and/or OH{sup -} groups contain approximately three times less fluorine and consist of indium and arsenic oxyfluorides. No distinction between the compositions of the layers grown in both types of fluorine-free electrolytes is established.« less

Effects of surface poisons on the oxidation of binary alloys

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

Hagan, P.S.; Polizzotti, R.S.; Luckman, G.

1985-10-01

A system of reaction-diffusion equations describing the oxidation of binary alloys in environments containing small amounts of surface poisons is analyzed. These poisons reduce the oxygen flux into the alloy, which causes the alloy to oxidize in two stages.During the initial stage, the oxidation reaction occurs in a stationary boundary layer at the alloy surface. Consequently, a thin zone containing a very high concentration of the metal oxide is created at the alloy surface. During the second stage, the oxidation reaction occurs in a moving boundary layer. This leads to a Stefan problem, which is analyzed by using asymptotic andmore » numerical techniques. By comparing the solutions to those of alloys in unpoisoned environments, it is concluded that surface poisons can lead to the formation of protective external oxide scales in alloys which would not normally form such scales. 11 references.« less

The Interaction of Water and Aerosols in the Marine Boundary Layer: A Study of Selected Processes Impacting Radiative Transfer and Cloudiness

DTIC Science & Technology

2013-01-01

formate and oxalate , both breakdown products of fatty acid oxidation. We hypothesize that surfactants from the marine surface layer coat much of the...characteristics as CCN activity and light scattering k mg be form oxal Species Figurei. Comparison of the mean chemical concentration of the dominant...Figure 1. The insert shows more clearly the changes in formate and oxalate efficiency has been a main objective of this study. To address this, we

Formation of ZrO{sub 2} in coating on Mg–3 wt.%Al–1 wt.%Zn alloy via plasma electrolytic oxidation: Phase and structure of zirconia

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

Lee, Kang Min; Kim, Yeon Sung; Yang, Hae Woong

2015-01-15

An investigation of the coating structure formed on Mg–3 wt.%Al–1 wt.%Zn alloy sample subjected to plasma electrolytic oxidation was examined by field-emission transmission electron microscopy. The plasma electrolytic oxidation process was conducted in a phosphoric acid electrolyte containing K{sub 2}ZrF{sub 6} for 600 s. Microstructural observations showed that the coating consisting of MgO, MgF{sub 2}, and ZrO{sub 2} phases was divided into three distinctive parts, the barrier, intermediate, and outer layers. Nanocrystalline MgO and MgF{sub 2} compounds were observed mainly in the barrier layer of ~ 1 μm thick near to the substrate. From the intermediate to outer layers, variousmore » ZrO{sub 2} polymorphs appeared due to the effects of the plasma arcing temperature on the phase transition of ZrO{sub 2} compounds during the plasma electrolytic oxidation process. In the outer layer, MgO compound grew in the form of a dendrite-like structure surrounded by cubic ZrO{sub 2}. - Highlights: • The barrier layer containing MgO and MgF{sub 2} was observed near to the Mg substrate. • In the intermediate layer, m-, t-, and o-ZrO{sub 2} compounds were additionally detected. • The outer layer contained MgO with the dendrite-like structure surrounded by c-ZrO{sub 2}. • The grain sizes of compounds in oxide layer increased from barrier to outer layer.« less

Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction

NASA Astrophysics Data System (ADS)

Gao, Shan; Sun, Zhongti; Liu, Wei; Jiao, Xingchen; Zu, Xiaolong; Hu, Qitao; Sun, Yongfu; Yao, Tao; Zhang, Wenhua; Wei, Shiqiang; Xie, Yi

2017-02-01

The role of oxygen vacancies in carbon dioxide electroreduction remains somewhat unclear. Here we construct a model of oxygen vacancies confined in atomic layer, taking the synthetic oxygen-deficient cobalt oxide single-unit-cell layers as an example. Density functional theory calculations demonstrate the main defect is the oxygen(II) vacancy, while X-ray absorption fine structure spectroscopy reveals their distinct oxygen vacancy concentrations. Proton transfer is theoretically/experimentally demonstrated to be a rate-limiting step, while energy calculations unveil that the presence of oxygen(II) vacancies lower the rate-limiting activation barrier from 0.51 to 0.40 eV via stabilizing the formate anion radical intermediate, confirmed by the lowered onset potential from 0.81 to 0.78 V and decreased Tafel slope from 48 to 37 mV dec-1. Hence, vacancy-rich cobalt oxide single-unit-cell layers exhibit current densities of 2.7 mA cm-2 with ca. 85% formate selectivity during 40-h tests. This work establishes a clear atomic-level correlation between oxygen vacancies and carbon dioxide electroreduction.

The formation of hydrogen permeation barriers on steels by aluminising

NASA Astrophysics Data System (ADS)

Forcey, K. S.; Ross, D. K.; Wu, C. H.

1991-06-01

An extensive investigation has been carried out into the effectiveness of aluminised layers as permeation barriers on AISI 316L stainless and DIN 1.4914 martensitic steels. The study involved measurement of the hydrogen permeation rate through commercially aluminised steel discs of thicknesses in the range 1-1.6 mm, at temperatures between 250 and 600 °C and for an upstream hydrogen pressure of 10 5 Pa. The composition and structure of the aluminide layers were investigated by a number of techniques such as SEM, electron beam microprobe and X-ray diffraction. Accelerator based techniques such as RBS and NRA were employed to study the top micron or so of the surfaces of the samples. By these techniques it was found that the effectiveness of the permeation barrier depended on the formation of a thin surface oxide layer consisting of Al 2O 3. It was found that the permeation rate through the aluminised steels could be reduced by 3-4 orders of magnitude by forming a surface oxide layer up to a micron or so in thickness.

In vitro degradation and biocompatibility of a strontium-containing micro-arc oxidation coating on the biodegradable ZK60 magnesium alloy

NASA Astrophysics Data System (ADS)

Lin, Xiao; Yang, Xiaoming; Tan, Lili; Li, Mei; Wang, Xin; Zhang, Yu; Yang, Ke; Hu, Zhuangqi; Qiu, Jianhong

2014-01-01

Magnesium alloys are promising biodegradable implant candidates for orthopedic application. In the present study, a phosphate-based micro-arc oxidation (MAO) coating was applied on the ZK60 alloy to decrease its initial degradation rate. Strontium (Sr) was incorporated into the coating in order to improve the bioactivity of the coating. The in vitro degradation studies showed that the MAO coating containing Sr owned a better initial corrosion resistance, which was mainly attributed to the superior inner barrier layer, and a better long-term protective ability, probably owning to its larger thickness, superior inner barrier layer and the superior apatite formation ability. The degradation of MAO coating was accompanied by the formation of degradation layer and Ca-P deposition layer. The in vitro cell tests demonstrated that the incorporation of Sr into the MAO coating enhanced both the proliferation of preosteoblast cells and the alkaline phosphatase activity of the murine bone marrow stromal cells. In conclusion, the MAO coating with Sr is a promising surface treatment for the biodegradable magnesium alloys.

Effect of oxide layer formation on deformation of aluminum alloys under fire conditions

DOE PAGES

Yilmaz, Nadir; Vigil, Francisco M.; Tolendino, Greg; ...

2015-05-14

The purpose of this study is to investigate the structural behavior of aluminum alloys used in the aerospace industry when exposed to conditions similar to those of an accident scenario, such as a fuel fire. This study focuses on the role that the aluminum oxide layer plays in the deformation and the strength of the alloy above melting temperature. To replicate some of the thermal and atmospheric conditions that the alloys might experience in an accident scenario, aluminum rod specimens were subjected to temperatures near to or above their melting temperature in air, nitrogen, and vacuum environments. The characteristics ofmore » their deformation, such as geometry and rate of deformation, were observed. Tests were conducted by suspending aluminum rods vertically from an enclosure. This type of experiment was performed in two different environments: air and nitrogen. The change in environments allowed the effects of the oxide layer on the material strength to be analyzed by inhibiting the growth of the oxide layer. Observations were reported from imaging taken during the experiment showing creep behavior of aluminum alloys at elevated temperatures and time to failure. In addition, an example of tensile load–displacement data obtained in air and vacuum was reported to understand the effect of oxide layer on aluminum deformation and strength.« less

Tuning electronic properties by oxidation-reduction reactions at graphene-ruthenium interface

DOE PAGES

Kandyba, Viktor; Al-Mahboob, Abdullah; Giampietri, Alessio; ...

2018-06-06

Mass production of graphene is associated with the growth on catalysts used also in other chemical reactions. In this study, we exploit the oxidation-reduction to tailor the properties of single layer graphene domains with incorporated bi-layer patches on ruthenium. Using photoelectron spectromicroscopy techniques, we find that oxygen, intercalating under single layer and making it p-doped by the formation of Ru-O x, does not intercalate under the bilayer patches with n-doped upper layer, but decorates them under single layer surrounding creating lateral p-n junctions with chemical potential difference of 1.2 eV. O-reduction by thermal treatment in vacuum results in C-vacancy defectsmore » enhancing electronic coupling of remained graphene to Ru, whereas in H 2, vacancy formation is suppressed. Also, for the domains below 15–25 μm size, after O-reduction in H 2, graphene/Ru coupling is restored, while wrinkle pattern produced by O-intercalation is irreversible and can trap reaction products between the wrinkles and Ru surface step edges. In fact, in certain regions of bigger domains, the products, containing H 2O and/or its fragments, remain at the interface, making graphene decoupled and undoped.« less

Vacuum deposition and curing of liquid monomers apparatus

DOEpatents

Affinito, J.D.

1996-08-20

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of ``standard`` polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface. 3 figs.

The role of polymer films on the oxidation of magnetite nanoparticles

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

Letti, C.J.; Paterno, L.G.; Pereira-da-Silva, M.A.

2017-02-15

A detailed investigation about the role of polymer films on the oxidation process of magnetite nanoparticles (∼7 nm diameter), under laser irradiation is performed employing micro Raman spectroscopy. To support this investigation, Fe{sub 3}O{sub 4}-np are synthesized by the co-precipitation method and assembled layer-by-layer with sodium sulfonated polystyrene (PSS). Polymer films (Fe{sub 3}O{sub 4}-np/PSS){sub n} with n=2,3,5,7,10 and 25 bilayers are employed as a model system to study the oxidation process under laser irradiation. Raman data are further processed by principal component analysis. Our findings suggest that PSS protects Fe{sub 3}O{sub 4}-np from oxidation when compared to powder samples, evenmore » for the sample with the greater number of bilayers. Further, the oxidation of magnetite to maghemite occurs preferably for thinner films up to 7 bilayers, while the onset for the formation of the hematite phase depends on the laser intensity for thicker films. Water takes part on the oxidation processes of magnetite, the oxidation/phase transformation of Fe{sub 3}O{sub 4}-np is intensified in films with more bilayers, since more water is included in those films. Encapsulation of Fe{sub 3}O{sub 4}-np by PSS in layer-by-layer films showed to be very efficient to avoid the oxidation process in nanosized magnetite. - Graphical abstract: Encapsulation of Fe{sub 3}O{sub 4}-np by PSS in layer-by-layer films avoids the oxidation and phase transformation of nanosized magnetite. - Highlights: • (Fe{sub 3}O{sub 4}-np/PSS){sub n} nanofilms, with n=2 up to 25, where layer-by-layer assembled. • The influence of film architecture on the Fe{sub 3}O{sub 4}-np oxidation was investigated through Raman spectroscopy. • Encapsulation of Fe{sub 3}O{sub 4}-np by PSS showed to be very efficient to avoid the Fe{sub 3}O{sub 4}-np oxidation.« less

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

Genevée, Pascal, E-mail: pascal-genevee@chimie-paristech.fr, E-mail: a.szeghalmi@uni-jena.de; Ahiavi, Ernest; Janunts, Norik

The authors report on the formation of blisters during the atomic layer deposition of iridium using iridium acetylacetonate and oxygen precursors. Films deposited on fused silica substrates led to sparsely distributed large blisters while in the case of silicon with native oxide additional small blisters with a high density was observed. It is found that the formation of blisters is favored by a higher deposition temperature and a larger layer thickness. Postdeposition annealing did not have a significant effect on the formation of blisters. Finally, changing purge duration during the film growth allowed us to avoid blistering and evidenced thatmore » impurities released from the film in gas phase were responsible for the formation of blisters.« less

National Hypersonic Science Center for Materials and Structures

DTIC Science & Technology

2014-08-31

Hence, ( Zr , Nb )B2 showed improved oxidation resistance compared to pure ZrB2. 9.2 Effects of W Additives on Oxide Scale Thickness and the...TM Additives on Oxide Scale Growth on ZrB2 The oxidation behavior of ( Zr , Nb )B2 ceramics was studied to determine the effect of Nb on the thickness...and morphology of the oxide scales on ZrB2 [B6]. At 1500 °C, exposure to air resulted in the formation of a two-layer oxide scale structure on ( Zr , Nb

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Characterization of corrosion resistant on NiCoCr coating layer exposed to 5%NaCl

NASA Astrophysics Data System (ADS)

Sugiarti, E.; Sundawa, R.; Desiati, R. D.; Zaini, K. A.

2018-03-01

Highly corrosion resistant of carbon steel coated NiCoCr was applied in corrosive of marine environtment. Carbon steel coated NiCoCr was prepared by a two step technique of NiCo electro-deposition and Cr pack cementation. The samples were exposed to 5 wt.% NaCl for 48 and 168 hours. The microstructure and corrosion product were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The corrosion resistance of carbon steel coated NiCoCr was found to be better than that of carbon steel substrate without coating. The results showed the microstructure of 48 h corroded sample has duplex layer composed of inner α-(Ni,Co), α-Cr and outer Cr2O3, while a quite thin and continues protective oxide of Cr2O3 was observed in outer layer of 168 h corroded sample. The formation of oxide scale rich in Cr2O3 has contributed for the better corrosion resistance of carbon steel coated NiCoCr, whereas the formation of non protective oxide of iron might caused low corrosion resistance of carbon steel substrate.

Polymer Photovoltaic Cells with Rhenium Oxide as Anode Interlayer.

PubMed

Wei, Jinyu; Bai, Dongdong; Yang, Liying

2015-01-01

The effect of a new transition metal oxide, rhenium oxide (ReO3), on the performance of polymer solar cells based on regioregular poly(3-hexylthiophene) (P3HT) and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend as buffer layer was investigated. The effect of the thickness of ReO3 layer on electrical characteristics of the polymer solar cells was studied. It is found that insertion of ReO3 interfacial layer results in the decreased performance for P3HT: PCBM based solar cells. In order to further explore the mechanism of the decreasing of the open-circuit voltage (Voc), the X-ray photoelectron spectroscopy (XPS) is used to investigate the ReO3 oxidation states. Kelvin Probe method showed that the work function of the ReO3 is estimated to be 5.13eV after thermal evaporation. The results indicated the fact that a portion of ReO3 decomposed during thermal evaporation process, resulting in the formation of a buffer layer with a lower work function. As a consequence, a higher energy barrier was generated between the ITO and the active layer.

Polymer Photovoltaic Cells with Rhenium Oxide as Anode Interlayer

PubMed Central

Wei, Jinyu; Bai, Dongdong; Yang, Liying

2015-01-01

The effect of a new transition metal oxide, rhenium oxide (ReO3), on the performance of polymer solar cells based on regioregular poly(3-hexylthiophene) (P3HT) and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend as buffer layer was investigated. The effect of the thickness of ReO3 layer on electrical characteristics of the polymer solar cells was studied. It is found that insertion of ReO3 interfacial layer results in the decreased performance for P3HT: PCBM based solar cells. In order to further explore the mechanism of the decreasing of the open-circuit voltage (Voc), the X-ray photoelectron spectroscopy (XPS) is used to investigate the ReO3 oxidation states. Kelvin Probe method showed that the work function of the ReO3 is estimated to be 5.13eV after thermal evaporation. The results indicated the fact that a portion of ReO3 decomposed during thermal evaporation process, resulting in the formation of a buffer layer with a lower work function. As a consequence, a higher energy barrier was generated between the ITO and the active layer. PMID:26226439

Effect of oxygen partial pressure on oxidation of Mo-metal

NASA Astrophysics Data System (ADS)

Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

2018-05-01

This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

Thermochemical Compatibility and Oxidation Resistance of Advanced LWR Fuel Cladding

DOE PAGES

Besmann, T. M.; Yamamoto, Y.; Unocic, K. A.

2016-06-21

We assessed the thermochemical compatibility of potential replacement cladding materials for zirconium alloys in light water reactors. Considered were FeCrAl steel (similar to Kanthal APMT), Nb-1%Zr (similar to PWC-11), and a hybrid SiC-composite with a metallic barrier layer. The niobium alloy was also seen as requiring an oxidation protective layer, and a diffusion silicide was investigated. Metallic barrier layers for the SiC-composite reviewed included a FeCrAl alloy, Nb-1%Zr, and chromium. Thermochemical calculations were performed to determine oxidation behavior of the materials in steam, and for hybrid SiC-composites possible interactions between the metallic layer and SiC. Additionally, experimental exposures of SiC-alloymore » reaction couples at 673K, 1073K, and 1273K for 168 h in an inert atmosphere were made and microanalysis performed. Whereas all materials were determined to oxidize under higher oxygen partial pressures in the steam environment, these varied by material with expected protective oxides forming. Finally, the computed and experimental results indicate the formation of liquid phase eutectic in the FeCrAl-SiC system at the higher temperatures.« less

Epitaxial ferromagnetic oxide thin films on silicon with atomically sharp interfaces

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

Coux, P. de; CEMES-CNRS, 29 rue Jeanne Marvig, BP 94347, Toulouse Cedex 4; Bachelet, R.

A bottleneck in the integration of functional oxides with silicon, either directly grown or using a buffer, is the usual formation of an amorphous interfacial layer. Here, we demonstrate that ferromagnetic CoFe{sub 2}O{sub 4} films can be grown epitaxially on Si(111) using a Y{sub 2}O{sub 3} buffer layer, and remarkably the Y{sub 2}O{sub 3}/Si(111) interface is stable and remains atomically sharp. CoFe{sub 2}O{sub 4} films present high crystal quality and high saturation magnetization.

The effect of different oxygen exchange layers on TaO x based RRAM devices

NASA Astrophysics Data System (ADS)

Alamgir, Zahiruddin; Holt, Joshua; Beckmann, Karsten; Cady, Nathaniel C.

2018-01-01

In this work, we investigated the effect of the oxygen exchange layer (OEL) on the resistive switching properties of TaO x based memory cells. It was found that the forming voltage, SET-RESET voltage, R off, R on and retention properties are strongly correlated with the oxygen scavenging ability of the OEL, and the resulting oxygen vacancy formation ability of this layer. Higher forming voltage was observed for OELs having lower electronegativity/lower Gibbs free energy for oxide formation, and devices fabricated with these OELs exhibited an increased memory window, when using similar SET-RESET voltage range.

TiN/Al2O3/ZnO gate stack engineering for top-gate thin film transistors by combination of post oxidation and annealing

NASA Astrophysics Data System (ADS)

Kato, Kimihiko; Matsui, Hiroaki; Tabata, Hitoshi; Takenaka, Mitsuru; Takagi, Shinichi

2018-04-01

Control of fabrication processes for a gate stack structure with a ZnO thin channel layer and an Al2O3 gate insulator has been examined for enhancing the performance of a top-gate ZnO thin film transistor (TFT). The Al2O3/ZnO interface and the ZnO layer are defective just after the Al2O3 layer formation by atomic layer deposition. Post treatments such as plasma oxidation, annealing after the Al2O3 deposition, and gate metal formation (PMA) are promising to improve the interfacial and channel layer qualities drastically. Post-plasma oxidation effectively reduces the interfacial defect density and eliminates Fermi level pinning at the Al2O3/ZnO interface, which is essential for improving the cut-off of the drain current of TFTs. A thermal effect of post-Al2O3 deposition annealing at 350 °C can improve the crystalline quality of the ZnO layer, enhancing the mobility. On the other hand, impacts of post-Al2O3 deposition annealing and PMA need to be optimized because the annealing can also accompany the increase in the shallow-level defect density and the resulting electron concentration, in addition to the reduction in the deep-level defect density. The development of the interfacial control technique has realized the excellent TFT performance with a large ON/OFF ratio, steep subthreshold characteristics, and high field-effect mobility.

Surface Selective Oxidation of Sn-Added CMnSi TRIP Steel

NASA Astrophysics Data System (ADS)

Cho, Lawrence; Seo, Eun Jung; Jung, Geun Su; Suh, Dong Woo; De Cooman, Bruno C.

2016-04-01

The influence of the addition of Sn on the selective oxidation and the reactive wetting of CMnSi transformation-induced plasticity (TRIP) steels was studied by means of galvanizing simulator tests. A reference TRIP steel and TRIP steels containing Sn in the range of 0.05 to 1 wt pct were intercritically annealed at 1093 K (820 °C) in an N2+ 5 pct H2 gas atmosphere with a dew point of -60 °C. The thin-film oxides formed on the surface of the Sn-added CMnSi TRIP steel were investigated using transmission electron microscopy and 3-dimensional atom probe tomography. The addition of Sn (≥0.05 wt pct) changed the morphology of the xMnO·SiO2 surface oxides from a continuous film morphology to a lens-shaped island morphology. It also suppressed the formation of the Mn-rich oxides of MnO and 2MnO·SiO2. The changes in the morphology and chemistry of the surface oxides were clearly related to the surface segregation of Sn, which appeared to result in a decrease of the oxygen permeability at the surface. The formation of lens-shaped oxides improved the wettability of the CMnSi TRIP steel surface by the molten Zn. The improved wetting effect was attributed to an increased area fraction of the surface where the oxide layer was thinner. This enabled a direct, unhindered reaction between Fe and the Al in the liquid Zn and the formation of the inhibition layer in the initial stages of the hot dipping. The addition of a small amount of Sn was also found to decrease significantly the density of Zn-coating defects on CMnSi TRIP steel.

High-temperature oxidation/corrosion of iron-based superalloys

NASA Technical Reports Server (NTRS)

Lemkey, F. D.; Smeggil, J. G.; Bailey, R. S.; Schuster, J. C.; Nowotny, H.

1987-01-01

The oxidation and sulfidation of several novel iron-base superalloys were evaluated in high-temperature cyclic tests. The experimental austenitic alloys examined were modifications of NASAUT-4GA which were developed for Stirling-engine application. The weight gains and resulting surface scales were measured and analyzed. Mixed oxide scales were found to form on all specimens exposed above 871 C. The build-up of these scales led to a depletion of Mn and Cr in a zone adjacent to the oxides. In addition, the initial oxidation of the Fe-rich alloy was inhibited by a thin but tenacious Si layer which formed at the interface between oxides and the parent layer. Sulfidation tests using Na2SO4 coatings resulted in the formation of a protective spinel and alpha-Fe2O3 phases. Preferential attack of the carbide phase by hydrogen was not observed after 350 h at 871 C.

Oxidation behavior of TD-NiCr in a dynamic high temperature environment

NASA Technical Reports Server (NTRS)

Tenney, D. R.; Young, C. T.; Herring, H. W.

1974-01-01

The oxidation behavior of TD-NiCr has been studied in static and high-speed flowing air environments at 1100 and 1200 C. It has been found that the stable oxide morphologies formed on the specimens exposed to the static and dynamic environments were markedly different. The faceted crystal morphology characteristic of static oxidation was found to be unstable under high-temperature, high-speed flow conditions and was quickly replaced by a porous NiO 'mushroom' type structure. Also, it was found that the rate of formation of CrO3 from Cr2O3 was greatly enhanced by high gas velocity conditions. The stability of Cr2-O3 was found to be greatly improved by the presence of an outer NiO layer, even though the NiO layer was very porous. An oxidation model is proposed to explain the observed microstructures and overall oxidation behavior of TD-NiCr alloys.

Passivation of Plasmonic Colors on Bulk Silver by Atomic Layer Deposition of Aluminum Oxide.

PubMed

Guay, Jean-Michel; Killaire, Graham; Gordon, Peter G; Barry, Sean T; Berini, Pierre; Weck, Arnaud

2018-05-01

We report the passivation of angle-independent plasmonic colors on bulk silver by atomic layer deposition (ALD) of thin films of aluminum oxide. The colors are rendered by silver nanoparticles produced by laser ablation and redeposition on silver. We then apply a two-step approach to aluminum oxide conformal film formation via ALD. In the first step, a low-density film is deposited at low temperature to preserve and pin the silver nanoparticles. In the second step, a second denser film is deposited at a higher temperature to provide tarnish protection. This approach successfully protects the silver and plasmonic colors against tarnishing, humidity, and temperature, as demonstrated by aggressive exposure trials. The processing time associated with deposition of the conformal passivation layers meets industry requirements, and the approach is compatible with mass manufacturing.

Fabrication of Total-Dose-Radiation-Hardened (TDRH) SOI wafer with embedded silicon nanoclusters

NASA Astrophysics Data System (ADS)

Wu, Aimin; Wang, Xi; Wei, Xing; Chen, Jing; Chen, Ming; Zhang, Zhengxuan

2009-05-01

Si ion-implantation and post annealing of silicon wafers prior to wafer bonding were used to radiation-harden the thermal oxide layer of Silicon on Insulator structures. After grinding and polishing, Total-Dose-Radiation-Hardened SOI (TDRH-SOI) wafers with several-micron-thick device layers were prepared. Electrical characterization before and after X-ray irradiation showed that the flatband voltage shift induced by irradiation was reduced by this preprocessing. Photoluminescence Spectroscopy (PL), Transmission Electron Microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) results indicated that the improvement of the total dose response of the TDRH-SOI wafer was associated with formation of Si nanoclusters in the implanted oxide layer, suggesting that these were the likely candidates for electron and proton trapping centers that reduce the positive charge buildup effect in the buried oxide.

Effects of ultrathin oxides in conducting MIS structures on GaAs

NASA Technical Reports Server (NTRS)

Childs, R. B.; Ruths, J. M.; Sullivan, T. E.; Fonash, S. J.

1978-01-01

Schottky barrier-type GaAs baseline devices (semiconductor surface etched and then immediately metalized) and GaAs conducting metal oxide-semiconductor devices are fabricated and characterized. The baseline surfaces (no purposeful oxide) are prepared by a basic or an acidic etch, while the surface for the MIS devices are prepared by oxidizing after the etch step. The metallizations used are thin-film Au, Ag, Pd, and Al. It is shown that the introduction of purposeful oxide into these Schottky barrier-type structures examined on n-type GaAs modifies the barrier formation, and that thin interfacial layers can modify barrier formation through trapping and perhaps chemical reactions. For Au- and Pd-devices, enhanced photovoltaic performance of the MIS configuration is due to increased barrier height.

Oxygen in the Martian atmosphere: Regulation of PO2 by the deposition of iron formations on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

During Earth's early history, and prior to the evolution of its present day oxygenated atmosphere, extensive iron rich siliceous sedimentary rocks were deposited, consisting of alternating layers of silica (chert) and iron oxide minerals (hematite and magnetite). The banding in iron formations recorded changes of atmosphere-hydrosphere interactions near sea level in the ancient ocean, which induced the oxidation of dissolved ferrous iron, precipitation of insoluble ferric oxides and silica, and regulation of oxygen in Earth's early atmosphere. Similarities between the Archean Earth and the composition of the present day atmosphere on Mars, together with the pervasive presence of ferric oxides in the Martian regolith suggest that iron formation might also have been deposited on Mars and influenced the oxygen content of the Martian atmosphere. Such a possibility is discussed here with a view to assessing whether the oxygen content of the Martian atmosphere has been regulated by the chemical precipitation of iron formations on Mars.

Chromium Vaporization Reduction by Nickel Coatings For SOEC Interconnect Materials

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

Michael V. Glazoff; Sergey N. Rashkeev; J. Stephen Herring

2014-09-01

The vaporization of Cr-rich volatile species from interconnect materials is a major source of degradation that limits the lifetime of planar solid oxide devices systems with metallic interconnects, including Solid Oxide Electrolysis Cells, or SOECs. Some metallic coatings (Ni, Co, and Cu) significantly reduce the Cr release from interconnects and slow down the oxide scale growth on the steel substrate. To shed additional light upon the mechanisms of such protection and find a suitable coating material for ferritic stainless steel materials, we used a combination of first-principles calculations, thermodynamics, and diffusion modeling to investigate which factors determine the quality ofmore » the Ni metallic coating at stainless steel interconnector. We found that the Cr migration in Ni coating is determined by a delicate combination of the nickel oxidation, Cr diffusion, and phase transformation processes. Although the formation of Cr2O3 oxide is more exothermic than that of NiO, the kinetic rate of the chromia formation in the coating layer and its surface is significantly reduced by the low mobility of Cr in nickel oxide and in NiCr2O4 spinel. These results are in a good agreement with diffusion modeling for Cr diffusion through Ni coating layer on the ferritic 441 steel substrate.« less

Transmission electron microscopy study of erbium silicide formation from Ti/Er stack for Schottky contact applications.

PubMed

Ratajczak, J; Łaszcz, A; Czerwinski, A; Katcki, J; Phillipp, F; Van Aken, P A; Reckinger, N; Dubois, E

2010-03-01

In this paper, we present results of transmission electron microscopy studies on erbium silicide structures fabricated under various thermal conditions. A titanium cap has been used as a protective layer against oxidation during rapid thermal annealing of an erbium layer in a temperature range of 300-700 degrees C. Both layers (200 nm Ti and 25 nm Er) were deposited by electron-beam sputtering. The investigations have shown that the transformation of the 25-nm-thick erbium into erbium silicide is completed after annealing at 500 degrees C. At higher temperatures, the formation of a titanium silicide layer above erbium silicide is observed. The lowest Schottky barrier has been measured in the sample annealed at 700 degrees C.

Enhanced spin-valve giant magneto-resistance in non-exchange biased sandwich films

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

Mao, M; Cerjan, C; Law, B

2000-02-17

A large giant magnetoresistance (GMR) value of 7.5% has been measured in simple NiFeCo(1)/Cu/NiFeCo(2) sandwich films grown on a 30 {angstrom} Cr seed layer. This spin-valve GMR effect is consistent with the differential switching of the two NiFeCo layers due to an enhanced coercivity of the NiFeCo(1) layer grown on the Cr seed layer. A change in growth texture of the NiFeCo(1) layer from fcc (111) to bcc (110) crystallographic orientation leads to an increase in magnetic anisotropy and an enhancement in coercivity. The GMR value increases to 8.7% when a thin CoFe interfacial enhancing layer is incorporated. Further enhancementmore » in GMR values up to 14% is seen in the sandwich films by nano-oxide layer formation. The specular reflection at oxide/magnetic layer interface further extends the mean free path of spin-polarized electrons.« less

Specular spin-valve films with an FeCo nano-oxide layer by ion-assisted oxidation

NASA Astrophysics Data System (ADS)

Fukuzawa, Hideaki; Koi, Katsuhiko; Tomita, Hiroshi; Fuke, Hiromi Niu; Iwasaki, Hitoshi; Sahashi, Masashi

2002-05-01

We compared the specular spin-valve films with an Fe50Co50 nano-oxide layer (NOL) and a Co90Fe10 NOL in a pinned layer, prepared by natural oxidation (NO) and ion-assisted oxidation (IAO). For the IAO, an Ar-ion beam was used for the energy-assist effect during the oxidation, resulting in thermally stable NOL formation. With small oxygen exposures during the oxidation for the Fe50Co50 NOL by IAO, good ferromagnetic coupling through the NOL and high specularity at the NOL interface were concurrently obtained. Moreover, twisted coupling through the NOL was observed for the Fe50Co50 NOL by IAO for higher oxygen exposures. On the other hand, the NO did not cause large magnetoresistance (MR) enhancement for either the Co90Fe10 or Fe50Co50 NOLs, and the Co90Fe10 NOL by IAO caused weak magnetic coupling through the NOL, resulting in a small MR ratio. The Fe50Co50 NOL for small oxygen exposures is a good candidate for a final specular spin-valve film head for 100-Giga-bit per square inch recording.

Effect of the nano-oxide layer as a Mn diffusion barrier in specular spin valves

NASA Astrophysics Data System (ADS)

Jang, S. H.; Kang, T.; Kim, H. J.; Kim, K. Y.

2002-07-01

In previous work an enhanced giant magnetoresistance (GMR) effect in spin valves (SVs) with a nano-oxide layer (NOL) after annealing at about 250-300 degC has been reported. We have shown that SVs with a NOL also have higher thermal stability of the MR ratio at 300 degC. From secondary-ion-mass spectroscopy and x-ray photoelectron spectroscopy depth profile analysis, the mechanism of the improved thermal stability of the SVs with a NOL is shown to be related to MnO formation within the NOL. Thus, Mn atoms from the FeMn layer are trapped, and Mn diffusion is inhibited by the NOL during annealing.

ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

NASA Astrophysics Data System (ADS)

Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

2018-04-01

Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

Kinetic modeling of low density lipoprotein oxidation in arterial wall and its application in atherosclerotic lesions prediction.

PubMed

Karimi, Safoora; Dadvar, Mitra; Modarress, Hamid; Dabir, Bahram

2013-01-01

Oxidation of low-density lipoprotein (LDL) is one of the major factors in atherogenic process. Trapped oxidized LDL (Ox-LDL) in the subendothelial matrix is taken up by macrophage and leads to foam cell generation creating the first step in atherosclerosis development. Many researchers have studied LDL oxidation using in vitro cell-induced LDL oxidation model. The present study provides a kinetic model for LDL oxidation in intima layer that can be used in modeling of atherosclerotic lesions development. This is accomplished by considering lipid peroxidation kinetic in LDL through a system of elementary reactions. In comparison, characteristics of our proposed kinetic model are consistent with the results of previous experimental models from other researches. Furthermore, our proposed LDL oxidation model is added to the mass transfer equation in order to predict the LDL concentration distribution in intima layer which is usually difficult to measure experimentally. According to the results, LDL oxidation kinetic constant is an important parameter that affects LDL concentration in intima layer so that existence of antioxidants that is responsible for the reduction of initiating rates and prevention of radical formations, have increased the concentration of LDL in intima by reducing the LDL oxidation rate. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Evaluation of quantum confinement effect in nanocrystal Si dot layer by Raman spectroscopy.

PubMed

Mizukami, Y; Kosemura, D; Numasawa, Y; Ohshita, Y; Ogura, A

2012-11-01

Quantum confinement effect in the nanocrystal-Si (nc-Si) was evaluated by Raman spectroscopy. The nc-Si dot layers were fabricated by the H2 plasma treatment for the nucleation site formation followed by the SiH4 irradiation for the nc-Si growth. Post-oxidation annealing was also performed to improve the crystalline quality. After post-oxidation annealing for 5 or 10 min, the asymmetric broadening on the lower frequency sides in Raman spectra were obtained, which can be attributed to the phonon confinement effect in nc-Si. Furthermore we confirmed that hydrostatic stress of approximately 500 MPa was induced in nc-Si after post-oxidation annealing.

Comparison between semiconducting and oxide layers as a reflection layer in spin-valve films

NASA Astrophysics Data System (ADS)

Dinia, A.; Schmerber, G.; Ulhaq, C.

2003-07-01

It is well established that appropriate oxide capping is effective in forming nano-oxide layers (NOL) in spin-valve films for specular enhancement of giant magnetoresistance (GMR) effect. However, the beneficial effect of a NOL is strongly dependent on its process of formation. Therefore, we are interested to use a nano-semiconducting layer (NSL) for specular reflection instead of oxide layers because its achievement is easier since no specific growth conditions are needed. Moreover, we intend to compare the efficiency of the electronic confinement inside the spin valve induced either by NSL or NOLs for structures with the same stack. We have prepared hard-soft spin valve structures by sputtering on glass substrates with the following stacking sequence: Fe6 nm/Cu3 nm/CoFe1.8 nmRu0.8 nmCoFe3 nmCu2 nmRu2 nm. The reflecting layers have been inserted in the middle of the Fe soft layer and on the top of the spin valve. The GMR effect is enhanced by 60% and 75% respectively for the NSL and the NOL. This shows that the NOL is more efficient in term of electronic confinement. To understand the origin of the difference between the NOL and NSL magnetization measurements as well as transmission electron microscopy are presented.

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

Stair, Peter C.

The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supportedmore » metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.« less

Perpendicular magnetic anisotropy in Mo/Co2FeAl0.5Si0.5/MgO/Mo multilayers with optimal Mo buffer layer thickness

NASA Astrophysics Data System (ADS)

Saravanan, L.; Raja, M. Manivel; Prabhu, D.; Pandiyarasan, V.; Ikeda, H.; Therese, H. A.

2018-05-01

Perpendicular Magnetic Anisotropy (PMA) was realized in as-deposited Mo(10)/Co2FeAl0.5Si0.5(CFAS)(3)/MgO(0.5)/Mo multilayer stacks with large perpendicular magnetic anisotropy energy (Keff). PMA of this multilayer is found to be strongly dependent on the thickness of the individual CFAS (tCFAS), Mo (tMo) and MgO (tMgO) layers and annealing temperatures. The interactions at the Mo/CFAS/MgO interfaces are critical to induce PMA and are tuned by the interfacial oxidation. The major contribution to PMA is due to iron oxide at the CFAS/MgO interface. X-ray diffraction (XRD) and infrared spectroscopic (FT-IR) studies further ascertain this. However, an adequate oxidation of MgO and the formation of (0 2 4) and (0 1 8) planes of α-Fe2O3 at the optimal Mo buffer layer thickness is mainly inducing PMA in Mo/CFAS/MgO/Mo stack. Microstructural changes in the films are observed by atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) demonstrates the oxidation of CFAS/MgO interface and the formation of Fe-O bonds confirming that the real origin of PMA in Mo/CFAS/MgO is due to hybridization of Fe (3dz2) and O (2pz) orbitals and the resulted spin-orbit interaction at their interface. The half-metallic nature CFAS with Mo layer exhibiting PMA can be a potential candidate as p-MTJs electrodes for the new generation spintronic devices.

Factors controlling the size of graphene oxide sheets produced via the graphite oxide route.

PubMed

Pan, Shuyang; Aksay, Ilhan A

2011-05-24

We have studied the effect of the oxidation path and the mechanical energy input on the size of graphene oxide sheets derived from graphite oxide. The cross-planar oxidation of graphite from the (0002) plane results in periodic cracking of the uppermost graphene oxide layer, limiting its lateral dimension to less than 30 μm. We use an energy balance between the elastic strain energy associated with the undulation of graphene oxide sheets at the hydroxyl and epoxy sites, the crack formation energy, and the interaction energy between graphene layers to determine the cell size of the cracks. As the effective crack propagation rate in the cross-planar direction is an order of magnitude smaller than the edge-to-center oxidation rate, graphene oxide single sheets larger than those defined by the periodic cracking cell size are produced depending on the aspect ratio of the graphite particles. We also demonstrate that external energy input from hydrodynamic drag created by fluid motion or sonication, further reduces the size of the graphene oxide sheets through tensile stress buildup in the sheets.

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

Poletika, T. M., E-mail: poletm@ispms.tsc.ru; Girsova, S. L., E-mail: llm@ispms.tsc.ru; Meisner, L. L., E-mail: girs@ispms.tsc.ru

The structure of the surface and near-surface layers of single crystals of NiTi, differently oriented relative to the direction of ion beam treatment was investigated. The role of the crystallographic orientation in formation of structure of surface layers after ion-plasma alloying was revealed. It was found that the orientation effects of selective sputtering and channeling determine the thickness of the oxide and amorphous layers, the depth of penetration of ions and impurities, the distribution of Ni with depth.

Formation of an Anti-Core–Shell Structure in Layered Oxide Cathodes for Li-Ion Batteries

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

Zhang, Hanlei; Omenya, Fredrick; Whittingham, M. Stanley

The layered → rock-salt phase transformation in the layered dioxide cathodes for Li-ion batteries is believed to result in a “core-shell” structure of the primary particles, in which the core region maintains as the layered phase while the surface region undergoes the phase transformation to the rock-salt phase. Using transmission electron microscopy, here we demonstrate the formation of an “anti-core-shell” structure in cycled primary particles with a formula of LiNi0.80Co0.15Al0.05O2, in which the surface and subsurface regions remain as the layered structure while the rock-salt phase forms as domains in the bulk with a thin layer of the spinel phasemore » between the rock-salt core and the skin of the layered phase. Formation of this anti-core-shell structure is attributed to the oxygen loss at the surface that drives the migration of oxygen from the bulk to the surface, thereby resulting in localized areas of significantly reduced oxygen levels in the bulk of the particle, which subsequently undergoes the phase transformation to the rock-salt domains. The formation of the anti-core-shell rock-salt domains is responsible for the reduced capacity, discharge voltage and ionic conductivity in cycled cathode.« less

The Provenance of Sulfur that Becomes Non-Seasalt Sulfate (NSS)

NASA Astrophysics Data System (ADS)

Huebert, B. J.; Simpson, R. M.; Howell, S. G.

2012-12-01

As a part of the Pacific Atmospheric Sulfur Experiment (PASE), we measured sulfur gases and aerosol chemistry (vs size) from the NCAR C-130 near Christmas Island. Monthly (project) average concentrations in the Marine Boundary Layer (MBL, the lowest mixed layer) and Buffer Layer (BuL, a more stable layer atop the MBL, with clouds) are used to evaluate the formation, loss, and exchange rates for DMS, SO2, and NSS in each layer. We evaluate entrainment, divergence, vertical mixing, chemical formation and loss for each to make a self-consistent budget of oxidized sulfur in the remote marine atmosphere. We find that long-range transport of sulfur from continental sources can be larger than the sulfur source from biogenic dimethyl sulfide, DMS. DMS does not appear to control either the number of NSS particles or NSS mass.

Multi-Scale Investigation of the Formation and Breakdown of Passive Films on Carbon Steel Rebar in Concrete

NASA Astrophysics Data System (ADS)

Ghods, Pouria

The multi-scale investigation presented in this thesis was carried out to understand better the mechanisms of passivation and chloride-induced depassivation of carbon steel reinforcement in concrete. The study consisted of electrochemical experiments (electrochemical impedance spectroscopy, linear polarization resistance, free corrosion potential, anodic polarization), microscopic examinations (scanning electron microscopy, transmission electron microscopy, selected area diffraction, convergent beam electron diffraction), numerical modeling (finite element method), and spectroscopic studies (x-ray photoelectron, energy dispersed x-ray, electron energy loss). Electrochemical and microscopic studies showed that the composition of the pore solution and the surface conditions of the rebar affect the passivity and depassivation of carbon steel in concrete. It was demonstrated that crevices between mill scale and steel may become potential sites for depassivation and pit nucleation. The numerical investigation that was carried out to test this hypothesis confirmed that the ratio of chloride to hydroxide concentrations, Cl-/OH-, in crevices increased to levels higher than that of the bulk pore solution, making crevices more vulnerable to depassivation. Therefore, it was concluded that the variability associated with reported chloride thresholds might be attributed, at least in part, to the variability in mill scale properties resulting from the variability in manufacturing. The nano-scale microscopic and spectroscopic studies indicated the formation of 4-10 nm-thick passive oxide films on carbon steel in simulated concrete pore solutions, and these films consisted of two layers separated with an indistinct border. The inner layer was mainly composed of protective Fe2+-rich oxides that are in epitaxial relationship with the underlying steel surface; while the outer layer mostly consisted of (possibly porous) Fe3+-rich oxides, through which chlorides can penetrate. It was proposed that, in the presence of chlorides, Fe+2-rich oxides in the inner layer transform into Fe+3-rich oxides and potentially become un-protective. Although how this transformation occurs is still subject of future research, there are evidences showing that the process most likely leads to the formation of local anodic and cathodic sites on the steel surface.

Hydrogen blistering under extreme radiation conditions

NASA Astrophysics Data System (ADS)

Sznajder, Maciej; Geppert, Ulrich; Dudek, Miroslaw

2018-01-01

Metallic surfaces, exposed to a proton flux, start to degradate by molecular hydrogen blisters. These are created by recombination of protons with metal electrons. Continued irradiation progresses blistering, which is undesired for many technical applications. In this work, the effect of the proton flux magnitude onto the degradation of native metal oxide layers and its consequences for blister formation has been examined. To study this phenomenon, we performed proton irradiation experiments of aluminium surfaces. The proton kinetic energy was chosen so that all recombined hydrogen is trapped within the metal structure. As a result, we discovered that intense proton irradiation increases the permeability of aluminium oxide layers for hydrogen atoms, thereby counteracting blister formation. These findings may improve the understanding of the hydrogen blistering process, are valid for all metals kept under terrestrial ambient conditions, and important for the design of proton irradiation tests.

Study of nickel silicide formation by physical vapor deposition techniques

NASA Astrophysics Data System (ADS)

Pancharatnam, Shanti

Metal silicides are used as contacts to the highly n-doped emitter in photovoltaic devices. Thin films of nickel silicide (NiSi) are of particular interest for Si-based solar cells, as they form at lower temperature and consume less silicon. However, interfacial oxide limits the reduction in sheet resistance. Hence, different diffusion barriers were investigated with regard to optimizing the conductivity and thermal stability. The formation of NiSi, and if it can be doped to have good contact with the n-side of a p-n junction were studied. Reduction of the interfacial oxide by the interfacial Ti layer to allow the formation of NiSi was observed. Silicon was treated in dilute hydrofluoric acid for removing the surface oxide layer. Ni and a Ti diffusion barrier were deposited on Si by physical vapor deposition (PVD) methods - electron beam evaporation and sputtering. The annealing temperature and time were varied to observe the stability of the deposited film. The films were then etched to observe the retention of the silicide. Characterization was done using scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and Rutherford back scattering (RBS). Sheet resistance was measured using the four-point probe technique. Annealing temperatures from 300°C showed films began to agglomerate indicating some diffusion between Ni and Si in the Ti layer, also supported by the compositional analysis in the Auger spectra. Films obtained by evaporation and sputtering were of high quality in terms of coverage over substrate area and uniformity. Thicknesses of Ni and Ti were optimized to 20 nm and 10 nm respectively. Resistivity was low at these thicknesses, and reduced by about half post annealing at 300°C for 8 hours. Thus a low resistivity contact was obtained at optimized thicknesses of the metal layers. It was also shown that some silicide formation occurs at temperatures starting from 300°C and can thus be used to make good silicide contacts.

