Sample records for hafnium oxides

  1. Hafnium Oxide Film Etching Using Hydrogen Chloride Gas

    NASA Astrophysics Data System (ADS)

    Habuka, Hitoshi; Yamaji, Masahiko; Kobori, Yoshitsugu; Horii, Sadayoshi; Kunii, Yasuo

    2009-12-01

    Hydrogen chloride gas removes the hafnium oxide film formed by atomic layer deposition at the etch rate of about 1 nm/min. A 100 nm-thick hafnium oxide film was perfectly etched off at 1173 K for 60 min by 100% hydrogen chloride gas at 100 sccm. A weight decrease in the hafnium oxide film was observed at temperatures higher than ca. 600 K, which corresponds to the sublimation point of hafnium tetrachloride. The etching by-product is considered to be hafnium tetrachloride. The etching technique developed in this study is expected to be applicable to various processes, such as the cleaning of a hafnium oxide film deposition reactor.

  2. Formulation and method for preparing gels comprising hydrous hafnium oxide

    DOEpatents

    Collins, Jack L; Hunt, Rodney D; Montgomery, Frederick C

    2013-08-06

    Formulations useful for preparing hydrous hafnium oxide gels contain a metal salt including hafnium, an acid, an organic base, and a complexing agent. Methods for preparing gels containing hydrous hafnium oxide include heating a formulation to a temperature sufficient to induce gel formation, where the formulation contains a metal salt including hafnium, an acid, an organic base, and a complexing agent.

  3. Evidence for oxygen vacancies movement during wake-up in ferroelectric hafnium oxide

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

    Starschich, S.; Böttger, U.; Menzel, S.

    The wake-up effect which is observed in ferroelectric hafnium oxide is investigated in yttrium doped hafnium oxide prepared by chemical solution deposition. It can be shown that not the amount of cycles but the duration of the applied electrical field is essential for the wake-up. Temperature dependent wake-up cycling in a range of −160 °C to 100 °C reveals a strong temperature activation of the wake-up, which can be attributed to ion rearrangement during cycling. By using asymmetrical electrodes, resistive valence change mechanism switching can be observed coincident with ferroelectric switching. From the given results, it can be concluded that redistribution ofmore » oxygen vacancies is the origin of the wake-up effect.« less

  4. Ferroelectric memory based on molybdenum disulfide and ferroelectric hafnium oxide

    NASA Astrophysics Data System (ADS)

    Yap, Wui Chung; Jiang, Hao; Xia, Qiangfei; Zhu, Wenjuan

    Recently, ferroelectric hafnium oxide (HfO2) was discovered as a new type of ferroelectric material with the advantages of high coercive field, excellent scalability (down to 2.5 nm), and good compatibility with CMOS processing. In this work, we demonstrate, for the first time, 2D ferroelectric memories with molybdenum disulfide (MoS2) as the channel material and aluminum doped HfO2 as the ferroelectric gate dielectric. A 16 nm thick layer of HfO2, doped with 5.26% aluminum, was deposited via atomic layer deposition (ALD), then subjected to rapid thermal annealing (RTA) at 1000 °C, and the polarization-voltage characteristics of the resulting metal-ferroelectric-metal (MFM) capacitors were measured, showing a remnant polarization of 0.6 μC/cm2. Ferroelectric memories with embedded ferroelectric hafnium oxide stacks and monolayer MoS2 were fabricated. The transfer characteristics after program and erase pulses revealed a clear ferroelectric memory window. In addition, endurance (up to 10,000 cycles) of the devices were tested and effects associated with ferroelectric materials, such as the wake-up effect and polarization fatigue, were observed. This research can potentially lead to advances of 2D materials in low-power logic and memory applications.