Rock-Salt Growth-Induced (003) Cracking in a Layered Positive Electrode for Li-Ion Batteries

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

Zhang, Hanlei; Omenya, Fredrick; Yan, Pengfei

For the first time, the (003) cracking is observed and determined to be the major cracking mechanism for the primary particles of Ni-rich layered dioxides as the positive electrode for Li-ion batteries. Using transmission electron microscopy techniques, here we show that the propagation and fracturing of platelet-like rock-salt phase along the (003) plane of the layered oxide are the leading cause for the cracking of primary particles. The fracturing of the rock-salt platelet is induced by the stress discontinuity between the parent layered oxide and the rock-salt phase. The high nickel content is considered to be the key factor formore » the formation of the rock-salt platelet and thus the (003) cracking. The (003)-type cracking can be a major factor for the structural degradation and associated capacity fade of the layered positive electrode.« less

Control of the orbital ordering in manganite superlattices and impact on properties

NASA Astrophysics Data System (ADS)

Koçak, Ayşegül Begüm; Varignon, Julien; Lemal, Sébastien; Ghosez, Philippe; Lepetit, Marie-Bernadette

2017-09-01

The present paper theoretically studies the possibility to control the orbital ordering in manganite superlattices. Indeed, favored dz2eg -orbital occupancy is one of the proposed interpretations for the formation of a "dead" layer at the interfaces in manganite thin films and superlattices. We show here that favored dz2eg -orbital occupancy at the interfaces can be prevented by using alkaline-earth simple oxides as alternating layers in very thin superlattices. Such an alternating layer promotes the contraction of the manganite layers at the interfaces and favors a dx2-y2eg orbital occupancy. This result holds for different manganites, different alkaline-earth simple oxides, as well as different thicknesses of the two layers. While Boltzmann's transport calculations on different superlattices show unexpectedly only weak dependence of the electrical conductivity on the orbital ordering, the enhanced occupation of the dx2-y2 orbital should result in an increased Curie temperature.

Thin TiOx layer as a voltage divider layer located at the quasi-Ohmic junction in the Pt/Ta2O5/Ta resistance switching memory.

PubMed

Li, Xiang Yuan; Shao, Xing Long; Wang, Yi Chuan; Jiang, Hao; Hwang, Cheol Seong; Zhao, Jin Shi

2017-02-09

Ta 2 O 5 has been an appealing contender for the resistance switching random access memory (ReRAM). The resistance switching (RS) in this material is induced by the repeated formation and rupture of the conducting filaments (CFs) in the oxide layer, which are accompanied by the almost inevitable randomness of the switching parameters. In this work, a 1 to 2 nm-thick Ti layer was deposited on the 10 nm-thick Ta 2 O 5 RS layer, which greatly improved the RS performances, including the much-improved switching uniformity. The Ti metal layer was naturally oxidized to TiO x (x < 2) and played the role of a series resistor, whose resistance value was comparable to the on-state resistance of the Ta 2 O 5 RS layer. The series resistor TiO x efficiently suppressed the adverse effects of the voltage (or current) overshooting at the moment of switching by the appropriate voltage partake effect, which increased the controllability of the CF formation and rupture. The switching cycle endurance was increased by two orders of magnitude even during the severe current-voltage sweep tests compared with the samples without the thin TiO x layer. The Ti deposition did not induce any significant overhead to the fabrication process, making the process highly promising for the mass production of a reliable ReRAM.

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

Rodenbücher, C.; Hildebrandt, E.; Sharath, S. U.

On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO{sub 2−x}) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfC{sub x}) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfC{sub x} surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO{sub 2} thin films prepared and measured under identical conditions, the formation of HfC{sub x} was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films providesmore » a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.« less

Microstructural Study on Oxidation Resistance of Nonmodified and Platinum Modified Aluminide Coating

NASA Astrophysics Data System (ADS)

Zagula-Yavorska, Maryana; Sieniawski, Jan

2014-03-01

Platinum electroplating layers (3 and 7 μm thick) were deposited on the surface of the Inconel 713 LC, CMSX 4, and Inconel 625 Ni-base superalloys. Diffusion treatment at 1050°C for 2 h under argon atmosphere was performed after electroplating. Diffusion treated samples were aluminized according to the low activity CVD process at 1050°C for 8 h. The nonmodified aluminide coatings consist of NiAl phase. Platinum modification let to obtain the (Ni,Pt)Al phase in coatings. The coated samples were subjected to cyclic oxidation testing at 1100°C. It was discovered that increase of the platinum electroplating thickness from 3 to 7 μm provides the improvement of oxidation resistance of aluminide coatings. Increase of the platinum thickness causes decreases in weight change and decreases in parabolic constant during oxidation. The platinum provides the pure Al2O3 oxide formation, slow growth oxide layer, and delay the oxide spalling during heating-cooling thermal cycles.

Stabilization of Ag nanostructures by tuning their Fermi levels

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Kan, Ryota; Yamano, Yuka; Uchida, Takayuki

2018-05-01

The oxidation of Ag nanostructures has been studied as a key step for their degradation under the guiding principle in the previous paper that they are stable when their Fermi level is lower than those of their surroundings. The drop of the Fermi level of a thin Ag layer was caused by the formation of self-assembled monolayers (SAMs) of certain organic compounds including those of photographic interest and a monolayer of AgI, and attributed to the formation of dielectric layers, whose positive charges were closer to the Ag layer than negative charges. A consideration is given on further examinations needed to realize the above guiding principle in individual devices.

High-Temperature, Dual-Atmosphere Corrosion of Solid-Oxide Fuel Cell Interconnects

NASA Astrophysics Data System (ADS)

Gannon, Paul; Amendola, Roberta

2012-12-01

High-temperature corrosion of ferritic stainless steel (FSS) surfaces can be accelerated and anomalous when it is simultaneously subjected to different gaseous environments, e.g., when separating fuel (hydrogen) and oxidant (air) streams, in comparison with single-atmosphere exposures, e.g., air only. This so-called "dual-atmosphere" exposure is realized in many energy-conversion systems including turbines, boilers, gasifiers, heat exchangers, and particularly in intermediate temperature (600-800°C) planar solid-oxide fuel cell (SOFC) stacks. It is generally accepted that hydrogen transport through the FSS (plate or tube) and its subsequent integration into the growing air-side surface oxide layer can promote accelerated and anomalous corrosion—relative to single-atmosphere exposure—via defect chemistry changes, such as increased cation vacancy concentrations, decreased oxygen activity, and steam formation within the growing surface oxide layers. Establishment of a continuous and dense surface oxide layer on the fuel side of the FSS can inhibit hydrogen transport and the associated effects on the air side. Minor differences in FSS composition, microstructure, and surface conditions can all have dramatic influences on dual-atmosphere corrosion behaviors. This article reviews high-temperature, dual-atmosphere corrosion phenomena and discusses implications for SOFC stacks, related applications, and future research.

Trichite growth during oxidation of titanium and TA6V4 alloy by water vapor at high temperatures

NASA Technical Reports Server (NTRS)

Coddet, C.; Motte, F.; Sarrazin, P.

1982-01-01

Analysis by electron scanning microscope detected the formation of rutile trichites on the surface of specimens of titanium and titanium alloy TA6V4 oxidized in water vapor in the temperature range 650 to 950 C and the water vapor pressure range from 0.5 to 18 torr. In all specimens, two sublayers of rutile were formed: an external layer of basalt-like appearance, and a microcrystalline inner layer. Morphology of the trichites depends on temperature and the material (whether metal or alloy), but not on vapor pressure.

Epitaxial thin films

DOEpatents

Hunt, Andrew Tye; Deshpande, Girish; Lin, Wen-Yi; Jan, Tzyy-Jiuan

2006-04-25

Epitatial thin films for use as buffer layers for high temperature superconductors, electrolytes in solid oxide fuel cells (SOFC), gas separation membranes or dielectric material in electronic devices, are disclosed. By using CCVD, CACVD or any other suitable deposition process, epitaxial films having pore-free, ideal grain boundaries, and dense structure can be formed. Several different types of materials are disclosed for use as buffer layers in high temperature superconductors. In addition, the use of epitaxial thin films for electrolytes and electrode formation in SOFCs results in densification for pore-free and ideal gain boundary/interface microstructure. Gas separation membranes for the production of oxygen and hydrogen are also disclosed. These semipermeable membranes are formed by high-quality, dense, gas-tight, pinhole free sub-micro scale layers of mixed-conducting oxides on porous ceramic substrates. Epitaxial thin films as dielectric material in capacitors are also taught herein. Capacitors are utilized according to their capacitance values which are dependent on their physical structure and dielectric permittivity. The epitaxial thin films of the current invention form low-loss dielectric layers with extremely high permittivity. This high permittivity allows for the formation of capacitors that can have their capacitance adjusted by applying a DC bias between their electrodes.

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

DOE PAGES

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan; ...

2015-08-05

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

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

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

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.

Tin-Assisted Synthesis of ɛ -Ga2O3 by Molecular Beam Epitaxy

NASA Astrophysics Data System (ADS)

Kracht, M.; Karg, A.; Schörmann, J.; Weinhold, M.; Zink, D.; Michel, F.; Rohnke, M.; Schowalter, M.; Gerken, B.; Rosenauer, A.; Klar, P. J.; Janek, J.; Eickhoff, M.

2017-11-01

The synthesis of ɛ -Ga2O3 and β -Ga2O3 by plasma-assisted molecular beam epitaxy on (001 )Al2O3 substrates is studied. The growth window of β -Ga2O3 in the Ga-rich regime, usually limited by the formation of volatile gallium suboxide, is expanded due to the presence of tin during the growth process, which stabilizes the formation of gallium oxides. X-ray diffraction, transmission electron microscopy, time-of-flight secondary-ion mass spectrometry, Raman spectroscopy, and atomic force microscopy are used to analyze the influence of tin on the layer formation. We demonstrate that it allows the synthesis of phase-pure ɛ -Ga2O3 . A growth model based on the oxidation of gallium suboxide by reduction of an intermediate sacrificial tin oxide is suggested.

A Microstructural and Kinetic Investigation of the KCl-Induced Corrosion of an FeCrAl Alloy at 600 °C

DOE PAGES

Israelsson, Niklas; Unocic, Kinga A.; Hellström, K.; ...

2015-03-18

In this paper, the corrosion behaviour of a FeCrAl alloy was investigated at 600 °C in O 2 + H 2O with solid KCl applied. A kinetics and microstructural investigation showed that KCl accelerates corrosion and that potassium chromate formation depletes the protective scale in Cr, thus triggering the formation of a fast-growing iron-rich scale. Iron oxide was found to grow both inward and outward, on either side of the initial oxide. A chromia layer is formed with time underneath the iron oxide. Finally, it was found that although the alloy does not form a continuous pure alumina scale atmore » the investigated temperature, aluminium is, however, always enriched at the oxide/alloy interface.« less

CPP-GMR films with a current-confined-path nano-oxide layer (CCP-NOL)

NASA Astrophysics Data System (ADS)

Fukuzawa, Hideaki; Yuasa, Hiromi; Iwasaki, Hitoshi

2007-03-01

We investigated the film performance and nanostructure of current-perpendicular-to-plane giant magnetoresistance (CPP-GMR) spin-valve film with a current-confined-path nano-oxide layer (CCP-NOL). By applying ion-assisted oxidation (IAO) for the CCP-NOL formation, we enhanced the MR ratio to 5.4% at a small RA value of 500 mΩ µm2 for conventional Co90Fe10 layers. Furthermore, the use of bcc-Fe50Co50 also increased the MR ratio to 8.2% at a small RA value of 580 mΩ µm2. A modified Valet-Fert model for the CCP-NOL showed that the MR enhancement by the IAO is due to the improvement in resistivity of the CCP, and that by Fe50Co50 is due to a larger spin-dependent interface scattering effect. Analysis by cross-sectional TEM and three-dimensional atom probe confirmed the formation of the CCP-NOL structure. A reliability test for test element devices showed almost no change even under acceleration stress. The CPP-GMR spin-valve film with the CCP-NOL is extendable to future high-density recording heads due to its potential for a higher MR ratio at a small value of RA.

Synthesis and characterization of magnesium oxide nanocrystallites and probing the vacancy-type defects through positron annihilation studies

NASA Astrophysics Data System (ADS)

Das, Anjan; Mandal, Atis Chandra; Roy, Soma; Prashanth, Pendem; Ahamed, Sk Izaz; Kar, Subhrasmita; Prasad, Mithun S.; Nambissan, P. M. G.

2016-09-01

Magnesium oxide nanocrystallites exhibit certain abnormal characteristics when compared to those of other wide band gap oxide semiconductors in the sense they are most prone to water absorption and formation of a hydroxide layer on the surface. The problem can be rectified by heating and pure nanocrystallites can be synthesized with controllable sizes. Inevitably the defect properties are distinctly divided between two stages, the one with the hydroxide layer (region I) and the other after the removal of the layer by annealing (region II). The lattice parameters, the optical band gap and even the positron annihilation characteristics are conspicuous by their distinct behavior in the two stages of the surface configurations of nanoparticles. While region I was specific with the formation of positronium-hydrogen complexes that drastically altered the defect-specific positron lifetimes, pick-off annihilation of orthopositronium atoms marked region II. The vacancy clusters within the nanocrystallites also trapped positrons. They agglomerated due to the effect of the higher temperatures and resulted in the growth of the nanocrystallites. The coincidence Doppler broadening spectroscopic measurements supported these findings and all the more indicated the trapping of positrons additionally into the neutral divacancies and negatively charged trivacancies. This is apart from the Mg2+ monovacancies which acted as the dominant trapping centers for positrons.

Application of Formation MicroScanner Log in Structural Analysis of an Ultra-slow Spreading Environment, ODP Hole 1105A

NASA Astrophysics Data System (ADS)

Zarian, P.; Casey, J. F.; Miller, J.

2002-12-01

One of the unconventional research efforts that have been directed to reveal the structure of the lower oceanic crust is the application of Formation MicroScanner log in an ultra-slow spreading environment. Hole 1105A was cored during ODP Leg 179 to a depth of 158m on the Atlantis Platform in the Southwest Indian Ridge with a relative high recovery of 82.8% of gabbroic rocks. Open-hole logs, including FMS borehole images were acquired after the coring operation. Detailed modal, grain size and microstructural analyses of 147 thin sections reveal the relationships between deformation intensity, modal composition and rheology. The microstructural analyses showed that the majority of the oxide-rich gabbros exhibit high deformation intensity textures, which are present only in a few of the oxide-free gabbros. The oxide-rich gabbros represent ductile deformation zones and control the location of major deformation zones within these rocks. Oxide-rich layers can be clearly identified on electrical images and enabled the identification of different deformation features.The calibration of borehole images with core data provides us with more detailed information about the geometry of these oxide-rich layers within the magma chamber such as the dip and true pseudo-stratigraphic thickness of these layers. Also within the intervals of no core recovery, electrical images provide valuable information of the borehole wall. Brittle deformation features such as natural mineralized fractures can be documented throughout the borehole. Statistical results show that oxide-rich layers are relatively steep with an average dip of about 50 degrees and have a dominant E-W strike which is parallel to the ridge. These layers may represent the insitu crystallization of cummulate layers on a magma chamber wall elongated parallel to the ridge, or they may represent shear zones associated with near surface high angle normal faults that cut the main low angle detachment surface which caused the unroofing of the lower oceanic crust at the inner corner of the Ridge-Transform Intersection. These ductile shear zones appear to strike in a ridge parallel orientation, may have acted as syntectonic permeable pathways for fractionated melts infiltrated during the unroofing. Core-log integration also demonstrates the capabilities of electrical borehole images for structural analyses within a hard rock environment.

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

Semiconductor structures having electrically insulating and conducting portions formed from an AlSb-alloy layer

DOEpatents

Spahn, O.B.; Lear, K.L.

1998-03-10

The semiconductor structure comprises a plurality of semiconductor layers formed on a substrate including at least one layer of a III-V compound semiconductor alloy comprising aluminum (Al) and antimony (Sb), with at least a part of the AlSb-alloy layer being chemically converted by an oxidation process to form superposed electrically insulating and electrically conducting portions. The electrically insulating portion formed from the AlSb-alloy layer comprises an oxide of aluminum (e.g., Al{sub 2}O{sub 3}), while the electrically conducting portion comprises Sb. A lateral oxidation process allows formation of the superposed insulating and conducting portions below monocrystalline semiconductor layers for forming many different types of semiconductor structures having particular utility for optoelectronic devices such as light-emitting diodes, edge-emitting lasers, vertical-cavity surface-emitting lasers, photodetectors and optical modulators (waveguide and surface normal), and for electronic devices such as heterojunction bipolar transistors, field-effect transistors and quantum-effect devices. The invention is expected to be particularly useful for forming light-emitting devices for use in the 1.3--1.6 {mu}m wavelength range, with the AlSb-alloy layer acting to define an active region of the device and to effectively channel an electrical current therein for efficient light generation. 10 figs.

Semiconductor structures having electrically insulating and conducting portions formed from an AlSb-alloy layer

DOEpatents

Spahn, Olga B.; Lear, Kevin L.

1998-01-01

A semiconductor structure. The semiconductor structure comprises a plurality of semiconductor layers formed on a substrate including at least one layer of a III-V compound semiconductor alloy comprising aluminum (Al) and antimony (Sb), with at least a part of the AlSb-alloy layer being chemically converted by an oxidation process to form superposed electrically insulating and electrically conducting portions. The electrically insulating portion formed from the AlSb-alloy layer comprises an oxide of aluminum (e.g. Al.sub.2 O.sub.3), while the electrically conducting portion comprises Sb. A lateral oxidation process allows formation of the superposed insulating and conducting portions below monocrystalline semiconductor layers for forming many different types of semiconductor structures having particular utility for optoelectronic devices such as light-emitting diodes, edge-emitting lasers, vertical-cavity surface-emitting lasers, photodetectors and optical modulators (waveguide and surface normal), and for electronic devices such as heterojunction bipolar transistors, field-effect transistors and quantum-effect devices. The invention is expected to be particularly useful for forming light-emitting devices for use in the 1.3-1.6 .mu.m wavelength range, with the AlSb-alloy layer acting to define an active region of the device and to effectively channel an electrical current therein for efficient light generation.

Reactive metal-oxide interfaces: A microscopic view

NASA Astrophysics Data System (ADS)

Picone, A.; Riva, M.; Brambilla, A.; Calloni, A.; Bussetti, G.; Finazzi, M.; Ciccacci, F.; Duò, L.

2016-03-01

Metal-oxide interfaces play a fundamental role in determining the functional properties of artificial layered heterostructures, which are at the root of present and future technological applications. Magnetic exchange and magnetoelectric coupling, spin filtering, metal passivation, catalytic activity of oxide-supported nano-particles are just few examples of physical and chemical processes arising at metal-oxide hybrid systems, readily exploited in working devices. These phenomena are strictly correlated with the chemical and structural characteristics of the metal-oxide interfacial region, making a thorough understanding of the atomistic mechanisms responsible of its formation a prerequisite in order to tailor the device properties. The steep compositional gradient established upon formation of metal-oxide heterostructures drives strong chemical interactions at the interface, making the metal-oxide boundary region a complex system to treat, both from an experimental and a theoretical point of view. However, once properly mastered, interfacial chemical interactions offer a further degree of freedom for tuning the material properties. The goal of the present review is to provide a summary of the latest achievements in the understanding of metal/oxide and oxide/metal layered systems characterized by reactive interfaces. The influence of the interface composition on the structural, electronic and magnetic properties will be highlighted. Particular emphasis will be devoted to the discussion of ultra-thin epitaxial oxides stabilized on highly oxidizable metals, which have been rarely exploited as oxide supports as compared to the much more widespread noble and quasi noble metallic substrates. In this frame, an extensive discussion is devoted to the microscopic characterization of interfaces between epitaxial metal oxides and the Fe(001) substrate, regarded from the one hand as a prototypical ferromagnetic material and from the other hand as a highly oxidizable metal.

Critical temperature determination of detectable Cr diffusion enhancement by nanostructure through structural evolution analysis of the oxide films at 25-450 °C on 304 stainless steel

NASA Astrophysics Data System (ADS)

Gui, Y.; Meng, X. B.; Zheng, Z. J.; Gao, Y.

2017-10-01

The structural evolution of the oxide films at 25-450 °C on nanocrystalline (NC) and coarse crystalline (CC) 304 stainless steels (SS) was investigated. The structure of the oxide film on both NC and CC SSs was observed to undergo transient processes from a bi-layer to a single-layer and then back to a bi-layer when the temperature changed from the low range (25-150 °C) to the medium range (150-300 °C) and subsequently to the high range (300-450 °C), respectively. These formation mechanisms of the oxide films on SS were attributed to the different diffusion properties of Cr and Fe in the three temperature ranges. The thickness of the oxide films was similar between the NC and CC SSs below 300 °C due to their similar Crox/Feox concentration ratios in their oxide films at this temperature. Above 300 °C, Cr diffusion enhancement in the NC matrix led to a higher Crox/Feox ratio and better compactness of the oxide film, which resulted in a slower atomic diffusion rate in the oxide film and a thinner oxide film. Therefore, the temperature of 300 °C was concluded to be the critical temperature of the detectable Cr diffusion enhancement in the NC SS compared to the CC SS.

Corrosion fatigue in nitrocarburized quenched and tempered steels

NASA Astrophysics Data System (ADS)

Khani, M. Karim; Dengel, D.

1996-05-01

In order to investigate the fatigue strength and fracture mechanism of salt bath nitrocarburized steels, specimens of the steels SAE 4135 and SAE 4140, in a quenched and tempered state, and additionally in a salt bath nitrocarburized and oxidizing cooled state as well as in a polished (after the oxidizing cooling) and renewed oxidized state, were subjected to comparative rotating bending fatigue tests in inert oil and 5 pct NaCl solution. In addition, some of the quenched and tempered specimens of SAE 4135 material were provided with an approximately 50-μm-thick electroless Ni-P layer, in order to compare corrosion fatigue behavior between the Ni-P layer and the nitride layers. Long-life corrosion fatigue tests of SAE 4135 material were carried out under small stresses in the long-life range up to 108 cycles with a test frequency of 100 Hz. Fatigue tests of SAE 4140 material were carried out in the range of finite life (low-cycle range) with a test frequency of 13 Hz. The results show that the 5 pct NaCl environment drastically reduced fatigue life, but nitrocarburizing plus oxidation treatment was found to improve the corrosion fatigue life over that of untreated and Ni-P coated specimens. The beneficial effect of nitrocarburizing followed by oxidation treatment on cor-rosion fatigue life results from the protection rendered by the compound layer by means of a well-sealed oxide layer, whereby the pores present in the compound layer fill up with oxides. The role of inclusions in initiating fatigue cracks was investigated. It was found that under corrosion fatigue conditions, the fatigue cracks started at cavities along the interfaces of MnS inclusions and matrix in the case of quenched and tempered specimens. The nitrocarburized specimens, however, showed a superposition of pitting corrosion and corrosion fatigue in which pores and nonmetallic inclusions in the compound layer play a predominant role concerning the formation of pits in the substrate.

Dye-sensitized photoelectrochemical water oxidation through a buried junction.

PubMed

Xu, Pengtao; Huang, Tian; Huang, Jianbin; Yan, Yun; Mallouk, Thomas E

2018-06-18

Water oxidation has long been a challenge in artificial photosynthetic devices that convert solar energy into fuels. Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) provide a modular approach for integrating light-harvesting molecules with water-oxidation catalysts on metal-oxide electrodes. Despite recent progress in improving the efficiency of these devices by introducing good molecular water-oxidation catalysts, WS-DSPECs have poor stability, owing to the oxidation of molecular components at very positive electrode potentials. Here we demonstrate that a solid-state dye-sensitized solar cell (ss-DSSC) can be used as a buried junction for stable photoelectrochemical water splitting. A thin protecting layer of TiO 2 grown by atomic layer deposition (ALD) stabilizes the operation of the photoanode in aqueous solution, although as a solar cell there is a performance loss due to increased series resistance after the coating. With an electrodeposited iridium oxide layer, a photocurrent density of 1.43 mA cm -2 was observed in 0.1 M pH 6.7 phosphate solution at 1.23 V versus reversible hydrogen electrode, with good stability over 1 h. We measured an incident photon-to-current efficiency of 22% at 540 nm and a Faradaic efficiency of 43% for oxygen evolution. While the potential profile of the catalyst layer suggested otherwise, we confirmed the formation of a buried junction in the as-prepared photoelectrode. The buried junction design of ss-DSSs adds to our understanding of semiconductor-electrocatalyst junction behaviors in the presence of a poor semiconducting material.

X-ray photoelectron spectroscopy study of the stability of Fomblin Z25 on the native oxide of aluminum

NASA Technical Reports Server (NTRS)

Herrera-Fierro, Pilar; Pepper, Stephen V.; Jones, William R.

1992-01-01

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum, and onto sapphire surfaces, and their behavior at different temperatures was studied using X-ray photoelectron spectroscopy and temperature desorption spectroscopy (TDS). The interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on the clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. The native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At higher temperatures (150 C), degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formation of a debris layer.

Understanding of interface structures and reaction mechanisms induced by Ge or GeO diffusion in Al{sub 2}O{sub 3}/Ge structure

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

Shibayama, Shigehisa; JSPS, 5-3-1 Kojimachi, Chiyoda-ku, Tokyo 102-0083; Kato, Kimihiko

2013-08-19

The reaction mechanisms at Al{sub 2}O{sub 3}/Ge interfaces with thermal oxidation through the Al{sub 2}O{sub 3} layer have been investigated. X-ray photoelectron spectroscopy reveals that an Al{sub 6}Ge{sub 2}O{sub 13} layer is formed near the interface, and a GeO{sub 2} layer is formed on the Al{sub 2}O{sub 3} surface, suggesting Ge or GeO diffusion from the Ge surface. It is also clarified that the Al{sub 6}Ge{sub 2}O{sub 13} layer is formed by the different mechanism with a small activation energy of 0.2 eV, compared with the GeO{sub 2} formation limited by oxygen diffusion. Formation of Al-O-Ge bonds due to themore » AlGeO formation could lead appropriate interface structures with high interface qualities.« less

Interfacial micropore defect formation in PEDOT:PSS-Si hybrid solar cells probed by TOF-SIMS 3D chemical imaging.

PubMed

Thomas, Joseph P; Zhao, Liyan; Abd-Ellah, Marwa; Heinig, Nina F; Leung, K T

2013-07-16

Conducting p-type polymer layers on n-type Si have been widely studied for the fabrication of cost-effective hybrid solar cells. In this work, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is used to provide three-dimensional chemical imaging of the interface between poly(3,4-ethylene-dioxythiophene):polystyrenesulfonate (PEDOT:PSS) and SiOx/Si in a hybrid solar cell. To minimize structural damage to the polymer layer, an Ar cluster sputtering source is used for depth profiling. The present result shows the formation of micropore defects in the interface region of the PEDOT:PSS layer on the SiOx/Si substrate. This interfacial micropore defect formation becomes more prominent with increasing thickness of the native oxide layer, which is a key device parameter that greatly affects the hybrid solar cell performance. Three-dimensional chemical imaging coupled with Ar cluster ion sputtering has therefore been demonstrated as an emerging technique for probing the interface of this and other polymer-inorganic systems.

Formation of thick stratiform Fe-Ti oxide layers in layered intrusion and frequent replenishment of fractionated mafic magma: Evidence from the Panzhihua intrusion, SW China

NASA Astrophysics Data System (ADS)

Song, Xie-Yan; Qi, Hua-Wen; Hu, Rui-Zhong; Chen, Lie-Meng; Yu, Song-Yue; Zhang, Jia-Fei

2013-03-01

Panzhihua intrusion is one of the largest layered intrusions that hosts huge stratiform Fe-Ti oxide layers in the central part of the Emeishan large igneous province, SW China. Up to 60 m thick stratiform massive Fe-Ti oxide layers containing 85 modal% of magnetite and ilmenite and overlying magnetite gabbro compose cyclic units of the Lower Zone of the intrusion. The cyclic units of the Middle Zone consist of magnetite gabbro and overlying gabbro. In these cyclic units, contents of Fe2O3(t), TiO2 and Cr and Fe3+/Ti4+ ratio of the rocks decrease upward, Cr content of magnetite and forsterite percentage of olivine decrease as well. The Upper Zone consists of apatite gabbro characterized by enrichment of incompatible elements (e.g., 12-18 ppm La, 20-28 ppm Y) and increasing of Fe3+/Ti4+ ratio (from 1.3 to 2.3) upward. These features indicate that the Panzhihua intrusion was repeatedly recharged by more primitive magma and evolved magmas had been extracted. Calculations using MELTS indicate that extensive fractionation of olivine and clinopyroxene in deep level resulted in increasing Fe and Ti contents in the magma. When these Fe-Ti-enriched magmas were emplaced along the base of the Panzhihua intrusion, Fe-Ti oxides became an early crystallization phase, leading to a residual magma of lower density. We propose that the unusually thick stratiform Fe-Ti oxide layers resulted from coupling of gravity settling and sorting of the crystallized Fe-Ti oxides from Fe-Ti-enriched magmas and frequent magma replenishment along the floor of the magma chamber.

High temperature Oxidation of ODS alloy with zirconia dispersions synthesized using Arc Plasma Sintering

NASA Astrophysics Data System (ADS)

Bandriyana; Sujatno, A.; Salam, R.; Sugeng, B.; Dimyati, A.

2017-02-01

Microstructure formation and oxidation behaviour of the Oxide Dispersion Strengthened (ODS) steels for application as structure material in Nuclear Power Plant was investigated. A mixture composed of Fe and 12 wt. % Cr powder with addition of 0.5 and 1 wt.% ZrO2 particles was milled and isostatic pressed to form a sample coin. The coin was then consolidated in the Arc Plasma Sintering (APS) for 4 minutes. The samples were subjected to the high temperature oxidation test in the Magnetic Suspension Balance (MSB). The oxidation test was carried out at 700°C for 6 hours to evaluate the oxide growth in the early stage of it formation by extraction the mass gain curve. The Scanning Electron Microscope (SEM) imaging and X-ray Diffraction Spectroscopy (EDX) elemental mapping were performed to study the microstructure change and compositional distribution. SEM and EDX observation revealed the time dependent development of the Fe-Cr-phases during consolidation. The oxidation rate behaviour of the samples followed the parabolic rate characteristic for inward oxidation process driven by oxygen inward diffusion through the oxide scale with the maximum weight gain around of 60 g/m2. The oxidation resistance was strongly affected by the formation of the oxide protective layer on the surface. In so far, addition of zirconia particles has played no significant role to the oxidation behaviour.

Effects of interfacial layer on characteristics of TiN/ZrO2 structures.

PubMed

Kim, Younsoo; Kang, Sang Yeol; Choi, Jae Hyoung; Lim, Jae Soon; Park, Min Young; Chung, Suk-Jin; Chung, Jaegwan; Lee, Hyung Ik; Kim, Ki Hong; Kyoung, Yong Koo; Heo, Sung; Yoo, Cha Young; Kang, Ho-Kyu

2011-09-01

To minimize the formation of unwanted interfacial layers, thin interfacial layer (ZrCN layer) was deposited between TiN bottom electrode and ZrO2 dielectric in TiN/ZrO2/TiN capacitor. Carbon and nitrogen were also involved in the layer because ZrCN layer was thermally deposited using TEMAZ without any reactant. Electrical characteristics of TiN/ZrO2/TiN capacitor were improved by insertion of ZrCN layer. The oxidation of TiN bottom electrode was largely inhibited at TiN/ZrCN/ZrO2 structure compared to TiN/ZrO2 structure. While the sheet resistance of TiN/ZrCN/ZrO2 structure was constantly sustained with increasing ZrO2 thickness, the large increase of sheet resistance was observed in TiN/ZrO2 structure after 6 nm ZrO2 deposition. When ZrO2 films were deposited on ZrCN layer, the deposition rate of ZrO2 also increased. It is believed that ZrCN layer acted both as a protection layer of TiN oxidation and a seed layer of ZrO2 growth.

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

PubMed

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

2017-02-22

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

Tuning the Phase and Microstructural Properties of TiO2 Films Through Pulsed Laser Deposition and Exploring Their Role as Buffer Layers for Conductive Films

NASA Astrophysics Data System (ADS)

Agarwal, S.; Haseman, M. S.; Leedy, K. D.; Winarski, D. J.; Saadatkia, P.; Doyle, E.; Zhang, L.; Dang, T.; Vasilyev, V. S.; Selim, F. A.

2018-04-01

Titanium oxide (TiO2) is a semiconducting oxide of increasing interest due to its chemical and thermal stability and broad applicability. In this study, thin films of TiO2 were deposited by pulsed laser deposition on sapphire and silicon substrates under various growth conditions, and characterized by x-ray diffraction (XRD), atomic force microscopy (AFM), optical absorption spectroscopy and Hall-effect measurements. XRD patterns revealed that a sapphire substrate is more suitable for the formation of the rutile phase in TiO2, while a silicon substrate yields a pure anatase phase, even at high-temperature growth. AFM images showed that the rutile TiO2 films grown at 805°C on a sapphire substrate have a smoother surface than anatase films grown at 620°C. Optical absorption spectra confirmed the band gap energy of 3.08 eV for the rutile phase and 3.29 eV for the anatase phase. All the deposited films exhibited the usual high resistivity of TiO2; however, when employed as a buffer layer, anatase TiO2 deposited on sapphire significantly improves the conductivity of indium gallium zinc oxide thin films. The study illustrates how to control the formation of TiO2 phases and reveals another interesting application for TiO2 as a buffer layer for transparent conducting oxides.

Thin-film fractal nanostructures formed by electrical breakdown

NASA Astrophysics Data System (ADS)

Tadtaev, P. O.; Bobkov, A. A.; Borodzyulya, V. F.; Lamkin, I. A.; Mihailov, I. I.; Moshnikov, V. A.; Permyakov, N. V.; Solomonov, A. V.; Sudar, N. T.; Tarasov, S. A.

2017-11-01

This is a study of the fractal micro- and nanostructures formation caused by the electrical breakdown of the indium-tin oxide (ITO) covered with various organic coatings. The samples were created by covering a glass substrate with a 1 to 10um-thick layer of indium-tin oxide. Some of the samples were then coated with organic layers of polycarbonate, poly(methyl methacrylate) and others. In order to create high local electrical field densities a special setup based on a eutectic GaIn liquid needle was created: it allowed for the contact area of 60um in diameter and application of the step voltage swept from 20 to 300 volts. The setup also contained a spectrometer for measuring the spectra of the breakdown optical effects. The results showed that the destruction of ITO led to the formation of the spiral fractal nanostructures, parameters of which depended on the thickness of the layer and the presence of the organic cover. In case of the latter, polymer coating was shown to visualize and zoom the topography of the nanostructures which might be used as a method of “polymer photography” for such fractal formations. The analysis of the spectra showed their dependence on the parameters of the structures which proves the possibility of conducting optical diagnostics of the created structures.

Oxidation of ZrB2 SiC TaSi2 Materials at Ultra High Temperatures

NASA Technical Reports Server (NTRS)

Opila, E.; Smith, J.; Levine, S.; Lorincz, J.; Reigel, M.

2008-01-01

ZrB2 - 20v% SiC - 20v% TaSi2 was oxidized in stagnant air for ten minute cycles for times up to 100 minutes at 1627 C and 1927 C. The sample oxidized at 1627 C showed oxidation resistance better than that of the standard ZrB2 - 20v% SiC. The sample oxidized at 1927 C, however, showed evidence of liquid phase formation and complex oxidation products. The sample exposed at 1927 C was analyzed in detail by scanning electron microprobe and wavelength dispersive spectroscopy to understand the complex oxidation and melting reactions occurring during exposure. The as hot-pressed material shows the formation of a Zr(Ta)B2 phase in addition to the three phases in the nominal composition already noted. After oxidation, the TaSi2 in the matrix was completely reacted to form Ta(Zr)C. The layered oxidation products included SiO2, ZrO2, Ta2O5, and a complex oxide containing both Zr and Ta. Likely reactions are proposed based on thermodynamic phase stability and phase morphology.

Reversible formation of ammonium persulfate/sulfuric acid graphite intercalation compounds and their peculiar Raman spectra.

PubMed

Dimiev, Ayrat M; Bachilo, Sergei M; Saito, Riichiro; Tour, James M

2012-09-25

Graphite intercalation compounds (GICs) can be considered stacks of individual doped graphene layers. Here we demonstrate a reversible formation of sulfuric acid-based GICs using ammonium persulfate as the chemical oxidizing agent. No covalent chemical oxidation leading to the formation of graphite oxide occurs, which inevitably happens when other compounds such as potassium permanganate are used to charge carbon layers. The resulting acid/persulfate-induced stage-1 and stage-2 GICs are characterized by suppression of the 2D band in the Raman spectra and by unusually strong enhancement of the G band. The G band is selectively enhanced at different doping levels with different excitations. These observations are in line with recent reports for chemically doped and gate-modulated graphene and support newly proposed theories of Raman processes. At the same time GICs have some advantageous differences over graphene, which are demonstrated in this report. Our experimental observations, along with earlier reported data, suggest that at high doping levels the G band cannot be used as the reference peak for normalizing Raman spectra, which is a commonly used practice today. A Fermi energy shift of 1.20-1.25 eV and ∼1.0 eV was estimated for the stage-1 and stage-2 GICs, respectively, from the Raman and optical spectroscopy data.

Formation of multiple levels of porous silicon for buried insulators and conductors in silicon device technologies

DOEpatents

Blewer, Robert S.; Gullinger, Terry R.; Kelly, Michael J.; Tsao, Sylvia S.

1991-01-01

A method of forming a multiple level porous silicon substrate for semiconductor integrated circuits including anodizing non-porous silicon layers of a multi-layer silicon substrate to form multiple levels of porous silicon. At least one porous silicon layer is then oxidized to form an insulating layer and at least one other layer of porous silicon beneath the insulating layer is metallized to form a buried conductive layer. Preferably the insulating layer and conductive layer are separated by an anodization barrier formed of non-porous silicon. By etching through the anodization barrier and subsequently forming a metallized conductive layer, a fully or partially insulated buried conductor may be fabricated under single crystal silicon.

Optimized capping layers for EUV multilayers

DOEpatents

Bajt, Sasa [Livermore, CA; Folta, James A [Livermore, CA; Spiller, Eberhard A [Livermore, CA

2004-08-24

A new capping multilayer structure for EUV-reflective Mo/Si multilayers consists of two layers: A top layer that protects the multilayer structure from the environment and a bottom layer that acts as a diffusion barrier between the top layer and the structure beneath. One embodiment combines a first layer of Ru with a second layer of B.sub.4 C. Another embodiment combines a first layer of Ru with a second layer of Mo. These embodiments have the additional advantage that the reflectivity is also enhanced. Ru has the best oxidation resistance of all materials investigated so far. B.sub.4 C is an excellent barrier against silicide formation while the silicide layer formed at the Si boundary is well controlled.

Mobility Enhancement in Amorphous In-Ga-Zn-O Thin-Film Transistor by Induced Metallic in Nanoparticles and Cu Electrodes.

PubMed

Hu, Shiben; Ning, Honglong; Lu, Kuankuan; Fang, Zhiqiang; Li, Yuzhi; Yao, Rihui; Xu, Miao; Wang, Lei; Peng, Junbiao; Lu, Xubing

2018-03-27

In this work, we fabricated a high-mobility amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) based on alumina oxide (Al 2 O 3 ) passivation layer (PVL) and copper (Cu) source/drain electrodes (S/D). The mechanism of the high mobility for a-IGZO TFT was proposed and experimentally demonstrated. The conductivity of the channel layer was significantly improved due to the formation of metallic In nanoparticles on the back channel during Al 2 O 3 PVL sputtering. In addition, Ar atmosphere annealing induced the Schottky contact formation between the Cu S/D and the channel layer caused by Cu diffusion. In conjunction with high conductivity channel and Schottky contact, the a-IGZO TFT based on Cu S/D and Al 2 O 3 PVL exhibited remarkable mobility of 33.5-220.1 cm 2 /Vs when channel length varies from 60 to 560 μ m. This work presents a feasible way to implement high mobility and Cu electrodes in a-IGZO TFT, simultaneously.

Mobility Enhancement in Amorphous In-Ga-Zn-O Thin-Film Transistor by Induced Metallic in Nanoparticles and Cu Electrodes

PubMed Central

Lu, Kuankuan; Li, Yuzhi; Xu, Miao; Wang, Lei; Peng, Junbiao; Lu, Xubing

2018-01-01

In this work, we fabricated a high-mobility amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) based on alumina oxide (Al2O3) passivation layer (PVL) and copper (Cu) source/drain electrodes (S/D). The mechanism of the high mobility for a-IGZO TFT was proposed and experimentally demonstrated. The conductivity of the channel layer was significantly improved due to the formation of metallic In nanoparticles on the back channel during Al2O3 PVL sputtering. In addition, Ar atmosphere annealing induced the Schottky contact formation between the Cu S/D and the channel layer caused by Cu diffusion. In conjunction with high conductivity channel and Schottky contact, the a-IGZO TFT based on Cu S/D and Al2O3 PVL exhibited remarkable mobility of 33.5–220.1 cm2/Vs when channel length varies from 60 to 560 μm. This work presents a feasible way to implement high mobility and Cu electrodes in a-IGZO TFT, simultaneously. PMID:29584710

Identification and paleoclimatic significance of magnetite nanoparticles in soils

NASA Astrophysics Data System (ADS)

Ahmed, Imad A. M.; Maher, Barbara A.

2018-02-01

In the world-famous sediments of the Chinese Loess Plateau, fossil soils alternate with windblown dust layers to record monsoonal variations over the last ˜3 My. The less-weathered, weakly magnetic dust layers reflect drier, colder glaciations. The fossil soils (paleosols) contain variable concentrations of nanoscale, strongly magnetic iron oxides, formed in situ during the wetter, warmer interglaciations. Mineralogical identification of the magnetic soil oxides is essential for deciphering these key paleoclimatic records. Formation of magnetite, a mixed Fe2+/Fe3+ ferrimagnet, has been linked to soil redox oscillations, and thence to paleorainfall. An opposite hypothesis states that magnetite can only form if the soil is water saturated for significant periods in order for Fe3+ to be reduced to Fe2+, and suggests instead the temperature-dependent formation of maghemite, an Fe3+-oxide, much of which ages subsequently into hematite, typically aluminum substituted. This latter, oxidizing pathway would have been temperature, but not rainfall dependent. Here, through structural fingerprinting and scanning transmission electron microscopy and electron energy loss spectroscopy analysis, we prove that magnetite is the dominant soil-formed ferrite. Maghemite is present in lower concentrations, and shows no evidence of aluminum substitution, negating its proposed precursor role for the aluminum-substituted hematite prevalent in the paleosols. Magnetite dominance demonstrates that magnetite formation occurs in well-drained, generally oxidizing soils, and that soil wetting/drying oscillations drive the degree of soil magnetic enhancement. The magnetic variations of the Chinese Loess Plateau paleosols thus record changes in monsoonal rainfall, over timescales of millions of years.

Electrical properties of zinc-oxide-based thin-film transistors using strontium-oxide-doped semiconductors

NASA Astrophysics Data System (ADS)

Wu, Shao-Hang; Zhang, Nan; Hu, Yong-Sheng; Chen, Hong; Jiang, Da-Peng; Liu, Xing-Yuan

2015-10-01

Strontium-zinc-oxide (SrZnO) films forming the semiconductor layers of thin-film transistors (TFTs) are deposited by using ion-assisted electron beam evaporation. Using strontium-oxide-doped semiconductors, the off-state current can be dramatically reduced by three orders of magnitude. This dramatic improvement is attributed to the incorporation of strontium, which suppresses carrier generation, thereby improving the TFT. Additionally, the presence of strontium inhibits the formation of zinc oxide (ZnO) with the hexagonal wurtzite phase and permits the formation of an unusual phase of ZnO, thus significantly changing the surface morphology of ZnO and effectively reducing the trap density of the channel. Project supported by the National Natural Science Foundation of China (Grant No. 6140031454) and the Innovation Program of Chinese Academy of Sciences and State Key Laboratory of Luminescence and Applications.

Water Vapor Effects on Silica-Forming Ceramics

NASA Technical Reports Server (NTRS)

Opila, E. J.; Greenbauer-Seng, L. (Technical Monitor)

2000-01-01

Silica-forming ceramics such as SiC and Si3N4 are proposed for applications in combustion environments. These environments contain water vapor as a product of combustion. Oxidation of silica-formers is more rapid in water vapor than in oxygen. Parabolic oxidation rates increase with the water vapor partial pressure with a power law exponent value close to one. Molecular water vapor is therefore the mobile species in silica. Rapid oxidation rates and large amounts of gases generated during the oxidation reaction in high water vapor pressures may result in bubble formation in the silica and nonprotective scale formation. It is also shown that silica reacts with water vapor to form Si(OH)4(g). Silica volatility has been modeled using a laminar flow boundary layer controlled reaction equation. Silica volatility depends on the partial pressure of water vapor, the total pressure, and the gas velocity. Simultaneous oxidation and volatilization reactions have been modeled with paralinear kinetics.

Mechanistic insights into the oxidation behavior of Ni alloys in high-temperature CO 2

DOE PAGES

Oleksak, Richard P.; Baltrus, John P.; Nakano, Jinichiro; ...

2017-06-01

We present results of a Ni superalloy oxidized for short times in high purity CO 2 and similarly in Ar containing ≤ 1 ppb O 2. A detailed analysis of the oxidized surfaces reveals striking similarities for the two exposure environments, suggesting O 2 impurities control the oxidation process in high-temperature CO 2. Selective oxidation results in Cr-rich oxide layers grown by 2 outward diffusion, while Cr vacancies left in the metal contribute to significant void formation at the oxide/metal interface. Unlike for most of the alloy surface, the oxidation behavior of secondary phase metal carbides is considerably different inmore » the two environments.« less

Microstructure formation on liquid metal surface under pulsed action

NASA Astrophysics Data System (ADS)

Genin, D. E.; Beloplotov, D. V.; Panchenko, A. N.; Tarasenko, V. F.

2018-04-01

Experimental study and theoretical analysis of growth of microstructures (microtowers) on liquid metals by fs laser pulses have been carried out. Theoretical analysis has been performed on the basis of the two-temperature model. Compared to ns laser pulses, in fs irradiation regimes the heat-affected zone is strongly localized resulting in much larger temperatures and temperature gradients. In the experimental irradiation regimes, the surface temperature of liquid metals studied may reach or even exceed a critical level that culminates in phase explosion or direct atomization of a metal surface layer. However, before explosive ablation starts, a stress wave with an amplitude up to several GPa is formed which demolishes oxide covering. Moreover, at high laser fluences laser-induced breakdown is developed in oxide layer covering the metal surface that leads to destruction/ablation of oxide without damaging metal underneath. An overall scenario of microstructure growth with fs laser pulses is similar to that obtained for ns irradiation regimes though the growth threshold is lower due to smaller heat-conduction losses. Also we managed to obtain microstructures formation by the action of spark discharge.

Plasma sprayed ceramic thermal barrier coating for NiAl-based intermetallic alloys

NASA Technical Reports Server (NTRS)

Miller, Robert A. (Inventor); Doychak, Joseph (Inventor)

1994-01-01

A thermal barrier coating system consists of two layers of a zirconia-yttria ceramic. The first layer is applied by low pressure plasma spraying. The second layer is applied by conventional atmospheric pressure plasma spraying. This facilitates the attachment of a durable thermally insulating ceramic coating directly to the surface of a highly oxidation resistant NiAl-based intermetallic alloy after the alloy has been preoxidized to promote the formation of a desirable Al2O3 scale.

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

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

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Interfaces in Oxides Formed on NiAlCr Doped with Y, Hf, Ti, and B

DOE PAGES

Boll, Torben; Unocic, Kinga A.; Pint, Bruce A.; ...

2017-03-20

Abstract This study applies atom probe tomography (APT) to analyze the oxide scales formed on model NiAlCr alloys doped with Hf, Y, Ti, and B. Due to its ability to measure small amounts of alloying elements in the oxide matrix and its ability to quantify segregation, t he technique offers a possibility for detailed studies of the dopant’s fate during high-temperature oxidation. Three model NiAlCr alloys with different additions of Hf, Y, Ti, and B were prepared and oxidized in O 2at 1,100°C for 100 h. All specimens showed an outer region consisting of different spinel oxides with relativelymore » small grains and the protective Al 2O 3-oxide layer below. APT analyses focused mainly on this protective oxide layer. In all the investigated samples segregation of both Hf and Y to the oxide grain boundaries was observed and quantified. Neither B nor Ti were observed in the alumina grains or at the analyzed interfaces. The processes of formation of oxide scales and segregation of the alloying elements are discussed. The experimental challenges of the oxide analyses by APT are also addressed.« less

Formation of multicomponent matrix metal oxide films in anodic alumina matrixes by chemical deposition

NASA Astrophysics Data System (ADS)

Gorokh, G. G.; Zakhlebayeva, A. I.; Metla, A. I.; Zhilinskiy, V. V.; Murashkevich, A. N.; Bogomazova, N. V.

2017-11-01

The metal oxide films of SnxZnyOz and SnxMoyOz systems deposited onto anodic alumina matrixes by chemical and ion layering from an aqueous solutions were characterized by scanning electron microscopy, Raman spectroscopy, electron probe X-ray microanalysis and IR spectroscopy. The obtained matrix films had reproducible composition and structure and possessed certain morphological characteristics and properties.

Formation of porous silicon oxide from substrate-bound silicon rich silicon oxide layers by continuous-wave laser irradiation

NASA Astrophysics Data System (ADS)

Wang, Nan; Fricke-Begemann, Th.; Peretzki, P.; Ihlemann, J.; Seibt, M.

2018-03-01

Silicon nanocrystals embedded in silicon oxide that show room temperature photoluminescence (PL) have great potential in silicon light emission applications. Nanocrystalline silicon particle formation by laser irradiation has the unique advantage of spatially controlled heating, which is compatible with modern silicon micro-fabrication technology. In this paper, we employ continuous wave laser irradiation to decompose substrate-bound silicon-rich silicon oxide films into crystalline silicon particles and silicon dioxide. The resulting microstructure is studied using transmission electron microscopy techniques with considerable emphasis on the formation and properties of laser damaged regions which typically quench room temperature PL from the nanoparticles. It is shown that such regions consist of an amorphous matrix with a composition similar to silicon dioxide which contains some nanometric silicon particles in addition to pores. A mechanism referred to as "selective silicon ablation" is proposed which consistently explains the experimental observations. Implications for the damage-free laser decomposition of silicon-rich silicon oxides and also for controlled production of porous silicon dioxide films are discussed.

High temperature corrosion of a nickel base alloy by helium impurities

NASA Astrophysics Data System (ADS)

Rouillard, F.; Cabet, C.; Wolski, K.; Terlain, A.; Tabarant, M.; Pijolat, M.; Valdivieso, F.

2007-05-01

High temperature corrosion properties of Haynes 230 were investigated in a purposely-designed facility under a typical very high temperature reactor (VHTR) impure helium medium. The study was focused on the surface oxide scale formation and its stability at about 1223 K. The alloy developed a Mn/Cr rich oxide layer on its surface under impure helium at 1173 K. Nevertheless, a deleterious reaction destructing the chromium oxide was evidenced above a critical temperature, TA. Reagents and products of this last reaction were investigated.

Characterization of ion beam modified ceramic wear surfaces using Auger electron spectroscopy

NASA Technical Reports Server (NTRS)

Wei, W.; Lankford, J.

1987-01-01

An investigation of the surface chemistry and morphology of the wear surfaces of ceramic material surfaces modified by ion beam mixing has been conducted using Auger electron spectroscopy and secondary electron microscopy. Studies have been conducted on ceramic/ceramic friction and wear couples made up of TiC and NiMo-bonded TiC cermet pins run against Si3N4 and partially stabilized zirconia disc surfaces modified by the ion beam mixing of titanium and nickel, as well as ummodified ceramic/ceramic couples in order to determine the types of surface changes leading to the improved friction and wear behavior of the surface modified ceramics in simulated diesel environments. The results of the surface analyses indicate that the formation of a lubricating oxide layer of titanium and nickel, is responsible for the improvement in ceramic friction and wear behavior. The beneficial effect of this oxide layer depends on several factors, including the adherence of the surface modified layer or subsequently formed oxide layer to the disc substrate, the substrate materials, the conditions of ion beam mixing, and the environmental conditions.

Oxide layer stability in lead-bismuth at high temperature

NASA Astrophysics Data System (ADS)

Martín, F. J.; Soler, L.; Hernández, F.; Gómez-Briceño, D.

2004-11-01

Materials protection by 'in situ' oxidation has been studied in stagnant lead-bismuth, with different oxygen levels (H 2/H 2O ratios of 0.3 and 0.03), at temperatures from 535 °C to 600 °C and times from 100 to 3000 h. The materials tested were the martensitic steels F82Hmod, EM10 and T91 and the austenitic stainless steels, AISI 316L and AISI 304L. The results obtained point to the existence of an apparent threshold temperature above which corrosion occurs and the formation of a protective and stable oxide layer is not possible. This threshold temperature depends on material composition, oxygen concentration in the liquid lead-bismuth and time. The threshold temperature is higher for the austenitic steels, especially for the AISI 304L, and it increases with the oxygen concentration in the lead-bismuth. The oxide layer formed disappear with time and, after 3000 h all the materials, except AISI 304L, suffer corrosion, more severe for the martensitic steels and at the highest temperature tested.

Methane oxidation in Saanich Inlet during summer stratification

NASA Technical Reports Server (NTRS)

Ward, B. B.; Kilpatrick, K. A.; Wopat, A. E.; Minnich, E. C.; Lidstrom, M. E.

1989-01-01

Saanich Inlet, British Columbia, an fjord on the southeast coast of Vancouver Island, typically stratifies in summer, leading to the formation of an oxic-anoxic interface in the water column and accumulation of methane in the deep water. The results of methane concentration measurements in the water column of the inlet at various times throughout the summer months in 1983 are presented. Methane gradients and calculated diffusive fluxes across the oxic-anoxic interface increased as the summer progressed. Methane distribution and consumption in Saanich Inlet were studied in more detail during August 1986. At this time, a typical summer stratification with an oxic-anoxic interface around 140 m was present. At the interface, steep gradients in nutrient concentrations, bacterial abundance and methane concentration were observed. Methane oxidation was detected in the aerobic surface waters and in the anaerobic deep layer, but highest rates occurred in a narrow layer at the oxic-anoxic interface. Estimated methane oxidation rates were suffcient to consume 100 percent of the methane provided by diffusive flux from the anoxic layer. Methane oxidation is thus a mechanism whereby atmospheric flux from anoxic waters is minimized.

Micro-arc oxidation treatment to improve the hard-tissue compatibility of Ti-29Nb-13Ta-4.6Zr alloy

NASA Astrophysics Data System (ADS)

Tsutsumi, Yusuke; Niinomi, Mitsuo; Nakai, Masaaki; Tsutsumi, Harumi; Doi, Hisashi; Nomura, Naoyuki; Hanawa, Takao

2012-12-01

Micro-arc oxidation (MAO) was performed on a β-type Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) in this study to improve its bioactivity in a body fluid and its hard-tissue compatibility. The surface oxide layer formed on TNTZ by MAO treatment in a mixture of calcium glycerophosphate and magnesium acetate was characterized using various surface analyses. The oxide layer was mainly composed of two types of TiO2 (rutile and anatase), and it also contained Ca, P, and Mg, which were incorporated from the electrolyte during the treatment. The calcium phosphate formation on the surface of the specimens after immersion in Hanks' solution was evaluated to determine the bioactivity of TNTZ with and without MAO treatment. As a result, thick calcium phosphate layers formed on the TNTZ specimen that underwent MAO treatment, whereas only a small amount of precipitate was observed on TNTZ without treatment. Thus, the MAO treatment is a promising method to improve the bioactivity and hard-tissue compatibility of TNTZ.

Chemical models for martian weathering profiles: Insights into formation of layered phyllosilicate and sulfate deposits

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.; Mironenko, Mikhail V.

2016-09-01

Numerical chemical models for water-basalt interaction have been used to constrain the formation of stratified mineralogical sequences of Noachian clay-bearing rocks exposed in the Mawrth Vallis region and in other places on cratered martian highlands. The numerical approaches are based on calculations of water-rock type chemical equilibria and models which include rates of mineral dissolution. Results show that the observed clay-bearing sequences could have formed through downward percolation and neutralization of acidic H2SO4-HCl solutions. A formation of weathering profiles by slightly acidic fluids equilibrated with current atmospheric CO2 requires large volumes of water and is inconsistent with observations. Weathering by solutions equilibrated with putative dense CO2 atmospheres leads to consumption of CO2 to abundant carbonates which are not observed in clay stratigraphies. Weathering by H2SO4-HCl solutions leads to formation of amorphous silica, Al-rich clays, ferric oxides/oxyhydroxides, and minor titanium oxide and alunite at the top of weathering profiles. Mg-Fe phyllosilicates, Ca sulfates, zeolites, and minor carbonates precipitate from neutral and alkaline solutions at depth. Acidic weathering causes leaching of Na, Mg, and Ca from upper layers and accumulation of Mg-Na-Ca sulfate-chloride solutions at depth. Neutral MgSO4 type solutions dominate in middle parts of weathering profiles and could occur in deeper layers owing to incomplete alteration of Ca minerals and a limited trapping of Ca to sulfates. Although salts are not abundant in the Noachian geological formations, the results suggest the formation of Noachian salty solutions and their accumulation at depth. A partial freezing and migration of alteration solutions could have separated sulfate-rich compositions from low-temperature chloride brines and contributed to the observed diversity of salt deposits. A Hesperian remobilization and release of subsurface MgSO4 type solutions into newly-formed depressions could account for formation of some massive layered sulfate deposits through freezing or evaporation. This scenario explains the observed deficiency of salts in Noachian formations, a paucity of Hesperian phyllosilicates, and the occurrence of sulfate deposits in Valles Marineris troughs, chaotic terrains, and some craters of the Hesperian age.

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

PubMed Central

2012-01-01

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

Microhardness and wear resistance of PEO-coated 5754 aluminum alloy

NASA Astrophysics Data System (ADS)

Vyaliy, I. E.; Egorkin, V. S.; Sinebryukhov, S. L.; Minaev, A. N.; Gnedenkov, S. V.

2017-09-01

We present results of the study aimed at assessing the effect of duty cycle (D) during plasma electrolytic oxidation (PEO) on protective properties of the coatings produced on 5754 aluminum alloy. It is shown that increasing the duty cycle of a microsecond current pulses leads to increased hardness and reduced abrasive wear of the PEO-layers, improving mechanical properties. The obtained data allowed confirming, that increasing the amount of energy consumed for coating growth leads to the formation of thicker PEO-layers with improved tribological properties. The effect of duty cycle during plasma electrolytic oxidation on protective properties of the produced coatings was assessed.

Pulsed laser deposited MnCo{sub 2}O{sub 4} protective layer on SS430 for solid oxide fuel cell application

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

Gaur, Anshu, E-mail: gauranshu20@gmail.com, E-mail: ahamed.vza@gmail.com; Mohiddon, Md. Ahamad, E-mail: gauranshu20@gmail.com, E-mail: ahamed.vza@gmail.com; Prasad, Muvva D.

2016-05-23

The growth and oxidation study of pulsed laser deposited MnCo{sub 2}O{sub 4} protective layer on SS430 substrate for solid oxide fuel cell application is demonstrated. MnCo{sub 2}O{sub 4} has been achieved in three different ways including, deposition at higher substrate temperature (700°C), and deposition at room temperature on pre-oxidized and untreated SS430 substrate followed by annealing at 700°C for 2 hrs. X-ray diffraction and Raman spectroscopy has been applied to demonstrate the kind of phases developed in each case. These three samples were subjected to heat treatment at 750°C for 5 hr. The extent of undesired Fe{sub 2}O{sub 3} phasemore » formation in the post deposition heat treated samples is discussed based on Raman spectroscopic results.« less

Thermal stability and specular reflection behaviour of CoNbZr-based bottom spin valves with nano-oxide layer

NASA Astrophysics Data System (ADS)

Kim, Jong Soo; Lee, Seong-Rae

2004-06-01

The thermal stability and specularity aspects of a CoNbZr-based bottom spin valve (SV) employing a nano-oxide layer (NOL) were investigated. The magnetoresistance (MR) ratio of the as-deposited CoNbZr-based bottom SV increased by 62% (from 6.3 to 10.2%) with incorporation of the NOL. The enhancement of the MR ratio was considered to be due to the specular effect ( increased from 0.722 to 1.363 cm) of the NOL. The MR ratio of a Ta-based bottom SV decreased by about 45% (from 6.9 to 3.8%) when the samples were annealed at 300 °C for 240 min. By contrast, the MR ratio of the CoNbZr-based bottom SV with NOL increase d by 14 % (from 10.2 to 11.7%). The root mean square roughness value of the CoNbZr layer (0.07 nm) was superior to that of the Ta layer (0.43 nm). Although Mn in IrMn diffused out to the surface through the active layers resulting in the formation of Mn oxide at the surface in the CoNbZr-based bottom SV, no trace of Mn was found in the active layers and no significant degradation occurred.

Surface Selective Oxide Reduction During the Intercritical Annealing of Medium Mn Steel

NASA Astrophysics Data System (ADS)

Jo, Kyoung Rae; Cho, Lawrence; Oh, Jong Han; Kim, Myoung Soo; Kang, Ki Cheol; De Cooman, Bruno C.

2017-08-01

Third generation advanced high-strength steels achieve an excellent strength-ductility balance using a cost-effective alloy composition. During the continuous annealing of medium Mn steel, the formation of an external selective oxide layer of MnO has a negative impact on the coating quality after galvanizing. A procedure to reduce the selective oxide was therefore developed. It involves annealing in the temperature range of 1073 K to 1323 K (800 °C to 1050 °C) in a HNx gas atmosphere. Annealing at higher temperatures and the use of larger H2 volume fractions are shown to make the gas atmosphere reducing with respect to MnO. The reduction of the surface MnO layer was observed by SEM, GDOES, and cross-sectional TEM analysis.

Moisture barrier properties of single-layer graphene deposited on Cu films for Cu metallization

NASA Astrophysics Data System (ADS)

Gomasang, Ploybussara; Abe, Takumi; Kawahara, Kenji; Wasai, Yoko; Nabatova-Gabain, Nataliya; Thanh Cuong, Nguyen; Ago, Hiroki; Okada, Susumu; Ueno, Kazuyoshi

2018-04-01

The moisture barrier properties of large-grain single-layer graphene (SLG) deposited on a Cu(111)/sapphire substrate are demonstrated by comparing with the bare Cu(111) surface under an accelerated degradation test (ADT) at 85 °C and 85% relative humidity (RH) for various durations. The change in surface color and the formation of Cu oxide are investigated by optical microscopy (OM) and X-ray photoelectron spectroscopy (XPS), respectively. First-principle simulation is performed to understand the mechanisms underlying the barrier properties of SLG against O diffusion. The correlation between Cu oxide thickness and SLG quality are also analyzed by spectroscopic ellipsometry (SE) measured on a non-uniform SLG film. SLG with large grains shows high performance in preventing the Cu oxidation due to moisture during ADT.

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.

Room-Temperature Oxidation of Formaldehyde by Layered Manganese Oxide: Effect of Water.

PubMed

Wang, Jinlong; Zhang, Pengyi; Li, Jinge; Jiang, Chuanjia; Yunus, Rizwangul; Kim, Jeonghyun

2015-10-20

Layered manganese oxide, i.e., birnessite was prepared via the reaction of potassium permanganate with ammonium oxalate. The water content in the birnessite was adjusted by drying/calcining the samples at various temperatures (30 °C, 100 °C, 200 °C, 300 °C, and 500 °C). Thermogravimetry-mass spectroscopy showed three types of water released from birnessite, which can be ascribed to physically adsorbed H2O, interlayer H2O and hydroxyl, respectively. The activity of birnessite for formaldehyde oxidation was positively associated with its water content, i.e., the higher the water content, the better activity it has. In-situ DRIFTS and step scanning XRD analysis indicate that adsorbed formaldehyde, which is promoted by bonded water via hydrogen bonding, is transformed into formate and carbonate with the consumption of hydroxyl and bonded water. Both bonded water and water in air can compensate the consumed hydroxyl groups to sustain the mineralization of formaldehyde at room temperature. In addition, water in air stimulates the desorption of carbonate via water competitive adsorption, and accordingly the birnessite recovers its activity. This investigation elucidated the role of water in oxidizing formaldehyde by layered manganese oxides at room temperature, which may be helpful for the development of more efficient materials.

Characterization and corrosion behavior of F6NM stainless steel treated in high temperature water

NASA Astrophysics Data System (ADS)

Li, Zheng-yang; Cai, Zhen-bing; Yang, Wen-jin; Shen, Xiao-yao; Xue, Guo-hong; Zhu, Min-hao

2018-03-01

F6NM martensitic stainless steel was exposed to 350 °C water condition for 500, 1500, and 2500 h to simulate pressurized water reactor (PWR) condition. The characterization and corrosion behavior of the oxide film were investigated. Results indicate that the exposed steel surface formed a double-layer oxide film. The outer oxide film is Fe-rich and contains two type oxide particles. However, the inner oxide film is Cr-rich, and two oxide films, whose thicknesses increase with increasing exposure time. The oxide film reduces the corrosion behavior because the outer oxide film has many crack and pores. Finally, the mechanism and factors affecting the formation of the oxide film were investigated.

High-performance heterostructured cathodes for lithium-ion batteries with a Ni-rich layered oxide core and a Li-rich layered oxide shell

DOE PAGES

Oh, Pilgun; Oh, Seung -Min; Li, Wangda; ...

2016-05-30

The Ni-rich layered oxides with a Ni content of >0.5 are drawing much attention recently to increase the energy density of lithium-ion batteries. However, the Ni-rich layered oxides suffer from aggressive reaction of the cathode surface with the organic electrolyte at the higher operating voltages, resulting in consequent impedance rise and capacity fade. To overcome this difficulty, we present here a heterostructure composed of a Ni-rich LiNi 0.7Co 0.15Mn 0.15O 2 core and a Li-rich Li 1.2-xNi 0.2Mn 0.6O 2 shell, incorporating the advantageous features of the structural stability of the core and chemical stability of the shell. With amore » unique chemical treatment for the activation of the Li 2MnO 3 phase of the shell, a high capacity is realized with the Li-rich shell material. Aberration-corrected scanning transmission electron microscopy (STEM) provides direct evidence for the formation of surface Li-rich shell layer. Finally, the heterostructure exhibits a high capacity retention of 98% and a discharge- voltage retention of 97% during 100 cycles with a discharge capacity of 190 mA h g -1 (at 2.0–4.5 V under C/3 rate, 1C = 200 mA g -1).« less

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: a field evaluation.

PubMed

Nason, Peter; Johnson, Raymond H; Neuschütz, Clara; Alakangas, Lena; Öhlander, Björn

2014-02-28

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation. Copyright © 2014 Elsevier B.V. All rights reserved.

A Cuprous Oxide Thin Film Non-Enzymatic Glucose Sensor Using Differential Pulse Voltammetry and Other Voltammetry Methods and a Comparison to Different Thin Film Electrodes on the Detection of Glucose in an Alkaline Solution

PubMed Central

Molazemhosseini, Alireza; Liu, Chung Chiun

2018-01-01

A cuprous oxide (Cu2O) thin layer served as the base for a non-enzymatic glucose sensor in an alkaline medium, 0.1 NaOH solution, with a linear range of 50–200 mg/dL using differential pulse voltammetry (DPV) measurement. An X-ray photoelectron spectroscopy (XPS) study confirmed the formation of the cuprous oxide layer on the thin gold film sensor prototype. Quantitative detection of glucose in both phosphate-buffered saline (PBS) and undiluted human serum was carried out. Neither ascorbic acid nor uric acid, even at a relatively high concentration level (100 mg/dL in serum), interfered with the glucose detection, demonstrating the excellent selectivity of this non-enzymatic cuprous oxide thin layer-based glucose sensor. Chronoamperometry and single potential amperometric voltammetry were used to verify the measurements obtained by DPV, and the positive results validated that the detection of glucose in a 0.1 M NaOH alkaline medium by DPV measurement was effective. Nickel, platinum, and copper are commonly used metals for non-enzymatic glucose detection. The performance of these metal-based sensors for glucose detection using DPV were also evaluated. The cuprous oxide (Cu2O) thin layer-based sensor showed the best sensitivity for glucose detection among the sensors evaluated. PMID:29316652

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: A field evaluation

USGS Publications Warehouse

Nason, Peter; Johnson, Raymond H.; Neuschutz, Clara; Alakangas, Lena; Ohlander, Bjorn

2014-01-01

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2 m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6 m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3 m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

Initial stages of oxide formation on the Zr surface at low oxygen pressure: An in situ FIM and XPS study

PubMed Central

Bespalov, I.; Datler, M.; Buhr, S.; Drachsel, W.; Rupprechter, G.; Suchorski, Y.

2015-01-01

An improved methodology of the Zr specimen preparation was developed which allows fabrication of stable Zr nanotips suitable for FIM and AP applications. Initial oxidation of the Zr surface was studied on a Zr nanotip by FIM and on a polycrystalline Zr foil by XPS, both at low oxygen pressure (10−8–10−7 mbar). The XPS data reveal that in a first, fast stage of oxidation, a Zr suboxide interlayer is formed which contains three suboxide components (Zr+1, Zr+2 and Zr+3) and is located between the Zr surface and a stoichiometric ZrO2 overlayer that grows in a second, slow oxidation stage. The sole suboxide layer has been observed for the first time at very early states of the oxidation (oxygen exposure ≤4 L). The Ne+ FIM observations are in accord with a two stage process of Zr oxide formation. PMID:25766998

Solid oxide fuel cells with bi-layered electrolyte structure

NASA Astrophysics Data System (ADS)

Zhang, Xinge; Robertson, Mark; Decès-Petit, Cyrille; Xie, Yongsong; Hui, Rob; Qu, Wei; Kesler, Olivera; Maric, Radenka; Ghosh, Dave

In this work, we have developed solid oxide fuel cells with a bi-layered electrolyte of 2 μm SSZ and 4 μm SDC using tape casting, screen printing, and co-firing processes. The cell reached power densities of 0.54 W cm -2 at 650 °C and 0.85 W cm -2 at 700 °C, with open circuit voltage (OCV) values larger than 1.02 V. The electrical leaking between anode and cathode through an SDC electrolyte has been blocked in the bi-layered electrolyte structure. However, both the electrolyte resistance (R el) and electrode polarization resistance (R p,a+c) increased in comparison to cells with single-layered SDC electrolytes. The formation of a solid solution of (Ce, Zr)O 2- x during sintering process and the flaws in the bi-layered electrolyte structure seem to be the main causes for the increase in the R el value (0.32 Ω cm 2) at 650 °C, which is almost one order of magnitude higher than the calculated value.

Optical and electrical characterization methods of plasma-induced damage in silicon nitride films

NASA Astrophysics Data System (ADS)

Kuyama, Tomohiro; Eriguchi, Koji

2018-06-01

We proposed evaluation methods of plasma-induced damage (PID) in silicon nitride (SiN) films. The formation of an oxide layer by air exposure was identified for damaged SiN films by X-ray photoelectron spectroscopy (XPS). Bruggeman’s effective medium approximation was employed for an optical model consisting of damaged and undamaged layers, which is applicable to an in-line monitoring by spectroscopic ellipsometry (SE). The optical thickness of the damaged layer — an oxidized layer — extended after plasma exposure, which was consistent with the results obtained by a diluted hydrofluoric acid (DHF) wet etching. The change in the conduction band edge of the damaged SiN films was presumed from two electrical techniques, i.e., current–voltage (I–V) measurement and time-dependent dielectric breakdown (TDDB) test with a constant voltage stress. The proposed techniques can be used for assigning the plasma-induced structural change in an SiN film widely used as an etch-protecting layer.

In situ study of electric field controlled ion transport in the Fe/BaTiO3 interface

NASA Astrophysics Data System (ADS)

Merkel, D. G.; Bessas, D.; Bazsó, G.; Jafari, A.; Rüffer, R.; Chumakov, A. I.; Khanh, N. Q.; Sajti, Sz; Celse, J.-P.; Nagy, D. L.

2018-01-01

Electric field controlled ion transport and interface formation of iron thin films on a BaTiO3 substrate have been investigated by in situ nuclear resonance scattering and x-ray reflectometry techniques. At early stage of deposition, an iron-II oxide interface layer was observed. The hyperfine parameters of the interface layer were found insensitive to the evaporated layer thickness. When an electric field was applied during growth, a 10 Å increase of the nonmagnetic/magnetic thickness threshold and an extended magnetic transition region was measured compared to the case where no field was applied. The interface layer was found stable under this threshold when further evaporation occurred, contrary to the magnetic layer where the magnitude and orientation of the hyperfine magnetic field vary continuously. The obtained results of the growth mechanism and of the electric field effect of the Fe/BTO system will allow the design of novel applications by creating custom oxide/metallic nanopatterns using laterally inhomogeneous electric fields during sample preparation.

Uranium passivation by C + implantation: A photoemission and secondary ion mass spectrometry study

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Felter, T. E.; Wu, K. J.; Evans, C.; Ferreira, J. L.; Siekhaus, W. J.; McLean, W.

2006-03-01

Implantation of 33 keV C + ions into polycrystalline U 238 with a dose of 4.3 × 10 17 cm -2 produces a physically and chemically modified surface layer that prevents further air oxidation and corrosion. X-ray photoelectron spectroscopy and secondary ion mass spectrometry were used to investigate the surface chemistry and electronic structure of this C + ion implanted polycrystalline uranium and a non-implanted region of the sample, both regions exposed to air for more than a year. In addition, scanning electron microscopy was used to examine and compare the surface morphology of the two regions. The U 4f, O 1s and C 1s core-level and valence band spectra clearly indicate carbide formation in the modified surface layer. The time-of-flight secondary ion mass spectrometry depth profiling results reveal an oxy-carbide surface layer over an approximately 200 nm thick UC layer with little or no residual oxidation at the carbide layer/U metal transitional interface.

The formation and potential importance of cemented layers in inactive sulfide mine tailings

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

Blowes, D.W.; Reardon, E.J.; Cherry, J.A.

Investigations of inactive sulfide-rich tailings impoundments at the Heath Steele (New Brunswick) and Waite Amulet (Quebec) minesites have revealed two distinct types of cemented layers or hardpans. That at Heath Steele is 10-15 cm thick, occurs 20-30 cm below the depth of active oxidation, is continuous throughout the tailings impoundment, and is characterized by cementation of tailings by gypsum and Fe(II) solid phases, principally melanterite. Hardpan at the Waite Amulet site is only 1-5 cm thick, is laterally discontinuous (10-100 cm), occurs at the depth of active oxidation, and is characterized by cementation of tailings by Fe(III) minerals, principally goethite,more » lepidocrocite, ferrihydrite, and jarosite. At Heath Steele, an accumulation of gas-phase CO{sub 2}, of up to 60{percent} of the pore gas, occurs below the hardpan. The calculated diffusivity of the hardpan layer is only about 1/100 that of the overlying, uncemented tailings. The pore-water chemistry at Heath Steele has changed little over a 10-year period, suggesting that the cemented layer restricts the movement of dissolved metals through the tailings and also acts as a zone of metal accumulation. Generation of a cemented layer therefore has significant environmental and economic implications. It is likely that, in sulfide-rich tailings impoundments, the addition of carbonate-rich buffering material during the late stages of tailings deposition would enhance the formation of hardpan layers.« less

Growth behavior and properties of atomic layer deposited tin oxide on silicon from novel tin(II)acetylacetonate precursor and ozone

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

Kannan Selvaraj, Sathees; Feinerman, Alan; Takoudis, Christos G., E-mail: takoudis@uic.edu

In this work, a novel liquid tin(II) precursor, tin(II)acetylacetonate [Sn(acac){sub 2}], was used to deposit tin oxide films on Si(100) substrate, using a custom-built hot wall atomic layer deposition (ALD) reactor. Three different oxidizers, water, oxygen, and ozone, were tried. Resulting growth rates were studied as a function of precursor dosage, oxidizer dosage, reactor temperature, and number of ALD cycles. The film growth rate was found to be 0.1 ± 0.01 nm/cycle within the wide ALD temperature window of 175–300 °C using ozone; no film growth was observed with water or oxygen. Characterization methods were used to study the composition, interface quality, crystallinity, microstructure,more » refractive index, surface morphology, and resistivity of the resulting films. X-ray photoelectron spectra showed the formation of a clean SnO{sub x}–Si interface. The resistivity of the SnO{sub x} films was calculated to be 0.3 Ω cm. Results of this work demonstrate the possibility of introducing Sn(acac){sub 2} as tin precursor to deposit conducting ALD SnO{sub x} thin films on a silicon surface, with clean interface and no formation of undesired SiO{sub 2} or other interfacial reaction products, for transparent conducting oxide applications.« less

Effects of substrate microstructure on the formation of oriented oxide nanotube arrays on Ti and Ti alloys

NASA Astrophysics Data System (ADS)

Ferreira, C. P.; Gonçalves, M. C.; Caram, R.; Bertazzoli, R.; Rodrigues, C. A.

2013-11-01

The formation of nanotubular oxide layers on Ti and Ti alloys has been widely investigated for the photocatalytic degradation of organic compounds due to their excellent catalytic efficiency, chemical stability, and low cost and toxicity. Aiming to improve the photocatalytic efficiency of this nanostructured oxide, this work investigated the influence of substrate grain size on the growth of nanotubular oxide layers. Ti and Ti alloys (Ti-6Al, Ti-6Al-7Nb) were produced by arc melting with non-consumable tungsten electrode and water-cooled copper hearth under argon atmosphere. Some of the ingots were heat-treated at 1000 °C for 12 and 24 h in argon atmosphere, followed by slow cooling rates to reduce crystalline defects and increase the grain size of their microstructures. Three types of samples were anodized: commercial substrate, as-prepared and heat-treated samples. The anodization was performed using fluoride solution and a cell potential of 20 V. The samples were characterized by optical microscopy, field-emission scanning electron microscopy and X-ray diffraction. The heat treatment preceding the anodization process increased the grain size of pure Ti and Ti alloys and promoted the formation of Widmanstätten structures in Ti6Al7Nb. The nanotubes layers grown on smaller grain and thermally untreated samples were more regular and homogeneous. In the case of Ti-6Al-7Nb alloy, which presents a α + β phase microstructure, the morphology of nanotubes nucleated on α matrix was more regular than those of nanotubes nucleated on β phase. After the annealing process, the Ti-6Al-7Nb alloy presented full diffusion process and the growth of equilibrium phases resulting in the appearance of regions containing higher concentrations of Nb, i.e. beta phase. In those regions the dissolution rate of Nb2O5 is lower than that of TiO2, resulting in a nanoporous layer. In general, heat treating reduces crystalline defects and promotes the increasing of the grain sizes, not favoring the process of nanotube nucleation and growth on the metallic surface.

Chemical-mechanical planarization of aluminum and copper interconnects with magnetic liners

NASA Astrophysics Data System (ADS)

Wang, Bin

2000-10-01

Chemical Mechanical Planarization (CMP) has been employed to achieve Damascene patterning of aluminum and copper interconnects with unique magnetic liners. A one-step process was developed for each interconnect scheme, using a double-layered pad with mesh cells, pores, and perforations on a top hard layer. In a hydrogen peroxide-based slurry, aluminum CMP was a process of periodic removal and formation of a surface oxide layer. Cu CMP in the same slurry, however, was found to be a dissolution dominant process. In a potassium iodate-based slurry, copper removal was the result of two competing reactions: copper dissolution and a non-native surface layer formation. Guided by electrochemistry, slurries were developed to remove nickel in different regimes of the corrosion kinetics diagram. Nickel CMP in a ferric sulfate-based slurry resulted in periodic removal and formation of a passive surface layer. In a potassium permanganate-based slurry, nickel removal is a dissolution dominant process. Visible Al(Cu) surface damages obtained with copper-doped aluminum could be eliminated by understanding the interactions between the substrate, the pad, and the abrasive agglomerate. Increasing substrate hardness by annealing prior to CMP led to a surface finish free of visible scratches. A similar result was also obtained by preventing formation of abrasive agglomerates and minimizing their contact with the substrate.

Sputter-Deposited Oxides for Interface Passivation of CdTe Photovoltaics

DOE PAGES

Kephart, Jason M.; Kindvall, Anna; Williams, Desiree; ...

2018-01-18

Commercial CdTe PV modules have polycrystalline thin films deposited on glass, and devices made in this format have exceeded 22% efficiency. Devices made by the authors with a magnesium zinc oxide window layer and tellurium back contact have achieved efficiency over 18%, but these cells still suffer from an open-circuit voltage far below ideal values. Oxide passivation layers made by sputter deposition have the potential to increase voltage by reducing interface recombination. CdTe devices with these passivation layers were studied with photoluminescence (PL) emission spectroscopy and time-resolved photoluminescence (TRPL) to detect an increase in minority carrier lifetime. Because these oxidemore » materials exhibit barriers to carrier collection, micropatterning was used to expose small point contacts while still allowing interface passivation. TRPL decay lifetimes have been greatly enhanced for thin polycrystalline absorber films with interface passivation. Device performance was measured and current collection was mapped spatially by light-beam-induced current.« less

Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

NASA Technical Reports Server (NTRS)

Heinemann, K.; Rao, D. B.; Douglass, D. L.

1975-01-01

Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Synthesis of Lithium Metal Oxide Nanoparticles by Induction Thermal Plasmas.

PubMed

Tanaka, Manabu; Kageyama, Takuya; Sone, Hirotaka; Yoshida, Shuhei; Okamoto, Daisuke; Watanabe, Takayuki

2016-04-06

Lithium metal oxide nanoparticles were synthesized by induction thermal plasma. Four different systems-Li-Mn, Li-Cr, Li-Co, and Li-Ni-were compared to understand formation mechanism of Li-Me oxide nanoparticles in thermal plasma process. Analyses of X-ray diffractometry and electron microscopy showed that Li-Me oxide nanoparticles were successfully synthesized in Li-Mn, Li-Cr, and Li-Co systems. Spinel structured LiMn₂O₄ with truncated octahedral shape was formed. Layer structured LiCrO₂ or LiCoO₂ nanoparticles with polyhedral shapes were also synthesized in Li-Cr or Li-Co systems. By contrast, Li-Ni oxide nanoparticles were not synthesized in the Li-Ni system. Nucleation temperatures of each metal in the considered system were evaluated. The relationship between the nucleation temperature and melting and boiling points suggests that the melting points of metal oxides have a strong influence on the formation of lithium metal oxide nanoparticles. A lower melting temperature leads to a longer reaction time, resulting in a higher fraction of the lithium metal oxide nanoparticles in the prepared nanoparticles.

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.

The magnetic properties of a magnetic detector using oxidized amorphous Co 95- xFe 5(BSi) x alloys

NASA Astrophysics Data System (ADS)

Ahn, S. J.; Kim, C. K.; Kim, S. J.; Choi, D. K.; O'Handley, R. C.

2000-07-01

A comparative oxidation study of several amorphous Co 75- xFe 5(BSi) 20+ x alloys was carried out. Reentrant magnetization behavior and field-induced anisotropy which are of a critical importance for a magnetic detector were obtained after oxidation of the amorphous Co-rich ribbons. During this oxidation, the ribbons develop surface oxides which are primarily nonmagnetic borosilicate or a combination of borosilicate and magnetic oxides such CoO or FeO. Beneath this lies a 100-1000 Å thick Co-rich magnetic alloy which may be either HCP or FCC in its crystal structure. The thickness of the Co-crystallized layer is determined by the type of the surface oxides. The oxidation products such as appear to affect the reentrant magnetization behavior of Co-rich amorphous alloys significantly. We have determined the amount of metalloids (a critical concentration of B and Si) which is necessary to form a continuous layer of the most thermodynamically stable oxide, in our case borosilicate, on the surface. We also observed that there is a good correlation between reentrant magnetization and the thickness of Co layer. The best reentrant M- H loop for the magnetic detector was obtained in ribbons with a surface borate-rich borosilicate since it ensures conditions such as (1) metalloid depletion in the substrate and (2) formation of oxygen impurity faults in Co grains that are required for strong reentrant magnetization behavior.

Facile One-pot Transformation of Iron Oxides from Fe2O3 Nanoparticles to Nanostructured Fe3O4@C Core-Shell Composites via Combustion Waves

PubMed Central

Shin, Jungho; Lee, Kang Yeol; Yeo, Taehan; Choi, Wonjoon

2016-01-01

The development of a low-cost, fast, and large-scale process for the synthesis and manipulation of nanostructured metal oxides is essential for incorporating materials with diverse practical applications. Herein, we present a facile one-pot synthesis method using combustion waves that simultaneously achieves fast reduction and direct formation of carbon coating layers on metal oxide nanostructures. Hybrid composites of Fe2O3 nanoparticles and nitrocellulose on the cm scale were fabricated by a wet impregnation process. We demonstrated that self-propagating combustion waves along interfacial boundaries between the surface of the metal oxide and the chemical fuels enabled the release of oxygen from Fe2O3. This accelerated reaction directly transformed Fe2O3 into Fe3O4 nanostructures. The distinctive color change from reddish-brown Fe2O3 to dark-gray Fe3O4 confirmed the transition of oxidation states and the change in the fundamental properties of the material. Furthermore, it simultaneously formed carbon layers of 5–20 nm thickness coating the surfaces of the resulting Fe3O4 nanoparticles, which may aid in maintaining the nanostructures and improving the conductivity of the composites. This newly developed use of combustion waves in hybridized nanostructures may permit the precise manipulation of the chemical compositions of other metal oxide nanostructures, as well as the formation of organic/inorganic hybrid nanostructures. PMID:26902260

Preparation of sulfonic-functionalized graphene oxide as ion-exchange material and its application into electrochemiluminescence analysis.

PubMed

Chen, Guifen; Zhai, Shengyong; Zhai, Yanling; Zhang, Ke; Yue, Qiaoli; Wang, Lei; Zhao, Jinsheng; Wang, Huaisheng; Liu, Jifeng; Jia, Jianbo

2011-03-15

Graphene oxide (GO) obtained from chemical oxidation of flake graphite was derivatized with sulfonic groups to form sulfonic-functionalized GO (GO-SO(3)(-)) through four sulfonation routes: through amide formation between the carboxylic group of GO and amine of sulfanilic acid (AA-GO-SO(3)(-)), aryl diazonium reaction of sulfanilic acid (AD-GO-SO(3)(-)), amide formation between the carboxylic group of GO and amine of cysteamine and oxidation by H(2)O(2) (CA-GO-SO(3)(-)), and alkyl diazonium reaction of cysteamine and oxidation by H(2)O(2) (CD-GO-SO(3)(-)). Results of Fourier transform infrared spectroscopy and X-ray photoelectrospectrocopy showed that -SO(3)(-) groups were attached onto GO. Thermo gravimetric analysis showed that derivatization with sulfonic groups improved thermo stability of GO. X-ray diffraction results indicated that GO-SO(3)(-) had more ordered π-π stacking structure than the original GO. GO-SO(3)(-) and cationic polyelectrote, poly (diallyldimethylammoniumchloride) (PDDA) were adsorbed at indium tin oxide (ITO) glass surface through layer-by-layer assembling to form (GO-SO(3)(-)/PDDA)(n)/ITO multilayers. After tris-(2,2'-bipyridyl) ruthenium (II) dichloride (Ru(bpy)(3)(2+)) was incorporated into the multilayers, the obtained Ru(bpy)(3)(2+)/(GO-SO(3)(-)/PDDA)(n)/ITO electrodes can be used as electrochemiluminescence sensors for detection of organic amine with high sensitivity (limit of detection of 1 nM) and stability. Copyright © 2010 Elsevier B.V. All rights reserved.

Probing Interfacial Processes on Graphene Surface by Mass Detection

NASA Astrophysics Data System (ADS)

Kakenov, Nurbek; Kocabas, Coskun

2013-03-01

In this work we studied the mass density of graphene, probed interfacial processes on graphene surface and examined the formation of graphene oxide by mass detection. The graphene layers were synthesized by chemical vapor deposition method on copper foils and transfer-printed on a quartz crystal microbalance (QCM). The mass density of single layer graphene was measured by investigating the mechanical resonance of the QCM. Moreover, we extended the developed technique to probe the binding dynamics of proteins on the surface of graphene, were able to obtain nonspecific binding constant of BSA protein of graphene surface in aqueous solution. The time trace of resonance signal showed that the BSA molecules rapidly saturated by filling the available binding sites on graphene surface. Furthermore, we monitored oxidation of graphene surface under oxygen plasma by tracing the changes of interfacial mass of the graphene controlled by the shifts in Raman spectra. Three regimes were observed the formation of graphene oxide which increases the interfacial mass, the release of carbon dioxide and the removal of small graphene/graphene oxide flakes. Scientific and Technological Research Council of Turkey (TUBITAK) grant no. 110T304, 109T209, Marie Curie International Reintegration Grant (IRG) grant no 256458, Turkish Academy of Science (TUBA-Gebip).

Microstructural Characterization of High Burn-up Mixed Oxide Fast Reactor Fuel

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

Melissa C. Teague; Brian P. Gorman; Steven L. Hayes

2013-10-01

High burn-up mixed oxide fuel with local burn-ups of 3.4–23.7% FIMA (fissions per initial metal atom) were destructively examined as part of a research project to understand the performance of oxide fuel at extreme burn-ups. Optical metallography of fuel cross-sections measured the fuel-to-cladding gap, clad thickness, and central void evolution in the samples. The fuel-to-cladding gap closed significantly in samples with burn-ups below 7–9% FIMA. Samples with burn-ups in excess of 7–9% FIMA had a reopening of the fuel-to-cladding gap and evidence of joint oxide-gain (JOG) formation. Signs of axial fuel migration to the top of the fuel column weremore » observed in the fuel pin with a peak burn-up of 23.7% FIMA. Additionally, high burn-up structure (HBS) was observed in the two highest burn-up samples (23.7% and 21.3% FIMA). The HBS layers were found to be 3–5 times thicker than the layers found in typical LWR fuel. The results of the study indicate that formation of JOG and or HBS prevents any significant fuel-cladding mechanical interaction from occurring, thereby extending the potential life of the fuel elements.« less

Core-shell-structured nanothermites synthesized by atomic layer deposition

NASA Astrophysics Data System (ADS)

Qin, Lijun; Gong, Ting; Hao, Haixia; Wang, Keyong; Feng, Hao

2013-12-01

Thermite materials feature very exothermic solid-state redox reactions. However, the energy release rates of traditional thermite mixtures are limited by the reactant diffusion velocities. In this work, atomic layer deposition (ALD) is utilized to synthesize thermite materials with greatly enhanced reaction rates. By depositing certain types of metal oxides (oxidizers) onto a commercial Al nanopowder, core-shell-structured nanothermites can be produced. The average film deposition rate on the Al nanopowder is 0.17 nm/cycle for ZnO and 0.031 nm/cycle for SnO2. The thickness of the oxidizer layer can be precisely controlled by adjusting the ALD cycle number. The compositions, morphologies, and structures of the ALD nanothermites are characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The characterization results reveal nearly perfect coverage of the Al nanoparticles by uniform ALD oxidizer layers and confirm the formation of core-shell nanoparticles. Combustion properties of the nanothermites are probed by laser ignition technique. Reactions of the core-shell-structured nanothermites are several times faster than the mixture of nanopowders. The promoted reaction rate is mostly attributed to the uniform distribution of reactants on the nanometer scale. These core-shell-structured nanothermites provide a potential pathway to control and enhance thermite reactions.