  5. The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

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

    Miao, Yinbin, E-mail: miao2@illinois.edu; Mo, Kun; Cui, Bai

    2015-03-15

    This work reports comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y{sub 2}O{sub 3}, fluorite Y{sub 2}O{sub 3}–HfO{sub 2} solid solution and pyrochlore (or fluorite) Y{sub 2}(Ti,Hf){sub 2−x}O{sub 7−x}. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Two different coherency relationships along with one axis-parallel relation between themore » oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. The results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation. - Highlights: • The oxide nanoparticles in a hafnium-containing austenitic ODS were characterized. • The nanoparticles are Y–Hf–Ti–O enriched phases according to APT and STEM–EDS. • Two coherency and an axis-parallel orientation relationships were found by HR-TEM. • Particle size has a prominent effect on the orientation relationship (OR). • Formation mechanism of the oxide nanoparticles was discussed based on the ORs.« less

  6. Cathodoluminescence Study of Hafnium Oxide

    NASA Astrophysics Data System (ADS)

    Purcell, Emily; Hengehold, Robert; McClory, John

    2011-10-01

    Hafnium dioxide (HfO2) is increasingly being used in place of silicon oxide as a gate insulator in field effect transistors. This is primarily due to its high dielectric constant, κ, of 25. Samples of HfO2 were grown by either atomic layer deposition (ALD) or pulsed laser deposition (PLD), with the PLD samples having assorted substrate temperatures during deposition (300 C, 500 C, and 750 C). Cathodoluminescence (CL) was chosen as the technique used for studying these HfO2 samples. The CL system used was capable of beam energies ranging from 1 keV to 20 keV and beam currents ranging from 10 μA to 50 μA. A Monte Carlo calculation using CASINO software was performed in order to determine the beam energy for the desired depth of penetration. Measurements were taken at sample temperatures ranging from 7K (closed cycled cryostat) to 300K (room temperature), as well as at various beam energies and beam currents. Comparison will be made between the PLD and ALD spectra.

  7. Slow DNA Transport through Nanopores in Hafnium Oxide Membranes

    PubMed Central

    Bell, David C.; Cohen-Karni, Tzahi; Rosenstein, Jacob K.; Wanunu, Meni

    2016-01-01

    We present a study of double- and single-stranded DNA transport through nanopores fabricated in ultrathin (2–7 nm thick) free-standing hafnium oxide (HfO2) membranes. The high chemical stability of ultrathin HfO2 enables long-lived experiments with <2 nm diameter pores that last several hours, in which we observe >50 000 DNA translocations with no detectable pore expansion. Mean DNA velocities are slower than velocities through comparable silicon nitride pores, providing evidence that HfO2 nanopores have favorable physicochemical interactions with nucleic acids that can be leveraged to slow down DNA in a nanopore. PMID:24083444

  8. Hafnium transistor process design for neural interfacing.

    PubMed

    Parent, David W; Basham, Eric J

    2009-01-01

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

  9. Atomic layer deposition and characterization of hafnium oxide grown on silicon from tetrakis(diethylamino)hafnium and water vapor

    NASA Astrophysics Data System (ADS)

    Deshpande, Anand; Inman, Ronald; Jursich, Gregory; Takoudis, Christos

    2004-09-01

    In this work thin films of hafnium oxide are deposited on Si(100) substrates by means of atomic layer deposition (ALD) using tetrakis(diethylamino)hafnium and water vapor at substrate temperatures of 250-350ºC. Our system capabilities include fast transient delivery of reactive fluids, real-time vapor phase detection (in situ tunable diode laser hygrometer), precursor thermochemical capabilities, and ppt level elemental analysis by inductive coupling plasma mass spectrometry. The composition, purity, and other properties of the films and resulting interfaces are determined using x-ray and Fourier transform infrared spectroscopies, Z-contrast imaging and electron energy loss spectroscopy in a scanning transmission electron microscope with A˚ scale resolution, and spectroscopic ellipsometry. The observed ALD rate is ~1.4 A˚ per cycle. The nonuniformity across the film is less than 4%. Negligible carbon contamination is found in the resulting stoichiometric films under all conditions studied. The pulse sequence was optimized to prevent disastrous particulate problems while still minimizing purge times. The film deposition is investigated as a function of substrate temperature and reagent pulsing characteristics. A mild inverse temperature dependence of the ALD rate is observed. The initial stage of the HfO2 growth is investigated in detail.