Bonding of sapphire to sapphire by eutectic mixture of aluminum oxide and zirconium oxide

NASA Technical Reports Server (NTRS)

Deluca, J. J. (Inventor)

1975-01-01

Bonding of an element comprising sapphire, ruby or blue sapphire to another element of such material with a eutectic mixture of aluminum oxide and zirconium oxide is discussed. The bonding mixture may be applied in the form of a distilled water slurry or by electron beam vapor deposition. In one embodiment the eutectic is formed in situ by applying a layer of zirconium oxide and then heating the assembly to a temperature above the eutectic temperature and below the melting point of the material from which the elements are formed. The formation of a sapphire rubidium maser cell utilizing eutectic bonding is shown.

Casein mediated green synthesis and decoration of reduced graphene oxide

NASA Astrophysics Data System (ADS)

Maddinedi, Sireesh Babu; Mandal, Badal Kumar; Vankayala, Raviraj; Kalluru, Poliraju; Tammina, Sai Kumar; Kiran Kumar, H. A.

This research is mainly focusing on one-step biosynthesis of graphene from graphene oxide and its stabilization using naturally occurring milk protein, casein. The synthesis of casein reduced graphene oxide (CRGO) was completed within 7 h under reflux at 90 °C with the formation of few layered fine graphene nanosheets. UV-Vis, XRD, XPS analysis data revealed the reduction process of the graphene oxide. Results of FT-IR, HPLC and TEM analysis have shown that the ensuing material consists of graphene decorated with casein molecules. Aspartic acid and glutamic acid residue present in casein molecules are responsible for the reduction of graphene oxide.

Structure and high temperature oxidation of mechanical alloyed Fe-Al coating

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

Aryanto, Didik, E-mail: Didik-phys@yahoo.co.id, E-mail: didi027@lipi.go.id; Sudiro, Toto; Wismogroho, Agus S.

2016-04-19

The structure and high temperature oxidation resistance of Fe-Al coating on low carbon steel were investigated. The Fe-Al coating was deposited on the surface of low carbon steel using a mechanical alloying method. The coating was then annealed at 600°C for 2 hour in a vacuum of 5 Pa. The cyclic-oxidation tests of low carbon steel, Fe-Al coatings with and without annealing were performed at 600°C for up to 60h in air. The structure of oxidized samples was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy X-ray spectroscopy (EDS). The results show that the Fe-Al coatingsmore » exhibit high oxidation resistance compared to the uncoated steel. After 60 h exposure, the uncoated steel formed mainly Fe{sub 3}O{sub 4} and Fe{sub 2}O{sub 3} layers with the total thickness of around 75.93 µm. Fe-Al coating without annealing formed a thin oxide layer, probably (Fe,Al){sub 2}O{sub 3}. Meanwhile, for annealed sample, EDX analysis observed the formation of two Fe-Al layers with difference in elements concentration. The obtained results suggest that the deposition of Fe-Al coating on low carbon steel can improve the oxidation resistance of low carbon steel.« less

(S)TEM analysis of functional transition metal oxides

NASA Astrophysics Data System (ADS)

Chi, Miaofang

Perovskite vanadates (AVO3) form an ideal family to study the structure-property relationships in transition metal oxides because their physical properties can easily be tailored by varying the A-site cations. (S)TEM is an ideal tool for this type of study due to its capacity for simultaneous imaging and chemical analysis. Determination of the oxidation state of vanadium in complex oxides have been carried out by electron energy loss spectroscopy. SrVO3/LaAlO3 is then studied both experimentally and theoretically as a prototype system. Extra electrons have been detected on the interface layer, and further proven to originate mainly from a change in the local bonding configuration of V at the La-O terminated substrate surface. Cr-containing stainless steel deposited with a LaCrO3 thin-film layer is a promising interconnect material of Solid Oxide Fuel Cells (SOFC). Our investigation on its microstructural evolution reveals that the LaCrO 3 thin film plays a role in inhibiting the growth of an oxide layer on the metal surface and thus protects the surface of the stainless steel. Ca-doped LaCoO3 is a promising SOFC cathode material. The domain structures and the oxidation state of Co in Ca-doped LaCoO3, which are directly related to its mechanical properties and electronic conductivity, are investigated by in-situ TEM and EELS. The formation of microcracks is observed during thermal cycles. Ca-doping in LaCoO3 is shown to not only improve the electronic conductivity of the material, but is also likely to strengthen the grain boundaries. The realization of its application in SOFCs depends on depressing the ferroelastisity to reduce strain formation during thermal cycles. The application of the (S)TEM techniques used for studying the perovskite systems are further extended to other compounds containing transition metal elements. The refractory minerals from Comet 81 P/Wild-2 are studied to investigate the formation of the early solar system. A relatively high Ti3+/Ti 4+ ratio in fassaite and the presence of osbornite indicate that the Comet refractory minerals formed in the inner solar nebula and were later transported to the outer solar system where the comet formed. This implies a much more dynamic and perhaps more violent solar nebula than was previously suspected.

The effect of thermal pre-treatment of titanium hydride (TiH2) powder in argon condition

NASA Astrophysics Data System (ADS)

Franciska P., L.; Erryani, Aprilia; Annur, Dhyah; Kartika, Ika

2018-04-01

Titanium hydride (TiH2) powders are used to enhance the foaming process in the formation of a highly porous metallic material with a cellular structure. But, the low temperature of hydrogen release is one of its problems. The present study, different thermal pre-treatment temperatures were employed to investigate the decomposition behavior of TiH2 to retard or delay a hydrogen gas release process during foaming. As a foaming agent, TiH2 was subjected to various heat treatments prior at 450 and 500°C during 2 hours in argon condition. To study the formation mechanism, the thermal behavior of titanium hydride and hydrogen release are investigated by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The morphology of pre-treated titanium hydride powders were examined using Scanning Electron Microscope (SEM) while unsure mapping and elemental composition of the pre-treated powders processed by Energy Dispersive Spectroscopy (EDS). To study the phase formation was characterized by X-ray diffraction analysis (XRD). In accordance with the results, an increase in pre-treatment temperature of TiH2 to higher degrees are changing the process of releasing hydrogen from titanium hydride powder. DTA/TGA results showed that thermal pre-treatment TiH2 at 450°C, released the hydrogen gas at 560°C in heat treatment when foaming process. Meanwhile, thermal pre-treatment in TiH2 at 500°C, released the hydrogen gas at 670°C when foaming process. There is plenty of direct evidence for the existence of oxide layers that showed by EDS analysis obtained in SEM. As oxygen is a light element and qualitative proof shows that the higher pre-treatment temperature produces more and thicker oxygen layers on the surface of the TiH2 powder particles. It might the thickness of oxide layer are different from different pre-treatment temperatures, which leading to the differences in the decomposition temperature. But from SEM result that oxidation of the powder does not change the powder morphology. The oxidation process also confirmed by XRD result, which showed higher thermal pre-treatment TiH2, more oxide higher peak is formed. The oxide layer of TiH2 particles is responsible for the observed shift in decomposition temperature and can prepare the stable foam that stabilizes forming of cell walls and avoid their collapse at higher temperatures.

Surface coating of ceria nanostructures for high-temperature oxidation protection

NASA Astrophysics Data System (ADS)

Aadhavan, R.; Bhanuchandar, S.; Babu, K. Suresh

2018-04-01

Stainless steels are used in high-temperature structural applications but suffer from degradation at an elevated temperature of operation due to thermal stress which leads to spallation. Ceria coating over chromium containing alloys induces protective chromia layer formation at alloy/ceria interface thereby preventing oxidative degradation. In the present work, three metals of differing elemental composition, namely, AISI 304, AISI 410, and Inconel 600 were tested for high-temperature stability in the presence and absence of ceria coating. Nanoceria was used as the target to deposit the coating through electron beam physical vapor deposition method. After isothermal oxidation at 1243 K for 24 h, Ceria coated AISI 304 and Inconel 600 exhibited a reduced rate of oxidation by 4 and 1 orders, respectively, in comparison with the base alloy. The formation of spinel structure was found to be lowered in the presence of ceria due to the reduced migration of cations from the alloy.

Highly efficient organic light-emitting diodes with a quantum dot interfacial layer.

PubMed

Ryu, Seung Yoon; Hwang, Byoung Har; Park, Ki Wan; Hwang, Hyeon Seok; Sung, Jin Woo; Baik, Hong Koo; Lee, Chang Ho; Song, Seung Yong; Lee, Jun Yeob

2009-02-11

Advanced organic light-emitting diodes (OLEDs), based on a multiple structure, were achieved in combination with a quantum dot (QD) interfacial layer. The authors used core/shell CdSe/ZnS QDs passivated with trioctylphosphine oxide (TOPO) and TOPO-free QDs as interlayers. Multiple-structure OLEDs (MOLEDs) with TOPO-free QDs showed higher device efficiency because of a well-defined interfacial monolayer formation. Additionally, the three-unit MOLED showed high performance for device efficiency with double-structured QD interfacial layers due to the enhanced charge balance and recombination probability.

Layer Protecting the Surface of Zirconium Used in Nuclear Reactors.

PubMed

Ashcheulov, Petr; Skoda, Radek; Skarohlíd, Jan; Taylor, Andrew; Fendrych, Frantisek; Kratochvílová, Irena

2016-01-01

Zirconium alloys have very useful properties for nuclear facilities applications having low absorption cross-section of thermal electrons, high ductility, hardness and corrosion resistance. However, there is also a significant disadvantage: it reacts with water steam and during this (oxidative) reaction it releases hydrogen gas, which partly diffuses into the alloy forming zirconium hydrides. A new strategy for surface protection of zirconium alloys against undesirable oxidation in nuclear reactors by polycrystalline diamond film has been patented- Czech patent 305059: Layer protecting the surface of zirconium alloys used in nuclear reactors and PCT patent: Layer for protecting surface of zirconium alloys (Patent Number: WO2015039636-A1). The zirconium alloy surface was covered by polycrystalline diamond layer grown in plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. Substantial progress in the description and understanding of the polycrystalline diamond/ zirconium alloys interface and material properties under standard and nuclear reactors conditions (irradiation, hot steam oxidation experiments and heating-quenching cycles) was made. In addition, process technology for the deposition of protective polycrystalline diamond films onto the surface of zirconium alloys was optimized. Zircaloy2 nuclear fuel pins were covered by 300 nm thick protective polycrystalline diamond layer (PCD) using plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. The polycrystalline diamond layer protects the zirconium alloy surface against undesirable oxidation and consolidates its chemical stability while preserving its functionality. PCD covered Zircaloy2 and standard Zircaloy2 pins were for 30 min. oxidized in 1100°C hot steam. Under these conditions α phase of zirconium changes to β phase (more opened for oxygen/hydrogen diffusion). PCD anticorrosion protection of Zircaloy nuclear fuel assemblies can significantly prolong lifetime of Zirconium alloy in nuclear reactors even above Zirconium phase transition temperatures. Even after ion beam irradiation (10 dpa, 3 MeV Fe(2+)) the diamond film still shows satisfactory structural integrity with both sp(3) and sp(2) carbon phases. Zircaloy2 under the carbon-based protective layer after hot steam oxidation test differed from the original Zircaloy2 material composition only very slightly, proving that the diamond coating increases the material resistance to high temperature oxidation. Zirconium alloys nuclear fuel pins' surfaces were covered by compact and homogeneous polycrystalline diamond layers consisting of sp(3) and sp(2) carbon phases with a high crystalline diamond content and low roughness. Diamond withstands very high temperatures, has excellent thermal conductivity and low chemical reactivity, it does not degrade over time and (important for the nuclear fuel cladding) being pure carbon, it has perfect neutron cross-section properties. Moreover, polycrystalline diamond layers consisting of crystalline (sp(3)) and amorphous (sp(2)) carbon phases could have suitable thermal expansion. Zirconium alloys coated with polycrystalline diamond film are protected against undesirable changes and processes. Further, the polycrystalline diamond layer prevents the reaction between the alloy surface and water vapor. During such reaction, water molecules dissociate and initiate formation of zirconium dioxide and hydrogen, accompanied by the release of large amount of heat. Thus the protective layer prevents the formation of hydrogen and the release of reaction heat. Few relevant patents to the topic have been reviewed and cited.

Stability of Fe-Cr alloy interconnects under CH 4-H 2O atmosphere for SOFCs

NASA Astrophysics Data System (ADS)

Horita, Teruhisa; Xiong, Yueping; Yamaji, Katsuhiko; Sakai, Natsuko; Yokokawa, Harumi

The chemical stability of Fe-Cr alloys (ZMG232 and SUS430) was examined under humidified CH 4 gases at 1073 K to simulate the real anode atmosphere in SOFC operation. Surface microstructure change and oxide scale layer formation were observed on the oxidized Fe-Cr alloy surfaces. The main reaction products were Mn-Cr-(Fe) spinels for both alloys. Secondary ion mass spectrometry (SIMS) was applied to measure the elemental distribution of minor and major elements around the oxide scale/alloy interface. A high concentration of Mn on the oxide scale surface suggested the fast diffusion of Mn in the oxide scale to form the spinels. Annealing in CH 4-H 2O made the oxide scale thicker with duration time on the alloy surface. The parabolic growth rates ( kp) of oxide scale layer were evaluated from the thickness of oxide scales by secondary ion mass spectrometry (SIMS) depth profiles, which were calculated to the following: kp=6.25×10 -6 μm 2/s for SUS430 and kp=4.42×10 -6 μm 2/s for ZMG232. The electrical conductivity of oxidized alloys showed the semi-conductor temperature dependence for both alloys. The electrical conductivity of oxidized ZMG232 alloy was higher than that of oxidized SUS430.

Patterning with metal-oxide EUV photoresist: patterning capability, resist smoothing, trimming, and selective stripping

NASA Astrophysics Data System (ADS)

Mao, Ming; Lazzarino, Frederic; De Schepper, Peter; De Simone, Danilo; Piumi, Daniele; Luong, Vinh; Yamashita, Fumiko; Kocsis, Michael; Kumar, Kaushik

2017-03-01

Inpria metal-oxide photoresist (PR) serves as a thin spin-on patternable hard mask for EUV lithography. Compared to traditional organic photoresists, the ultrathin metal-oxide photoresist ( 12nm after development) effectively mitigates pattern collapse. Because of the high etch resistance of the metal-oxide resist, this may open up significant scope for more aggressive etches, new chemistries, and novel integration schemes. We have previously shown that metal-oxide PR can be successfully used to pattern the block layer for the imec 7-nm technology node[1] and advantageously replace a multiple patterning approach, which significantly reduces the process complexity and effectively decreases the cost. We also demonstrated the formation of 16nm half pitch 1:1 line/space with EUV single print[2], which corresponds to a metal 2 layer for the imec 7-nm technology node. In this paper, we investigate the feasibility of using Inpria's metal-oxide PR for 16nm line/space patterning. In meanwhile, we also explore the different etch process for LWR smoothing, resist trimming and resist stripping.

Influence of intermediate layers on the surface condition of laser crystallized silicon thin films and solar cell performance

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

Höger, Ingmar, E-mail: ingmar.hoeger@ipht-jena.de; Gawlik, Annett; Brückner, Uwe

The intermediate layer (IL) between glass substrate and silicon plays a significant role in the optimization of multicrystalline liquid phase crystallized silicon thin film solar cells on glass. This study deals with the influence of the IL on the surface condition and the required chemical surface treatment of the crystallized silicon (mc-Si), which is of particular interest for a-Si:H heterojunction thin film solar cells. Two types of IL were investigated: sputtered silicon nitride (SiN) and a layer stack consisting of silicon nitride and silicon oxide (SiN/SiO). X-ray photoelectron spectroscopy measurements revealed the formation of silicon oxynitride (SiO{sub x}N{sub y}) ormore » silicon oxide (SiO{sub 2}) layers at the surface of the mc-Si after liquid phase crystallization on SiN or SiN/SiO, respectively. We propose that SiO{sub x}N{sub y} formation is governed by dissolving nitrogen from the SiN layer in the silicon melt, which segregates at the crystallization front during crystallization. This process is successfully hindered, when additional SiO layers are introduced into the IL. In order to achieve solar cell open circuit voltages above 500 mV, a removal of the formed SiO{sub x}N{sub y} top layer is required using sophisticated cleaning of the crystallized silicon prior to a-Si:H deposition. However, solar cells crystallized on SiN/SiO yield high open circuit voltage even when a simple wet chemical surface treatment is applied. The implementation of SiN/SiO intermediate layers facilitates the production of mesa type solar cells with open circuit voltages above 600 mV and a power conversion efficiency of 10%.« less

Factors Affecting the Development of Oxide Scales on Austenitic Stainless Steels during Hot Rolling in Steckel Mills

NASA Astrophysics Data System (ADS)

Cobo, S. J.; Rainforth, W. M.

2008-10-01

The hot rolling of austenitic stainless steels in Steckel Mills introduces particular characteristics to the development of oxides scales and surface structures. In this work, the formation of oxide structures during multipass hot rolling of 302 steel was studied under different sets of processing parameters in a laboratory system designed for the simulation of the Steckel process. The resulting surface structures were characterized by a set of complementary techniques involving scanning electron microscopy, energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), and glow discharge optical spectroscopy (GDOS). The surface analysis revealed two alternative surface structures: one consisting in a thin protective oxide layer rich in Cr2O3 and the other consisting in thick complex structures containing several successive nonprotective oxide scale and metal layers resulting from a cyclic oxidation pattern involving stages of protective oxidation, chemical breakaway, and duplex oxidation. The critical condition that determined the activation of one mechanism or the other was identified associated with the parabolic rate constant for Cr2O3 growth and the diffusivity of Cr in the alloy. The effects of changes in temperature, deformation, and furnace atmosphere are discussed. Alternatives for controlling scale development are presented.

Nanoscale electrical and structural modification induced by rapid thermal oxidation of AlGaN/GaN heterostructures.

PubMed

Greco, Giuseppe; Fiorenza, Patrick; Giannazzo, Filippo; Alberti, Alessandra; Roccaforte, Fabrizio

2014-01-17

In this paper, the structural and electrical modifications induced, in the nanoscale, by a rapid thermal oxidation process on AlGaN/GaN heterostructures, are investigated. A local rapid oxidation (900 ° C in O2, 10 min) localized under the anode region of an AlGaN/GaN diode enabled a reduction of the leakage current with respect to a standard Schottky contact. The insulating properties of the near-surface oxidized layer were probed by a nanoscale electrical characterization using scanning probe microscopy techniques. The structural characterization indicated the formation of a thin uniform oxide layer on the surface, with preferential oxidation paths along V-shaped defects penetrating through the AlGaN/GaN interface. The oxidation process resulted in an expansion of the lattice parameters due to the incorporation of oxygen atoms, accompanied by an increase of the crystal mosaicity. As a consequence, a decrease of the sheet carrier density of the two-dimensional electron gas and a positive shift of the threshold voltage are observed. The results provide useful insights for a possible future integration of rapid oxidation processes during GaN device fabrication.

Role of surface oxidation on the size dependent mechanical properties of nickel nanowires: a ReaxFF molecular dynamics study.

PubMed

Aral, Gurcan; Islam, Md Mahbubul; van Duin, Adri C T

2017-12-20

Highly reactive metallic nickel (Ni) is readily oxidized by oxygen (O 2 ) molecules even at low temperatures. The presence of the naturally resulting pre-oxide shell layer on metallic Ni nano materials such as Ni nanowires (NW) is responsible for degrading the deformation mechanisms and related mechanical properties. However, the role of the pre-oxide shell layer on the metallic Ni NW coupled with the complicated mechanical deformation mechanism and related properties have not yet been fully and independently understood. For this reason, the ReaxFF reactive force field for Ni/O interactions was used to investigate the effect of surface oxide layers and the size-dependent mechanical properties of Ni NWs under precisely controlled tensile loading conditions. To directly quantify the size dependent surface oxidation effect on the tensile mechanical deformation behaviour and related properties for Ni NWs, first, ReaxFF-molecular dynamics (MD) simulations were carried out to study the oxidation kinetics on the free surface of Ni NWs in a molecular O 2 environment as a function of various diameters (D = 5.0, 6.5, and 8.0 nm) of the NWs, but at the same length. Single crystalline, pure metallic Ni NWs were also studied as a reference. The results of the oxidation simulations indicate that a surface oxide shell layer with limiting thickness of ∼1.0 nm was formed on the free surface of the bare Ni NW, typically via dissociation of the O-O bonds and the subsequent formation of Ni-O bonds. Furthermore, we investigated the evolution of the size-dependent intrinsic mechanical elastic properties of the core-oxide shell (Ni/Ni x O y ) NWs by comparing them with their un-oxidized counterparts under constant uniaxial tensile loading. We found that the oxide shell layer significantly decreases the mechanical properties of metallic Ni NW as well as facilitates the initiation of plastic deformation as a function of decreasing diameter. The disordered oxide shell layer on the Ni NW's surface remarkably reduces the yield stress and Young's modulus, due to the increased softening effects with the decreasing NW diameter, compared to un-oxidized counterparts. Moreover, the onset of plastic deformation occurs at a relatively low yielding strain and stress level for the smaller diameter of oxide-coated Ni NWs in comparison to their pure counterparts. Furthermore, for pure Ni NWs, Young's modulus, the yielding stress and strain slightly decrease with the decrease in the diameter size of Ni NWs.

Laser method for forming low-resistance ohmic contacts on semiconducting oxides

DOEpatents

Narayan, Jagdish

1981-01-01

This invention is a new method for the formation of high-quality ohmic contacts on wide-band-gap semiconducting oxides. As exemplified by the formation of an ohmic contact on n-type BaTiO.sub.3 containing a p-n junction, the invention entails depositing a film of a metallic electroding material on the BaTiO.sub.3 surface and irradiating the film with a Q-switched laser pulse effecting complete melting of the film and localized melting of the surface layer of oxide immediately underlying the film. The resulting solidified metallic contact is ohmic, has unusually low contact resistance, and is thermally stable, even at elevated temperatures. The contact does not require cleaning before attachment of any suitable electrical lead. This method is safe, rapid, reproducible, and relatively inexpensive.

Method for forming low-resistance ohmic contacts on semiconducting oxides

DOEpatents

Narayan, J.

1979-10-01

The invention provides a new method for the formation of high-quality ohmic contacts on wide-band-gap semiconducting oxides. As exemplified by the formation of an ohmic contact on n-type BaTiO/sub 3/ containing a p-n junction, the invention entails depositing a film of a metallic electroding material on the BaTiO/sub 3/ surface and irradiating the film with a Q-switched laser pulse effecting complete melting of the film and localized melting of the surface layer of oxide immediately underlying the film. The resulting solidified metallic contact is ohmic, has unusually low contact resistance, and is thermally stable, even at elevated temmperatures. The contact does not require cleaning before attachment of any suitable electrical lead. This method is safe, rapid, reproducible, and relatively inexpensive.

Effects of oxygen-inserted layers on diffusion of boron, phosphorus, and arsenic in silicon for ultra-shallow junction formation

NASA Astrophysics Data System (ADS)

Zhang, X.; Connelly, D.; Takeuchi, H.; Hytha, M.; Mears, R. J.; Rubin, L. M.; Liu, T.-J. K.

2018-03-01

The effects of oxygen-inserted (OI) layers on the diffusion of boron (B), phosphorus (P), and arsenic (As) in silicon (Si) are investigated, for ultra-shallow junction formation by high-dose ion implantation followed by rapid thermal annealing. The projected range (Rp) of the implanted dopants is shallower than the depth of the OI layers. Secondary ion mass spectrometry is used to compare the dopant profiles in silicon samples that have OI layers against the dopant profiles in control samples that do not have OI layers. Diffusion is found to be substantially retarded by the OI layers for B and P, and less for As, providing shallower junction depth. The experimental results suggest that the OI layers serve to block the diffusion of Si self-interstitials and thereby effectively reduce interstitial-aided diffusion beyond the depth of the OI layers. The OI layers also help to retain more dopants within the Si, which technology computer-aided design simulations indicate to be beneficial for achieving shallower junctions with lower sheet resistance to enable further miniaturization of planar metal-oxide-semiconductor field-effect transistors for improved integrated-circuit performance and cost per function.

Magnetite solubility and phase stability in alkaline media at elevated temperatures

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

Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

Magnetite, Fe{sub 3}O{sub 4}, is the dominant oxide constituent of the indigenous corrosion layers that form on iron base alloys in high purity, high temperature water. The apparent simultaneous stability of two distinct oxidation states of iron in this metal oxide is responsible for its unique solubility behavior. The present work was undertaken to extend the experimental and theoretical bases for estimating solubilities of an iron corrosion product (Fe{sub 3}O{sub 4}/Fe(OH){sub 2}) over a broader temperature range and in the presence of complexing, pH-controlling reagents. These results indicate that a surface layer of ferrous hydroxide controls magnetite solubility behavior atmore » low temperatures in much the same manner as a surface layer of nickel(II) hydroxide was previously reported to control the low temperature solubility behavior of NiO. The importance of Fe(III) ion complexes implies not only that most previously-derived thermodynamic properties of the Fe(OH){sub 3}{sup {minus}} ion are incorrect, but that magnetite phase stability probably shifts to favor a sodium ferric hydroxyphosphate compound in alkaline sodium phosphate solutions at elevated temperatures. The test methodology involved pumping alkaline solutions of known composition through a bed of Fe{sub 3}O{sub 4} granules and analyzing the emerging solution for Fe. Two pH-controlling reagents were tested: sodium phosphate and ammonia. Equilibria for the following reactions were described in thermodynamic terms: (a) Fe(OH){sub 2}/Fe{sub 3}O{sub 4} dissolution and transformation, (b) Fe(II) and Fe(III) ion hydroxocomplex formation (hydrolysis), (c) Fe(II) ion amminocomplex formation, and (d) Fe(II) and Fe(III) ion phosphatocomplex formation. 36 refs.« less

Thermal barrier coatings

DOEpatents

Alvin, Mary Anne [Pittsburg, PA

2010-06-22

This disclosure addresses the issue of providing a metallic-ceramic overlay coating that potentially serves as an interface or bond coat layer to provide enhanced oxidation resistance to the underlying superalloy substrate via the formation of a diffusion barrier regime within the supporting base material. Furthermore, the metallic-ceramic coating is expected to limit the growth of a continuous thermally grown oxide (TGO) layer that has been primarily considered to be the principal cause for failure of existing TBC systems. Compositional compatibility of the metallic-ceramic with traditional yttria-stabilized zirconia (YSZ) top coats is provided to further limit debond or spallation of the coating during operational use. A metallic-ceramic architecture is disclosed wherein enhanced oxidation resistance is imparted to the surface of nickel-based superalloy or single crystal metal substrate, with simultaneous integration of the yttria stabilized zirconia (YSZ) within the metallic-ceramic overlayer.

Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

NASA Astrophysics Data System (ADS)

Brown, S. S.; Dubé, W. P.; Bahreini, R.; Middlebrook, A. M.; Brock, C. A.; Warneke, C.; de Gouw, J. A.; Washenfelder, R. A.; Atlas, E.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Schwarz, J. P.; Spackman, R.; Trainer, M.; Parrish, D. D.; Fehshenfeld, F. C.; Ravishankara, A. R.

2013-11-01

Organic compounds are a large component of aerosol mass, but organic aerosol (OA) sources remain poorly characterized. Recent model studies have suggested nighttime oxidation of biogenic hydrocarbons as a potentially large OA source, but analysis of field measurements to test these predictions is sparse. We present nighttime vertical profiles of nitrogen oxides, ozone, VOCs and aerosol composition measured during low approaches of the NOAA P-3 aircraft to airfields in Houston, TX. This region has large emissions of both biogenic hydrocarbons and nitrogen oxides. The latter category serves as a source of the nitrate radical, NO3, a key nighttime oxidant. Biogenic VOCs (BVOC) and urban pollutants were concentrated within the nocturnal boundary layer (NBL), which varied in depth from 100-400 m. Despite concentrated NOx at low altitude, ozone was never titrated to zero, resulting in rapid NO3 radical production rates of 0.2-2.7 ppbv h-1 within the NBL. Monoterpenes and isoprene were frequently present within the NBL and underwent rapid oxidation (up to 1 ppbv h-1), mainly by NO3 and to a lesser extent O3. Concurrent enhancement in organic and nitrate aerosol on several profiles was consistent with primary emissions and with secondary production from nighttime BVOC oxidation, with the latter equivalent to or slightly larger than the former. Some profiles may have been influenced by biomass burning sources as well, making quantitative attribution of organic aerosol sources difficult. Ratios of organic aerosol to CO within the NBL ranged from 14 to 38 μg m-3 OA/ppmv CO. A box model simulation incorporating monoterpene emissions, oxidant formation rates and monoterpene SOA yields suggested overnight OA production of 0.5 to 9 μg m-3.

Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

NASA Astrophysics Data System (ADS)

Brown, S. S.; Dubé, W. P.; Bahreini, R.; Middlebrook, A. M.; Brock, C. A.; Warneke, C.; de Gouw, J. A.; Washenfelder, R. A.; Atlas, E.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Schwarz, J. P.; Spackman, R.; Trainer, M.; Parrish, D. D.; Fehshenfeld, F. C.; Ravishankara, A. R.

2013-05-01

Organic compounds are a large component of aerosol mass, but organic aerosol (OA) sources remain poorly characterized. Recent model studies have suggested nighttime oxidation of biogenic hydrocarbons as a potentially large OA source, but analysis of field measurements to test these predictions is sparse. We present nighttime vertical profiles of nitrogen oxides, ozone, VOCs and aerosol composition measured during low approaches of the NOAA P-3 aircraft to airfields in Houston, TX. This region has large emissions of both biogenic hydrocarbons and nitrogen oxides. The latter serves as a source of the nitrate radical, NO3, a key nighttime oxidant. Biogenic VOCs (BVOC) and urban pollutants were concentrated within the nocturnal boundary layer (NBL), which varied in depth from 100-400 m. Despite concentrated NOx at low altitude, ozone was never titrated to zero, resulting in rapid NO3 radical production rates of 0.2-2.7ppbv h-1 within the NBL. Monoterpenes and isoprene were frequently present within the NBL and underwent rapid oxidation (up to 1ppbv h-1), mainly by NO3 and to a lesser extent O3. Concurrent enhancement in organic and nitrate aerosol on several profiles was consistent with primary emissions and with secondary production from nighttime BVOC oxidation, with the latter equivalent to or slightly larger than the former. Ratios of organic aerosol to CO within the NBL ranged from 14 to 38 μg m-3 OA/ppmv CO. A box model simulation incorporating monoterpene emissions, oxidant formation rates and monoterpene SOA yields suggested overnight OA production of 0.5 to 9 μg m-3.

Effects of humidity during formation of zinc oxide electron contact layers from a diethylzinc precursor solution

DOE PAGES

Mauger, Scott A.; Steirer, K. Xerxes; Boe, Jonas; ...

2016-01-19

Here, this work focuses on the role of humidity in the formation of ZnO thin films from a reactive diethylzinc precursor solution for use as the electron contact layer (ECL) in organic photovoltaic (OPV) devices. This method is well suited for flexible devices because the films are annealed at 120 °C, making the process compatible with polymer substrates. ZnO films were prepared by spin coating and annealing at different relative humidity (RH) levels. It is found that RH during coating and annealing affects the chemical and physical properties of the ZnO films. Using x-ray photoelectron spectroscopy it is found thatmore » increasing RH during the formation steps produces a more stoichiometric oxide and a higher Zn/O ratio. Spectroscopic ellipsometry data shows a small decrease in the optical band gap with increased humidity, consistent with a more stoichiometric oxide. Kelvin probe measurements show that increased RH during formation results in a larger work function (i.e. further from vacuum). Consistent with these data, but counter to what might be expected, when these ZnO films are used as ECLs in OPV devices those with ZnO ECLs processed in low RH (less stoichiometric) had higher power conversion efficiency than those with high-RH processed ZnO due to improved open-circuit voltage. The increase in open-circuit voltage with decreasing humidity was observed with two different donor polymers and fullerene acceptors, which shows the trend is due to changes in ZnO. The observed changes in open-circuit voltage follow the same trend as the ZnO work function indicating that the increase in open-circuit voltage with decreasing humidity is the result of improved energetics at the interface between the bulk-heterojunction and the ZnO layer due to a vacuum level shift.« less

Real-time observations of interface formation for barium strontium titanate films on silicon

NASA Astrophysics Data System (ADS)

Mueller, A. H.; Suvorova, N. A.; Irene, E. A.; Auciello, O.; Schultz, J. A.

2002-05-01

Ba.5Sr.5TiO3 (BST) film growth by ion sputtering on bare and thermally oxidized silicon was observed in real time using in-situ spectroscopic ellipsometry and time of flight ion scattering and recoil spectrometry techniques. At the outset of BST film deposition on silicon, an approximately 30 Å film with intermediate static dielectric constant (K˜12) and refractive index (n˜2.6 at photon energies of 1.5-3.25 eV) interface layer formed on bare silicon. The interface layer growth rate was greatly reduced on an oxidized silicon substrate. The results have profound implications on the static dielectric constant of BST.

Post-test characterization of a solid oxide fuel cell stack operated for more than 30,000 hours: The cell

NASA Astrophysics Data System (ADS)

Menzler, Norbert H.; Sebold, Doris; Guillon, Olivier

2018-01-01

A four-layer solid oxide fuel cell stack with planar anode-supported cells was operated galvanostatically at 700 °C and 0.5Acm-2 for nearly 35,000 h. One of the four planes started to degrade more rapidly after ∼28,000 h and finally more progressively after ∼33,000 h. The stack was then shut down and a post-test analysis was carefully performed. The cell was characterized with respect to cathodic impurities and clarification of the reason(s) for failure. Wet chemical analysis revealed very low chromium incorporation into the cathode. However, SEM and TEM observations on polished and fractured surfaces showed catastrophic failure in the degraded layer. The cathode-barrier-electrolyte cell layer system delaminated from the entire cell over large areas. The source of delamination was the formation of a porous, sponge-like secondary phase consisting of zirconia, yttria and manganese (oxide). Large secondary phase islands grew from the electrolyte-anode interface towards the anode and cracked the bonding between both layers. The manganese originated from the contact or protection layers used on the air side. This stack result shows that volatile species - in this case manganese - should be avoided, especially when long-term applications are envisaged.

Dimensionally Controlled Lithiation of Chromium Oxide

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

Fister, Tim T.; Hu, Xianyi; Esbenshade, Jennifer

Oxide conversion reactions are an alternative approach for high capacity lithium ion batteries but are known to suffer from structural irreversibility associated with the phase separation and reconstitution of reduced metal species and Li2O. In particular, the morphology of the reduced metal species is thought to play a critical role in the electrochemical properties of a conversion material. Here we use a model electrode with alternating layers of chromium and chromium oxide to better understand and control these phase changes in real-time and at molecular length scales. Despite lacking crystallinity at the atomic scale, this superstructure is observed (with X-raymore » reflectivity, XR) to lithiate and delithiate in a purely one-dimensional manner, preserving the layered structure. The XR data show that the metal layers act as nucleation sites for the reduction of chromium in the conversion reaction. Irreversibility during delithiation is due to the formation of a ternary phase, LiCrO2, which can be further delithiated at higher potentials. The results reveal that the combination of confining lithiation to nanoscale sheets of Li2O and the availability of reaction sites in the metal layers in the layered structure is a strategy for improving the reversibility and mass transport properties that can be used in a wide range of conversion materials.« less

Growth of aluminum-free porous oxide layers on titanium and its alloys Ti-6Al-4V and Ti-6Al-7Nb by micro-arc oxidation.

PubMed

Duarte, Laís T; Bolfarini, Claudemiro; Biaggio, Sonia R; Rocha-Filho, Romeu C; Nascente, Pedro A P

2014-08-01

The growth of oxides on the surfaces of pure Ti and two of its ternary alloys, Ti-6Al-4V and Ti-6Al-7Nb, by micro-arc oxidation (MAO) in a pH 5 phosphate buffer was investigated. The primary aim was to form thick, porous, and aluminum-free oxide layers, because these characteristics favor bonding between bone and metal when the latter is implanted in the human body. On Ti, Ti-6Al-4 V, and Ti-6Al-7Nb, the oxides exhibited breakdown potentials of about 200 V, 130 V, and 140 V, respectively, indicating that the oxide formed on the pure metal is the most stable. The use of the MAO procedure led to the formation of highly porous oxides, with a uniform distribution of pores; the pores varied in size, depending on the anodizing applied voltage and time. Irrespective of the material being anodized, Raman analyses allowed us to determine that the oxide films consisted mainly of the anatase phase of TiO2, and XPS results indicated that this oxide is free of Al and any other alloying element. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of the conditions of anodizing on the morphology of nanotitania

NASA Astrophysics Data System (ADS)

Root, N. V.; Kultin, D. Yu.; Kustov, L. M.; Kudryavtsev, I. K.; Lebedeva, O. K.

2017-02-01

The effect the current density, treatment time, surface pretreatment, and electrolyte composition have on the morphology of titania obtained via electrochemical treatment in such ionic liquids (ILs) as 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][NTf2] and 1-butyl-3-methylimidazolium chloride [BMIM]Cl is studied. The anodic formation of titania nanostructures in the form of nanotubes or nanorods is found to occur in times of up to 100 s. The role of water in the formation of these titania nanostructures is shown. Pretreatment has no effect on the morphology of the formed oxide. The formation of products that are poorly soluble in ILs (e.g., hydrated oxides) results in the emergence of a layer partially covering the open parts of nanotubes, preventing their further growth.

Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

PubMed

Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

2009-03-01

To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements.

Preparation and Layer-by-Layer Solution Deposition of Cu(In,Ga)O2 Nanoparticles with Conversion to Cu(In,Ga)S2 Films

PubMed Central

Dressick, Walter J.; Soto, Carissa M.; Fontana, Jake; Baker, Colin C.; Myers, Jason D.; Frantz, Jesse A.; Kim, Woohong

2014-01-01

We present a method of Cu(In,Ga)S2 (CIGS) thin film formation via conversion of layer-by-layer (LbL) assembled Cu-In-Ga oxide (CIGO) nanoparticles and polyelectrolytes. CIGO nanoparticles were created via a novel flame-spray pyrolysis method using metal nitrate precursors, subsequently coated with polyallylamine (PAH), and dispersed in aqueous solution. Multilayer films were assembled by alternately dipping quartz, Si, and/or Mo substrates into a solution of either polydopamine (PDA) or polystyrenesulfonate (PSS) and then in the CIGO-PAH dispersion to fabricate films as thick as 1–2 microns. PSS/CIGO-PAH films were found to be inadequate due to weak adhesion to the Si and Mo substrates, excessive particle diffusion during sulfurization, and mechanical softness ill-suited to further processing. PDA/CIGO-PAH films, in contrast, were more mechanically robust and more tolerant of high temperature processing. After LbL deposition, films were oxidized to remove polymer and sulfurized at high temperature under flowing hydrogen sulfide to convert CIGO to CIGS. Complete film conversion from the oxide to the sulfide is confirmed by X-ray diffraction characterization. PMID:24941104

Strain-Engineered Oxygen Vacancies in CaMnO3 Thin Films.

PubMed

Chandrasena, Ravini U; Yang, Weibing; Lei, Qingyu; Delgado-Jaime, Mario U; Wijesekara, Kanishka D; Golalikhani, Maryam; Davidson, Bruce A; Arenholz, Elke; Kobayashi, Keisuke; Kobata, Masaaki; de Groot, Frank M F; Aschauer, Ulrich; Spaldin, Nicola A; Xi, Xiaoxing; Gray, Alexander X

2017-02-08

We demonstrate a novel pathway to control and stabilize oxygen vacancies in complex transition-metal oxide thin films. Using atomic layer-by-layer pulsed laser deposition (PLD) from two separate targets, we synthesize high-quality single-crystalline CaMnO 3 films with systematically varying oxygen vacancy defect formation energies as controlled by coherent tensile strain. The systematic increase of the oxygen vacancy content in CaMnO 3 as a function of applied in-plane strain is observed and confirmed experimentally using high-resolution soft X-ray absorption spectroscopy (XAS) in conjunction with bulk-sensitive hard X-ray photoemission spectroscopy (HAXPES). The relevant defect states in the densities of states are identified and the vacancy content in the films quantified using the combination of first-principles theory and core-hole multiplet calculations with holistic fitting. Our findings open up a promising avenue for designing and controlling new ionically active properties and functionalities of complex transition-metal oxides via strain-induced oxygen-vacancy formation and ordering.

Electron irradiation induced amorphous SiO2 formation at metal oxide/Si interface at room temperature; electron beam writing on interfaces.

PubMed

Gurbán, S; Petrik, P; Serényi, M; Sulyok, A; Menyhárd, M; Baradács, E; Parditka, B; Cserháti, C; Langer, G A; Erdélyi, Z

2018-02-01

Al 2 O 3 (5 nm)/Si (bulk) sample was subjected to irradiation of 5 keV electrons at room temperature, in a vacuum chamber (pressure 1 × 10 -9 mbar) and formation of amorphous SiO 2 around the interface was observed. The oxygen for the silicon dioxide growth was provided by the electron bombardment induced bond breaking in Al 2 O 3 and the subsequent production of neutral and/or charged oxygen. The amorphous SiO 2 rich layer has grown into the Al 2 O 3 layer showing that oxygen as well as silicon transport occurred during irradiation at room temperature. We propose that both transports are mediated by local electric field and charged and/or uncharged defects created by the electron irradiation. The direct modification of metal oxide/silicon interface by electron-beam irradiation is a promising method of accomplishing direct write electron-beam lithography at buried interfaces.

Facile synthesis of 3D MnNi-layered double hydroxides (LDH)/graphene composites from directly graphites for pseudocapacitor and their electrochemical analysis

NASA Astrophysics Data System (ADS)

Lee, Ilbok; Jeong, Gyoung Hwa; An, Soyeon; Kim, Sang-Wook; Yoon, Songhun

2018-01-01

Herein, MnNi-layered double hydroxides (LDH) were imbibed within the interlayers of graphene nanosheets. The anionic surfactant, sodium dodecyl sulfate played a role of graphite exfoliator adding interaction with metal cations. Using this process, layered MnNi-LDH-graphene nanocomposite was prepared without formation of graphene oxide. When applied into pseudocapacitor electrode, LDH-graphene with optimal ratio between Mn and Ni exhibited very stable cycle with 90% at 1400 cycles and high energy 47.29 Wh kg-1 at the power density of 7473 W kg-1, which was attributed to highly stable layered LDH structure within conductive graphene layers.

Porous TiO₂ surface formed on nickel-titanium alloy by plasma electrolytic oxidation: a prospective polymer-free reservoir for drug eluting stent applications.

PubMed

Huan, Zhiguang; Fratila-Apachitei, Lidy E; Apachitei, Iulian; Duszczyk, Jurek

2013-07-01

In this study, a porous oxide layer was formed on the surface of nickel-titanium alloy (NiTi) by plasma electrolytic oxidation (PEO) with the aim to produce a polymer-free drug carrier for drug eluting stent (DES) applications. The oxidation was performed galvanostatically in concentrated phosphoric acid electrolyte at low temperature. It was found that the response of NiTi substrate during the PEO process was different from that of bulk Ti, since the presence of large amount of Ni delayed the initial formation of a compact oxide layer that is essential for the PEO to take place. Under optimized PEO conditions, the resultant surface showed porosity, pore density and oxide layer thickness of 14.11%, 2.40 × 10⁵ pores/mm² and 0.8 μm, respectively. It was additionally noted that surface roughness after PEO did not significantly increase as compared with that of original NiTi substrate and the EDS analyses revealed a decrease in Ni/Ti ratio on the surface after PEO. The cross-section morphology showed no discontinuity between the PEO layer and the NiTi substrate. Furthermore, wettability and surface free energy of the NiTi substrate increased significantly after PEO treatment. The PEO process could be successfully translated to NiTi stent configuration proving for the first time its feasibility for such a medical device and offering potential for development of alternative, polymer-free drug carriers for NiTi DES. Copyright © 2013 Wiley Periodicals, Inc.

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

The effect of Ca/P concentration and temperature of simulated body fluid on the growth of hydroxyapatite coating on alkali-treated 316L stainless steel.

PubMed

Lin, Feng-Huei; Hsu, Yao-Shan; Lin, Shih-Hsun; Sun, Jui-Sheng

2002-10-01

316L-SS is one of the important materials both in orthopaedics and dentistry for bone screw/plate, intra-medullary rod, fixation wire, HIP joint, and knee joint. However, the biocompatibility and bone-bonding ability troubled researches for years. In the study, a simple chemical method was tried so as to establish and induce a bioactive HA layer on the surface of 316L stainless steel. When the metallic substrates treated with 10 M NaOH aqueous solution and subsequently heated at 600 degrees C, a thin sodium chromium oxide layer was formed on the surfaces as the linking layer for HA and 316L-SS. After 316L-SS treated with alkali solution, it would soak into a simulated body fluid with higher concentration of calcium and phosphorous ions to increase the possibility of nucleation of HA. However, the iron oxide and iron chromium oxides were formed on the surface when calcium and phosphorous ions increased. This resulted in loosening the HA layer. When the alkali-treated 316L-SS was soaked into SBF at a temperature of 80 degrees C, it could form a dense and uniform bone-like hydroxyapatite layer on the surface. In the research, the mechanism of the formation of sodium chromium oxide and HA would also be described by the analysis of X-ray diffractometer, scanning electron microscope, energy-dispersion spectrophotometer, and Fourier transformation infrared.

The effects of different types of investments on the alpha-case layer of titanium castings.

PubMed

Guilin, Yu; Nan, Li; Yousheng, Li; Yining, Wang

2007-03-01

Different types of investments affect the formation of the alpha-case (alpha-case) layer on titanium castings. This alpha-case layer may possibly alter the mechanical properties of cast titanium, which may influence the fabrication of removable and fixed prostheses. The formation mechanism for the alpha-case layer is not clear. The aim of this study was to evaluate the effect of 3 types of investments on the microstructure, composition, and microhardness of the alpha-case layer on titanium castings. Fifteen wax columns with a diameter of 5 mm and a length of 40 mm were divided into 3 groups of 5 patterns each. Patterns were invested using 3 types of investment materials, respectively, and were cast in pure titanium. The 3 types of materials tested were SiO(2)-, Al(2)O(3)-, and MgO-based investments. All specimens were sectioned and prepared for metallographic observation. The microstructure and composition of the surface reaction layer of titanium castings were investigated by scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). The surface microhardness (VHN) for all specimens was measured using a hardness testing machine, and a mean value for each group was calculated. The alpha-case layer on titanium castings invested with SiO(2)-, Al(2)O(3)-, and MgO-based investments consisted of 3 layers-namely, the oxide layer, alloy layer, and hardening layer. In this study, the oxide layer and alloy layer were called the reaction layer. The thickness of the reaction layer for titanium castings using SiO(2)-, Al(2)O(3)-, and MgO-based investments was approximately 80 microm, 50 microm, and 14 microm, respectively. The surface microhardness of titanium castings made with SiO(2)-based investments was the highest, and that with MgO-based investments was the lowest. The type of investment affects the microstructure and microhardness of the alpha-case layer of titanium castings. Based on the thickness of the surface reaction layer and the surface microhardness of titanium castings, MgO-based investment materials may be the best choice for casting these materials.

Peleolakes and impact basins in southern Arabia Terra, including Meridiani Planum: Implications for the formation of hematite deposits on Mars

USGS Publications Warehouse

Newsom, Horton E.; Barber, C.A.; Hare, T.M.; Schelble, R.T.; Sutherland, V.A.; Feldman, W.C.

2003-01-01

The hematite deposit in Meridiani Planum was selected for a Mars Exploration Rover (MER) landing site because water could be involved in the formation of hematite, and water is a key ingredient in the search for life. Our discovery of a chain of paleolake basins and channels along the southern margin of the hematite deposits in Meridiani Planum with the presence of the strongest hematite signature adjacent to a paleolake basin, supports the possible role of water in the formation of the hematite and the deposition of other layered materials in the region. The hematite may have formed by direct precipitation from lake water, as coatings precipitated from groundwater, or by oxidation of preexisting iron oxide minerals. The paleolake basins were fed by an extensive channel system, originating from an area larger than Texas and located south of the Schiaparelli impact basin. On the basis of stratigraphic relationships, the formation of channels in the region occurred over much of Mars' history, from before the layered materials in Meridiani Planum were deposited until recently. The location of the paleolake basins and channels is connected with the impact cratering history of the region. The earliest structure identified in this study is an ancient circular multiringed basin (800-1600 km diameter) that underlies the entire Meridiani Planum region. The MER landing site is located on the buried northern rim of a later 150 km diameter crater. This crater is partially filled with layered deposits that contained a paleolake in its southern portion. Copyright 2003 by the American Geophysical Union.

Surface spectroscopy studies of the oxidation behavior of uranium

NASA Astrophysics Data System (ADS)

Bloch, J.; Atzmony, U.; Dariel, M. P.; Mintz, M. H.; Shamir, N.

1982-02-01

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) techniques were utilized to study the oxidation behavior of clean uranium surfaces, at very low pressures of various atmospheres (UHV, H 2, O 2, and CO 2), at room temperature. Both for O 2 and CO 2, a precursor chemisorbed oxygen species has been identified at the very initial stage of the oxidation reaction. This chemisorbed oxygen transforms to the oxide form at a rate which depends on the pressure of the oxidizing atmosphere. Residual gaseous carbon compounds which are present even under UHV conditions result in the simultaneous formation of surface carbide which accompanies the initial stage of oxidation. This carbide however decomposes later as oxidation proceeds. Adventitious hydrocarbon adsorption occurs on the formed oxide layer.

Influence of oxygen on the carbide formation on tungsten

NASA Astrophysics Data System (ADS)

Luthin, J.; Linsmeier, Ch.

2001-03-01

As a first wall material in nuclear fusion devices, tungsten will interact with carbon and oxygen from the plasma. In this study, we report on the process of thermally induced carbide formation of thin carbon films on polycrystalline tungsten and the influence of oxygen on this process. All investigations are performed using X-ray photoelectron spectroscopy (XPS). Carbon films are supplied through electron beam evaporation of graphite. The carbidization process, monitored during increased substrate temperature, can be divided into four phases. In phase I disordered carbon converts into graphite-like carbon. In phase II significant diffusion and the reaction to W 2C is observed, followed by phase III which is dominated by the presence of W 2C and the beginning reaction to WC. Finally in phase IV only WC is present, but the total carbon amount has strongly decreased. Different mechanisms of oxygen influence on the carbide formation are proposed and measurements of the reaction of carbon on tungsten with intermediate oxide layers are presented in detail. A WO 2+ x intermediate layer completely inhibits the carbide formation, while a WO 2 layer leads to WC formation at temperatures above 1270 K.

Surface and Interface Chemistry for Gate Stacks on Silicon

NASA Astrophysics Data System (ADS)

Frank, M. M.; Chabal, Y. J.

This chapter addresses the fundamental silicon surface science associated with the continued progress of nanoelectronics along the path prescribed by Moore's law. Focus is on hydrogen passivation layers and on ultrathin oxide films encountered during silicon cleaning and gate stack formation in the fabrication of metal-oxide-semiconductor field-effect transistors (MOSFETs). Three main topics are addressed. (i) First, the current practices and understanding of silicon cleaning in aqueous solutions are reviewed, including oxidizing chemistries and cleans leading to a hydrogen passivation layer. The dependence of the final surface termination and morphology/roughness on reactant choice and pH and the influence of impurities such as dissolved oxygen or metal ions are discussed. (ii) Next, the stability of hydrogen-terminated silicon in oxidizing liquid and gas phase environments is considered. In particular, the remarkable stability of hydrogen-terminated silicon surface in pure water vapor is discussed in the context of atomic layer deposition (ALD) of high-permittivity (high-k) gate dielectrics where water is often used as an oxygen precursor. Evidence is also provided for co-operative action between oxygen and water vapor that accelerates surface oxidation in humid air. (iii) Finally, the fabrication of hafnium-, zirconium- and aluminum-based high-k gate stacks is described, focusing on the continued importance of the silicon/silicon oxide interface. This includes a review of silicon surface preparation by wet or gas phase processing and its impact on high-k nucleation during ALD growth, and the consideration of gate stack capacitance and carrier mobility. In conclusion, two issues are highlighted: the impact of oxygen vacancies on the electrical characteristics of high-k MOS devices, and the way alloyed metal ions (such as Al in Hf-based gate stacks) in contact with the interfacial silicon oxide layer can be used to control flatband and threshold voltages.

Oxidation behavior of Al/Cr coating on Ti2AlNb alloy at 900 °C

NASA Astrophysics Data System (ADS)

Yang, Zhengang; Liang, Wenping; Miao, Qiang; Chen, Bowen; Ding, Zheng; Roy, Nipon

2018-04-01

In this paper, the Al/Cr coating was fabricated on the surface of Ti2AlNb alloy via rf magnetron sputtering and double glow treatment to enhance oxidation resistance. The protective coating with an outer layer of Al and inner layer of Cr has great bonding strength due to the in-diffusion of Cr and the inter-diffusion between Al and Cr to form Al-Cr alloyed layer which has great hardness. Acoustic emission curve which was detected via WS-2005 scratch tester indicates the bonding strength between Al/Cr coating and substrate is great. Morphology of Ti2AlNb alloy with Al/Cr coating after scratch test shows that the scratch is smooth without disbanding, and the depth and breadth of scratch are changed uniformly. The mass change was reduced after oxidation test due to the Al/Cr protective coating. Isothermal oxidation test at 900 °C was researched. Results indicate that Al/Cr coating provided oxidation resistance of Ti2AlNb alloy with prolonged air exposure at 900 °C. Al2O3 was detected by XRD patterns and SEM images, and was formed on the surface of Ti2AlNb alloy to protect substrate during oxidation test. A certain content of Cr is beneficial for the formation of Al2O3. Besides, Cr2O3 was produced under Al2O3 by outward diffusion of Cr to protect substrate sequentially, no cracks were discovered on Al/Cr protective coating. The process of Ti outward diffusion into surface was suppressive due to integration of Cr-Ti and Al-Ti intermetallics. A steady, adherent and continuous coated layer of Al/Cr on Ti2AlNb alloy increases oxidation resistance.

Delay in micro-discharges appearance during PEO of Al: Evidence of a mechanism of charge accumulation at the electrolyte/oxide interface

NASA Astrophysics Data System (ADS)

Martin, J.; Nominé, A.; Brochard, F.; Briançon, J.-L.; Noël, C.; Belmonte, T.; Czerwiec, T.; Henrion, G.

2017-07-01

PEO was conducted on Al by applying a pulsed bipolar current. The role of the cathodic polarization on the appearance of micro-discharges (MDs) and on the subsequent formation of the PEO oxide layers is investigated. Various ratios of the charge quantity RCQ = Qp/Qn (defined as the anodic Qp to cathodic Qn charge quantity ratio over one current pulse period) in the range [0.5; 6.0] were selected by changing the waveform parameters of the cathodic current while keeping the waveform of the anodic current unchanged. Results show that the appearance of MDs is delayed with respect to the rising edge of the anodic current; this delay strongly depends on both the processing time and the applied cathodic charge quantity. It is also evidenced that shorter delays promoted by high RCQ values (RCQ > 1) are associated with stronger MDs (large size and long life) that have detrimental effects on the formed PEO oxide layers. Thicker and the more compact oxide layer morphology is achieved with the intermediate RCQ value (RCQ = 0.9) for which the delay of the MDs appearance is high and the MDs softer. Low RCQ (RCQ < 0.9) results in an earlier extinction of the MDs as the process goes on, which leads to poorly oxidized metal. A mechanism of charge accumulation taking place at the oxide/electrolyte interface and arising before the occurrence of dielectric breakdown is proposed to explain the ignition of MDs during pulsed bipolar PEO of aluminium. A close examination of the voltage-time response which can be adequately simulated with an equivalent RC circuit evidences the capacitive behaviour of the oxide layer and therefore confirms this proposed mechanism of charge accumulation.

Lanthanide-based oxides and silicates for high-kappa gate dielectric applications

NASA Astrophysics Data System (ADS)

Jur, Jesse Stephen

The ability to improve performance of the high-end metal oxide semiconductor field effect transistor (MOSFET) is highly reliant on the dimensional scaling of such a device. In scaling, a decrease in dielectric thickness results in high current leakage between the electrode and the substrate by way of direct tunneling through the gate dielectric. Observation of a high leakage current when the standard gate dielectric, SiO2, is decreased below a thickness of 1.5 nm requires engineering of a replacement dielectric that is much more scalable. This high-kappa dielectric allows for a physically thicker oxide, reducing leakage current. Integration of select lanthanide-based oxides and silicates, in particular lanthanum oxide and silicate, into MOS gate stack devices is examined. The quality of the high-kappa dielectrics is monitored electrically to determine properties such as equivalent oxide thickness, leakage current density and defect densities. In addition, analytical characterization of the dielectric and the gate stack is provided to examine the materialistic significance to the change of the electrical properties of the devices. In this work, lanthanum oxide films have been deposited by thermal evaporation on to a pre-grown chemical oxide layer on silicon. It is observed that the SiO2 interfacial layer can be consumed by a low-temperature reaction with lanthanum oxide to produce a high-quality silicate. This is opposed to depositing lanthanum oxide directly on silicon, which can possibly favor silicide formation. The importance of oxygen regulation in the surrounding environment of the La2O3-SiO2 reaction-anneal is observed. By controlling the oxygen available during the reaction, SiO2 growth can be limited to achieve high stoichiometric ratios of La2O 3 to SiO2. As a result, MOS devices with an equivalent oxide thickness (EOT) of 5 A and a leakage current density of 5.0 A/cm 2 are attained. This data equals the best value achieved in this field and is a substantial improvement over SiO(N) dielectrics, allowing for increased device scaling. High-temperature processing, consistent with the source/drain activation anneal in MOSFET processing, is performed on lanthanum-silicate based MOS devices with Ta or TaN gate electrodes and a W metal capping layer. The thermal limit of Ta is observed to be less than 800°C, resulting in a phase transformation that can result in uncontrolled shifting of the MOS device flat-band voltage. TaN is observed to be more thermally stable (up to 1000°C) and results in an increase in the capacitance density suggesting that it impedes oxygen reaction with silicon to produce SiO2. It is later observed that a W metal capping layer can serve as a high-oxygen source, which results in an increased interfacial SiO2 formation. By limiting the oxygen content in the W capping layer and by utilizing a thermally stable TaN gate electrode, control over the electrical properties of the MOS device is acquired. To determine the stability of amorphous lanthanum-silicate in contact with investigated by means of back-side secondary ion mass spectroscopy profiling. The results are the first reported data showing that the lanthanum incorporated in the silica matrix doe not diffuse into the silicon substrate after high temperature processing. The decrease in the device effective work function (φM,eff ) observed in these samples is examined in detail. First, as a La 2O3 capping layer on HfSiO(N), the shift yields ideal-φ M,eff values for nMOSFET deices (4.0 eV) that were previously inaccessible. Other lanthanide oxides (Dy, Ho and Yb) used as capping layers show similar effects. It is also shown that tuning of φM,eff can be realized by controlling the extent of lanthanide-silicate formation. This research, conducted in conjunction with SEMATECH and the SRC, represents a significant technological advancement in realizing 45 and sub-45 nm MOSFET device nodes.

Volatile organic compounds and isoprene oxidation products at a temperate deciduous forest site

NASA Astrophysics Data System (ADS)

Helmig, Detlev; Greenberg, Jim; Guenther, Alex; Zimmerman, Pat; Geron, Chris

1998-09-01

Biogenic volatile organic compounds (BVOCs) and their role in atmospheric oxidant formation were investigated at a forest site near Oak Ridge, Tennessee, as part of the Nashville Southern Oxidants Study (SOS) in July 1995. Of 98 VOCs detected, a major fraction were anthropogenic VOCs such as chlorofluorocarbons (CFCs), alkanes, alkenes and aromatic compounds. Isoprene was the dominant BVOC during daytime. Primary products from BVOC oxidation were methylvinylketone, methacrolein and 3-methylfuran. Other compounds studied include the BVOCs α-pinene, camphene, β-pinene, p-cymene, limonene and cis-3-hexenyl acetate and a series of light alkanes, aromatic hydrocarbons and seven of the CFCs. The correlation of meteorological parameters, with the mixing ratios of these different compounds, reveals information on atmospheric oxidation processes and transport. Long-lived VOCs show very steady mixing ratio time series. Regionally and anthropogenically emitted VOCs display distinct diurnal cycles with a strong mixing ratio decrease in the morning from the breakup of the nocturnal boundary layer. Nighttime mixing ratio increases of CFCs and anthropogenic VOCs are suspected to derive from emissions within the Knoxville urban area into the shallow nocturnal boundary layer. In contrast, the time series of BVOCs and their oxidation products are determined by a combination of emission control, atmospheric oxidation and deposition, and boundary layer dynamics. Mixing ratio time series data for monoterpenes and cis-3-hexenyl acetate suggest a temporarily emission rate increase during and after heavy rain events. The isoprene oxidation products demonstrate differences in the oxidation pathways during night and day and in their dry and wet deposition rates.

Thin Film Transistors On Plastic Substrates

DOEpatents

Carey, Paul G.; Smith, Patrick M.; Sigmon, Thomas W.; Aceves, Randy C.

2004-01-20

A process for formation of thin film transistors (TFTs) on plastic substrates replaces standard thin film transistor fabrication techniques, and uses sufficiently lower processing temperatures so that inexpensive plastic substrates may be used in place of standard glass, quartz, and silicon wafer-based substrates. The silicon based thin film transistor produced by the process includes a low temperature substrate incapable of withstanding sustained processing temperatures greater than about 250.degree. C., an insulating layer on the substrate, a layer of silicon on the insulating layer having sections of doped silicon, undoped silicon, and poly-silicon, a gate dielectric layer on the layer of silicon, a layer of gate metal on the dielectric layer, a layer of oxide on sections of the layer of silicon and the layer of gate metal, and metal contacts on sections of the layer of silicon and layer of gate metal defining source, gate, and drain contacts, and interconnects.

Stability Criteria of Fullerene-like Nanoparticles: Comparing V₂O5 to Layered Metal Dichalcogenides and Dihalides.

PubMed

Levi, Roi; Bar-Sadan, Maya; Albu-Yaron, Ana; Popovitz-Biro, Ronit; Houben, Lothar; Prior, Yehiam; Tenne, Reshef

2010-08-18

Numerous examples of closed-cage nanostructures, such as nested fullerene-like nanoparticles and nanotubes, formed by the folding of materials with layered structure are known. These compounds include WS₂, NiCl₂, CdCl₂, Cs₂O, and recently V₂O₅. Layered materials, whose chemical bonds are highly ionic in character, possess relatively stiff layers, which cannot be evenly folded. Thus, stress-relief generally results in faceted nanostructures seamed by edge-defects. V₂O₅, is a metal oxide compound with a layered structure. The study of the seams in nearly perfect inorganic "fullerene-like" hollow V₂O 5 nanoparticles (NIF-V₂O₅) synthesized by pulsed laser ablation (PLA), is discussed in the present work. The relation between the formation mechanism and the seams between facets is examined. The formation mechanism of the NIF-V₂O 5 is discussed in comparison to fullerene-like structures of other layered materials, like IF structures of MoS₂, CdCl₂, and Cs₂O. The criteria for the perfect seaming of such hollow closed structures are highlighted.

Same-View Nano-XAFS/STEM-EDS Imagings of Pt Chemical Species in Pt/C Cathode Catalyst Layers of a Polymer Electrolyte Fuel Cell.

PubMed

Takao, Shinobu; Sekizawa, Oki; Samjeské, Gabor; Nagamatsu, Shin-ichi; Kaneko, Takuma; Yamamoto, Takashi; Higashi, Kotaro; Nagasawa, Kensaku; Uruga, Tomoya; Iwasawa, Yasuhiro

2015-06-04

We have made the first success in the same-view imagings of 2D nano-XAFS and TEM/STEM-EDS under a humid N2 atmosphere for Pt/C cathode catalyst layers in membrane electrode assemblies (MEAs) of polymer electrolyte fuel cells (PEFCs) with Nafion membrane to examine the degradation of Pt/C cathodes by anode gas exchange cycles (start-up/shut-down simulations of PEFC vehicles). The same-view imaging under the humid N2 atmosphere provided unprecedented spatial information on the distribution of Pt nanoparticles and oxidation states in the Pt/C cathode catalyst layer as well as Nafion ionomer-filled nanoholes of carbon support in the wet MEA, which evidence the origin of the formation of Pt oxidation species and isolated Pt nanoparticles in the nanohole areas of the cathode layer with different Pt/ionomer ratios, relevant to the degradation of PEFC catalysts.

Bulk heterojunction formation between indium tin oxide nanorods and CuInS2 nanoparticles for inorganic thin film solar cell applications.

PubMed

Cho, Jin Woo; Park, Se Jin; Kim, Jaehoon; Kim, Woong; Park, Hoo Keun; Do, Young Rag; Min, Byoung Koun

2012-02-01

In this study, we developed a novel inorganic thin film solar cell configuration in which bulk heterojunction was formed between indium tin oxide (ITO) nanorods and CuInS(2) (CIS). Specifically, ITO nanorods were first synthesized by the radio frequency magnetron sputtering deposition method followed by deposition of a dense TiO(2) layer and CdS buffer layer using atomic layer deposition and chemical bath deposition method, respectively. The spatial region between the nanorods was then filled with CIS nanoparticle ink, which was presynthesized using the colloidal synthetic method. We observed that complete gap filling was achieved to form bulk heterojunction between the inorganic phases. As a proof-of-concept, solar cell devices were fabricated by depositing an Au electrode on top of the CIS layer, which exhibited the best photovoltaic response with a V(oc), J(sc), FF, and efficiency of 0.287 V, 9.63 mA/cm(2), 0.364, and 1.01%, respectively.

Stability domain of alumina thermally grown on Fe-Cr-Al-based model alloys and modified surface layers exposed to oxygen-containing molten Pb

NASA Astrophysics Data System (ADS)

Jianu, A.; Fetzer, R.; Weisenburger, A.; Doyle, S.; Bruns, M.; Heinzel, A.; Hosemann, P.; Mueller, G.

2016-03-01

The paper gives experimental results concerning the morphology, composition, structure and thickness of the oxide scales grown on Fe-Cr-Al-based bulk alloys during exposure to oxygen-containing molten lead. The results are discussed and compared with former results obtained on Al-containing surface layers, modified by melting with intense pulsed electron beam and exposed to similar conditions. The present and previous results provide the alumina stability domain and also the criterion of the Al/Cr ratio for the formation of a highly protective alumina layer on the surface of Fe-Cr-Al-based alloys and on modified surface layers exposed to molten lead with 10-6 wt.% oxygen at 400-600 °C. The protective oxide scales, grown on alumina-forming Fe-Cr-Al alloys under the given experimental conditions, were transient aluminas, namely, kappa-Al2O3 and theta-Al2O3.

Polyethylenimine/kappa carrageenan: Micro-arc oxidation coating for passivation of magnesium alloy.

PubMed

Golshirazi, A; Kharaziha, M; Golozar, M A

2017-07-01

The aim of this study was to combine micro-arc oxidation (MAO) and self-assembly technique to improve corrosion resistivity of AZ91 alloy. While a silicate-fluoride electrolyte was adopted for MAO treatment, polyethylenimine (PEI)/kappa carrageenan (KC) self-assembly coating was applied as the second coating layer. Resulted demonstrated the formation of forsterite-fluoride containing MAO coating on AZ91 alloy depending on the voltage and time of anodizing process. Addition of the second PEI/KC coating layer on MAO treated sample effectively enhanced the adhesive strength of MAO coated sample due to filling the pores with polymers and increase in the mechanical interlocking of coating to the substrate. Moreover, the corrosion evaluation considered by potentiodynamic polarization and electrochemical impedance spectroscopy confirmed that double layered PEI/KC:MAO coating presented superior resistance to corrosion attack. It is envisioned that the proposed double layered PEI/KC:MAO coating could be useful for biomedical applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interaction between U/UO2 bilayers and hydrogen studied by in-situ X-ray diffraction

NASA Astrophysics Data System (ADS)

Darnbrough, J. E.; Harker, R. M.; Griffiths, I.; Wermeille, D.; Lander, G. H.; Springell, R.

2018-04-01

This paper reports experiments investigating the reaction of H2 with uranium metal-oxide bilayers. The bilayers consist of ≤ 100 nm of epitaxial α-U (grown on a Nb buffer deposited on sapphire) with a UO2 overlayer of thicknesses of between 20 and 80 nm. The oxides were made either by depositing via reactive magnetron sputtering, or allowing the uranium metal to oxidise in air at room temperature. The bilayers were exposed to hydrogen, with sample temperatures between 80 and 200 C, and monitored via in-situ x-ray diffraction and complimentary experiments conducted using Scanning Transmission Electron Microscopy - Electron Energy Loss Spectroscopy (STEM-EELS). Small partial pressures of H2 caused rapid consumption of the U metal and lead to changes in the intensity and position of the diffraction peaks from both the UO2 overlayers and the U metal. There is an orientational dependence in the rate of U consumption. From changes in the lattice parameter we deduce that hydrogen enters both the oxide and metal layers, contracting the oxide and expanding the metal. The air-grown oxide overlayers appear to hinder the H2-reaction up to a threshold dose, but then on heating from 80 to 140 C the consumption is more rapid than for the as-deposited overlayers. STEM-EELS establishes that the U-hydride layer lies at the oxide-metal interface, and that the initial formation is at defects or grain boundaries, and involves the formation of amorphous and/or nanocrystalline UH3. This explains why no diffraction peaks from UH3 are observed.

High rate buffer layer for IBAD MgO coated conductors

DOEpatents

Foltyn, Stephen R [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM; Arendt, Paul N [Los Alamos, NM

2007-08-21

Articles are provided including a base substrate having a layer of an oriented material thereon, and, a layer of hafnium oxide upon the layer of an oriented material. The layer of hafnium oxide can further include a secondary oxide such as cerium oxide, yttrium oxide, lanthanum oxide, scandium oxide, calcium oxide and magnesium oxide. Such articles can further include thin films of high temperature superconductive oxides such as YBCO upon the layer of hafnium oxide or layer of hafnium oxide and secondary oxide.

Influence of Gas Atmosphere Dew Point on the Selective Oxidation and the Reactive Wetting During Hot Dip Galvanizing of CMnSi TRIP Steel

NASA Astrophysics Data System (ADS)

Cho, Lawrence; Lee, Seok Jae; Kim, Myung Soo; Kim, Young Ha; De Cooman, Bruno C.

2013-01-01

The selective oxidation and reactive wetting of intercritically annealed Si-bearing CMnSi transformation-induced plasticity steels were investigated by high-resolution transmission electron microscopy. In a N2 + 10 pct H2 gas atmosphere with a dew point (DP) ranging from 213 K to 278 K (-60 °C to 5 °C), a continuous layer of selective oxides was formed on the surface. Annealing in a higher DP gas atmosphere resulted in a thinner layer of external oxidation and a greater depth of internal oxidation. The hot dipping was carried out in a Zn bath containing 0.22 mass pct Al, and the bath temperature was 733 K (460 °C). Coarse and discontinuous Fe2Al5- x Zn x grains and Fe-Zn intermetallics (ζ and δ) were observed at the steel/coating interface after the hot dip galvanizing (HDG) of panels were annealed in a low DP atmosphere 213 K (-60 °C). The Fe-Zn intermetallics were formed both in areas where the Fe2Al5- x Zn x inhibition layer had not been formed and on top of non-stoichiometric Fe-Al-Zn crystals. Poor wetting was observed on panels annealed in a low DP atmosphere because of the formation of thick film-type oxides on the surface. After annealing in higher DP gas atmospheres, i.e., 263 K and 278 K (-10 °C and 5 °C), a continuous and fine-grained Fe2Al5- x Zn x layer was formed. No Fe-Zn intermetallics were formed. The small grain size of the inhibition layer was attributed to the nucleation of the Fe2Al5- x Zn x grains on small ferrite sub-surface grains and the presence of granular surface oxides. A high DP atmosphere can therefore significantly contribute to the decrease of Zn-coating defects on CMnSi TRIP steels processed in HDG lines.

Secondary Fe- and Mn-Oxides Associated with Faults Near Moab, Utah: Records of Past Fluid Flow

NASA Astrophysics Data System (ADS)

Garcia, V. H.; Reiners, P. W.

2015-12-01

Secondary Fe- and Mn-oxides are locally common near faults and fractures, and as cements within sandstones of the Colorado Plateau, and provide evidence of past fluid-flow. Here we describe textural, mineralogic, and geochronologic observations from fault-zone Fe- and Mn-oxide mineralization in Flat Iron Mesa, near Moab, Utah. Several hypotheses have been proposed for their origin, including reactions associated with the mixing of deep reduced and near-surface oxygenated waters. We integrate field observations, detailed SEM and petrographic observations, geochemical models, (U-Th)/He and Ar/Ar dating, and other data to develop interpretations of the formation of these deposits. SEM imaging shows that sandstone matrix cement adjacent to the faults follows two precipitation sequences: Fe-oxide followed by barite and Fe-oxide followed by Mn-oxide. Dense oxide layers also accumulated in cm-scale fractures near faults, and show the following precipitation sequence: Fe-oxide, barite, Ba rich Mn-oxide, and pure Mn-oxide. The latter sequence is observed at larger scale across faults in one site in Flat Iron Mesa. Our new He dates for Mn-oxides are 1.7-2.9 Ma while Fe-oxide dates are 2.7-3.0 Ma. If these dates represent formation ages, they are consistent with the interpreted precipitation sequence but would require protracted mineralization over Ma-timescales. Alternatively, they may represent varying degrees of He retentivity in earlier formed deposits. Previous Ar/Ar dates have been interpreted as a 20-25 Ma formation age. Ongoing Ar/Ar and He diffusion studies will resolve this discordance. Assuming the previous Ar dates do not reflect contamination by detrital K-bearing phases and do reflect oxide formation, potential interpretations for the younger He ages include recent U-Th addition, recrystallization, later oxide growth, or large diffusive He loss at low temperatures.

Engineering of highly ordered TiO2 nanopore arrays by anodization

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

Detection of thermally grown oxides in thermal barrier coatings by nondestructive evaluation

NASA Astrophysics Data System (ADS)

Fahr, A.; Rogé, B.; Thornton, J.

2006-03-01

The thermal-barrier coatings (TBC) sprayed on hot-section components of aircraft turbine engines commonly consist of a partially stabilized zirconia top-coat and an intermediate bond-coat applied on the metallic substrate. The bond-coat is made of an aluminide alloy that at high engine temperatures forms thermally grown oxides (TGO). Although formation of a thin layer of aluminum oxide at the interface between the ceramic top-coat and the bond-coat has the beneficial effect of protecting the metallic substrate from hot gases, oxide formation at splat boundaries or pores within the bond-coat is a source of weakness. In this study, plasma-sprayed TBC specimens are manufactured from two types of bond-coat powders and exposed to elevated temperatures to form oxides at the ceramic-bond-coat boundary and within the bond-coat. The specimens are then tested using nondestructive evaluation (NDE) and destructive metallography and compared with the as-manufactured samples. The objective is to determine if NDE can identify the oxidation within the bond-coat and give indication of its severity. While ultrasonic testing can provide some indication of the degree of bond-coat oxidation, the eddy current (EC) technique clearly identifies severe oxide formation within the bond-coat. Imaging of the EC signals as the function of probe location provides information on the spatial variations in the degree of oxidation, and thereby identifies which components or areas are prone to premature damage.

The influence of heat treatment and plastic deformation on the bio-degradation of a Mg-Y-RE alloy.

PubMed

Gunde, Petra; Furrer, Angela; Hänzi, Anja C; Schmutz, Patrik; Uggowitzer, Peter J

2010-02-01

In this study the bio-degradation behavior of a Mg-Y-RE alloy in different heat treatment states with respect to the alloy's potential application as biodegradable implant material was investigated by electrochemical impedance spectroscopy in two body-similar fluids. The heat treatments increase the degradation resistance of the alloy and lead to the formation of a thermal oxide layer on the sample surface and to a change in microstructure such as the distribution of yttrium. The varying Y distribution in the alloy does not significantly influence the degradation behavior, and all samples show a similar low polarization resistance. However, samples with a thermal oxide layer, which consists mainly of Y(2)O(3), degrade much more slowly and feature remarkably high polarization resistance. Nevertheless, in some cases localized corrosion attack occurs and drastically impairs performance. Cracks in the oxide layer, intentionally induced by straining of the samples and which in practice could originate from the implantation process, reduce the corrosion resistance. However, these samples perform still better than polished specimens and show a macroscopically homogeneous degradation behavior without localized corrosion. Microscopically, corrosion attacks start at the cracks and undermining of the oxide layer occurs with time. For all the material conditions a remarkable dependence of the degradation rate on the electrolyte is noted. (c) 2009 Wiley Periodicals, Inc.

Effects of SiO 2 overlayer at initial growth stage of epitaxial Y 2O 3 film growth

NASA Astrophysics Data System (ADS)

Cho, M.-H.; Ko, D.-H.; Choi, Y. G.; Lyo, I. W.; Jeong, K.; Whang, C. N.

2000-12-01

We investigated the dependence of the Y 2O 3 film growth on Si surface at initial growth stage. The reflection high-energy electron diffraction, X-ray scattering, and atomic force microscopy showed that the film crystallinity and morphology strongly depended on whether Si surface contained O or not. In particular, the films grown on oxidized surfaces revealed significant improvement in crystallinity and surface smoothness. A well-ordered atomic structure of Y 2O 3 film was formed on 1.5 nm thick SiO 2 layer with the surface and interfacial roughness markedly enhanced, compared with the film grown on the clean Si surfaces. The epitaxial film on the oxidized Si surface exhibited extremely small mosaic structures at interface, while the film on the clean Si surface displayed an island-like growth with large mosaic structures. The nucleation sites for Y 2O 3 were provided by the reaction between SiO 2 and Y at the initial growth stage. The SiO 2 layer known to hinder crystal growth is found to enhance the nucleation of Y 2O 3, and provides a stable buffer layer against the silicide formation. Thus, the formation of the initial SiO 2 layer is the key to the high-quality epitaxial growth of Y 2O 3 on Si.

Influence of SrO substitution for CaO on the properties of bioactive glass S53P4.

PubMed

Massera, Jonathan; Hupa, Leena

2014-03-01

Commercial melt-quenched bioactive glasses consist of the oxides of silicon, phosphorus, calcium and sodium. Doping of the glasses with oxides of some other elements is known to affect their capability to support hydroxyapatite formation and thus bone tissue healing but also to modify their high temperature processing parameters. In the present study, the influence of gradual substitution of SrO for CaO on the properties of the bioactive glass S53P4 was studied. Thermal analysis and hot stage microscopy were utilized to measure the thermal properties of the glasses. The in vitro bioactivity and solubility was measured by immersing the glasses in simulated body fluid for 6 h to 1 week. The formation of silica rich and hydroxyapatite layers was assessed from FTIR spectra analysis and SEM images of the glass surface. Increasing substitution of SrO for CaO decreased all characteristic temperatures and led to a slightly stronger glass network. The initial glass dissolution rate increased with SrO content. Hydroxyapatite layer was formed on all glasses but on the SrO containing glasses the layer was thinner and contained also strontium. The results suggest that substituting SrO for CaO in S53P4 glass retards the bioactivity. However, substitution greater than 10 mol% allow for precipitation of a strontium substituted hydroxyapatite layer.

Direct formation of a current collector layer on a partially reduced graphite oxide film using sputter-assisted metal deposition to fabricate high-power micro-supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Byun, Segi; Yu, Jin

2016-03-01

When a reduced graphite oxide (RGO) freestanding film is fabricated on a supercapacitor cell via compression onto a current collector, there are gaps between the film and the current collector, even if the cell is carefully assembled. These gaps can induce increases in the electrical series resistance (ESR) of the cell, resulting in degradation of the cell's electrochemical performance. Here, to effectively reduce the ESR of the supercapacitor, metal sputtering deposition is introduced. This enables the direct formation of the current collector layer on a partially reduced GO (pRGO) film, the model system. Using metal sputtering, a nickel (Ni) layer with a thickness <1 μm can be created easily on one side of the pRGO film. Good electrical interconnection between the pRGO film and the current collector can be obtained using a Ni layer formed on the pRGO film. The pRGO film sustains its film form with high packing density (∼1.31 g cm-3). Furthermore, the Ni-sputtered pRGO film with optimized Ni thickness exhibits remarkable enhancement of its electrochemical performance. This includes a superior rate capability and semi-permanent cycle life compared with the untreated pRGO film. This is due to the significant decrease in the ESR of the film.

Actinide oxide photodiode and nuclear battery

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

Sykora, Milan; Usov, Igor

Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxidesmore » are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.« less

Computational Spectroscopy of Structured Carbon Nanotube Interfaces for Biochemical Sensing

DTIC Science & Technology

2010-04-01

oxidized layer of SiCh served as a diffusion barrier to prevent Pt silicide formation and was shown to aide the formation of well dispersed catalytic nano...Three types of fluorescent mi- crospheres (Fluospheres) from Invitrogen were tested. The fluorescent microspheres were prepared in a 10:1 solution with...spectral channels for a given pixel location. Carbon Nanotube Growth on Pt Sample preparation involved cleaving silicon (100) wafers to desired

Interface formation of epitaxial MgO/Co2MnSi(001) structures: Elemental segregation and oxygen migration

NASA Astrophysics Data System (ADS)

McFadden, Anthony; Wilson, Nathaniel; Brown-Heft, Tobias; Pennachio, Daniel; Pendharkar, Mihir; Logan, John A.; Palmstrøm, Chris J.

2017-12-01

The interface formation in epitaxial MgO /Co2MnSi (001) films was studied using in-situ X-ray photoelectron spectroscopy (XPS). MgO was deposited on single crystal Co2MnSi (001) layers using e-beam evaporation: a technique which is expected to oxidize the Co2MnSi layer somewhat due to the rise in oxygen partial pressure during MgO deposition while leaving the deposited MgO oxygen deficient. Not unexpectedly, we find that e-beam evaporation of MgO raises the oxygen background in the deposition chamber to a level that readily oxidizes the Co2MnSi surface, with oxygen bonding preferentially to Mn and Si over Co. Interestingly, this oxidation causes an elemental segregation, with Mn-Si effectively moving toward the surface, resulting in an MgO /Co2MnSi interface with a composition significantly differing from the original surface of the unoxidized Co2MnSi film. As MgO is deposited on the oxidized Co2MnSi , the Mn-oxides are reduced, while the Si oxide remains, and is only somewhat reduced after additional annealing in ultrahigh vacuum. Annealing after the MgO is grown on Co2MnSi causes oxygen to move away from the oxidized Co2MnSi interface toward the surface and into the MgO. This observation is consistent with an increase in the tunneling magnetoresistance ratio with post-growth annealing measured in fabricated magnetic tunnel junctions (MTJs). The findings are discussed in light of fabrication of MgO/Heusler based MTJs, where the exponential decay of tunneling probability with contact separation exemplifies the importance of the ferromagnet/tunnel barrier interface.

Functional Layer-by-Layer Thin Films of Inducible Nitric Oxide (NO) Synthase Oxygenase and Polyethylenimine: Modulation of Enzyme Loading and NO-Release Activity.

PubMed

Gunasekera, Bhagya; Abou Diwan, Charbel; Altawallbeh, Ghaith; Kalil, Haitham; Maher, Shaimaa; Xu, Song; Bayachou, Mekki

2018-03-07

Nitric oxide (NO) release counteracts platelet aggregation and prevents the thrombosis cascade in the inner walls of blood vessels. NO-release coatings also prevent thrombus formation on the surface of blood-contacting medical devices. Our previous work has shown that inducible nitric oxide synthase (iNOS) films release NO fluxes upon enzymatic conversion of the substrate l-arginine. In this work, we report on the modulation of enzyme loading in layer-by-layer (LbL) thin films of inducible nitric oxide synthase oxygenase (iNOSoxy) on polyethylenimine (PEI). The layer of iNOSoxy is electrostatically adsorbed onto the PEI layer. The pH of the iNOSoxy solution affects the amount of enzyme adsorbed. The overall negative surface charge of iNOSoxy in solution depends on the pH and hence determines the density of adsorbed protein on the positively charged PEI layer. We used buffered iNOSoxy solutions adjusted to pHs 8.6 and 7.0, while saline PEI solution was used at pH 7.0. Atomic force microscopy imaging of the outermost layer shows higher protein adsorption with iNOSoxy at pH 8.6 than with a solution of iNOSoxy at pH 7.0. Graphite electrodes with PEI/iNOSoxy films show higher catalytic currents for nitric oxide reduction mediated by iNOSoxy. The higher enzyme loading translates into higher NO flux when the enzyme-modified surface is exposed to a solution containing the substrate and a source of electrons. Spectrophotometric assays showed higher NO fluxes with iNOSoxy/PEI films built at pH 8.6 than with films built at pH 7.0. Fourier transform infrared analysis of iNOSoxy adsorbed on PEI at pH 8.6 and 7.0 shows structural differences of iNOSoxy in films, which explains the observed changes in enzymatic activity. Our findings show that pH provides a strategy to optimize the NOS loading and enzyme activity in NOS-based LbL thin films, which enables improved NO release with minimum layers of PEI/NOS.

Suppressed Sr segregation and performance of directly assembled La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode on Y2O3-ZrO2 electrolyte of solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Ai, Na; He, Shuai; Li, Na; Zhang, Qi; Rickard, William D. A.; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Active and stable oxygen electrode is probably the most important in the development of solid oxide electrolysis cells (SOECs) technologies. Herein, we report the successful development of mixed ionic and electronic conducting (MIEC) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) perovskite oxides directly assembled on barrier-layer-free yttria-stabilized zirconia (YSZ) electrolyte as highly active and stable oxygen electrodes of SOECs. Electrolysis polarization effectively induces the formation of electrode/electrolyte interface, similar to that observed under solid oxide fuel cell (SOFC) operation conditions. However, in contrast to the significant performance decay under SOFC operation conditions, the cell with directly assembled LSCF oxygen electrodes shows excellent stability, tested for 300 h at 0.5 A cm-2 and 750 °C under SOEC operation conditions. Detailed microstructure and phase analysis reveal that Sr segregation is inevitable for LSCF electrode, but anodic polarization substantially suppresses Sr segregation and migration to the electrode/electrolyte interface, leading to the formation of stable and efficient electrode/electrolyte interface for water and CO2 electrolysis under SOECs operation conditions. The present study demonstrates the feasibility of using directly assembled MIEC cobaltite based oxygen electrodes on barrier-layer-free YSZ electrolyte of SOECs.

Novel halogen chemistry in the marine boundary layer

NASA Astrophysics Data System (ADS)

Plane, J. M.; Saiz-Lopez, A.; Shillito, J. A.

2003-12-01

This paper will report the first observations of I2 in the marine boundary layer, made by Differential Optical Absorption (DOAS) spectroscopy during a field campaign at Mace Head (Ireland) in the summer of 2002. Very large I2 concentrations correlating with low tide indicate that the source is emission from macro-algae. Simple scaling suggests that this coastal emission could approach 2 Tg per year, making it a major contribution to the global iodine budget. During the same campaign, DOAS observations were also made of the halogen oxides IO, OIO and BrO. The pulses of IO and BrO that were measured at sunrise are strong evidence for heterogeneous processing on sea-salt aerosol producing high levels of IBr during the night. Simple modelling shows that the observed concentrations of the halogen radicals will play important roles in ozone depletion, the oxidation of dimethyl sulfide, and the formation of new particles in the marine boundary layer.

Effect of high-pressure H{sub 2}O treatment on elimination of interfacial GeO{sub X} layer between ZrO{sub 2} and Ge stack

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

Huang, Chen-Shuo; Liu, Po-Tsun

2011-08-22

This investigation demonstrates the effect of high-pressure H{sub 2}O treatment on the elimination of the interfacial germanium suboxide (GeO{sub X}) layer between ZrO{sub 2} and Ge. The formation of GeO{sub X} interlayer increases the gate-leakage current and worsen the controllability of the gate during deposition or thermal cycles. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy reveal that high-pressure H{sub 2}O treatment eliminates the interfacial GeO{sub X} layer. The physical mechanism involves the oxidation of non-oxidized Zr with H{sub 2}O and the reduction of GeO{sub X} by H{sub 2}. Treatment with H{sub 2}O reduces the gate-leakage current of a ZrO{submore » 2}/Ge capacitor by a factor of 1000.« less

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

Kephart, Jason M.; Kindvall, Anna; Williams, Desiree

Commercial CdTe PV modules have polycrystalline thin films deposited on glass, and devices made in this format have exceeded 22% efficiency. Devices made by the authors with a magnesium zinc oxide window layer and tellurium back contact have achieved efficiency over 18%, but these cells still suffer from an open-circuit voltage far below ideal values. Oxide passivation layers made by sputter deposition have the potential to increase voltage by reducing interface recombination. CdTe devices with these passivation layers were studied with photoluminescence (PL) emission spectroscopy and time-resolved photoluminescence (TRPL) to detect an increase in minority carrier lifetime. Because these oxidemore » materials exhibit barriers to carrier collection, micropatterning was used to expose small point contacts while still allowing interface passivation. TRPL decay lifetimes have been greatly enhanced for thin polycrystalline absorber films with interface passivation. Device performance was measured and current collection was mapped spatially by light-beam-induced current.« less

Surface electrical properties of stainless steel fibres: An AFM-based study

NASA Astrophysics Data System (ADS)

Yin, Jun; D'Haese, Cécile; Nysten, Bernard

2015-03-01

Atomic force microscopy (AFM) electrical modes were used to study the surface electrical properties of stainless steel fibres. The surface electrical conductivity was studied by current sensing AFM and I-V spectroscopy. Kelvin probe force microscopy was used to measure the surface contact potential. The oxide film, known as passivation layer, covering the fibre surface gives rise to the observation of an apparently semiconducting behaviour. The passivation layer generally exhibits a p-type semiconducting behaviour, which is attributed to the predominant formation of chromium oxide on the surface of the stainless steel fibres. At the nanoscale, different behaviours are observed from points to points, which may be attributed to local variations of the chemical composition and/or thickness of the passivation layer. I-V curves are well fitted with an electron tunnelling model, indicating that electron tunnelling may be the predominant mechanism for electron transport.

Petrography and trace element signatures in silicates and Fe-Ti-oxides from the Lanjiahuoshan deposit, Panzhihua layered intrusion, Southwest China

NASA Astrophysics Data System (ADS)

Gao, Wenyuan; Ciobanu, Cristiana L.; Cook, Nigel J.; Huang, Fei; Meng, Lin; Gao, Shang

2017-12-01

Permian mafic-ultramafic layered intrusions in the central part of the Emeishan Large Igneous Province (ELIP), Southwestern China, host Fe-Ti-V-oxide ores that have features which distinguish them from other large layered intrusion-hosted deposits. The origin of these ores is highly debated. Careful petrographic examination, whole rock analysis, electron probe microanalysis, and measurement and mapping of trace element concentrations by laser ablation inductively coupled plasma mass spectrometry in all major and minor minerals (clinopyroxene, plagioclase, olivine, amphibole, titanomagnetite, ilmenite, pleonaste and pyrrhotite) has been undertaken on samples from the Lanjiahuoshan deposit, representing the Middle, Lower and Marginal Zone of the Panzhihua intrusion. Features are documented that impact on interpretation of intrusion petrology and with implications for genesis of the Fe-Ti-V-oxide ores. Firstly, there is evidence, as symplectites between clinopyroxene and plagioclase, for introduction of complex secondary melts. Secondly, reaction between a late hydrothermal fluid and clinopyroxene is recognized, which has led to formation of hydrated minerals (pargasite, phlogopite), as well as a potassium metasomatic event, postdating intrusion solidification, which led to formation of K-feldspar. Lastly, partitioning of trace elements between titanomagnetite and silicates needs to consider scavenging of metals by ilmenite (Mn, Sc, Zr, Nb, Sn, Hf and Ta) and sulfides, as well as the marked partitioning of Co, Ni, Zn, Ga, As and Sb into spinels exsolved from titanomagnetite. The role of these less abundant phases may have been understated in previous studies, highlighting the importance of petrographic examination of complex silicate-oxide-sulfide assemblages, as well as the need for a holistic approach to trace element analysis, acknowledging all minerals within the assemblage.