  10. Hafnium silicate and hafnium silicon oxynitride gate dielectrics for strained Si_xGe_1-x: Interface stability

    NASA Astrophysics Data System (ADS)

    Addepalli, Swarna; Sivasubramani, Prasanna; El-Bouanani, Mohamed; Kim, Moon; Gnade, Bruce; Wallace, Robert

    2003-03-01

    Strained Si_xGe_1-x layers have gained considerable attention due to hole mobility enhancement, and ease of integration with Si-based CMOS technology. The deposition of stable high-κ dielectrics [1] such as hafnium silicate and hafnium silicon oxynitride in direct contact with SiGe would simultaneously improve the capacitance of the gate stack and lower the leakage current for high performance SiGe devices. However, the oxidation of the Si_xGe_1-x substrate either during dielectric deposition or post-deposition processing would degrade device performance due to the thermodynamic instability of germanium oxide [2,3]. Results from XPS, HR-TEM, and C-V, and I-V analyses after various annealing treatments will be presented for hafnium silicate and hafnium silicon oxynitride films deposited on strained Si_xGe_1-x(100), and correlated with dielectric-Si_xGe_1-x(100) interface stability. Implications to the introduction of these oxides as viable gate dielectric candidates for SiGe-based CMOS technology will be discussed. This work is supported by DARPA through SPAWAR Grant No. N66001-00-1-8928, and the Texas Advanced Technology Program. References: [1] G. D. Wilk, R. M. Wallace and J. M. Anthony, Journal of Applied Physics, 89, 5243 (2001) [2] W. S. Liu, J .S. Chen, M.-A. Nicolet, V. Arbet-Engels, K. L. Wang, Journal of Applied Physics, 72, 4444 (1992), and, Applied Physics Letters, 62, 3321 (1993) [3] W. S. Liu, M. -A. Nicolet, H. -H. Park, B. -H. Koak, J. -W. Lee, Journal of Applied Physics, 78, 2631 (1995)

  11. Study of bulk Hafnium oxide (HfO2) under compression

    NASA Astrophysics Data System (ADS)

    Pathak, Santanu; Mandal, Guruprasad; Das, Parnika

    2018-04-01

    Hafnium oxide (HfO2) is a technologically important material. This material has K-value of 25 and band gap 5.8 eV. A k value of 25-30 is preferred for a gate dielectric [1]. As it shows good insulating and capacitive properties, HfO2 is being considered as a replacement to SiO2 in microelectronic devices as gate dielectrics. On the other hand because of toughening mechanism due to phase transformation induced by stress field observed in these oxides, HFO2 has been a material of investigations in various configurations for a very long time. However the controversies about phase transition of HfO2 under pressure still exists. High quality synchrotron radiation has been used to study the structural phase transition of HfO2 under pressure.

  12. Multimode resistive switching in nanoscale hafnium oxide stack as studied by atomic force microscopy

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

    Hou, Y., E-mail: houyi@pku.edu.cn, E-mail: lfliu@pku.edu.cn; IMEC, Kapeldreef 75, B-3001 Heverlee; Department of Physics and Astronomy, KU Leuven, Celestijnenlaan 200D, B-3001 Heverlee

    2016-07-11

    The nanoscale resistive switching in hafnium oxide stack is investigated by the conductive atomic force microscopy (C-AFM). The initial oxide stack is insulating and electrical stress from the C-AFM tip induces nanometric conductive filaments. Multimode resistive switching can be observed in consecutive operation cycles at one spot. The different modes are interpreted in the framework of a low defect quantum point contact theory. The model implies that the optimization of the conductive filament active region is crucial for the future application of nanoscale resistive switching devices.

  13. RF sputtered silicon and hafnium nitrides as applied to 440C steel

    NASA Technical Reports Server (NTRS)

    Grill, A.; Aron, P. R.

    1984-01-01

    Silicon nitride and hafnium nitride coatings were deposited on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. The coatings and the interface between the coating and substrate were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. Oxide was found at all interfaces with an interface width of at least 600 A for the oxidized substrates and at least 300 A for the unoxidized substrates. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C. Coatings of both nitrides deposited at 8 mtorr were found to have increased adhesion to both oxidized and unoxidized 440C over those deposited at 20 mtorr.

  14. Studies on Optical and Electrical Properties of Hafnium Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Jayaraman, Venkatachalam; Sagadevan, Suresh; Sudhakar, Rajesh

    2017-07-01

    In this paper, the synthesis and physico-chemical properties of hafnium oxide nanoparticles (HfO2 NPs) are analyzed and reported. The synthesis was carried out by the precipitation route by using hafnium tetrachloride (HfCl4) as precursor material with potassium hydroxide (KOH) dissolved in Millipore water. In the precipitation technique, the chemical reaction is comparatively simple, low-cost and non-toxic compared to other synthetic methods. The synthesized HfO2 NPs were characterized by using powder x-ray diffraction (PXRD), ultraviolet-visible (UV-Vis) spectroscopy, Raman analysis, and high-resolution transmission electron microscopy (HRTEM). The monoclinic structure of the HfO2 NPs was resolved utilizing x-ray diffraction (XRD). The optical properties were studied from the UV-Vis absorption spectrum. The optical band gap of the HfO2NPs was observed to be 5.1 eV. The Raman spectrum shows the presence of HfO2 NPs. The HRTEM image showed that the HfO2 NPs were of spherical shape with an average particle size of around 28 nm. The energy-dispersive x-ray spectroscopy (EDS) spectrum obviously demonstrated the presence of HfO2 NPs. Analysis and studies on the dielectric properties of the HfO2 NPs such as the dielectric constant, the dielectric loss, and alternating current (AC) conductivity were carried out at varying frequencies and temperatures.

  15. Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

    NASA Astrophysics Data System (ADS)

    Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

    2003-03-01

    Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.

  16. Zirconium and hafnium

    USGS Publications Warehouse

    Jones, James V.; Piatak, Nadine M.; Bedinger, George M.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Zirconium and hafnium are corrosion-resistant metals that are widely used in the chemical and nuclear industries. Most zirconium is consumed in the form of the main ore mineral zircon (ZrSiO4, or as zirconium oxide or other zirconium chemicals. Zirconium and hafnium are both refractory lithophile elements that have nearly identical charge, ionic radii, and ionic potentials. As a result, their geochemical behavior is generally similar. Both elements are classified as incompatible because they have physical and crystallochemical properties that exclude them from the crystal lattices of most rock-forming minerals. Zircon and another, less common, ore mineral, baddeleyite (ZrO2), form primarily as accessory minerals in igneous rocks. The presence and abundance of these ore minerals in igneous rocks are largely controlled by the element concentrations in the magma source and by the processes of melt generation and evolution. The world’s largest primary deposits of zirconium and hafnium are associated with alkaline igneous rocks, and, in one locality on the Kola Peninsula of Murmanskaya Oblast, Russia, baddeleyite is recovered as a byproduct of apatite and magnetite mining. Otherwise, there are few primary igneous deposits of zirconium- and hafnium-bearing minerals with economic value at present. The main ore deposits worldwide are heavy-mineral sands produced by the weathering and erosion of preexisting rocks and the concentration of zircon and other economically important heavy minerals, such as ilmenite and rutile (for titanium), chromite (for chromium), and monazite (for rare-earth elements) in sedimentary systems, particularly in coastal environments. In coastal deposits, heavy-mineral enrichment occurs where sediment is repeatedly reworked by wind, waves, currents, and tidal processes. The resulting heavy-mineral-sand deposits, called placers or paleoplacers, preferentially form at relatively low latitudes on passive continental margins and supply 100 percent of

  17. Hafnium transistor design for neural interfacing.

    PubMed

    Parent, David W; Basham, Eric J

    2008-01-01

    A design methodology is presented that uses the EKV model and the g(m)/I(D) biasing technique to design hafnium oxide field effect transistors that are suitable for neural recording circuitry. The DC gain of a common source amplifier is correlated to the structural properties of a Field Effect Transistor (FET) and a Metal Insulator Semiconductor (MIS) capacitor. This approach allows a transistor designer to use a design flow that starts with simple and intuitive 1-D equations for gain that can be verified in 1-D MIS capacitor TCAD simulations, before final TCAD process verification of transistor properties. The DC gain of a common source amplifier is optimized by using fast 1-D simulations and using slower, complex 2-D simulations only for verification. The 1-D equations are used to show that the increased dielectric constant of hafnium oxide allows a higher DC gain for a given oxide thickness. An additional benefit is that the MIS capacitor can be employed to test additional performance parameters important to an open gate transistor such as dielectric stability and ionic penetration.