Materials Challenges and Opportunities of Lithium-ion Batteries for Electrical Energy Storage

NASA Astrophysics Data System (ADS)

Manthiram, Arumugam

2011-03-01

Electrical energy storage has emerged as a topic of national and global importance with respect to establishing a cleaner environment and reducing the dependence on foreign oil. Batteries are the prime candidates for electrical energy storage. They are the most viable near-term option for vehicle applications and the efficient utilization of intermittent energy sources like solar and wind. Lithium-ion batteries are attractive for these applications as they offer much higher energy density than other rechargeable battery systems. However, the adoption of lithium-ion battery technology for vehicle and stationary storage applications is hampered by high cost, safety concerns, and limitations in energy, power, and cycle life, which are in turn linked to severe materials challenges. This presentation, after providing an overview of the current status, will focus on the physics and chemistry of new materials that can address these challenges. Specifically, it will focus on the design and development of (i) high-capacity, high-voltage layered oxide cathodes, (ii) high-voltage, high-power spinel oxide cathodes, (iii) high-capacity silicate cathodes, and (iv) nano-engineered, high-capacity alloy anodes. With high-voltage cathodes, a critical issue is the instability of the electrolyte in contact with the highly oxidized cathode surface and the formation of solid-electrolyte interfacial (SEI) layers that degrade the performance. Accordingly, surface modification of cathodes with nanostructured materials and self-surface segregation during the synthesis process to suppress SEI layer formation and enhance the energy, power, and cycle life will be emphasized. With the high-capacity alloy anodes, a critical issue is the huge volume change occurring during the charge-discharge process and the consequent poor cycle life. Dispersion of the active alloy nanoparticles in an inactive metal oxide-carbon matrix to mitigate this problem and realize long cycle life will be presented.

Thermal behavior and catalytic activity in naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium

NASA Astrophysics Data System (ADS)

Vasilyeva, Marina S.; Rudnev, Vladimir S.; Wiedenmann, Florian; Wybornov, Svetlana; Yarovaya, Tatyana P.; Jiang, Xin

2011-11-01

The present paper is devoted to studies of the composition and surface structure, including those after annealing at high temperatures, and catalytic activity in the reaction of naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium obtained by means of the plasma electrolytic oxidation (PEO) method. The composition and structure of the obtained systems were investigated using the methods of X-ray phase and energy dispersive analysis and scanning electron microscopy (SEM). It was demonstrated that Ce- and Zr- containing structures had relatively high thermal stability: their element and phase compositions and surface structure underwent virtually no changes after annealing in the temperature range 600-800 °C. Annealing of Ce- and Zr-containing coatings in the temperature range 850-900 °C resulted in substantial changes of their surface composition and structure: a relatively homogeneous and porous surface becomes coated by large pole-like crystals. The catalytic studies showed rather high activity of Ce- and Zr-containing coatings in the reaction of naphthalene destruction at temperatures up to 850 °C. Mn-containing structures of the type MnOx + SiO2 + TiO2/Ti have a well-developed surface coated by “nano-whiskers”. The phase composition and surface structure of manganese-containing layers changes dramatically in the course of thermal treatment. After annealing above 600 °C nano-whiskers vanish with formation of molten structures on the surface. The Mn-containing oxide systems demonstrated lower conversion degrees than the Ce- and Zr-containing coatings, which can be attributed to substantial surface modification and formation of molten manganese silicates at high temperatures.

Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Zhang, Yijun; Liu, Ming; Peng, Bin; Zhou, Ziyao; Chen, Xing; Yang, Shu-Ming; Jiang, Zhuang-De; Zhang, Jie; Ren, Wei; Ye, Zuo-Guang

2016-01-01

Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe3O4 with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. The ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.

Atomic layer deposition of Al{sub 2}O{sub 3} for single electron transistors utilizing Pt oxidation and reduction

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

McConnell, Michael S., E-mail: mmcconn5@nd.edu; Schneider, Louisa C.; Karbasian, Golnaz

This work describes the fabrication of single electron transistors using electron beam lithography and atomic layer deposition to form nanoscale tunnel transparent junctions of alumina (Al{sub 2}O{sub 3}) on platinum nanowires using either water or ozone as the oxygen precursor and trimethylaluminum as the aluminum precursor. Using room temperature, low frequency conductance measurements between the source and drain, it was found that devices fabricated using water had higher conductance than devices fabricated with ozone. Subsequent annealing caused both water- and ozone-based devices to increase in conductance by more than 2 orders of magnitude. Furthermore, comparison of devices at low temperaturesmore » (∼4 K) showed that annealed devices displayed much closer to the ideal behavior (i.e., constant differential conductance) outside of the Coulomb blockade region and that untreated devices showed nonlinear behavior outside of the Coulomb blockade region (i.e., an increase in differential conductance with source-drain voltage bias). Transmission electron microscopy cross-sectional images showed that annealing did not significantly change device geometry, but energy dispersive x-ray spectroscopy showed an unusually large amount of oxygen in the bottom platinum layer. This suggests that the atomic layer deposition process results in the formation of a thin platinum surface oxide, which either decomposes or is reduced during the anneal step, resulting in a tunnel barrier without the in-series native oxide contribution. Furthermore, the difference between ozone- and water-based devices suggests that ozone promotes atomic layer deposition nucleation by oxidizing the surface but that water relies on physisorption of the precursors. To test this theory, devices were exposed to forming gas at room temperature, which also reduces platinum oxide, and a decrease in resistance was observed, as expected.« less

Unsupported single-atom-thick copper oxide monolayers

NASA Astrophysics Data System (ADS)

Yin, Kuibo; Zhang, Yu-Yang; Zhou, Yilong; Sun, Litao; Chisholm, Matthew F.; Pantelides, Sokrates T.; Zhou, Wu

2017-03-01

Oxide monolayers may present unique opportunities because of the great diversity of properties of these materials in bulk form. However, reports on oxide monolayers are still limited. Here we report the formation of single-atom-thick copper oxide layers with a square lattice both in graphene pores and on graphene substrates using aberration-corrected scanning transmission electron microscopy. First-principles calculations find that CuO is energetically stable and its calculated lattice spacing matches well with the measured value. Furthermore, free-standing copper oxide monolayers are predicted to be semiconductors with band gaps ˜3 eV. The new wide-bandgap single-atom-thick copper oxide monolayers usher a new frontier to study the highly diverse family of two-dimensional oxides and explore their properties and their potential for new applications.

The friction and wear properties of sputtered hard refractory compounds

NASA Technical Reports Server (NTRS)

Brainard, W. A.

1978-01-01

Several refractory silicide, boride, and carbide coatings were examined. The coatings were applied to type 440C steel surfaces by radio-frequency sputtering. The friction and wear properties of the coatings were found to be related to stoichiometry and impurity content of the bulk coating as well as the degree of interfacial adherence between coating and substrate. Bulk coating stoichiometry could to a large extent be controlled by the application of a negative bias voltage during deposition. Adherence was promoted by the formation of an oxidized layer at the interface. Deliberate preoxidizing of the 440C produced enhanced adherence for many compounds which are related to the formation of a mixed oxide transition region.

Thermally Stable Silver Nanowires-Embedding Metal Oxide for Schottky Junction Solar Cells.

PubMed

Kim, Hong-Sik; Patel, Malkeshkumar; Park, Hyeong-Ho; Ray, Abhijit; Jeong, Chaehwan; Kim, Joondong

2016-04-06

Thermally stable silver nanowires (AgNWs)-embedding metal oxide was applied for Schottky junction solar cells without an intentional doping process in Si. A large scale (100 mm(2)) Schottky solar cell showed a power conversion efficiency of 6.1% under standard illumination, and 8.3% under diffused illumination conditions which is the highest efficiency for AgNWs-involved Schottky junction Si solar cells. Indium-tin-oxide (ITO)-capped AgNWs showed excellent thermal stability with no deformation at 500 °C. The top ITO layer grew in a cylindrical shape along the AgNWs, forming a teardrop shape. The design of ITO/AgNWs/ITO layers is optically beneficial because the AgNWs generate plasmonic photons, due to the AgNWs. Electrical investigations were performed by Mott-Schottky and impedance spectroscopy to reveal the formation of a single space charge region at the interface between Si and AgNWs-embedding ITO layer. We propose a route to design the thermally stable AgNWs for photoelectric device applications with investigation of the optical and electrical aspects.

Positron annihilation on the surfaces of SiO 2 films thermally grown on single crystal of Cz-Si

NASA Astrophysics Data System (ADS)

Deng, Wen; Yue, Li; Zhang, Wei; Cheng, Xu-xin; Zhu, Yan-yan; Huang, Yu-yang

2009-09-01

Two-detector coincidence system and mono-energetic slow positron beam has been applied to measure the Doppler broadening spectra for single crystals of SiO2, SiO2 films with different thickness thermally grown on single crystal of Cz-Si, and single crystal of Si without oxide film. Oxygen is recognized as a peak at about 11.85 × 10-3m0c on the ratio curves. The S parameters decrease with the increase of positron implantation energy for the single crystal of SiO2 and Si without oxide film. However, for the thermally grown SiO2-Si sample, the S parameters in near surface of the sample increase with positron implantation energy. It is due to the formation of silicon oxide at the surface, which lead to lower S value. S and W parameters vary with positron implantation depth indicate that the SiO2-Si system consist of a surface layer, a SiO2 layer, a SiO2-Si interface layer and a semi-infinite Si substrate.

The effect of a Ta oxygen scavenger layer on HfO 2-based resistive switching behavior: Thermodynamic stability, electronic structure, and low-bias transport

DOE PAGES

Zhong, Xiaoliang; Rungger, Ivan; Zapol, Peter; ...

2016-02-15

Reversible resistive switching between high-resistance and low-resistance states in metal-oxide-metal heterostructures makes them very interesting for applications in random access memories. While recent experimental work has shown that inserting a metallic "oxygen scavenger layer'' between the positive electrode and oxide improves device performance, the fundamental understanding of how the scavenger layer modifies the heterostructure properties is lacking. We use density functional theory to calculate thermodynamic properties and conductance of TiN/HfO 2/TiN heterostructures with and without a Ta scavenger layer. First, we show that Ta insertion lowers the formation energy of low-resistance states. Second, while the Ta scavenger layer reduces themore » Schottky barrier height in the high-resistance state by modifying the interface charge at the oxide-electrode interface, the heterostructure maintains a high resistance ratio between high-and low-resistance states. Lastly, we show that the low-bias conductance of device on-states becomes much less sensitive to the spatial distribution of oxygen removed from the HfO 2 in the presence of the Ta layer. By providing a fundamental understanding of the observed improvements with scavenger layers, we open a path to engineer interfaces with oxygen scavenger layers to control and enhance device performance. In turn, this may enable the realization of a non-volatile low-power memory technology with concomitant reduction in energy consumption by consumer electronics and offering significant benefits to society.« less

Structural characterization of Co100-xFex nano-oxide layer

NASA Astrophysics Data System (ADS)

Endo, Hiroaki; Doi, Masaaki; Hasegawa, Naoya; Sahashi, Masashi

2006-04-01

For the structural characterization of a Co100-xFex nano-oxide layer (NOL), the exchange bias properties of the Co100-xFex-natural oxidized NOL in the specular spin-valve (SPSV) system were investigated. The exchange bias energy (Jex) increased monotonically with the increasing Fe content for the Co100-xFex-NOL. The enhancement of both the magnetoresistance ratio and the exchange bias field (Hex) was realized by increasing the Fe content in the Co100-xFex-NOL. It should be mentioned that Hex more than 800 Oe is obtained by the insertion of Co30Fe70-NOL, even in NOL-SPSV, which is a remarkably higher pinning field than that ever reported on IrMn-SV. This high exchange bias field is considered to be realized by the formation of an Fe-rich fcc phase at the interface of IrMn.

CO2-Assisted Conversion of Crystal Two-Dimensional Molybdenum Oxide to Amorphism with Plasmon Resonances.

PubMed

Liu, Wei; Xu, Qun

2018-04-20

Localized surface plasmon resonances (LSPRs) of ultra-thin two-dimensional (2D) nanomaterials opened a new regime in plasmonics in the last several years. 2D plasmonic materials are yet concentrated on the crystal structure, amorphous materials are hardly reported because of their limited preparation methods rather than undesired plasmonic properties. Taking molybdenum oxides as an example, herein, we elaborate the 2D amorphous plasmons prepared with the assistance of supercritical CO2. In brief, we examine the reported characteristic plasmonic properties of molybdenum oxides, and applications of supercritical CO2 in formations of 2D layer materials as well as introduced phase and disorder engineering based on our researchs. Furthermore, we propose our perspective on the development of 2D plasmons, especially for amorphous layer materials in the future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Dopants to Tune Oxygen Vacancy Formation in Transition Metal Oxide Resistive Memory.

PubMed

Jiang, Hao; Stewart, Derek A

2017-05-17

Introducing dopants is an important way to tailor and improve electronic properties of transition metal oxides used as high-k dielectric thin films and resistance switching layers in leading memory technologies, such as dynamic and resistive random access memory (ReRAM). Ta 2 O 5 has recently received increasing interest because Ta 2 O 5 -based ReRAM demonstrates high switching speed, long endurance, and low operating voltage. However, advances in optimizing device characteristics with dopants have been hindered by limited and contradictory experiments in this field. We report on a systematic study on how various metal dopants affect oxygen vacancy formation in crystalline and amorphous Ta 2 O 5 from first principles. We find that isoelectronic dopants and weak n-type dopants have little impact on neutral vacancy formation energy and that p-type dopants can lower the formation energy significantly by introducing holes into the system. In contrast, n-type dopants have a deleterious effect and actually increase the formation energy for charged oxygen vacancies. Given the similar doping trend reported for other binary transition metal oxides, this doping trend should be universally valid for typical binary transition metal oxides. Based on this guideline, we propose that p-type dopants (Al, Hf, Zr, and Ti) can lower the forming/set voltage and improve retention properties of Ta 2 O 5 ReRAM.

High power density solid oxide fuel cells

DOEpatents

Pham, Ai Quoc; Glass, Robert S.

2004-10-12

A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O (LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

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

Cats, K. H.; Andrews, J. C.; Stephan, O.

In this study, the Fischer-Tropsch synthesis (FTS) reaction is one of the most promising processes to convert alternative energy sources, such as natural gas, coal or biomass, into liquid fuels and other high-value products. Despite its commercial implementation, we still lack fundamental insights into the various deactivation processes taking place during FTS. In this work, a combination of three methods for studying single catalyst particles at different length scales has been developed and applied to study the deactivation of Co/TiO 2 Fischer-Tropsch synthesis (FTS) catalysts. By combining transmission X-ray microscopy (TXM), scanning transmission X-ray microscopy (STXM) and scanning transmission electronmore » microscopy-electron energy loss spectroscopy (STEM-EELS) we visualized changes in the structure, aggregate size and distribution of supported Co nanoparticles that occur during FTS. At the microscale, Co nanoparticle aggregates are transported over several μm leading to a more homogeneous Co distribution, while at the nanoscale Co forms a thin layer of ~1-2 nm around the TiO 2 support. The formation of the Co layer is the opposite case to the “classical” strong metal-support interaction (SMSI) in which TiO 2 surrounds the Co, and is possibly related to the surface oxidation of Co metal nanoparticles in combination with coke formation. In other words, the observed migration and formation of a thin CoO x layer are similar to a previously discussed reaction-induced spreading of metal oxides across a TiO 2 surface.« less

Remote catalyzation for direct formation of graphene layers on oxides.

PubMed

Teng, Po-Yuan; Lu, Chun-Chieh; Akiyama-Hasegawa, Kotone; Lin, Yung-Chang; Yeh, Chao-Hui; Suenaga, Kazu; Chiu, Po-Wen

2012-03-14

Direct deposition of high-quality graphene layers on insulating substrates such as SiO(2) paves the way toward the development of graphene-based high-speed electronics. Here, we describe a novel growth technique that enables the direct deposition of graphene layers on SiO(2) with crystalline quality potentially comparable to graphene grown on Cu foils using chemical vapor deposition (CVD). Rather than using Cu foils as substrates, our approach uses them to provide subliming Cu atoms in the CVD process. The prime feature of the proposed technique is remote catalyzation using floating Cu and H atoms for the decomposition of hydrocarbons. This allows for the direct graphitization of carbon radicals on oxide surfaces, forming isolated low-defect graphene layers without the need for postgrowth etching or evaporation of the metal catalyst. The defect density of the resulting graphene layers can be significantly reduced by tuning growth parameters such as the gas ratios, Cu surface areas, and substrate-to-Cu distance. Under optimized conditions, graphene layers with nondiscernible Raman D peaks can be obtained when predeposited graphite flakes are used as seeds for extended growth. © 2012 American Chemical Society

Synthesis, characterization, and evaluation of simple aluminum-based adsorbents for fluoride removal from drinking water.

PubMed

Du, Junyi; Sabatini, David A; Butler, Elizabeth C

2014-04-01

Simple aluminum (hydr)oxides and layered double hydroxides were synthesized using common chemicals and equipment by varying synthesis temperature, concentrations of extra sulfate and citrate, and metal oxide amendments. Aluminum (hydr)oxide samples were aged at either 25 or 200°C during synthesis and, in some cases, calcined at 600 °C. Despite yielding increased crystallinity and mineral phase changes, higher temperatures had a generally negative effect on fluoride adsorption. Addition of extra sulfate during synthesis of aluminum (hydr)oxides led to significantly higher fluoride adsorption capacity compared to aluminum (hydr)oxides prepared with extra citrate or no extra ligands. X-ray diffraction results suggest that extra sulfate led to the formation of both pseudoboehmite (γ-AlOOH) and basaluminite (Al4SO4(OH)10⋅4H2O) at 200 °C; energy dispersive X-ray spectroscopy confirmed the presence of sulfur in this solid. Treatment of aluminum (hydr)oxides with magnesium, manganese, and iron oxides did not significantly impact fluoride adsorption. While layered double hydroxides exhibited high maximum fluoride adsorption capacities, their adsorption capacities at dissolved fluoride concentrations close to the World Health Organization drinking water guideline of 1.5 mg L(-1) were much lower than those for the aluminum (hydr)oxides. Copyright © 2013 Elsevier Ltd. All rights reserved.

High-voltage SPM oxidation of ZrN: materials for multiscale applications

NASA Astrophysics Data System (ADS)

Farkas, N.; Comer, J. R.; Zhang, G.; Evans, E. A.; Ramsier, R. D.; Dagata, J. A.

2005-02-01

Scanning probe microscope (SPM) oxidation was used to form zirconium oxide features on 200 nm thick ZrN films. The features exhibit rapid yet controlled growth kinetics, even in contact mode with 70 V dc applied between the probe tip and substrate. The features grown for times longer than 10 s are higher than 200 nm, and reach more than 1000 nm in height after 300 s. Long-time oxidation experiments and selective etching of the oxides and nitrides lead us to propose that as the oxidation reaches the silicon substrate, delamination occurs with the simultaneous formation of a thin layer of new material at the ZrN/Si interface. High-voltage oxide growth on ZrN is fast and sustainable, and the robust oxide features are promising candidates for multiscale (nanometre-to-micrometre) applications.

Studies of electrochemical oxidation of Zircaloy nuclear reactor fuel cladding using time-of-flight-energy elastic recoil detection analysis

NASA Astrophysics Data System (ADS)

Whitlow, H. J.; Zhang, Y.; Wang, Y.; Winzell, T.; Simic, N.; Ahlberg, E.; Limbäck, M.; Wikmark, G.

2000-03-01

The trend towards increased fuel burn-up and higher operating temperatures in order to achieve more economic operation of nuclear power plants places demands on a better understanding of oxidative corrosion of Zircaloy (Zry) fuel rod cladding. As part of a programme to study these processes we have applied time-of-flight-energy elastic recoil detection (ToF-E ERD), electrochemical impedance measurements and scanning electron microscopy to quantitatively characterise thin-oxide films corresponding to the pre-transition oxidation regime. Oxide films of different nominal thickness in the 9-300 nm range were grown on a series of rolled Zr and Zry-2 plates by anodisation in dilute H 2SO 4 with applied voltages. The dielectric thickness of the oxide layer was determined from the electrochemical impedance measurements and the surface topography characterised by scanning electron microscopy. ToF-E ERD with a 60 MeV 127I 11+ ion beam was used to determine the oxygen content and chemical composition of the oxide layer. In the Zr samples, the oxygen content (O atom cm -2) that was determined by ERD was closely similar to the O content derived from impedance measurements from the dielectric film. The absolute agreement was well within the uncertainty associated with the stopping powers. Moreover, the measured composition of the thick oxide layers corresponded to ZrO 2 for the films thicker than 65 nm where the oxide layer was resolved in the ERD depth profile. Zry-2 samples exhibited a similar behaviour for small thickness ( ⩽130 nm) but had an enhanced O content at larger thicknesses that could be associated either with enhanced rough surface topography or porous oxide formation that was correlated with the presence of Second Phase Particles (SPP) in Zry-2. The concentration of SPP elements (Fe, Cr, Ni) in relation to Zr was the same in the outer 9×10 17 atom cm -2 of oxide as in the same thickness of metal. The results also revealed the presence of about 1 at.% 32S in the oxides on the Zr and Zry-2 samples which presumably originates from the electrolyte.

Characteristics of Reduced Graphene Oxide Quantum Dots for a Flexible Memory Thin Film Transistor.

PubMed

Kim, Yo-Han; Lee, Eun Yeol; Lee, Hyun Ho; Seo, Tae Seok

2017-05-17

Reduced graphene oxide quantum dot (rGOQD) devices in formats of capacitor and thin film transistor (TFT) were demonstrated and examined as the first trial to achieve nonambipolar channel property. In addition, through a gold nanoparticle (Au NP) layer embedded between the rGOQD active channel and dielectric layer, memory capacitor and TFT performances were realized by capacitance-voltage (C-V) hysteresis and gate program, erase, and reprogram biases. First, capacitor structure of the rGOQD memory device was constructed to examine memory charging effect featured in hysteretic C-V behavior with a 30 nm dielectric layer of cross-linked poly(vinyl alcohol). For the intervening Au NP charging layer, self-assembled monolayer (SAM) formation of the Au NP was executed to utilize electrostatic interaction by a dip-coating process under ambient environments with a conformal fabrication uniformity. Second, the rGOQD memory TFT device was also constructed in the same format of the Au NPs SAMs on a flexible substrate. Characteristics of the rGOQD TFT output showed novel saturation curves unlike typical graphene-based TFTs. However, The rGOQD TFT device reveals relatively low on/off ratio of 10 1 and mobility of 5.005 cm 2 /V·s. For the memory capacitor, the flat-band voltage shift (ΔV FB ) was measured as 3.74 V for ±10 V sweep, and for the memory TFT, the threshold voltage shift (ΔV th ) by the Au NP charging was detected as 7.84 V. In summary, it was concluded that the rGOQD memory device could accomplish an ideal graphene-based memory performance, which could have provided a wide memory window and saturated output characteristics.

Endothelium as a Potential Target for Treatment of Abdominal Aortic Aneurysm

PubMed Central

Sun, Jingyuan; Deng, Hongping; Zhou, Zhen

2018-01-01

Abdominal aortic aneurysm (AAA) was previously ascribed to weaken defective medial arterial/adventitial layers, for example, smooth muscle/fibroblast cells. Therefore, besides surgical repair, medications targeting the medial layer to strengthen the aortic wall are the most feasible treatment strategy for AAA. However, so far, it is unclear whether such drugs have any beneficial effect on AAA prognosis, rate of aneurysm growth, rupture, or survival. Notably, clinical studies have shown that AAA is highly associated with endothelial dysfunction in the aged population. Additionally, animal models of endothelial dysfunction and endothelial nitric oxide synthase (eNOS) uncoupling had a very high rate of AAA formation, indicating there is crucial involvement of the endothelium and a possible pharmacological solution targeting the endothelium in AAA treatment. Endothelial cells have been found to trigger vascular wall remodeling by releasing proteases, or recruiting macrophages along with other neutrophils, into the medial layer. Moreover, inflammation and oxidative stress of the arterial wall were induced by endothelial dysfunction. Interestingly, there is a paradoxical differential correlation between diabetes and aneurysm formation in retinal capillaries and the aorta. Deciphering the significance of such a difference may explain current unsuccessful AAA medications and offer a solution to this treatment challenge. It is now believed that AAA and atherosclerosis are two separate but related diseases, based on their different clinical patterns which have further complicated the puzzle. Therefore, a thorough investigation of the interaction between endothelium and medial/adventitial layer may provide us a better understanding and new perspective on AAA formation, especially after taking into account the importance of endothelium in the development of AAA. Moreover, a novel medication strategy replacing the currently used, but suboptimal treatments for AAA, could be informed with this analysis. PMID:29849906

Arsenic silicide formation by oxidation of arsenic implanted silicon

NASA Astrophysics Data System (ADS)

Hagmann, D.; Euen, W.; Schorer, G.; Metzger, G.

1989-07-01

Wet oxidations of (100) silicon implanted with an arsenic dose of 2 × 1016 cm-2 and an energy of 30 keV were carried out in the temperature range between 600 and 900° C. The oxidation rate is increased on the arsenic implanted samples up to a factor of 2000 as compared to undoped samples. During these oxidations the arsenic suicide phase AsSi is precipitated at the oxide/silicon interface. After short oxidation times at 600° C, a continuous AsSi layer is found. It is dissolved during extended oxidation times and finally almost all As is incorporated in the oxide. After 900° C oxidations, substantial AsSi crystallites remain at the Si/SiO2 interface. They are still observed up to the larg-est oxide thickness grown (2.3 µm). The AsSi phase and the distribution of the im-planted arsenic were analyzed by TEM, SIMS and XRF measurements.

Experimental Study of Acid Treatment Toward Characterization of Structural, Optical, and Morphological Properties of TiO2-SnO2 Composite Thin Film

NASA Astrophysics Data System (ADS)

Fajar, M. N.; Hidayat, R.; Triwikantoro; Endarko

2018-04-01

The TiO2-SnO2 thin film with single and double-layer structure has successfully synthesized on FTO (Fluorine-doped Tin Oxide) substrate using the screen printing technique. The structural, optical, and morphological properties of the film were investigated by XRD, UV-Vis, and SEM, respectively. The results showed that the single and double-layer structure of TiO2-SnO2 thin film has mixed phase with a strong formation of casseritte phase. The acid treatment effect on TiO2-SnO2 thin film decreases the peak intensity of anatase phase formation and thin film’s absorbance values. The morphological study is also revealed that the single layer TiO2-SnO2 thin film had a more porous nature and decreased particle size distribution after acid treatment, while the double-layer TiO2-SnO2 thin film Eroded due to acid treatment.

Self-propagated combustion synthesis of few-layered graphene: an optical properties perspective.

PubMed

Mohandoss, Manonmani; Sen Gupta, Soujit; Kumar, Ramesh; Islam, Md Rabiul; Som, Anirban; Mohd, Azhardin Ganayee; Pradeep, T; Maliyekkal, Shihabudheen M

2018-04-26

This paper describes a labour efficient and cost-effective strategy to prepare few-layered of reduced graphene oxide like (RGOL) sheets from graphite. The self-propagated combustion route enables the bulk production of RGOL sheets. Microscopic and spectroscopic analyses confirmed the formation of few-layer graphene sheets of an average thickness of ∼3 nm and the presence of some oxygen functional groups with a C/O ratio of 8.74. A possible mechanistic pathway for the formation of RGOL sheets is proposed. The optical properties of the RGOL sample were studied in detail by means of Spectroscopic Ellipsometry (SE). The experimental abilities of SE in relating the optical properties with the number of oxygen functionalities present in the samples are explored. The data were analysed by a double-layered optical model along with the Drude-Lorentz oscillatory dispersion relation. The refractive index (n = 2.24), extinction coefficient (k = 2.03), and dielectric functions are obtained using point-by-point analysis and are also checked for Kramers-Kronig (KK) consistency.

The Enzymatic Oxidation of Graphene Oxide

PubMed Central

Kotchey, Gregg P.; Allen, Brett L.; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A.; Tyurina, Yulia Y.; Klein-Seetharaman, Judith; Kagan, Valerian E.; Star, Alexander

2011-01-01

Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon – the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (~40 µM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, UV-Vis, EPR and FT-IR spectroscopy, TEM, AFM, SDS-PAGE, and GC-MS. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Due to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors. PMID:21344859

Immiscibility of Fluid Phases at Magmatic-hydrothermal Transition: Formation of Various PGE-sulfide Mineralization for Layered Basic Intrusions

NASA Astrophysics Data System (ADS)

Zhitova, L.; Borisenko, A.; Morgunov, K.; Zhukova, I.

2007-12-01

Fluid inclusions in quartz of the Merensky Reef (Bushveld Complex, South Africa) and the Chineisky Pluton (Transbaikal Region, Russia) were studied using cryometry, microthermometry, Raman-spectroscopy, LA ICP- MS, scanning electronic microscopy, gas-chromatography and isotopic methods. This allowed us to document some examples of fluid phase separation resulting in formation of different types of PGE-sulfide mineralization for layered basic intrusions. The results obtained show at least three generations of fluid separated from boiling residual alumosilicate intercumulus liquid of the Merensky Reef. The earliest fluid phase composed of homogenous high-dense methane and nitrogen gas mixture was identified in primary gas and co-existing anomalous fluid inclusions from symplectitic quartz. The next generation, heterophase fluid, composed of brines containing a free low-dense (mostly of carbon dioxide) gas phase, was observed in primary multiphase and coexisting gas-rich inclusions of miarolitic quartz crystals. The latest generation was also a heterophase fluid (low salinity water-salt solution and free low-dense methane gas phase) found in primary water-salt and syngenetic gas inclusions from peripheral zones of miarolitic quartz crystals. For the Chineisky Pluton reduced endocontact magmatogene fluids changed to oxidized low salinity hydrothermal fluids in exocontact zone. This resulted in formation of sulfide-PGE enrichment marginal zones of intrusion. The results obtained give us a possibility to suggest that: 1) Fluid phase separation is a typical feature of magmatogene fluids for layered basic intrusions. 2) Reduced fluids can extract and transport substantial PGE and sulfide concentrations. 3) Oxidation of reduced fluids is one of the most important geochemical barriers causing abundant PGE minerals and sulfides precipitation. This in turn results in both formation of PGE reefs or enriched contact zones of layered basic intrusions. This work was supported by the Ministry for Russian Science and Education, Grant DSP.2.1.1.702, by RFBR Grants ## 07-05-00685, 07-05-00803, Grant VMTK-2007 IGM SB RAS.

Evidence for biogenic processes during formation of ferromanganese crusts from the Pacific Ocean: implications of biologically induced mineralization.

PubMed

Wang, Xiao-Hong; Schlossmacher, Ute; Natalio, Filipe; Schröder, Heinz C; Wolf, Stephan E; Tremel, Wolfgang; Müller, Werner E G

2009-01-01

Ferromanganese [Fe/Mn] crusts formed on basaltic seamounts, gain considerable economic importance due to their high content of Co, Ni, Cu, Zn and Pt. The deposits are predominantly found in the Pacific Ocean in depths of over 1000m. They are formed in the mixing layer between the upper oxygen-minimum zone and the lower oxygen-rich bottom zone. At present an almost exclusive abiogenic origin of crust formation is considered. We present evidence that the upper layers of the crusts from the Magellan Seamount cluster are very rich in coccoliths/coccolithophores (calcareous phytoplankton) belonging to different taxa. Rarely intact skeletons of these unicellular algae are found, while most of them are disintegrated into their composing prisms or crystals. Studies on the chemical composition of crust samples by high resolution SEM combined with an electron probe microanalyzer (EPMA) revealed that they are built of distinct stacked piles of individual compartments. In the center of such piles Mn is the dominant element, while the rims of the piles are rich in Fe (mineralization aspect). The compartments contain coccospheres usually at the basal part. Energy dispersive X-ray spectroscopy (EDX) analyses showed that those coccospheres contain, as expected, CaCO3 but also Mn-oxide. Detailed analysis displayed on the surface of the coccolithophores a high level of CaCO3 while the concentration of Mn-oxide is relatively small. With increasing distance from the coccolithophores the concentration of Mn-oxide increases on the expense of residual CaCO3. We conclude that coccoliths/coccolithophores are crucial for the seed/nucleation phase of crust formation (biomineralization aspect). Subsequently, after the biologically induced mineralization phase Mn-oxide deposition proceeds "auto"catalytically.

Nested potassium hydroxide etching and protective coatings for silicon-based microreactors

NASA Astrophysics Data System (ADS)

de Mas, Nuria; Schmidt, Martin A.; Jensen, Klavs F.

2014-03-01

We have developed a multilayer, multichannel silicon-based microreactor that uses elemental fluorine as a reagent and generates hydrogen fluoride as a byproduct. Nested potassium hydroxide etching (using silicon nitride and silicon oxide as masking materials) was developed to create a large number of channels (60 reaction channels connected to individual gas and liquid distributors) of significantly different depths (50-650 µm) with sloped walls (54.7° with respect to the (1 0 0) wafer surface) and precise control over their geometry. The wetted areas were coated with thermally grown silicon oxide and electron-beam evaporated nickel films to protect them from the corrosive fluorination environment. Up to four Pyrex layers were anodically bonded to three silicon layers in a total of six bonding steps to cap the microchannels and stack the reaction layers. The average pinhole density in as-evaporated films was 3 holes cm-2. Heating during anodic bonding (up to 350 °C for 4 min) did not significantly alter the film composition. Upon fluorine exposure, nickel films (160 nm thick) deposited on an adhesion layer of Cr (10 nm) over an oxidized silicon substrate (up to 500 nm thick SiO2) led to the formation of a nickel fluoride passivation layer. This microreactor was used to investigate direct fluorinations at room temperature over several hours without visible signs of film erosion.

Oriented conductive oxide electrodes on SiO2/Si and glass

DOEpatents

Jia, Quanxi; Arendt, Paul N.

2001-01-01

A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

Reduction of Iron-Oxide-Carbon Composites: Part III. Shrinkage of Composite Pellets during Reduction

NASA Astrophysics Data System (ADS)

Halder, S.; Fruehan, R. J.

2008-12-01

This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

Investigating the connectivity between emissions of BVOC and rainfall formation in Amazonia using Genetic Programming

NASA Astrophysics Data System (ADS)

Von Randow, Celso; Sanches, Marcos B.; Santos, Rosa Maria N.; Chamecki, Marcelo; Fuentes, Jose D.

2017-04-01

A detailed field experiment measuring turbulent properties, trace gases and BVOCs was carried out from April 2014 to January 2015 within and above a central Amazonian rainforest, with the objective of understanding the role of emissions and reactions of BVOCs, formation and transport of aerosols out of the boundary layer on cloud formation and precipitation triggers. Our measurements show two-way aspects of connectivity: mesoscale convective systems transport ozone down from the middle troposphere, enriching the atmospheric boundary layer as well as the forest canopy and surface layer, and, through multiple chemical transformations, an ozone-enriched atmospheric surface layer that can oxidize rainforest-emitted hydrocarbons and generate aerosols that subsequently activate into cloud condensation nuclei, thereby possibly influencing the formation of new convective precipitation. Qualitatively, we address the connectivity between emissions of BVOCs near the surface and rainfall generation, using the technique of Genetic Programing (GP), introduced by Koza (1992), based on the concepts of natural selection and genetics. The technique involves finding a mathematical expression that fits a given set of data, and constructing a population of mathematical models from different combinations of variables, constants and operators. An advantage of GP is that it can flexibly incorporate multivariate non-linear relations, and obtained numeric solutions are possibly interpreted and checked for physical consistency. A number of state variables (for example, surface fluxes, meteorological conditions, boundary layer stability conditions, BVOC and Ozone vertical profiles, etc), representing possible influences on BVOC emissions and their interrelations along the way through secondary organic aerosol and CCN formation to rainfall will be used.

Oxidation of high-temperature alloys (superalloys) at elevated temperatures in air: I

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

Hussain, N.; Shahid, K.A.; Rahman, S.

1994-04-01

Four commercial alloys - Hastelloy C-4, alloy 1.4306S (SS 304L), Incoloy 800H, and Incoloy 825 - were studied for their oxidation behavior at elevated temperatures. Specimens were exposed to air from 600 to 1200[degree]C for 1 to 400 hr. Reaction kinetics of oxidation were determined, and the morphology of the surface-oxide scales was investigated. Hastelloy C-4 showed better resistance to oxidation for exposure temperatures up to 1000[degree]C in comparison with the other three alloys. In this temperature range, it follows a cubic rate law of oxidation due to formation of uniform, protective, and adherent oxide scales. The latter three alloysmore » obeyed the parabolic rate law at 1000[degree]C and 1200[degree]C, but for lower temperatures a mixed behavior was shown. The oxide layer developed on the alloy 1.4306S was always in the form of stratified nodules/warts. For longer exposures the nodules joined each other to form continuous but discrete layers. Incoloy 800H and Incoloy 825 behaved in an almost identical manner, their reaction kinetics being governed by the parabolic rate law throughout the temperature range. Oxide spalling was observed at all temperatures. In contrast to Incoloy 800H the Incoloy 825 was totally oxidized for longer exposures at 1200[degree]C. 16 refs., 12 figs., 1 tab.« less

Topotactical growth of thick perovskite oxynitride layers by nitridation of single crystalline oxides

NASA Astrophysics Data System (ADS)

Ebbinghaus, Stefan G.; Aguiar, Rosiana; Weidenkaff, Anke; Gsell, Stefan; Reller, Armin

2008-06-01

Thick films of the perovskite-related oxynitrides LaTiO 2N, NdTiO 2N, SrNbO 2N and SrTaO 2N were synthesised by nitridation of single crystals of the corresponding oxides with general composition ABO 3.5. The oxide crystals were obtained by optical floating zone growth. They correspond to n = 4 member of the A nB nO 3 n+2 family of layered perovskites and were reacted at temperatures between 900 °C and 1050 °C to form the oxynitrides. Electron probe microanalysis proved the presence of nitrogen in a surface layer of a few micrometer thickness. Cross-section SEM revealed additional thin stripes of oxynitride within the bulk of the crystals, indicating that nitrogen is incorporated preferably parallel to the perovskite-type layers, which in turn are connected in a zipper-type mechanism. The formation of the desired perovskite-type oxynitrides was confirmed by X-ray diffraction. Pole figure measurements proved an epitaxial orientation ABO 2N (110)[001] ‖ ABO 3.5 (001)[100]. The mosaicity of the oxynitrides both in polar and azimuthal direction was very small (<2°) indicating a nearly single crystalline quality of the surface layer. The nitridation of the crystals results in a dramatic change in colour. Optical spectroscopy revealed shifts of the absorption edge by more than 200 nm to longer wavelengths with respect to the parent oxides, corresponding to a reduction of the band gap energies by 1.4-1.8 eV.

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

PubMed

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

2009-01-01

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

Processing of a Mullite Matrix, Molybdenum Disilicide Reinforced Composite

DTIC Science & Technology

1991-01-01

at high temperatures (best of the silicides and almost as good as SiC) is due to the formation of protective SiO2 layers on the surface of the MoSi 2...of the precipitation preparation process) consisted largely of sodium . Previous work 52 showed that the particle size was 160 A (TEM analysis) not...M.K. Brun, L.E. Szala, "Kinetics of Oxidation of Carbide and Silicide Dispersed Phases in Oxide Matrices," Adv. Ceram. Mat., 3 [5] 491-497 (1988). 5

X-ray absorption spectroscopy investigations on oxidized Ni/Au contacts to p-GaN.

PubMed

Jan, J C; Asokan, K; Chiou, J W; Pong, W F; Tseng, P K; Chen, L C; Chen, F R; Lee, J F; Wu, J S; Lin, H J; Chen, C T

2001-03-01

X-ray absorption spectroscopy was used to investigate the electronic structure of as-deposited and oxidized Ni/Au contacts to p-GaN and to elucidate the mechanism responsible for low impedance. X-ray absorption near edge spectra of Ni K- and L3,2-edges clearly indicate formation of NiO on the sample surface after annealing. The reason for low impedance may be attributed to increase in hole concentration and existence of p-NiO layer on the surface.

In-situ formation of multiphase air plasma sprayed barrier coatings for turbine components

DOEpatents

Subramanian, Ramesh

2001-01-01

A turbine component (10), such as a turbine blade, is provided which is made of a metal alloy (22) and a base, planar-grained thermal barrier layer (28) applied by air plasma spraying on the alloy surface, where a heat resistant ceramic oxide overlay material (32') covers the bottom thermal barrier coating (28), and the overlay material is the reaction product of the precursor ceramic oxide overlay material (32) and the base thermal barrier coating material (28).

Solid-state dewetting of single- and bilayer Au-W thin films: Unraveling the role of individual layer thickness, stacking sequence and oxidation on morphology evolution

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

Herz, A., E-mail: andreas.herz@tu-ilmenau.de, E-mail: dong.wang@tu-ilmenau.de; Franz, A.; Theska, F.

2016-03-15

Self-assembly of ultrathin Au, W, and Au-W bilayer thin films is investigated using a rapid thermal annealing technique in an inert ambient. The solid-state dewetting of Au films is briefly revisited in order to emphasize the role of initial film thickness. W films deposited onto SiO{sub 2} evolve into needle-like nanocrystals rather than forming particle-like agglomerates upon annealing at elevated temperatures. Transmission electron microscopy reveals that such nanocrystals actually consist of tungsten (VI) oxide (WO{sub 3}) which is related to an anisotropic oxide crystal growth out of the thin film. The evolution of W films is highly sensitive to themore » presence of any residual oxygen. Combination of both the dewetting of Au and the oxide crystal growth of WO{sub 3} is realized by using various bilayer film configurations of the immiscible Au and W. At low temperature, Au dewetting is initiated while oxide crystal growth is still suppressed. Depending on the stacking sequence of the Au-W bilayer thin film, W acts either as a substrate or as a passivation layer for the dewetting of Au. Being the ground layer, W changes the wettability of Au which clearly modifies its initial state for the dewetting. Being the top layer, W prevents Au from dewetting regardless of Au film thickness. Moreover, regular pattern formation of Au-WO{sub 3} nanoparticles is observed at high temperature demonstrating how bilayer thin film dewetting can create unique nanostructure arrangements.« less

Corrosion Behavior of Alloy 625 in PbSO4-Pb3O4-PbCl2-ZnO-10 Wt Pct CdO Molten Salt Medium

NASA Astrophysics Data System (ADS)

Mohammadi Zahrani, E.; Alfantazi, A. M.

2012-08-01

Corrosion behavior and degradation mechanisms of alloy 625 under a 47.288 PbSO4-12.776 Pb3O4-6.844PbCl2-23.108ZnO-10CdO (wt pct) molten salt mixture under air atmosphere were studied at 873 K, 973 K, and 1073 K (600 °C, 700 °C, and 800 °C). Electrochemical impedance spectroscopy (EIS), open circuit potential (OCP) measurements, and potentiodynamic polarization techniques were used to evaluate the degradation mechanisms and characterize the corrosion behavior of the alloy. Morphology, chemical composition, and phase structure of the corrosion products and surface layers of the corroded specimens were studied by scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) and X-ray map analyses. Results confirmed that during the exposure of alloy 625 to the molten salt, chromium was mainly dissolved through an active oxidation process as CrO3, Cr2O3, and CrNbO4, while nickel dissolved only as NiO in the system. Formation of a porous and nonprotective oxide layer with low resistance is responsible for the weak protective properties of the barrier layer at high temperatures of 973 K and 1073 K (700 °C and 800 °C). There were two kinds of attack for INCONEL 625, including general surface corrosion and pitting. Pitting corrosion occurred due to the breakdown of the initial oxide layer by molten salt dissolution of the oxide or oxide cracking.

Interaction of coal-derived synthesis gas impurities with solid oxide fuel cell metallic components

NASA Astrophysics Data System (ADS)

Marina, Olga A.; Pederson, Larry R.; Coyle, Christopher A.; Edwards, Danny J.; Chou, Yeong-Shyung; Cramer, Carolyn N.

Oxidation-resistant alloys find use as interconnect materials, heat exchangers, and gas supply tubing in solid oxide fuel cell (SOFC) systems, especially when operated at temperatures below ∼800 °C. If fueled with synthesis gas derived from coal or biomass, such metallic components could be exposed to impurities contained in those fuel sources. In this study, coupons of ferritic stainless steels Crofer 22 APU and SS 441, austenitic nickel-chromium superalloy Inconel 600, and an alumina-forming high nickel alloy alumel were exposed to synthesis gas containing ≤2 ppm phosphorus, arsenic and antimony, and reaction products were tested. Crofer 22 APU coupons coated with a (Mn,Co) 3O 4 protective layer were also evaluated. Phosphorus was found to be the most reactive. On Crofer 22 APU, the (Mn,Cr) 3O 4 passivation layer reacted to form an Mn-P-O product, predicted to be manganese phosphate from thermochemical calculations, and Cr 2O 3. On SS 441, reaction of phosphorus with (Mn,Cr) 3O 4 led to the formation of manganese phosphate as well as an Fe-P product, predicted from thermochemical calculations to be Fe 3P. Minimal interactions with antimony or arsenic in synthesis gas were limited to Fe-Sb and Fe-As solid solution formation. Though not intended for use on the anode side, a (Mn,Co) 3O 4 spinel coating on Crofer 22 APU reacted with phosphorus in synthesis gas to produce products consistent with Mn 3(PO 4) 2 and Co 2P. A thin Cr 2O 3 passivation layer on Inconel 600 did not prevent the formation of nickel phosphides and arsenides and of iron phosphides and arsenides, though no reaction with Cr 2O 3 was apparent. On alumel, an Al 2O 3 passivation layer rich in Ni did not prevent the formation of nickel phosphides, arsenides, and antimonides, though no reaction with Al 2O 3 occurred. This work shows that unprotected metallic components of an SOFC stack and system can provide a sink for P, As and Sb impurities that may be present in fuel gases, and thus complicate experimental studies of impurity interactions with the anode.