  18. Hafnium radioisotope recovery from irradiated tantalum

    DOEpatents

    Taylor, Wayne A.; Jamriska, David J.

    2001-01-01

    Hafnium is recovered from irradiated tantalum by: (a) contacting the irradiated tantalum with at least one acid to obtain a solution of dissolved tantalum; (b) combining an aqueous solution of a calcium compound with the solution of dissolved tantalum to obtain a third combined solution; (c) precipitating hafnium, lanthanide, and insoluble calcium complexes from the third combined solution to obtain a first precipitate; (d) contacting the first precipitate of hafnium, lanthanide and calcium complexes with at least one fluoride ion complexing agent to form a fourth solution; (e) selectively adsorbing lanthanides and calcium from the fourth solution by cationic exchange; (f) separating fluoride ion complexing agent product from hafnium in the fourth solution by adding an aqueous solution of ferric chloride to obtain a second precipitate containing the hafnium and iron; (g) dissolving the second precipitate containing the hafnium and iron in acid to obtain an acid solution of hafnium and iron; (h) selectively adsorbing the iron from the acid solution of hafnium and iron by anionic exchange; (i) drying the ion exchanged hafnium solution to obtain hafnium isotopes. Additionally, if needed to remove residue remaining after the product is dried, dissolution in acid followed by cation exchange, then anion exchange, is performed.

  19. Pyroelectricity of silicon-doped hafnium oxide thin films

    NASA Astrophysics Data System (ADS)

    Jachalke, Sven; Schenk, Tony; Park, Min Hyuk; Schroeder, Uwe; Mikolajick, Thomas; Stöcker, Hartmut; Mehner, Erik; Meyer, Dirk C.

    2018-04-01

    Ferroelectricity in hafnium oxide thin films is known to be induced by various doping elements and in solid-solution with zirconia. While a wealth of studies is focused on their basic ferroelectric properties and memory applications, thorough studies of the related pyroelectric properties and their application potential are only rarely found. This work investigates the impact of Si doping on the phase composition and ferro- as well as pyroelectric properties of thin film capacitors. Dynamic hysteresis measurements and the field-free Sharp-Garn method were used to correlate the reported orthorhombic phase fractions with the remanent polarization and pyroelectric coefficient. Maximum values of 8.21 µC cm-2 and -46.2 µC K-1 m-2 for remanent polarization and pyroelectric coefficient were found for a Si content of 2.0 at%, respectively. Moreover, temperature-dependent measurements reveal nearly constant values for the pyroelectric coefficient and remanent polarization over the temperature range of 0 ° C to 170 ° C , which make the material a promising candidate for IR sensor and energy conversion applications beyond the commonly discussed use in memory applications.

  20. Hafnium germanosilicate thin films for gate and capacitor dielectric applications: thermal stability studies

    NASA Astrophysics Data System (ADS)

    Addepalli, Swarna; Sivasubramani, Prasanna; El-Bouanani, Mohamed; Kim, Moon; Gnade, Bruce; Wallace, Robert