Argon-ion-induced formation of nanoporous GaSb layer: Microstructure, infrared luminescence, and vibrational properties

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

Datta, D. P.; Som, T., E-mail: tsom@iopb.res.in; Kanjilal, A.

2014-07-21

Room temperature implantation of 60 keV Ar{sup +}-ions in GaSb to the fluences of 7 × 10{sup 16} to 3 × 10{sup 18} ions cm{sup −2} is carried out at two incidence angles, viz 0° and 60°, leading to formation of a nanoporous layer. As the ion fluence increases, patches grow on the porous layer under normal ion implantation, whereas the porous layer gradually becomes embedded under a rough top surface for oblique incidence of ions. Grazing incidence x-ray diffraction and cross-sectional transmission electron microscopy studies reveal the existence of nanocrystallites embedded in the ion-beam amorphized GaSb matrix up to the highest fluence used inmore » our experiment. Oxidation of the nanoporous layers becomes obvious from x-ray photoelectron spectroscopy and Raman mapping. The correlation of ion-beam induced structural modification with photoluminescence signals in the infrared region has further been studied, showing defect induced emission of additional peaks near the band edge of GaSb.« less

Resistive switching in TiO2 nanocolumn arrays electrochemically grown

NASA Astrophysics Data System (ADS)

Marik, M.; Mozalev, A.; Hubalek, J.; Bendova, M.

2017-04-01

Resistive switching in metal oxides, especially in TiO2, has been intensively investigated for potential application in non-volatile memory microdevices. As one of the working mechanisms, a conducting filament consisting of a substoichiometric oxide phase is created within the oxide layer. With the aim of investigating the filament formation in spatially confined elements, we fabricate arrays of self-ordered TiO2 nanocolumns by porous-anodic-alumina (PAA)-assisted anodizing, incorporate them into solid-state microdevices, study their electron transport properties, and reveal that this anodizing approach is suitable for growing TiO2 nanostructures exhibiting resistive switching. The electrical properties and resistive switching behavior are both dependent on the electrolytic formation conditions, influencing the concentration and distribution of oxygen vacancies in the nanocolumn material during the film growth. Therefore, the PAA-assisted TiO2 nanocolumn arrays can be considered as a platform for investigating various phenomena related to resistive switching in valve metal oxides at the nanoscale.

Self-assembly of a thin highly reduced graphene oxide film and its high electrocatalytic activity

NASA Astrophysics Data System (ADS)

Bai, Yan-Feng; Zhang, Yong-Fang; Zhou, An-Wei; Li, Hai-Wai; Zhang, Yu; Luong, John H. T.; Cui, Hui-Fang

2014-10-01

A thin highly reduced graphene oxide (rGO) film was self-assembled at the dimethyl formamide (DMF)-air interface through evaporation-induced water-assisted thin film formation at the pentane-DMF interface, followed by complete evaporation of pentane. The thin film was transferred onto various solid substrates for film characterization and electrochemical sensing. UV-visible spectrometry, scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemistry techniques were used to characterize the film. An rGO film showing 82.8% of the transmittance at 550 nm corresponds to a few layers of rGO nanosheets. The rGO nanosheets cross-stack with each other, lying approximately in the plane of the film. An rGO film collected on a glassy carbon (GC) electrode exhibited improved electrical conductivity compared to GC, with the electrode charge-transfer resistance (Rct) reduced from 31 Ω to 22 Ω. The as-formed rGO/GC electrode was mechanically very stable, exhibiting significantly enhanced electrocatalytic activity to H2O2 and dopamine. Multiple layers of the rGO films on the GC electrode showed even stronger electrocatalytic activity to dopamine than that of the single rGO film layer. The controllable formation of a stable rGO film on various solid substrates has potential applications for nanoelectronics and sensors/biosensors.

Microstructure evolution of a dissimilar junction interface between an Al sheet and a Ni-coated Cu sheet joined by magnetic pulse welding

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

Itoi, Takaomi, E-mail: itoi@faculty.chiba-u.jp

An Al sheet and a Ni-coated Cu sheet were lap joined by using magnetic pulse welding (MPW). Tensile tests were performed on the joined sheets, and a good lap joint was achieved at a discharge energy of > 0.9 kJ. The weld interface exhibited a wavy morphology and an intermediate layer along the weld interface. Microstructure observations of the intermediate layer revealed that the Ni coating region consisted of a Ni–Al binary amorphous alloy and that the Al sheet region contained very fine Al nanograins. Ni fragments indicative of unmelted residual Ni from the coating were also observed in partsmore » of the intermediate layer. Formation of these features can be attributed to localize melting and a subsequent high rate cooling of molten Al and Ni confined to the interface during the MPW process. In the absence of an oxide film, atomic-scale bonding was also achieved between the intermediate layer and the sheet surfaces after the collision. MPW utilises impact energy, which affects the sheet surfaces. From the obtained results, good lap joint is attributed to an increased contact area, the anchor effect, work hardening, the absence of an oxide film, and suppressed formation of intermetallic compounds at the interface. - Highlights: •Good lap joint of an Al sheet and a Ni-coated Cu sheet was achieved by using magnetic pulse welding. •A Ni–Al binary amorphous alloy was formed as an intermediate layer at weld interface. •Atomic-scale bonding was achieved between the intermediate layer and the sheet surfaces.« less

Adsorption Isotherm Studies of Methyl Bromide on MgO

NASA Astrophysics Data System (ADS)

Burns, Teresa; Larese, John

2004-03-01

The adsorption of methyl bromine onto highly-uniform magnesium oxide powder was studied. Methyl bromide was condensed onto the MgO substrate at temperatures between 164 K and 179 K. The layering behavior of the gas molecules was studied by a series of vapor pressure isotherms, using a high-accuracy, computer-controller system. The isotherms clearly show first layer formation at all temperatures, with second layer formation at higher temperatures; the 2D compressibility and isosteric heat of adsorption were determined. TEB sponsored by the Department of Energy EPSCOR Grant No. DE-FG02-01ER45895. JZL sponsored by start-up funds from the University of Tennessee - Knoxville and by the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy, under contract No. DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC.

In situ observation of the formation of hollow zinc oxide shells

DOE PAGES

Tringe, J. W.; Levie, H. W.; El-Dasher, B. S.; ...

2011-06-14

Single crystal zinc particles, 1–2 μm1–2 μm in diameter, were observed in situ with transmission electron microscopy during sublimation. The rate of sublimation is strongly dependent on the presence of a surface oxide layer. Near 375°, minimally oxidized Zn surfaces sublime in tens of seconds, consistent with a model in which the particle behaves similarly to an isolated microscale effusion cell. By contrast, zinc particles fully enclosed by oxide sublime less than one-tenth as quickly. Here these results provide new insight into the synthesis mechanisms of hollow ZnO microspheres and related structures formed from metallic zinc at elevated temperatures.

Enhanced fatigue performance of porous coated Ti6Al4V biomedical alloy

NASA Astrophysics Data System (ADS)

Apachitei, I.; Leoni, A.; Riemslag, A. C.; Fratila-Apachitei, L. E.; Duszczyk, J.

2011-05-01

Biofunctional coatings are necessary to improve integration of titanium implants in the host tissue but they may be detrimental for the implant fatigue properties. This study presents an attempt towards enhancement of the in vitro fatigue strength of plasma electrolytic oxidation coated Ti6Al4V alloy by applying shot peening process prior to coating. The electrolytic oxidation was performed in calcium acetate and calcium glycerophosphate electrolytes that allowed formation of porous oxide coatings with high surface free energy and apatite like ability. A deformed surface layer coupled with induced residual compressive stresses seem to affect oxide growth rate and fatigue behavior of the titanium alloy.

Atomic and molecular layer deposition for surface modification

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

Vähä-Nissi, Mika, E-mail: mika.vaha-nissi@vtt.fi; Sievänen, Jenni; Salo, Erkki

2014-06-01

Atomic and molecular layer deposition (ALD and MLD, respectively) techniques are based on repeated cycles of gas–solid surface reactions. A partial monolayer of atoms or molecules is deposited to the surface during a single deposition cycle, enabling tailored film composition in principle down to molecular resolution on ideal surfaces. Typically ALD/MLD has been used for applications where uniform and pinhole free thin film is a necessity even on 3D surfaces. However, thin – even non-uniform – atomic and molecular deposited layers can also be used to tailor the surface characteristics of different non-ideal substrates. For example, print quality of inkjetmore » printing on polymer films and penetration of water into porous nonwovens can be adjusted with low-temperature deposited metal oxide. In addition, adhesion of extrusion coated biopolymer to inorganic oxides can be improved with a hybrid layer based on lactic acid. - Graphical abstract: Print quality of a polylactide film surface modified with atomic layer deposition prior to inkjet printing (360 dpi) with an aqueous ink. Number of printed dots illustrated as a function of 0, 5, 15 and 25 deposition cycles of trimethylaluminum and water. - Highlights: • ALD/MLD can be used to adjust surface characteristics of films and fiber materials. • Hydrophobicity after few deposition cycles of Al{sub 2}O{sub 3} due to e.g. complex formation. • Same effect on cellulosic fabrics observed with low temperature deposited TiO{sub 2}. • Different film growth and oxidation potential with different precursors. • Hybrid layer on inorganic layer can be used to improve adhesion of polymer melt.« less

Structural and dielectric properties of thin ZrO2 films on silicon grown by atomic layer deposition from cyclopentadienyl precursor

NASA Astrophysics Data System (ADS)

Niinistö, J.; Putkonen, M.; Niinistö, L.; Kukli, K.; Ritala, M.; Leskelä, M.

2004-01-01

ZrO2 thin films with thicknesses below 20 nm were deposited by the atomic layer deposition process on Si(100) substrates at 350 °C. An organometallic precursor, Cp2Zr(CH3)2 (Cp=cyclopentadienyl, C5H5) was used as the zirconium source and water or ozone as oxygen source. The influence of oxygen source and substrate pretreatment on the dielectric properties of ZrO2 films was investigated. Structural characterization with high-resolution transmission electron microscopy was performed to films grown onto HF-etched or native oxide covered silicon. Strong inhibition of ZrO2 film growth was observed with the water process on HF-etched Si. Ozone process on HF-etched Si resulted in interfacial SiO2 formation between the dense and uniform film and the substrate while water process produced interfacial layer with intermixing of SiO2 and ZrO2. The effective permittivity of ZrO2 in Al/ZrO2/Si/Al capacitor structures was dependent on the ZrO2 layer thickness and oxygen source used. The interfacial layer formation increased the capacitance equivalent oxide thickness (CET). CET of 2.0 nm was achieved with 5.9 nm ZrO2 film deposited with the H2O process on HF-stripped Si. The ozone-processed films showed good dielectric properties such as low hysteresis and nearly ideal flatband voltage. The leakage current density was lower and breakdown field higher for the ozone-processed ZrO2 films.

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.

Stable Organic Monolayers on Oxide-Free Silicon/Germanium in a Supercritical Medium: A New Route to Molecular Electronics.

PubMed

Puniredd, Sreenivasa Reddy; Jayaraman, Sundaramurthy; Yeong, Sai Hooi; Troadec, Cedric; Srinivasan, M P

2013-05-02

Oxide-free Si and Ge surfaces have been passivated and modified with organic molecules by forming covalent bonds between the surfaces and reactive end groups of linear alkanes and aromatic species using single-step deposition in supercritical carbon dioxide (SCCO2). The process is suitable for large-scale manufacturing due to short processing times, simplicity, and high resistance to oxidation. It also allows the formation of monolayers with varying reactive terminal groups, thus enabling formation of nanostructures engineered at the molecular level. Ballistic electron emission microscopy (BEEM) spectra performed on the organic monolayer on oxide-free silicon capped by a thin gold layer reveals for the first time an increase in transmission of the ballistic current through the interface of up to three times compared to a control device, in contrast to similar studies reported in the literature suggestive of oxide-free passivation in SCCO2. The SCCO2 process combined with the preliminary BEEM results opens up new avenues for interface engineering, leading to molecular electronic devices.

Low-temperature formation of Ga-oxide/GaN interface with remote oxygen plasma and its interface properties

NASA Astrophysics Data System (ADS)

Yamamoto, Taishi; Taoka, Noriyuki; Ohta, Akio; Truyen, Nguyen Xuan; Yamada, Hisashi; Takahashi, Tokio; Ikeda, Mitsuhisa; Makihara, Katsunori; Shimizu, Mitsuaki; Miyazaki, Seiichi

2018-06-01

The Ga-oxide/GaN structures formed by remote oxygen plasma (ROP) exposure at various temperatures (T s) and times have been systematically investigated. X-ray photoelectron spectroscopy clarified the formation of Ga2O3 layers with close-to-stoichiometric composition and a slight N incorporation of ∼6 at. %. Also, we found that a high T s increases the intensity of a signal related to the N–O bond, which is located near the Ga-oxide/GaN interfaces. Total photoelectron yield spectroscopy (PYS) also revealed that the ROP exposure at T s of 300 °C produces fewer filled defect states in the bandgap of GaN than at 500 °C. This difference in the filled defect states could be attributable to the amount of N–O bonds at the interface.

Improved open-circuit voltage in polymer/oxide-nanoarray hybrid solar cells by formation of homogeneous metal oxide core/shell structures.

PubMed

Wu, Fan; Cui, Qi; Qiu, Zeliang; Liu, Changwen; Zhang, Hui; Shen, Wei; Wang, Mingtai

2013-04-24

Incorporation of vertically aligned nanorod/nanowire arrays of metal oxide (oxide-NAs) with a polymer can produce efficient hybrid solar cells with an ideal bulk-heterojunction architecture. However, polymer/oxide-NAs solar cells still suffer from a rather low (normally, < 0.4 V) open-circuit voltage (Voc). Here we demonstrate, for the first time, a novel strategy to improve the Voc in polymer/oxide-NAs solar cells by formation of homogeneous core/shell structures and reveal the intrinsic principles involved therein. A feasible hydrothermal-solvothermal combined method is developed for preparing homogeneous core/shell nanoarrays of metal oxides with a single-crystalline nanorod as core and the aggregation layer of corresponding metal oxide quantum dots (QDs) as shell, and the shell thickness (L) is easily controlled by the solvothermal reaction time for growing QDs on the nanorod. The core/shell formation dramatically improves the device Voc up to ca. 0.7-0.8 V depending on L. Based on steady-state and dynamic measurements, as well as modeling by space-charge-limited current method, it is found that the improved Voc originates from the up-shifted conduction band edge in the core by the interfacial dipole field resulting from the decreased mobility difference between photogenerated electrons and holes after the shell growth, which increases the energy difference between the quasi-Fermi levels of photogenerated electrons in the core and holes in the polymer for a higher Voc. Our results indicate that increasing Voc by the core/shell strategy seems not to be dependent on the kinds of metal oxides.

Single and multi-layered core-shell structures based on ZnO nanorods obtained by aerosol assisted chemical vapor deposition

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

Sáenz-Trevizo, A.; Amézaga-Madrid, P.; Pizá-Ruiz, P.

2015-07-15

Core–shell nanorod structures were prepared by a sequential synthesis using an aerosol assisted chemical vapor deposition technique. Several samples consisting of ZnO nanorods were initially grown over TiO{sub 2} film-coated borosilicate glass substrates, following the synthesis conditions reported elsewhere. Later on, a uniform layer consisting of individual Al, Ni, Ti or Fe oxides was grown onto ZnO nanorod samples forming the so-called single MO{sub x}/ZnO nanorod core–shell structures, where MO{sub x} was the metal oxide shell. Additionally, a three-layer core–shell sample was developed by growing Fe, Ti and Fe oxides alternately, onto the ZnO nanorods. The microstructure of the core–shellmore » materials was characterized by grazing incidence X-ray diffraction, scanning and transmission electron microscopy. Energy dispersive X-ray spectroscopy was employed to corroborate the formation of different metal oxides. X-ray diffraction outcomes for single core–shell structures showed solely the presence of ZnO as wurtzite and TiO{sub 2} as anatase. For the multi-layered shell sample, the existence of Fe{sub 2}O{sub 3} as hematite was also detected. Morphological observations suggested the existence of an outer material grown onto the nanorods and further microstructural analysis by HR-STEM confirmed the development of core–shell structures in all cases. These studies also showed that the individual Al, Fe, Ni and Ti oxide layers are amorphous; an observation that matched with X-ray diffraction analysis where no apparent extra oxides were detected. For the multi-layered sample, the development of a shell consisting of three different oxide layers onto the nanorods was found. Overall results showed that no alteration in the primary ZnO core was produced during the growth of the shells, indicating that the deposition technique used herein was and it is suitable for the synthesis of homogeneous and complex nanomaterials high in quality and purity. In addition, materials absorptance determined from the total transmittance and reflectance spectra revealed a broader absorption interval including visible light, indicating potential uses of these nanostructures on solar energy appliances. - Graphical abstract: Display Omitted - Highlights: • Uniform ZnO nanorods (core)–metal oxide (shell) were obtained sequentially by AACVD. • Shells were structured of homogeneous single or multi-layered non-mixed metal oxides. • ZnO nanorod core was preserved during the shell synthesis. • Optical absorptance revealed visible interval absorption for FeO{sub x} shell samples. • Materials can be suitable for photocatalytic or photovoltaic applications.« less

Solar Power Wires Based on Organic Photovoltaic Materials

NASA Astrophysics Data System (ADS)

Lee, Michael R.; Eckert, Robert D.; Forberich, Karen; Dennler, Gilles; Brabec, Christoph J.; Gaudiana, Russell A.

2009-04-01

Organic photovoltaics in a flexible wire format has potential advantages that are described in this paper. A wire format requires long-distance transport of current that can be achieved only with conventional metals, thus eliminating the use of transparent oxide semiconductors. A phase-separated, photovoltaic layer, comprising a conducting polymer and a fullerene derivative, is coated onto a thin metal wire. A second wire, coated with a silver film, serving as the counter electrode, is wrapped around the first wire. Both wires are encased in a transparent polymer cladding. Incident light is focused by the cladding onto to the photovoltaic layer even when it is completely shadowed by the counter electrode. Efficiency values of the wires range from 2.79% to 3.27%.

Formation of porous surface layers in reaction bonded silicon nitride during processing

NASA Technical Reports Server (NTRS)

Shaw, N. J.; Glasgow, T. K.

1979-01-01

Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

Laser ablation of single-crystalline silicon by radiation of pulsed frequency-selective fiber laser

NASA Astrophysics Data System (ADS)

Veiko, V. P.; Skvortsov, A. M.; Huynh, C. T.; Petrov, A. A.

2015-07-01

We have studied the process of destruction of the surface of a single-crystalline silicon wafer scanned by the beam of a pulsed ytterbium-doped fiber laser radiation with a wavelength of λ = 1062 nm. It is established that the laser ablation can proceed without melting of silicon and the formation of a plasma plume. Under certain parameters of the process (radiation power, beam scan velocity, and beam overlap density), pronounced oxidation of silicon microparticles with the formation of a characteristic loose layer of fine powdered silicon dioxide has been observed for the first time. The range of lasing and beam scanning regimes in which the growth of SiO2 layer takes place is determined.

Characterization of chemical interactions during chemical mechanical polishing (CMP) of copper

NASA Astrophysics Data System (ADS)

Lee, Seung-Mahn

2003-10-01

Chemical mechanical polishing (CMP) has received much attention as an unique technique to provide a wafer level planarization in semiconductor manufacturing. However, despite the extensive use of CMP, it still remains one of the least understood areas in semiconductor processing. The lack of the fundamental understanding is a significant barrier to further advancements in CMP technology. One critical aspect of metal CMP is the formation of a thin surface layer on the metal surface. The formation and removal of this layer controls all the aspects of the CMP process, including removal rate, surface finish, etc. In this dissertation, we focus on the characterization of the formation and removal of the thin surface layer on the copper surface. The formation dynamics was investigated using static and dynamic electrochemical techniques, including potentiodynamic scans and chronoamperometry. The results were validated using XPS measurements. The mechanical properties of the surface layer were investigated using nanoindentation measurements. The electrochemical investigation showed that the thickness of the surface layer is controlled by the chemicals such as an oxidizer (hydrogen peroxide), a corrosion inhibitor (benzotriazole), a complexing agent (citric acid), and their concentrations. The dynamic electrochemical measurements indicated that the initial layer formation kinetics is unaffected by the corrosion inhibitors. The passivation due to the corrosion inhibitor becomes important only on large time scales (>200 millisecond). The porosity and the density of the chemically modified surface layer can be affected by additives of other chemicals such as citric acid. An optimum density of the surface layer is required for high polishing rate while at the same time maintaining a high degree of surface finish. Nanoindentation measurements indicated that the mechanical properties of the surface layer are strongly dependent on the chemical additives in the slurry. The CMP removal rates were found to be in good agreement with the initial reaction kinetics as well as the mechanical properties of the chemically modified surface layer. In addition, the material removal model based on the micro- and nano-scale interactions, which were measured experimentally, has been developed.

Stability Criteria of Fullerene-like Nanoparticles: Comparing V2O5 to Layered Metal Dichalcogenides and Dihalides

PubMed Central

Levi, Roi; Bar-Sadan, Maya; Albu-Yaron, Ana; Popovitz-Biro, Ronit; Houben, Lothar; Prior, Yehiam; Tenne, Reshef

2010-01-01

Numerous examples of closed-cage nanostructures, such as nested fullerene-like nanoparticles and nanotubes, formed by the folding of materials with layered structure are known. These compounds include WS2, NiCl2, CdCl2, Cs2O, and recently V2O5. Layered materials, whose chemical bonds are highly ionic in character, possess relatively stiff layers, which cannot be evenly folded. Thus, stress-relief generally results in faceted nanostructures seamed by edge-defects. V2O5, is a metal oxide compound with a layered structure. The study of the seams in nearly perfect inorganic "fullerene-like" hollow V2O5 nanoparticles (NIF-V2O5) synthesized by pulsed laser ablation (PLA), is discussed in the present work. The relation between the formation mechanism and the seams between facets is examined. The formation mechanism of the NIF-V2O5 is discussed in comparison to fullerene-like structures of other layered materials, like IF structures of MoS2, CdCl2, and Cs2O. The criteria for the perfect seaming of such hollow closed structures are highlighted. PMID:28883335

Analysis of surface scale on the Ni-based superalloy CMSX-10N and proposed mechanism of formation

NASA Astrophysics Data System (ADS)

Simmonds, S.; D'Souza, N.; Ryder, K. S.; Dong, H.

2012-01-01

There is a continuing demand to raise the operating temperature of jet engine turbine blades to meet the need for higher turbine entry temperatures (TET) in order to increase thermal efficiency and thrust. Modern, high-pressure turbine blades are made from Ni-based superalloys in single-crystal form via the investment casting process. One important post-cast surface defect, known as 'surface scale', has been investigated on the alloy CMSX-10N. This is an area of distinct discolouration of the aerofoil seen after casting. Auger electron and X-ray photoelectron spectroscopy analysis were carried out on both scaled and un-scaled areas. In the scaled region, a thin layer (~800nm) of Ni oxide is evident. In the un-scaled regions there is a thicker Al2O3 layer. It is shown that, as the blade cools during casting, differential thermal contraction of mould and alloy causes the solid blade to 'detach' from the mould in these scaled areas. The formation of Ni Oxides is facilitated by this separation.

Fluorinated reduced graphene oxide as a protective layer on the metallic lithium for application in the high energy batteries.

PubMed

Bobnar, Jernej; Lozinšek, Matic; Kapun, Gregor; Njel, Christian; Dedryvère, Rémi; Genorio, Boštjan; Dominko, Robert

2018-04-11

Metallic lithium is considered to be one of the most promising anode materials since it offers high volumetric and gravimetric energy densities when combined with high-voltage or high-capacity cathodes. However, the main impediment to the practical applications of metallic lithium is its unstable solid electrolyte interface (SEI), which results in constant lithium consumption for the formation of fresh SEI, together with lithium dendritic growth during electrochemical cycling. Here we present the electrochemical performance of a fluorinated reduced graphene oxide interlayer (FGI) on the metallic lithium surface, tested in lithium symmetrical cells and in combination with two different cathode materials. The FGI on the metallic lithium exhibit two roles, firstly it acts as a Li-ion conductive layer and electronic insulator and secondly, it effectively suppresses the formation of high surface area lithium (HSAL). An enhanced electrochemical performance of the full cell battery system with two different types of cathodes was shown in the carbonate or in the ether based electrolytes. The presented results indicate a potential application in future secondary Li-metal batteries.

Bacterial Phosphating of Mild (Unalloyed) Steel

PubMed Central

Volkland, Hans-Peter; Harms, Hauke; Müller, Beat; Repphun, Gernot; Wanner, Oskar; Zehnder, Alexander J. B.

2000-01-01

Mild (unalloyed) steel electrodes were incubated in phosphate-buffered cultures of aerobic, biofilm-forming Rhodococcus sp. strain C125 and Pseudomonas putida mt2. A resulting surface reaction leading to the formation of a corrosion-inhibiting vivianite layer was accompanied by a characteristic electrochemical potential (E) curve. First, E increased slightly due to the interaction of phosphate with the iron oxides covering the steel surface. Subsequently, E decreased rapidly and after 1 day reached −510 mV, the potential of free iron, indicating the removal of the iron oxides. At this point, only scattered patches of bacteria covered the surface. A surface reaction, in which iron was released and vivianite precipitated, started. E remained at −510 mV for about 2 days, during which the vivianite layer grew steadily. Thereafter, E increased markedly to the initial value, and the release of iron stopped. Changes in E and formation of vivianite were results of bacterial activity, with oxygen consumption by the biofilm being the driving force. These findings indicate that biofilms may protect steel surfaces and might be used as an alternative method to combat corrosion. PMID:11010888

Kinetics of 25-hydroperoxycholesterol formation during photo-oxidation of crystalline cholesterol.

PubMed

Medina-Meza, Ilce Gabriela; Rodriguez-Estrada, Maria Teresa; Lercker, Giovanni; Barnaba, Carlo; García, Hugo Sergio

2014-06-01

25-Hydroxycholesterol (25-OH), a side-chain product of cholesterol oxidation, has emerged as one of the important issues in food chemistry and biochemistry, because of its involvement in several human pathologies. This oxysterol is derived from both enzymatic and non-enzymatic pathways. However, the latter mechanism has been scarcely studied in either food or model systems. In this work, a kinetic model was developed to evaluate the formation of 25-OH and its precursor 25-hydroperoxycholesterol (25-OOH) during photo-oxidation of cholesterol for 28 days under fluorescent light. 25-OOH was estimated by an indirect method, using thin-layer chromatography coupled with gas chromatography-mass spectrometry. Peroxide value (POV) and cholesterol oxidation products (COPs) were determined. POV showed a hyperbolic behavior, typical of a crystalline system in which the availability of cholesterol is the limiting factor. Further reactions of hydroperoxides were followed; in particular, after photo-oxidation, 25-OOH (0.55 mg g(-1) ) and 25-OH (0.08 mg g(-1) ) were found in cholesterol, as well as seven other oxysterols, including 7-hydroxy and 5,6-epoxy derivatives. The application of kinetic models to the data showed good correlation with theoretical values, allowing derivation of the kinetic parameters for each oxidation route. The results of this work confirm that cholesterol in the crystalline state involves different oxidation patterns as compared to cholesterol in solution. Moreover, the numerical fit proved that hydroperoxidation is the rate-limiting step in 25-OH formation. © 2013 Society of Chemical Industry.

Substrate Structures For Growth Of Highly Oriented And/Or Epitaxial Layers Thereon

DOEpatents

Arendt, Paul N.; Foltyn, Stephen R.; Groves, James R.; Jia, Quanxi

2005-07-26

A composite substrate structure including a substrate, a layer of a crystalline metal oxide or crystalline metal oxynitride material upon the substrate, a layer of an oriented cubic oxide material having a rock-salt-like structure upon the crystalline metal oxide or crystalline metal oxynitride material layer is provided together with additional layers such as one or more layers of a buffer material upon the oriented cubic oxide material layer. Jc's of 2.3×106 A/cm2 have been demonstrated with projected Ic's of 320 Amperes across a sample 1 cm wide for a superconducting article including a flexible polycrystalline metallic substrate, an inert oxide material layer upon the surface of the flexible polycrystalline metallic substrate, a layer of a crystalline metal oxide or crystalline metal oxynitride material upon the layer of the inert oxide material, a layer of an oriented cubic oxide material having a rock-salt-like structure upon the crystalline metal oxide or crystalline metal oxynitride material layer, a layer of a buffer material upon the oriented cubic oxide material layer, and, a top-layer of a high temperature superconducting material upon the layer of a buffer material.

Role of different chelating agent in synthesis of copper doped tin oxide (Cu-SnO2) nanoparticles

NASA Astrophysics Data System (ADS)

Saravanakumar, B.; Anusiya, A.; Rani, B. Jansi; Ravi, G.; Yuvakkumar, R.

2018-05-01

An attempt was made to synthesis the copper doped tin oxide (Cu-SnO2) nanoparticles by adopting different chelating agents (NaOH, KOH and C2H2O4) by Sol-gel process. The synthesized products were characterized by XRD, Photoluminescence (PL), Infra- Red (FTIR) and SEM analysis. The XRD confirms the formation of Cu-SnO2 shows the maximum peak at 33.8° with lattice plane (101). The PL peak at 361 and 382 nm due to the recombination of electron in conduction band to valence band infers the optical properties. The IR spectra correspond to the peak at 551 and 620 cm-1 attributed to the characteristics peak for Cu-SnO2 nanoparticles. The SEM images for all three Cu-SnO2 nanoparticles formed by three chelating agent (NaOH, KOH and C2H2O4) facilitates the formation mechanism and the chelating agent Oxalic acid results in formation of nano flowers with diverse layers orientated in random direction. Further SEM studies reveal that, the Cu-SnO2 nanoparticles formed by oxalic acid could posses high surface area with large number layered structured enables the better electrochemical properties and its applications.

Influence of culture media on the physical and chemical properties of Ag-TiCN coatings

NASA Astrophysics Data System (ADS)

Carvalho, I.; Escobar Galindo, R.; Henriques, M.; Palacio, C.; Carvalho, S.

2014-08-01

The aim of this study was to verify the possible physical and chemical changes that may occur on the surface of Ag-TiCN coatings after exposure to the culture media used in microbiological and cytotoxic assays, respectively tryptic soy broth (TSB) and Dulbecco's modified eagle's medium (DMEM). After sample immersion for 24 h in the media, analyses were performed by glow discharge optical emission spectroscopy discharge radiation (GDOES), Rutherford backscattering spectroscopy (RBS) and x-ray photoelectron spectroscopy (XPS). The results of GDOES profile, RBS and XPS spectra, of samples immersed in TSB, demonstrated the formation of a thin layer of carbon, oxygen and nitrogen that could be due to the presence of proteins in TSB. After 24 h of immersion in DMEM, the results showed the formation of a thin layer of calcium phosphates on the surface, since the coatings displayed a highly oxidized surface in which calcium and phosphorus were detected. All these results suggested that the formation of a layer on the coating surface prevented the release of silver ions in concentrations that allow antibacterial activity.

Tube Formation in Nanoscale Materials

PubMed Central

2008-01-01

The formation of tubular nanostructures normally requires layered, anisotropic, or pseudo-layered crystal structures, while inorganic compounds typically do not possess such structures, inorganic nanotubes thus have been a hot topic in the past decade. In this article, we review recent research activities on nanotubes fabrication and focus on three novel synthetic strategies for generating nanotubes from inorganic materials that do not have a layered structure. Specifically, thermal oxidation method based on gas–solid reaction to porous CuO nanotubes has been successfully established, semiconductor ZnS and Nb2O5nanotubes have been prepared by employing sacrificial template strategy based on liquid–solid reaction, and an in situ template method has been developed for the preparation of ZnO taper tubes through a chemical etching reaction. We have described the nanotube formation processes and illustrated the detailed key factors during their growth. The proposed mechanisms are presented for nanotube fabrication and the important pioneering studies are discussed on the rational design and fabrication of functional materials with tubular structures. It is the intention of this contribution to provide a brief account of these research activities. PMID:20592945

Influence of source and drain contacts on the properties of indium-gallium-zinc-oxide thin-film transistors based on amorphous carbon nanofilm as barrier layer.

PubMed

Luo, Dongxiang; Xu, Hua; Zhao, Mingjie; Li, Min; Xu, Miao; Zou, Jianhua; Tao, Hong; Wang, Lei; Peng, Junbiao

2015-02-18

Amorphous indium-gallium-zinc-oxide thin film transistors (α-IGZO TFTs) with damage-free back channel wet-etch (BCE) process were achieved by introducing a carbon nanofilm as a barrier layer. We investigate the effects of different source-and-drain (S/D) materials on TFT performance. We find the TFT with Ti/C S/D electrodes exhibits a superior performance with higher output current, lower threshold voltage, and higher effective electron mobility compared to that of Mo/C S/D electrodes. Transmittance electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) are employed to analysis the interfacial interaction between S/D metal/C/α-IGZO layers. The results indicate that the better performance of TFTs with Ti/C electrodes should be attributed to the formations of Ti-C and Ti-O at the Ti/C-contact regions, which lead to a lower contact resistance, whereas Mo film is relatively stable and does not react easily with C nanofilm, resulting in a nonohmic contact behavior between Mo/C and α-IGZO layer. However, both kinds of α-IGZO TFTs show good stability under thermal bias stress, indicating that the inserted C nanofilms could avoid the impact on the α-IGZO channel regions during S/D electrodes formation. Finally, we successfully fabricated a high-definition active-matrix organic lighting emitting diode prototype driven by α-IGZO TFTs with Ti/C electrodes in a pilot line.

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.

Insights into Interfacial Changes and Photoelectrochemical Stability of In(x)Ga(1-x)N (0001) Photoanode Surfaces in Liquid Environments.

PubMed

Caccamo, Lorenzo; Cocco, Giulio; Martín, Gemma; Zhou, Hao; Fundling, Sönke; Gad, Alaaeldin; Mohajerani, Matin Sadat; Abdelfatah, Mahmoud; Estradé, Sonia; Peiró, Francesca; Dziony, Wanja; Bremers, Heiko; Hangleiter, Andreas; Mayrhofer, Leonhard; Lilienkamp, Gerhard; Moseler, Michael; Daum, Winfried; Waag, Andreas

2016-03-01

The long-term stability of InGaN photoanodes in liquid environments is an essential requirement for their use in photoelectrochemistry. In this paper, we investigate the relationships between the compositional changes at the surface of n-type In(x)Ga(1-x)N (x ∼ 0.10) and its photoelectrochemical stability in phosphate buffer solutions with pH 7.4 and 11.3. Surface analyses reveal that InGaN undergoes oxidation under photoelectrochemical operation conditions (i.e., under solar light illumination and constant bias of 0.5 VRHE), forming a thin amorphous oxide layer having a pH-dependent chemical composition. We found that the formed oxide is mainly composed of Ga-O bonds at pH 7.4, whereas at pH 11.3 the In-O bonds are dominant. The photoelectrical properties of InGaN photoanodes are intimately related to the chemical composition of their surface oxides. For instance, after the formation of the oxide layer (mainly Ga-O bonds) at pH 7.4, no photocurrent flow was observed, whereas the oxide layer (mainly In-O bonds) at pH 11.3 contributes to enhance the photocurrent, possibly because of its reported high photocatalytic activity. Once a critical oxide thickness was reached, especially at pH 7.4, no significant changes in the photoelectrical properties were observed for the rest of the test duration. This study provides new insights into the oxidation processes occurring at the InGaN/liquid interface, which can be exploited to improve InGaN stability and enhance photoanode performance for biosensing and water-splitting applications.

High Temperature Superconducting Thick Films

DOEpatents

Arendt, Paul N.; Foltyn, Stephen R.; Groves, James R.; Holesinger, Terry G.; Jia, Quanxi

2005-08-23

An article including a substrate, a layer of an inert oxide material upon the surface of the substrate, (generally the inert oxide material layer has a smooth surface, i.e., a RMS roughness of less than about 2 nm), a layer of an amorphous oxide or oxynitride material upon the inert oxide material layer, a layer of an oriented cubic oxide material having a rock-salt-like structure upon the amorphous oxide material layer is provided together with additional layers such as at least one layer of a buffer material upon the oriented cubic oxide material layer or a HTS top-layer of YBCO directly upon the oriented cubic oxide material layer. With a HTS top-layer of YBCO upon at least one layer of a buffer material in such an article, Jc's of 1.4×106 A/cm2 have been demonstrated with projected Ic's of 210 Amperes across a sample 1 cm wide.

Oxidation preventative capping layer for deep-ultra-violet and soft x-ray multilayers

DOEpatents

Prisbrey, Shon T.

2004-07-06

The invention uses iridium and iridium compounds as a protective capping layer on multilayers having reflectivity in the deep ultra-violet to soft x-ray regime. The iridium compounds can be formed in one of two ways: by direct deposition of the iridium compound from a prepared target or by depositing a thin layer (e.g., 5-50 angstroms) of iridium directly onto an element. The deposition energy of the incoming iridium is sufficient to activate the formation of the desired iridium compound. The compounds of most interest are iridium silicide (IrSi.sub.x) and iridium molybdenide (IrMo.sub.x).

Mechanical tearing of graphene on an oxidizing metal surface.

PubMed

George, Lijin; Gupta, Aparna; Shaina, P R; Das Gupta, Nandita; Jaiswal, Manu

2015-12-11

Graphene, the thinnest possible anticorrosion and gas-permeation barrier, is poised to transform the protective coatings industry for a variety of surface applications. In this work, we have studied the structural changes of graphene when the underlying copper surface undergoes oxidation upon heating. Single-layer graphene directly grown on a copper surface by chemical vapour deposition was annealed under ambient atmosphere conditions up to 400 °C. The onset temperature of the surface oxidation of copper is found to be higher for graphene-coated foils. Parallel arrays of graphene nanoripples are a ubiquitous feature of pristine graphene on copper, and we demonstrate that these form crucial sites for the onset of the oxidation of copper, particularly for ∼0.3-0.4 μm ripple widths. In these regions, the oxidation proceeds along the length of the nanoripples, resulting in the formation of parallel stripes of oxidized copper regions. We demonstrate from temperature-dependent Raman spectroscopy that the primary defect formation process in graphene involves boundary-type defects rather than vacancy or sp(3)-type defects. This observation is consistent with a mechanical tearing process that splits graphene into small polycrystalline domains. The size of these is estimated to be sub-50 nm.

Solvent polarity effect on quality of n-octadecanethiol self-assembled monolayers on copper and oxidized copper

NASA Astrophysics Data System (ADS)

Zhang, Yaozhong; Zhou, Jun; Zhang, Xiaoli; Hu, Jun; Gao, Han

2014-11-01

This article reports the effect of solvent polarity on the formation of n-octadecanethiol self-assembled monolayers (C18SH-SAMs) on pure copper surface and oxidized copper surface. The quality of SAMs prepared in different solvents (n-hexane, toluene, trichloroethylene, chloroform, acetone, acetonitrile, ethanol) was monitored by EIS, RAIRS and XPS. The results indicated that C18SH-SAMs formed in these solvents were in good barrier properties on pure copper surface and the structures of monolayers formed in high polarity solvents were more compact and orderly than that formed in low polarity solvents. For comparison, C18SH adsorbed on the surface of oxidized copper in these solvents were studied and the results indicated that C18SH could be adsorbed on oxidized copper surface after the reduction of copper oxide layer by thiols. Compared with high polarity solvents, a limited reduction process of oxidized copper by thiols led to the incompletely formation of monolayers in low polarity solvents. This can be interpreted that the generated water on solid-liquid interface and a smaller reaction force restrict the continuous reduction reaction in low polarity solvents

Method of Fabrication of High Power Density Solid Oxide Fuel Cells

DOEpatents

Pham, Ai Quoc; Glass, Robert S.

2008-09-09

A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O(LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

Creating fluid injectivity in tar sands formations

DOEpatents

Stegemeier, George Leo; Beer, Gary Lee; Zhang, Etuan

2012-06-05

Methods for treating a tar sands formation are described herein. Methods for treating a tar sands may include heating a portion of a hydrocarbon layer in the formation from one or more heaters located in the portion. The heat may be controlled to increase the permeability of at least part of the portion to create an injection zone in the portion with an average permeability sufficient to allow injection of a fluid through the injection zone. A drive fluid and/or an oxidizing fluid may be provided into the injection zone. At least some hydrocarbons including mobilized hydrocarbons are produced from the portion.

Creating fluid injectivity in tar sands formations

DOEpatents

Stegemeier, George Leo; Beer, Gary Lee; Zhang, Etuan

2010-06-08

Methods for treating a tar sands formation are described herein. Methods for treating a tar sands may include heating a portion of a hydrocarbon layer in the formation from one or more heaters located in the portion. The heat may be controlled to increase the permeability of at least part of the portion to create an injection zone in the portion with an average permeability sufficient to allow injection of a fluid through the injection zone. A drive fluid and/or an oxidizing fluid may be provided into the injection zone. At least some hydrocarbons are produced from the portion.

Perpendicularly magnetized (001)-textured D0{sub 22} MnGa films grown on an (Mg{sub 0.2}Ti{sub 0.8})O buffer with thermally oxidized Si substrates

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

Lee, Hwachol; Sukegawa, Hiroaki, E-mail: sukegawa.hiroaki@nims.go.jp; Liu, Jun

2015-10-28

We report the growth of (001)-textured polycrystalline D0{sub 22} MnGa films with perpendicular magnetic anisotropy (PMA) on thermally oxidized Si substrates using an (Mg{sub 0.2}Ti{sub 0.8})O (MTO) buffer layer. The ordered D0{sub 22} MnGa film grown at the optimum substrate temperature of 530 °C on the MTO buffer layer shows PMA with magnetization of 80 kA/m, PMA energy density of 0.28 MJ/m{sup 3}, and coercivity of 2.3 T. The scanning transmission electron microscope analysis confirms the formation of a highly (001)-textured structure and the elementally sharp interfaces between the MTO layer and the MnGa layer. The achieved D0{sub 22} MnGa PMA films on anmore » amorphous substrate will provide the possible pathway of integration of a Mn-based PMA film into Si-based substrates.« less

Influence of shielding gas on the mechanical and metallurgical properties of DP-GMA-welded 5083-H321 aluminum alloy

NASA Astrophysics Data System (ADS)

Koushki, Amin Reza; Goodarzi, Massoud; Paidar, Moslem

2016-12-01

In the present research, 6-mm-thick 5083-H321 aluminum alloy was joined by the double-pulsed gas metal arc welding (DP-GMAW) process. The objective was to investigate the influence of the shielding gas composition on the microstructure and properties of GMA welds. A macrostructural study indicated that the addition of nitrogen and oxygen to the argon shielding gas resulted in better weld penetration. Furthermore, the tensile strength and bending strength of the welds were improved when oxygen and nitrogen (at concentrations as high as approximately 0.1vol%) were added to the shielding gas; however, these properties were adversely affected when the oxygen and nitrogen contents were increased further. This behavior was attributed to the formation of excessive brown and black oxide films on the bead surface, the formation of intermetallic compounds in the weld metal, and the formation of thicker oxide layers on the bead surface with increasing nitrogen and oxygen contents in the argon-based shielding gas. Analysis by energy-dispersive X-ray spectroscopy revealed that most of these compounds are nitrides or oxides.

Thermal degradation study of silicon carbide threads developed for advanced flexible thermal protection systems

NASA Technical Reports Server (NTRS)

Tran, Huy Kim; Sawko, Paul M.

1992-01-01

Silicon carbide (SiC) fiber is a material that may be used in advanced thermal protection systems (TPS) for future aerospace vehicles. SiC fiber's mechanical properties depend greatly on the presence or absence of sizing and its microstructure. In this research, silicon dioxide is found to be present on the surface of the fiber. Electron Spectroscopy for Chemical Analysis (ESCA) and Scanning Electron Microscopy (SEM) show that a thin oxide layer (SiO2) exists on the as-received fibers, and the oxide thickness increases when the fibers are exposed to high temperature. ESCA also reveals no evidence of Si-C bonding on the fiber surface on both as-received and heat treated fibers. The silicon oxide layer is thought to signal the decomposition of SiC bonds and may be partially responsible for the degradation in the breaking strength observed at temperatures above 400 C. The variation in electrical resistivity of the fibers with increasing temperature indicates a transition to a higher band gap material at 350 to 600 C. This is consistent with a decomposition of SiC involving silicon oxide formation.

A highly active and stable IrO x/SrIrO 3 catalyst for the oxygen evolution reaction

DOE PAGES

Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori; ...

2016-09-02

Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrO x/SrIrO 3) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO 3. This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidicmore » electrolyte. Here, density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO 3 or anatase IrO 2 motifs. The IrO x/SrIrO 3 catalyst outperforms known IrO x and ruthenium oxide (RuO x) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte.« less

A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction.

PubMed

Seitz, Linsey C; Dickens, Colin F; Nishio, Kazunori; Hikita, Yasuyuki; Montoya, Joseph; Doyle, Andrew; Kirk, Charlotte; Vojvodic, Aleksandra; Hwang, Harold Y; Norskov, Jens K; Jaramillo, Thomas F

2016-09-02

Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrO x /SrIrO 3 ) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO 3 This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidic electrolyte. Density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO 3 or anatase IrO 2 motifs. The IrO x /SrIrO 3 catalyst outperforms known IrO x and ruthenium oxide (RuO x ) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte. Copyright © 2016, American Association for the Advancement of Science.

Formation and characterization of Ta2O5/TaOx films formed by O ion implantation

NASA Astrophysics Data System (ADS)

Ruffell, S.; Kurunczi, P.; England, J.; Erokhin, Y.; Hautala, J.; Elliman, R. G.

2013-07-01

Ta2O5/TaOx (oxide/suboxide) heterostructures are fabricated by high fluence O ion-implantation into deposited Ta films. The resultant films are characterized by depth profiling X-ray photoelectron spectroscopy (XPS), cross-sectional transmission electron microscopy (XTEM), four-point probe, and current-voltage and capacitance-voltage measurements. The measurements show that Ta2O5/TaOx oxide/suboxide heterostructures can be fabricated with the relative thicknesses of the layers controlled by implantation energy and fluence. Electrical measurements show that this approach has promise for high volume manufacturing of resistive switching memory devices based on oxide/suboxide heterostructures.