    2003-03-01

    The use of SiO_2-GeO2 mixtures in gate and capacitor dielectric applications is hampered by the inherent thermodynamic instability of germanium oxide. Studies to date have confirmed that germanium oxide is readily converted to elemental germanium [1,2]. In sharp contrast, germanium oxide is known to form stable compounds with transition metal oxides such as hafnium oxide (hafnium germanate, HfGeO_4) [3]. Thus, the incorporation of hafnium in SiO_2-GeO2 may be expected to enhance the thermal stability of germanium oxide via Hf-O-Ge bond formation. In addition, the introduction of a transition metal would simultaneously enhance the capacitance of the dielectric thereby permitting a thicker dielectric which reduces leakage current [4]. In this study, the thermal stability of PVD-grown hafnium germanosilicate (HfGeSiO) films was investigated. XPS, HR-TEM, C-V and I-V results of films after deposition and subsequent annealing treatments will be presented. The results indicate that the presence or formation of elemental germanium drastically affects the stability of the HfGeSiO films. This work is supported by DARPA through SPAWAR Grant No. N66001-00-1-8928, and the Texas Advanced Technology Program. References: [1] W. S. Liu, J .S. Chen, M.-A. Nicolet, V. Arbet-Engels, K. L. Wang, Journal of Applied Physics, 72, 4444 (1992), and, Applied Physics Letters, 62, 3321 (1993) [2] W. S. Liu, M. -A. Nicolet, H. -H. Park, B. -H. Koak, J. -W. Lee, Journal of Applied Physics, 78, 2631 (1995) [3] P. M. Lambert, Inorganic Chemistry, 37, 1352 (1998) [4] G. D. Wilk, R. M. Wallace and J. M. Anthony, Journal of Applied Physics, 89, 5243 (2001)

  1. Mineral resource of the month: zirconium and hafnium

    USGS Publications Warehouse

    Gambogi, Joseph

    2007-01-01

    Zirconium and hafnium are corrosion-resistant metals that are grouped in the same family as titanium on the periodic table. The two elements commonly occur in oxide and silicate minerals and have significant economic importance in everything from ink, ceramics and golf shoes to nuclear fuel rods.

  2. As-Received, Ozone Cleaned and Ar+ Sputtered Surfaces of Hafnium Oxide Grown by Atomic Layer Deposition and Studied by XPS

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

    Engelhard, Mark H.; Herman, Jacob A.; Wallace, Robert

    2012-06-27

    In this study, X-ray photoelectron spectroscopy (XPS) characterization was performed on 47 nm thick hafnium oxide (HfO{sub 2}) films grown by atomic layer deposition using TEMA-Hf/H{sub 2}O at 250 C substrate temperature. HfO{sub 2} is currently being studied as a possible replacement for Silicon Oxide (SiO{sub 2}) as a gate dielectric in electronics transistors. XPS spectra were collected on a Physical Electronics Quantum 2000 Scanning ESCA Microprobe using a monochromatic Al K{sub a} X-ray (1486.7 eV) excitation source. The sample was analyzed under the following conditions: as received, after UV irradiation for five minutes, and after sputter cleaning with 2more » kV Ar{sup +} ions for 180 seconds. Survey scans showed carbon, oxygen, and hafnium as the major species in the film, while the only minor species of argon and carbide was detected after sputtering. Adventitious carbon initially composed approximately 18.6 AT% of the surface, but after UV cleaning it was reduced to 2.4 AT%. This demonstrated that that the majority of carbon was due to adventitious carbon. However, after 2 kV Ar{sup +} sputtering there was still only trace amounts of carbon at {approx}1 AT%, Some of this trace carbon is now in the form of a carbide due to the interaction with Ar{sup +} used for sputter cleaning. Furthermore, the stoiciometric ratio of oxygen and hafnium is consistent with a high quality HfO{sub 2} film.« less

  3. Silicon doped hafnium oxide (HSO) and hafnium zirconium oxide (HZO) based FeFET: A material relation to device physics

    NASA Astrophysics Data System (ADS)

    Ali, T.; Polakowski, P.; Riedel, S.; Büttner, T.; Kämpfe, T.; Rudolph, M.; Pätzold, B.; Seidel, K.; Löhr, D.; Hoffmann, R.; Czernohorsky, M.; Kühnel, K.; Thrun, X.; Hanisch, N.; Steinke, P.; Calvo, J.; Müller, J.

    2018-05-01

    The recent discovery of ferroelectricity in thin film HfO2 materials renewed the interest in ferroelectric FET (FeFET) as an emerging nonvolatile memory providing a potential high speed and low power Flash alternative. Here, we report more insight into FeFET performance by integrating two types of ferroelectric (FE) materials and varying their properties. By varying the material type [HfO2 (HSO) versus hafnium zirconium oxide (HZO)], optimum content (Si doping/mixture ratio), and film thickness, a material relation to FeFET device physics is concluded. As for the material type, an improved FeFET performance is observed for HZO integration with memory window (MW) comparable to theoretical values. For different Si contents, the HSO based FeFET exhibited a MW trend with different stabilized phases. Similarly, the HZO FeFET shows MW dependence on the Hf:Zr mixture ratio. A maximized MW is obtained with cycle ratios of 16:1 (HfO2:Si) and 1:1 (Hf:Zr) as measured on HSO and HZO based FeFETs, respectively. The thickness variation shows a trend of increasing MW with the increased FE layer thickness confirming early theoretical predictions. The FeFET material aspects and stack physics are discussed with insight into the interplay factors, while optimum FE material parameters are outlined in relation to performance.