Modeling and observational constraints on the sulfur cycle in the marine troposphere: a focus on reactive halogens and multiphase chemistry

NASA Astrophysics Data System (ADS)

Chen, Q.; Breider, T.; Schmidt, J.; Sherwen, T.; Evans, M. J.; Xie, Z.; Quinn, P.; Bates, T. S.; Alexander, B.

2017-12-01

The radiative forcing from marine boundary layer clouds is still highly uncertain, which partly stems from our poor understanding of cloud condensation nuclei (CCN) formation. The oxidation of dimethyl sulfide (DMS) and subsequent chemical evolution of its products (e.g. DMSO) are key processes in CCN formation, but are generally very simplified in large-scale models. Recent research has pointed out the importance of reactive halogens (e.g. BrO and Cl) and multiphase chemistry in the tropospheric sulfur cycle. In this study, we implement a series of sulfur oxidation mechanisms into the GEOS-Chem global chemical transport model, involving both gas-phase and multiphase oxidation of DMS, DMSO, MSIA and MSA, to improve our understanding of the sulfur cycle in the marine troposphere. DMS observations from six locations around the globe and MSA/nssSO42- ratio observations from two ship cruises covering a wide range of latitudes and longitudes are used to assess the model. Preliminary results reveal the important role of BrO for DMS oxidation at high latitudes (up to 50% over Southern Ocean). Oxidation of DMS by Cl radicals is small in the model (within 10% in the marine troposphere), probably due to an underrepresentation of Cl sources. Multiphase chemistry (e.g. oxidation by OH and O3 in cloud droplets) is not important for DMS oxidation but is critical for DMSO oxidation and MSA production and removal. In our model, about half of the DMSO is oxidized in clouds, leading to the formation of MSIA, which is further oxidized to form MSA. Overall, with the addition of reactive halogens and multiphase chemistry, the model is able to better reproduce observations of seasonal variations of DMS and MSA/nssSO42- ratios.

Controlling Surface Chemistry of Gallium Liquid Metal Alloys to Enhance their Fluidic Properties

NASA Astrophysics Data System (ADS)

Ilyas, Nahid; Cumby, Brad; Cook, Alexander; Durstock, Michael; Tabor, Christopher; Materials; Manufacturing Directorate Team

Gallium liquid metal alloys (GaLMAs) are one of the key components of emerging technologies in reconfigurable electronics, such as tunable radio frequency antennas and electronic switches. Reversible flow of GaLMA in microchannels of these types of devices is hindered by the instantaneous formation of its oxide skin in ambient environment. The oxide film sticks to most surfaces leaving unwanted metallic residues that can cause undesired electronic properties. In this report, residue-free reversible flow of a binary alloy of gallium (eutectic gallium indium) is demonstrated via two types of surface modifications where the oxide film is either protected by an organic thin film or chemically removed. An interface modification layer (alkyl phosphonic acids) was introduced into the microfluidic system to modify the liquid metal surface and protect its oxide layer. Alternatively, an ion exchange membrane was utilized as a 'sponge-like' channel material to store and slowly release small amounts of HCl to react with the surface oxide of the liquid metal. Characterization of these interfaces at molecular level by surface spectroscopy and microscopy provided with mechanistic details for the interfacial interactions between the liquid metal surface and the channel materials.

Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

DOE PAGES

Zhang, Yijun; Liu, Ming; Peng, Bin; ...

2016-01-27

Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe 2O 3 and superparamagnetic Fe 2O 3with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe 2O 3 in a reducing atmosphere leads to the formation of the spinel Fe 3O 4 phase which displaysmore » a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. Finally, the ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.« less

The enzymatic oxidation of graphene oxide.

PubMed

Kotchey, Gregg P; Allen, Brett L; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A; Tyurina, Yulia Y; Klein-Seetharaman, Judith; Kagan, Valerian E; Star, Alexander

2011-03-22

Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon--the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (∼40 μM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, ultraviolet-visible, electron paramagnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, atomic force microscopy, sodium dodecyl sulfate-polyacrylamide gel electrophoresis, and gas chromatography-mass spectrometry. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Owing to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors.

Transport Properties of Anatase-TiO2 Polycrystalline-Thin-Film Field-Effect Transistors with Electrolyte Gate Layers

NASA Astrophysics Data System (ADS)

Horita, Ryohei; Ohtani, Kyosuke; Kai, Takahiro; Murao, Yusuke; Nishida, Hiroya; Toya, Taku; Seo, Kentaro; Sakai, Mio; Okuda, Tetsuji

2013-11-01

We have fabricated anatase-TiO2 polycrystalline-thin-film field-effect transistors (FETs) with poly(vinyl alcohol) (PVA), ion-liquid (IL), and ion-gel (IG) gate layers, and have tried to improve the response to gate voltage by varying the concentration of mobile ions in these electrolyte gate layers. The increase in the concentration of mobile ions by doping NaOH into the PVA gate layer or reducing the gelator in the IG gate layer markedly increases the drain-source current and reduces the driving gate voltage, which show that the mobile ions in the PVA, IL, and IG gate layers cause the formation of electric double layers (EDLs), which act as nanogap capacitors. In these TiO2-EDL-FETs, the slow formation of EDLs and the oxidation reaction at the interface between the surface of the TiO2 film and the electrolytes cause unideal FET properties. In the optimized IL and IG TiO2-EDL-FETs, the driving gate voltage is less than 1 V and the ON/OFF ratios of the transfer characteristics are about 1×104 at RT, and the nearly metallic state is realized at the interface purely by applying a gate voltage.

Development of Cu Clad Cu-Zr Based Metallic Glass and Its Solderability

NASA Astrophysics Data System (ADS)

Terajima, Takeshi; Kimura, Hisamichi; Inoue, Akihisa

Soldering is a candidate technique for joining metallic glasses. It can be processed far below the crystallization temperatures of the various metallic glasses so that there is no possibility of crystallization. However, wettability of Cu-Zr based metallic glass by Pb free solder is poor because a strong surface oxide film interferes direct contact between them. To overcome the problem, Cu thin film clad metallic glass was developed. It was preliminary produced by casting a melt of Cu36Zr48Al8Ag8 pre-alloy into Cu mold cavity, inside which Cu thin film with 2 mm in thickness was set on the wall. Cu36Zr48Al8Ag8 metallic glass, whose surface Cu thin film was welded to, was successfully produced. From the microstructure analyses, it was found that reaction layer was formed at the interface between Cu and Cu36Zr48Al8Ag8 metallic glass, however, there was no oxide in the Cu clad layer. Solderability to the metallic glass was drastically increased. The Cu clad layer played an important role to prevent the formation of surface oxide film and consequently improved the solderability.

Oxide-free aC/Zr0.65Al0.075Cu0.275/aC phase plates for transmission electron microscopy.

PubMed

Dries, M; Obermair, M; Hettler, S; Hermann, P; Seemann, K; Seifried, F; Ulrich, S; Fischer, R; Gerthsen, D

2018-06-01

Thin-film phase plates (PP) have become a valuable tool for the imaging of organic objects in transmission electron microscopy (TEM). The thin film usually consists of amorphous carbon (aC), which undergoes rapid aging under intense illumination with high-energy electrons. The limited lifetime of aC film PPs calls for alternative PP materials with improved material stability. This work presents thin-film PPs fabricated from the metallic glass alloy Zr 0.65 Al 0.075 Cu 0.275 (ZAC), which was identified as a promising PP material with beneficial properties, such as a large inelastic mean free path. An adverse effect of the ZAC alloy is the formation of a surface oxide layer in ambient air, which reduces the electrical conductivity and causes electrostatic charging in the electron beam. To avoid surface oxidation, the ZAC alloy is enclosed by thin aC layers. The resulting aC/ZAC/aC layer system is used to fabricate Zernike and Hilbert PPs. Phase-contrast TEM imaging is demonstrated for a sample of carbon nanotubes, which show strong contrast enhancement in PP TEM images. Copyright © 2018 Elsevier B.V. All rights reserved.

Synergistic Effect of Superhydrophobicity and Oxidized Layers on Corrosion Resistance of Aluminum Alloy Surface Textured by Nanosecond Laser Treatment.

PubMed

Boinovich, Ludmila B; Emelyanenko, Alexandre M; Modestov, Alexander D; Domantovsky, Alexandr G; Emelyanenko, Kirill A

2015-09-02

We report a new efficient method for fabricating a superhydrophobic oxidized surface of aluminum alloys with enhanced resistance to pitting corrosion in sodium chloride solutions. The developed coatings are considered very prospective materials for the automotive industry, shipbuilding, aviation, construction, and medicine. The method is based on nanosecond laser treatment of the surface followed by chemisorption of a hydrophobic agent to achieve the superhydrophobic state of the alloy surface. We have shown that the surface texturing used to fabricate multimodal roughness of the surface may be simultaneously used for modifying the physicochemical properties of the thick surface layer of the substrate itself. Electrochemical and wetting experiments demonstrated that the superhydrophobic state of the metal surface inhibits corrosion processes in chloride solutions for a few days. However, during long-term contact of a superhydrophobic coating with a solution, the wetted area of the coating is subjected to corrosion processes due to the formation of defects. In contrast, the combination of an oxide layer with good barrier properties and the superhydrophobic state of the coating provides remarkable corrosion resistance. The mechanisms for enhancing corrosion protective properties are discussed.

Retardation mechanism of ultrathin Al2O3 interlayer on Y2O3 passivated gallium nitride surface.

PubMed

Quah, Hock Jin; Cheong, Kuan Yew

2014-05-28

A systematic investigation was carried out by incorporating an ultrathin aluminum oxide (Al2O3) as an interlayer between yttrium oxide (Y2O3) passivation layer and GaN substrate. The sandwiched samples were then subjected to postdeposition annealing in oxygen ambient from 400 to 800 °C. The Al2O3 interlayer was discovered to play a significant role in slowing down inward diffusion of oxygen through the Y2O3 passivation layer as well as in impeding outward diffusion of Ga(3+) and N(3-) from the decomposed GaN surface. These beneficial effects have suppressed subsequent formation of interfacial layer. A mechanism in association with the function of Al2O3 as an interlayer was suggested and discussed. The mechanism was explicitly described on the basis of the obtained results from X-ray diffraction, X-ray photoelectron spectroscopy, energy-filtered transmission electron microscopy (TEM), high resolution TEM, and electron energy loss spectroscopy line scan. A correlation between the proposed mechanism and metal-oxide-semiconductor characteristics of Y2O3/Al2O3/GaN structure has been proposed.

Effect of electrolyte temperature on the formation of self-organized anodic niobium oxide microcones in hot phosphate-glycerol electrolyte

NASA Astrophysics Data System (ADS)

Yang, S.; Aoki, Y.; Habazaki, H.

2011-07-01

Nanoporous niobium oxide films with microcone-type surface morphology were formed by anodizing at 10 V in glycerol electrolyte containing 0.6 mol dm -3 K 2HPO 4 and 0.2 mol dm -3 K 3PO 4 in a temperature range of 428-453 K. The microcones appeared after prolonged anodizing, but the required time was largely reduced by increasing electrolyte temperature. The anodic oxide was initially amorphous at all temperatures, but crystalline oxide nucleated during anodizing. The anodic oxide microcones, which were crystalline, appeared on surface as a consequence of preferential chemical dissolution of initially formed amorphous oxide. The chemical dissolution of an initially formed amorphous layer was accelerated by increasing the electrolyte temperature, with negligible influence of the temperature on the morphology of microcones up to 448 K.

Bonding Cu to Al2O3 with Bi-B-Zn Oxide Glass Via Oxidation-Reduction Reaction

NASA Astrophysics Data System (ADS)

Chen, Jianqiang; Li, Yufeng; Miao, Weiliang; Mai, Chengle; Li, Mingyu

2018-01-01

Bonding Cu on Al2O3 is a key and difficult technology applied in high-power semiconductor devices. A method proposed in this work investigates bonding with a kind of Bi-B-Zn oxide glass powder paste as a solder. Oxidation-reduction reactions between the Cu plate and the solder took place and generated Bi metal during the joining procedure. With an increase in the joining temperature, the tensile strength increased due to the increase of Bi metal formation. The Bi metal played an important role in joining Cu and Al2O3 because of its much better wettability on Cu than that of the oxides. A compound ZnAl2O4 was observed to form between the Al2O3 ceramic and oxide layer, which strengthened the bond.

Oxidized crystalline (3 × 1)-O surface phases of InAs and InSb studied by high-resolution photoelectron spectroscopy

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

Tuominen, M., E-mail: tmleir@utu.fi, E-mail: pekka.laukkanen@utu.fi; Lång, J.; Dahl, J.

2015-01-05

The pre-oxidized crystalline (3×1)-O structure of InAs(100) has been recently found to significantly improve insulator/InAs junctions for devices, but the atomic structure and formation of this useful oxide layer are not well understood. We report high-resolution photoelectron spectroscopy analysis of (3×1)-O on InAs(100) and InSb(100). The findings reveal that the atomic structure of (3×1)-O consists of In atoms with unexpected negative (between −0.64 and −0.47 eV) and only moderate positive (In{sub 2}O type) core-level shifts; highly oxidized group-V sites; and four different oxygen sites. These fingerprint shifts are compared to those of previously studied oxides of III-V to elucidate oxidation processes.

Active phase distribution changes within a catalyst particle during Fischer–Tropsch synthesis as revealed by multi-scale microscopy

DOE PAGES

Cats, K. H.; Andrews, J. C.; Stephan, O.; ...

2016-02-16

In this study, the Fischer-Tropsch synthesis (FTS) reaction is one of the most promising processes to convert alternative energy sources, such as natural gas, coal or biomass, into liquid fuels and other high-value products. Despite its commercial implementation, we still lack fundamental insights into the various deactivation processes taking place during FTS. In this work, a combination of three methods for studying single catalyst particles at different length scales has been developed and applied to study the deactivation of Co/TiO 2 Fischer-Tropsch synthesis (FTS) catalysts. By combining transmission X-ray microscopy (TXM), scanning transmission X-ray microscopy (STXM) and scanning transmission electronmore » microscopy-electron energy loss spectroscopy (STEM-EELS) we visualized changes in the structure, aggregate size and distribution of supported Co nanoparticles that occur during FTS. At the microscale, Co nanoparticle aggregates are transported over several μm leading to a more homogeneous Co distribution, while at the nanoscale Co forms a thin layer of ~1-2 nm around the TiO 2 support. The formation of the Co layer is the opposite case to the “classical” strong metal-support interaction (SMSI) in which TiO 2 surrounds the Co, and is possibly related to the surface oxidation of Co metal nanoparticles in combination with coke formation. In other words, the observed migration and formation of a thin CoO x layer are similar to a previously discussed reaction-induced spreading of metal oxides across a TiO 2 surface.« less

Oxidation characteristics of porous-nickel prepared by powder metallurgy and cast-nickel at 1273 K in air for total oxidation time of 100 h.

PubMed

Mohamed, Lamiaa Z; Ghanem, Wafaa A; El Kady, Omayma A; Lotfy, Mohamed M; Ahmed, Hafiz A; Elrefaie, Fawzi A

2017-11-01

The oxidation behavior of two types of inhomogeneous nickel was investigated in air at 1273 K for a total oxidation time of 100 h. The two types were porous sintered-nickel and microstructurally inhomogeneous cast-nickel. The porous-nickel samples were fabricated by compacting Ni powder followed by sintering in vacuum at 1473 K for 2 h. The oxidation kinetics of the samples was determined gravimetrically. The topography and the cross-section microstructure of each oxidized sample were observed using optical and scanning electron microscopy. X-ray diffractometry and X-ray energy dispersive analysis were used to determine the nature of the formed oxide phases. The kinetic results revealed that the porous-nickel samples had higher trend for irreproducibility. The average oxidation rate for porous- and cast-nickel samples was initially rapid, and then decreased gradually to become linear. Linear rate constants were 5.5 × 10 -8  g/cm 2  s and 3.4 × 10 -8  g/cm 2  s for the porous- and cast-nickel samples, respectively. Initially a single-porous non-adherent NiO layer was noticed on the porous- and cast-nickel samples. After a longer time of oxidation, a non-adherent duplex NiO scale was formed. The two layers of the duplex scales were different in color. NiO particles were observed in most of the pores of the porous-nickel samples. Finally, the linear oxidation kinetics and the formation of porous non-adherent duplex oxide scales on the inhomogeneous nickel substrates demonstrated that the addition of new layers of NiO occurred at the scale/metal interface due to the thermodynamically possible reaction between Ni and the molecular oxygen migrating inwardly.

Control of the wrinkle structure on surface-reformed poly(dimethylsiloxane) via ion-beam bombardment

NASA Astrophysics Data System (ADS)

Park, Hong-Gyu; Jeong, Hae-Chang; Jung, Yoon Ho; Seo, Dae-Shik

2015-07-01

We investigated the surface reformation of poly(dimethylsiloxane) (PDMS) elastomers by means of ion beam bombardment for fabricating wrinkle structures. Oxidation on the PDMS surface formed a silica-like outer layer that interacted with the inner PDMS layer, leading to the formation of wrinkle structures that minimized the combined bending energy of the outer layer and stretching energy of the inner layer. In addition, we controlled the amplitude and period of the wrinkle structures by adjusting the PDMS annealing temperature. As the PDMS annealing temperature was increased, the amplitude and period of the wrinkles formed by IB irradiation changed from 604.35 to 69.01 nm and from 3.07 to 0.80 μm, respectively.

Influence of the Surface Layer on the Electrochemical Deposition of Metals and Semiconductors into Mesoporous Silicon

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

Chubenko, E. B., E-mail: eugene.chubenko@gmail.com; Redko, S. V.; Sherstnyov, A. I.

2016-03-15

The influence of the surface layer on the process of the electrochemical deposition of metals and semiconductors into porous silicon is studied. It is shown that the surface layer differs in structure and electrical characteristics from the host porous silicon bulk. It is established that a decrease in the conductivity of silicon crystallites that form the surface layer of porous silicon has a positive effect on the process of the filling of porous silicon with metals and semiconductors. This is demonstrated by the example of nickel and zinc oxide. The effect can be used for the formation of nanocomposite materialsmore » on the basis of porous silicon and nanostructures with a high aspect ratio.« less

In Situ Study of Silicon Electrode Lithiation with X-ray Reflectivity

DOE PAGES

Cao, Chuntian; Steinrück, Hans-Georg; Shyam, Badri; ...

2016-10-26

Surface sensitive X-ray reflectivity (XRR) measurements were performed to investigate the electrochemical lithiation of a native oxide terminated single crystalline silicon (100) electrode in real time during the first galvanostatic discharge cycle. This allows us to gain nanoscale, mechanistic insight into the lithiation of Si and the formation of the solid electrolyte interphase (SEI). We describe an electrochemistry cell specifically designed for in situ XRR studies and have determined the evolution of the electron density profile of the lithiated Si layer (Li xSi) and the SEI layer with subnanometer resolution. We propose a three-stage lithiation mechanism with a reaction limited,more » layer-by-layer lithiation of the Si at the Li xSi/Si interface.« less

Study on monatomic fraction improvement with alumina layer on metal electrode in hydrogen plasma ion source.

PubMed

Jung, Bong-Ki; Chung, Kyoung-Jae; Dang, Jeong-Jeung; Hwang, Y S

2012-02-01

A high monatomic beam fraction is an important factor in a hydrogen ion source to increase the application efficiency. The monatomic fraction of hydrogen plasmas with different plasma electrode materials is measured in a helicon plasma ion source, and aluminum shows the highest value compared to that with the other metals such as copper and molybdenum. Formation of an aluminum oxide layer on the aluminum electrode is determined by XPS analysis, and the alumina layer is verified as the high monatomic fraction. Both experiments and numerical simulations conclude that a low surface recombination coefficient of the alumina layer on the plasma electrode is one of the most important parameters for increasing the monatomic fraction in hydrogen plasma ion sources.

Study on monatomic fraction improvement with alumina layer on metal electrode in hydrogen plasma ion sourcea)

NASA Astrophysics Data System (ADS)

Jung, Bong-Ki; Chung, Kyoung-Jae; Dang, Jeong-Jeung; Hwang, Y. S.

2012-02-01

A high monatomic beam fraction is an important factor in a hydrogen ion source to increase the application efficiency. The monatomic fraction of hydrogen plasmas with different plasma electrode materials is measured in a helicon plasma ion source, and aluminum shows the highest value compared to that with the other metals such as copper and molybdenum. Formation of an aluminum oxide layer on the aluminum electrode is determined by XPS analysis, and the alumina layer is verified as the high monatomic fraction. Both experiments and numerical simulations conclude that a low surface recombination coefficient of the alumina layer on the plasma electrode is one of the most important parameters for increasing the monatomic fraction in hydrogen plasma ion sources.

Electrophoretic formation of semiconductor layers with adjustable band gap

NASA Astrophysics Data System (ADS)

Shindrov, Alexander; Yuvchenko, Sergey; Vikulova, Maria; Tretyachenko, Elena; Zimnyakov, Dmitry; Gorokhovsky, Alexander

2017-11-01

The ceramic layers of the potassium polytitanates modified by transition metal salts were electrophoretically deposited onto the surface of glassy substrate coated with indium-tin oxide. The deposition allows obtaining a dense ceramic layer formed by composite agglomerates consisting of nanoscale particles with average size of 130-190 nm. The optical absorption spectra of the coatings modified in the mixtures of aqueous solutions of different transition metal salts were investigated. It was recognized that a bandgap value of these composites can be adjusted in a range from 1.4 to 2.3 eV depending the chemical composition of layered double hydroxide obtained during modification. This might be very promising for optoelectronic applications of such coatings due to an explicit control of optical properties.

Redox Reactions between Mn(II) and Hexagonal Birnessite Change Its Layer Symmetry.

PubMed

Zhao, Huaiyan; Zhu, Mengqiang; Li, Wei; Elzinga, Evert J; Villalobos, Mario; Liu, Fan; Zhang, Jing; Feng, Xionghan; Sparks, Donald L

2016-02-16

Birnessite, a phyllomanganate and the most common type of Mn oxide, affects the fate and transport of numerous contaminants and nutrients in nature. Birnessite exhibits hexagonal (HexLayBir) or orthogonal (OrthLayBir) layer symmetry. The two types of birnessite contain contrasting content of layer vacancies and Mn(III), and accordingly have different sorption and oxidation abilities. OrthLayBir can transform to HexLayBir, but it is still vaguely understood if and how the reverse transformation occurs. Here, we show that HexLayBir (e.g., δ-MnO2 and acid birnessite) transforms to OrthLayBir after reaction with aqueous Mn(II) at low Mn(II)/Mn (in HexLayBir) molar ratios (5-24%) and pH ≥ 8. The transformation is promoted by higher pH values, as well as smaller particle size, and/or greater stacking disorder of HexLayBir. The transformation is ascribed to Mn(III) formation via the comproportionation reaction between Mn(II) adsorbed on vacant sites and the surrounding layer Mn(IV), and the subsequent migration of the Mn(III) into the vacancies with an ordered distribution in the birnessite layers. This study indicates that aqueous Mn(II) and pH are critical environmental factors controlling birnessite layer structure and reactivity in the environment.

Effect of solvents on morphology, magnetic and dielectric properties of (α-Fe2O3@SiO2) core-shell nanoparticles.

PubMed

Joshi, Deepika P; Pant, Geeta; Arora, Neha; Nainwal, Seema

2017-02-01

Present work describes the formation of α-Fe 2 O 3 @SiO 2 core shell structure by systematic layer by layer deposition of silica shell on core iron oxide nanoparticles prepared via various solvents. Sol-gel method has been used to synthesize magnetic core and the dielectric shell. The average crystallite size of iron oxide nanoparticles was calculated ∼20 nm by X-ray diffraction pattern. Morphological study by scanning electron microscopy revealed that the core-shell nanoparticles were spherical in shape and the average size of nanoparticles increased by varying solvent from methanol to ethanol to isopropanol due to different chemical structure and nature of the solvents. It was also observed that the particles prepared by solvent ethanol were more regular and homogeneous as compared to other solvents. Magnetic measurements showed the weak ferromagnetic behaviour of both core α-Fe 2 O 3 and silica-coated iron oxide nanoparticles which remained same irrespective of the solvent chosen. However, magnetization showed dependency on the types of solvent chosen due to the variation in shell thickness. At room temperature, dielectric constant and dielectric loss of silica nanoparticles for all the solvents showed decrement with the increment in frequency. Decrement in the value of dielectric constant and increment in dielectric loss was observed for silica coated iron oxide nanoparticles in comparison of pure silica, due to the presence of metallic core. Homogeneous and regular silica layer prepared by using ethanol as a solvent could serve as protecting layer to shield the magnetic behaviour of iron oxide nanoparticles as well as to provide better thermal insulation over pure α-Fe 2 O 3 nanoparticles.

In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

NASA Astrophysics Data System (ADS)

Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

Metal oxide composite enabled nanotextured Si photoanode for efficient solar driven water oxidation.

PubMed

Sun, Ke; Pang, Xiaolu; Shen, Shaohua; Qian, Xueqiang; Cheung, Justin S; Wang, Deli

2013-05-08

We present a study of a transition metal oxide composite modified n-Si photoanode for efficient and stable water oxidation. This sputter-coated composite functions as a protective coating to prevent Si from photodecomposition, a Schottky heterojunction, a hole conducting layer for efficient charge separation and transportation, and an electrocatalyst to reduce the reaction overpotential. The formation of mixed-valence oxides composed of Ni and Ru effectively modifies the optical, electrical, and catalytic properties of the coating material, as well as the interfaces with Si. The successful application of this oxide composite on nanotextured Si demonstrates improved conversion efficiency due to enhanced catalytic activity, minimized reflection, and increased surface reaction sites. Although the coated nanotextured Si shows a noticeable degradation from 500 cycles of operation, the oxide composite provides a simple method to enable unstable photoanode materials for solar fuel conversion.

A high performance transparent resistive switching memory made from ZrO2/AlON bilayer structure

NASA Astrophysics Data System (ADS)

Tsai, Tsung-Ling; Chang, Hsiang-Yu; Lou, Jesse Jen-Chung; Tseng, Tseung-Yuen

2016-04-01

In this study, the switching properties of an indium tin oxide (ITO)/zirconium oxide (ZrO2)/ITO single layer device and those of a device with an aluminum oxynitride (AlON) layer were investigated. The devices with highly transparent characteristics were fabricated. Compared with the ITO/ZrO2/ITO single layer device, the ITO/ZrO2/AlON/ITO bilayer device exhibited a larger ON/OFF ratio, higher endurance performance, and superior retention properties by using a simple two-step forming process. These substantial improvements in the resistive switching properties were attributed to the minimized influence of oxygen migration through the ITO top electrode (TE), which can be realized by forming an asymmetrical conductive filament with the weakest part at the ZrO2/AlON interface. Therefore, in the ITO/ZrO2/AlON/ITO bilayer device, the regions where conductive filament formation and rupture occur can be effectively moved from the TE interface to the interior of the device.

Investigation of atomic-layer-deposited TiO x as selective electron and hole contacts to crystalline silicon

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

Matsui, Takuya; Bivour, Martin; Ndione, Paul F.

Here, the applicability of atomic-layer-deposited titanium oxide (TiO x) thin films for the formation of carrier selective contacts to crystalline silicon (c-Si) is investigated. While relatively good electron selectivity was presented recently by other groups, we show that carrier selectivity can be engineered from electron to hole selective depending on the deposition conditions, post deposition annealing and the contact material covering the TiOx layer. For both the electron and hole contacts, an open-circuit voltage (Voc) of ~ >650 mV is obtained. The fact that the Voc is correlated with the (asymmetric) induced c-Si band bending suggests that carrier selectivity ismore » mainly governed by the effective work function and/or the fixed charge rather than by the asymmetric band offsets at the Si/TiOx interface, which provides important insight into the basic function of metal-oxide-based contact systems.« less

Investigation of atomic-layer-deposited TiO x as selective electron and hole contacts to crystalline silicon

DOE PAGES

Matsui, Takuya; Bivour, Martin; Ndione, Paul F.; ...

2017-09-21

Here, the applicability of atomic-layer-deposited titanium oxide (TiO x) thin films for the formation of carrier selective contacts to crystalline silicon (c-Si) is investigated. While relatively good electron selectivity was presented recently by other groups, we show that carrier selectivity can be engineered from electron to hole selective depending on the deposition conditions, post deposition annealing and the contact material covering the TiOx layer. For both the electron and hole contacts, an open-circuit voltage (Voc) of ~ >650 mV is obtained. The fact that the Voc is correlated with the (asymmetric) induced c-Si band bending suggests that carrier selectivity ismore » mainly governed by the effective work function and/or the fixed charge rather than by the asymmetric band offsets at the Si/TiOx interface, which provides important insight into the basic function of metal-oxide-based contact systems.« less

Modelling of thermal behaviour of iron oxide layers on boiler tubes

NASA Astrophysics Data System (ADS)

Angelo, J. D.; Bennecer, A.; Kaczmarczyk, S.; Picton, P.

2016-05-01

Slender boiler tubes are subject to localised swelling when they are expose to excessive heat. The latter is due to the formation of an oxide layer, which acts as an insulation barrier. This excessive heat can lead to microstructural changes in the material that would reduce the mechanical strength and would eventually lead to critical and catastrophic failure. Detecting such creep damage remains a formidable challenge for boiler operators. It involves a costly process of shutting down the plant, performing electromagnetic and ultrasonic non-destructive inspection, repairing or replacing damaged tubes and finally restarting the plant to resume its service. This research explores through a model developed using a finite element computer simulation platform the thermal behaviour of slender tubes under constant temperature exceeding 723 °K. Our simulation results demonstrate that hematite layers up to 15 μm thickness inside the tubes do not act as insulation. They clearly show the process of long term overheating on the outside of boiler tubes which in turn leads to initiation of flaws.

Synthesis and characterization of Graphene oxide/Zinc oxide nanorods sandwich structure

NASA Astrophysics Data System (ADS)

Boukhoubza, I.; Khenfouch, M.; Achehboune, M.; Mouthudi, B.; Zorkani, I.; Jorio, A.

2018-03-01

Graphene-ZnO nanostructures composite materials have been used as very efficient candidates for various optoelectronic applications. Nowadays, the composite structure formation of ZnO nanostructures with graphene or graphene oxide is a novel, cost effective and efficient approach to control the morphology, surface defect states, band gap of ZnO nanocrystals. In this paper, we have prepared ZnO nanorods between two layers graphene oxide (GO/ZnO NRs/GO) via a simple hydrothermal method. Their morphology, structural and optical properties have been investigated. The obtained results of our composites GO/ZnO NRs/GO presented here showing an enhancement in the structural and optical properties. Thus may hold great promise to the development of the optoelectronic devices.

Laser surface melting of 10 wt% Mo alloyed hardfacing Stellite 12 plasma transferred arc deposits: Structural evolution and high temperature wear performance

NASA Astrophysics Data System (ADS)

Dilawary, Shaikh Asad Ali; Motallebzadeh, Amir; Afzal, Muhammad; Atar, Erdem; Cimenoglu, Huseyin

2018-05-01

Laser surface melting (LSM) process has been applied on the plasma transferred arc (PTA) deposited Stellite 12 and 10 wt% Mo alloyed Stellite 12 in this study. Following the LSM process, structural and mechanical property comparison of the LSM'ed surfaces has been made. Hardness of the LSM'ed surfaces was measured as 549 HV and 623 HV for the Stellite 12 and Stellite 12 + 10 wt% Mo deposits, respectively. Despite their different hardness and structural features, the LSM'ed surfaces exhibited similar tribological performance at room temperature (RT), where fatigue wear mechanism operates. However, the wear at 500 °C promotes tribo-oxide layer formation whose composition depended on the alloying with Mo. Thus, addition of 10 wt% Mo into Stellite 12 PTA deposit has remarkably enhanced the high temperature wear performance of the LSM'ed surface as a result of participation of complex oxide (CoMoO4) in tribo-oxide layer.

Atomic Scale Study on Growth and Heteroepitaxy of ZnO Monolayer on Graphene.

PubMed

Hong, Hyo-Ki; Jo, Junhyeon; Hwang, Daeyeon; Lee, Jongyeong; Kim, Na Yeon; Son, Seungwoo; Kim, Jung Hwa; Jin, Mi-Jin; Jun, Young Chul; Erni, Rolf; Kwak, Sang Kyu; Yoo, Jung-Woo; Lee, Zonghoon

2017-01-11

Atomically thin semiconducting oxide on graphene carries a unique combination of wide band gap, high charge carrier mobility, and optical transparency, which can be widely applied for optoelectronics. However, study on the epitaxial formation and properties of oxide monolayer on graphene remains unexplored due to hydrophobic graphene surface and limits of conventional bulk deposition technique. Here, we report atomic scale study of heteroepitaxial growth and relationship of a single-atom-thick ZnO layer on graphene using atomic layer deposition. We demonstrate atom-by-atom growth of zinc and oxygen at the preferential zigzag edge of a ZnO monolayer on graphene through in situ observation. We experimentally determine that the thinnest ZnO monolayer has a wide band gap (up to 4.0 eV), due to quantum confinement and graphene-like structure, and high optical transparency. This study can lead to a new class of atomically thin two-dimensional heterostructures of semiconducting oxides formed by highly controlled epitaxial growth.

Electrochemical Formation of Multilayer SnO2-Sb x O y Coating in Complex Electrolyte

NASA Astrophysics Data System (ADS)

Maizelis, Antonina; Bairachniy, Boris

2017-02-01

The multilayer antimony-doped tin dioxide coating was obtained by cathodic deposition of multilayer metal-hydroxide coating with near 100-nm thickness layers on the alloy underlayer accompanied by the anodic oxidation of this coating. The potential regions of deposition of tin, antimony, tin-antimony alloy, and mixture of this metals and their hydroxides in the pyrophosphate-tartrate electrolyte were revealed by the cyclic voltammetric method. The possibility of oxidation of cathodic deposit consisting of tin and Sn(II) hydroxide compounds to the hydrated tin dioxide in the same electrolyte was demonstrated. The operations of alloy underlayer deposition and oxidation of multilayer metal-hydroxide coating were proposed to carry out in the diluted pyrophosphate-tartrate electrolyte, similar to the main electrolyte. The accelerated tests showed higher service life of the titanium electrode with multilayer antimony-doped tin dioxide coating compared to both electrode with single-layer electrodeposited coating and the electrode with the coating obtained using prolonged heat treatment step.

Electrochemical Formation of Multilayer SnO2-Sb x O y Coating in Complex Electrolyte.

PubMed

Maizelis, Antonina; Bairachniy, Boris

2017-12-01

The multilayer antimony-doped tin dioxide coating was obtained by cathodic deposition of multilayer metal-hydroxide coating with near 100-nm thickness layers on the alloy underlayer accompanied by the anodic oxidation of this coating. The potential regions of deposition of tin, antimony, tin-antimony alloy, and mixture of this metals and their hydroxides in the pyrophosphate-tartrate electrolyte were revealed by the cyclic voltammetric method. The possibility of oxidation of cathodic deposit consisting of tin and Sn(II) hydroxide compounds to the hydrated tin dioxide in the same electrolyte was demonstrated.The operations of alloy underlayer deposition and oxidation of multilayer metal-hydroxide coating were proposed to carry out in the diluted pyrophosphate-tartrate electrolyte, similar to the main electrolyte.The accelerated tests showed higher service life of the titanium electrode with multilayer antimony-doped tin dioxide coating compared to both electrode with single-layer electrodeposited coating and the electrode with the coating obtained using prolonged heat treatment step.

High-Temperature Carbon Deposition on Oxide Surfaces by CO Disproportionation

PubMed Central

2016-01-01

Carbon deposition due to the inverse Boudouard reaction (2CO → CO2 + C) has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 in comparison to CH4 by a variety of different chemical, structural, and spectroscopic characterization techniques, including electrochemical impedance spectroscopy (EIS), Fourier-transform infrared (FT-IR) spectroscopy and imaging, Raman spectroscopy, and electron microscopy. Consentaneously, all experimental methods prove the formation of a more or less conducting carbon layer (depending on the used oxide) of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in flowing CO at temperatures above ∼1023 K. All measurements show that during carbon deposition, a more or less substantial surface reduction of the oxides takes place. These results, therefore, reveal that the studied pure oxides can act as efficient nonmetallic substrates for CO-induced growth of highly distorted graphitic carbon with possible important technological implications especially with respect to treatment in pure CO or CO-rich syngas mixtures. Compared to CH4, more carbon is generally deposited in CO under otherwise similar experimental conditions. Although Raman and electron microscopy measurements do not show substantial differences in the structure of the deposited carbon layers, in particular, electrochemical impedance measurements reveal major differences in the dynamic growth process of the carbon layer, eventually leading to less percolated islands and suppressed metallic conductivity in comparison to CH4-induced graphite. PMID:26877828

Polyethylene oxide film coating enhances lithium cycling efficiency of an anode-free lithium-metal battery.

PubMed

Assegie, Addisu Alemayehu; Cheng, Ju-Hsiang; Kuo, Li-Ming; Su, Wei-Nien; Hwang, Bing-Joe

2018-03-29

The practical implementation of an anode-free lithium-metal battery with promising high capacity is hampered by dendrite formation and low coulombic efficiency. Most notably, these challenges stem from non-uniform lithium plating and unstable SEI layer formation on the bare copper electrode. Herein, we revealed the homogeneous deposition of lithium and effective suppression of dendrite formation using a copper electrode coated with a polyethylene oxide (PEO) film in an electrolyte comprising 1 M LiTFSI, DME/DOL (1/1, v/v) and 2 wt% LiNO3. More importantly, the PEO film coating promoted the formation of a thin and robust SEI layer film by hosting lithium and regulating the inevitable reaction of lithium with the electrolyte. The modified electrode exhibited stable cycling of lithium with an average coulombic efficiency of ∼100% over 200 cycles and low voltage hysteresis (∼30 mV) at a current density of 0.5 mA cm-2. Moreover, we tested the anode-free battery experimentally by integrating it with an LiFePO4 cathode into a full-cell configuration (Cu@PEO/LiFePO4). The new cell demonstrated stable cycling with an average coulombic efficiency of 98.6% and capacity retention of 30% in the 200th cycle at a rate of 0.2C. These impressive enhancements in cycle life and capacity retention result from the synergy of the PEO film coating, high electrode-electrolyte interface compatibility, stable polar oligomer formation from the reduction of 1,3-dioxolane and the generation of SEI-stabilizing nitrite and nitride upon lithium nitrate reduction. Our result opens up a new route to realize anode-free batteries by modifying the copper anode with PEO to achieve ever more demanding yet safe interfacial chemistry and control of dendrite formation.

Growth of High-Density Zinc Oxide Nanorods on Porous Silicon by Thermal Evaporation

PubMed Central

Rusli, Nurul Izni; Tanikawa, Masahiro; Mahmood, Mohamad Rusop; Yasui, Kanji; Hashim, Abdul Manaf

2012-01-01

The formation of high-density zinc oxide (ZnO) nanorods on porous silicon (PS) substrates at growth temperatures of 600–1000 °C by a simple thermal evaporation of zinc (Zn) powder in the presence of oxygen (O2) gas was systematically investigated. The high-density growth of ZnO nanorods with (0002) orientation over a large area was attributed to the rough surface of PS, which provides appropriate planes to promote deposition of Zn or ZnOx seeds as nucleation sites for the subsequent growth of ZnO nanorods. The geometrical morphologies of ZnO nanorods are determined by the ZnOx seed structures, i.e., cluster or layer structures. The flower-like hexagonal-faceted ZnO nanorods grown at 600 °C seem to be generated from the sparsely distributed ZnOx nanoclusters. Vertically aligned hexagonal-faceted ZnO nanorods grown at 800 °C may be inferred from the formation of dense arrays of ZnOx clusters. The formation of disordered ZnO nanorods formed at 1000 °C may due to the formation of a ZnOx seed layer. The growth mechanism involved has been described by a combination of self-catalyzed vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism. The results suggest that for a more precise study on the growth of ZnO nanostructures involving the introduction of seeds, the initial seed structures must be taken into account given their significant effects.

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †

PubMed Central

2018-01-01

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed. PMID:29677107

Low-temperature preparation of GaN-SiO2 interfaces with low defect density. II. Remote plasma-assisted oxidation of GaN and nitrogen incorporation

NASA Astrophysics Data System (ADS)

Bae, Choelhwyi; Lucovsky, Gerald

2004-11-01

Low-temperature remote plasma-assisted oxidation and nitridation processes for interface formation and passivation have been extended from Si and SiC to GaN. The initial oxidation kinetics and chemical composition of thin interfacial oxide were determined from analysis of on-line Auger electron spectroscopy features associated with Ga, N, and O. The plasma-assisted oxidation process is self-limiting with power-law kinetics similar to those for the plasma-assisted oxidation of Si and SiC. Oxidation using O2/He plasma forms nearly pure GaOx, and oxidation using 1% N2O in N2 forms GaOxNy with small nitrogen content, ~4-7 at. %. The interface and dielectric layer quality was investigated using fabricated GaN metal-oxide-semiconductor capacitors. The lowest density of interface states was achieved with a two-step plasma-assisted oxidation and nitridation process before SiO2 deposition.

Imprinted Oxide and MIP/Oxide Hybrid Nanomaterials for Chemical Sensors †.

PubMed

Afzal, Adeel; Dickert, Franz L

2018-04-20

The oxides of transition, post-transition and rare-earth metals have a long history of robust and fast responsive recognition elements for electronic, optical, and gravimetric devices. A wide range of applications successfully utilized pristine or doped metal oxides and polymer-oxide hybrids as nanostructured recognition elements for the detection of biologically relevant molecules, harmful organic substances, and drugs as well as for the investigative process control applications. An overview of the selected recognition applications of molecularly imprinted sol-gel phases, metal oxides and hybrid nanomaterials composed of molecularly imprinted polymers (MIP) and metal oxides is presented herein. The formation and fabrication processes for imprinted sol-gel layers, metal oxides, MIP-coated oxide nanoparticles and other MIP/oxide nanohybrids are discussed along with their applications in monitoring bioorganic analytes and processes. The sensor characteristics such as dynamic detection range and limit of detection are compared as the performance criterion and the miniaturization and commercialization possibilities are critically discussed.

Structure for HTS composite conductors and the manufacture of same

DOEpatents

Cotton, J.D.; Riley, G.N. Jr.

1999-06-01

A superconducting oxide composite structure including a superconducting oxide member, a metal layer surrounding the superconducting oxide member, and an insulating layer of a complex oxide formed in situ adjacent to the superconducting oxide member and the metal layer is provided together with a method of forming such a superconducting oxide composite structure including encapsulating a superconducting oxide member or precursor within a metal matrix layer from the group of: (1) a reactive metal sheath adjacent to the superconducting oxide member or precursor, the reactive metal sheath surrounded by a second metal layer or (2) an alloy containing a reactive metal; to form an intermediate product, and, heating the intermediate product at temperatures and for time sufficient to form an insulating layer of a complex oxide in situ, the insulating layer to the superconducting oxide member or precursor and the metal matrix layer. 10 figs.

Structure for hts composite conductors and the manufacture of same

DOEpatents

Cotton, James D.; Riley, Jr., Gilbert Neal

1999-01-01

A superconducting oxide composite structure including a superconducting oxide member, a metal layer surrounding the superconducting oxide member, and an insulating layer of a complex oxide formed in situ adjacent to the superconducting oxide member and the metal layer is provided together with a method of forming such a superconducting oxide composite structure including encapsulating a superconducting oxide member or precursor within a metal matrix layer from the group of: (i) a reactive metal sheath adjacent to the superconducting oxide member or precursor, the reactive metal sheath surrounded by a second metal layer or (ii) an alloy containing a reactive metal; to form an intermediate product, and, heating the intermediate product at temperatures and for time sufficient to form an insulating layer of a complex oxide in situ, the insulating layer to the superconducting oxide member or precursor and the metal matrix layer.

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

Zhang, Hanlei; May, Brian M.; Serrano-Sevillano, Jon

The surface configuration of pristine layered oxide cathode particles for Li-ion batteries significantly affects the electrochemical behavior, which is generally considered to be a thin rock-salt layer in the surface. Unfortunately, aside from its thin nature and spatial location on the surface, the true structural nature of this surface rock-salt layer remains largely unknown, creating the need to understand its configuration and the underlying mechanisms of formation. Using scanning transmission electron microscopy, we have found a correlation between the surface rock-salt formation and the crystal facets on pristine LiNi0.80Co0.15Al0.05O2 primary particles. It is found that the originally (01more » $$ \\overline{4}\\ $$) and (003) surfaces of the layered phase result in two kinds of rock-salt reconstructions: the (002) and (111) rock-salt surfaces, respectively. Stepped surface configurations are generated for both reconstructions. The (002) configuration is relatively flat with monoatomic steps while the (111) configuration shows significant surface roughening. Both reconstructions reduce the ionic and electronic conductivity of the cathode, leading to a reduced electrochemical performance.« less

Impact of a boron rich layer on minority carrier lifetime degradation in boron spin-on dopant diffused n-type crystalline silicon solar cells

NASA Astrophysics Data System (ADS)

Singha, Bandana; Singh Solanki, Chetan

2016-03-01

In the production of n-type crystalline silicon solar cells with boron diffused emitters, the formation of a boron rich layer (BRL) is a common phenomenon and is largely responsible for bulk lifetime degradation. The phenomenon of BRL formation during diffusion of boron spin-on dopant and its impact on bulk lifetime degradation are investigated in this work. The BRL formed beneath the borosilicate glass layer has thicknesses varying from 10 nm-150 nm depending on the diffusion conditions. The effective and bulk minority carrier lifetimes, measured with Al2O3 deposited layers and a quinhydron-methanol solution, show that carrier lifetime degradation is proportional to the BRL thicknesses and their surface recombination velocities. The controlled diffusion processes and different oxidation techniques used in this work can partially reduce the BRL thickness and improve carrier lifetime by more than 10%. But for BRL thicknesses higher than 50 nm, different etching techniques further lower the carrier lifetime and the degradation in the device cannot be recovered.