  4. Intrinsic Defect Ferromagnetism: The case of Hafnium Oxide

    NASA Astrophysics Data System (ADS)

    Das Pemmaraju, Chaitanya

    2005-03-01

    In view of the recent experimental reports of intrinsic ferromagnetism in Hafnium Oxide (HfO2) thin film systems ootnotetextM. Venkatesan, C. B. Fitzgerald, J. M. D. Coey Nature 430, 630 (2004) Brief Communications, we carried out first principles investigations to look for magnetic structure in HfO2 possibly brought about by the presence of small concentrations of intrinsic point defects. Ab initio electronic structure calculations using Density Functional Theory (DFT) show that isolated cation vacancy sites in HfO2 lead to the formation of high spin defect states which couple ferromagnetically to each other. Interestingly, these high spin states are observed in the low symmetry monoclinic and tetragonal phases while the highly symmetric cubic flourite phase exhibits a non-magnetic ground state. Detailed studies of the electronic structure of cation vacancies in the three crystalline phases of Hafnia show that symmetry leading to orbitally degenerate defect levels is not a pre-requsite for ferromagnetism and that the interplay between Kinetic, Coulomb and Exchange energy together with favourable coupling to the Crystalline environment can lead to high spin ferromagnetic ground states even in extreme low symmetry systems like monoclinic HfO2. These findings open up a much wider class of systems to the possibility of intrinsic defect ferromagnetism.

  5. Ablation Resistant Zirconium and Hafnium Ceramics

    NASA Technical Reports Server (NTRS)

    Bull, Jeffrey (Inventor); White, Michael J. (Inventor); Kaufman, Larry (Inventor)

    1998-01-01

    High temperature ablation resistant ceramic composites have been made. These ceramics are composites of zirconium diboride and zirconium carbide with silicon carbide, hafnium diboride and hafnium carbide with silicon carbide and ceramic composites which contain mixed diborides and/or carbides of zirconium and hafnium. along with silicon carbide.

  6. Atomic layer deposition of hafnium oxide: A detailed reaction mechanism from first principles

    NASA Astrophysics Data System (ADS)

    Widjaja, Yuniarto; Musgrave, Charles B.

    2002-08-01

    Atomic layer deposition (ALD) of hafnium oxide (HfO2) using HfCl4 and H2O as precursors is studied using density functional theory. The mechanism consists of two deposition half-reactions: (1) HfCl4 with Hf-OH sites, and (2) H2O with Hf-Cl sites. Both half-reactions exhibit stable intermediates with energies lower than those of the final products. We show that increasing the temperature reduces the stability of the complex. However, increasing temperature also increases the dissociation free-energy barrier, which in turn results in increased desorption of adsorbed precursors. Both half-reactions are qualitatively similar to the corresponding reactions of ZrO2 ALD using ZrCl4 and H2O.

  7. Thermal conductivity and thermal boundary resistance of atomic layer deposited high-k dielectric aluminum oxide, hafnium oxide, and titanium oxide thin films on silicon

    NASA Astrophysics Data System (ADS)

    Scott, Ethan A.; Gaskins, John T.; King, Sean W.; Hopkins, Patrick E.

    2018-05-01

    The need for increased control of layer thickness and uniformity as device dimensions shrink has spurred increased use of atomic layer deposition (ALD) for thin film growth. The ability to deposit high dielectric constant (high-k) films via ALD has allowed for their widespread use in a swath of optical, optoelectronic, and electronic devices, including integration into CMOS compatible platforms. As the thickness of these dielectric layers is reduced, the interfacial thermal resistance can dictate the overall thermal resistance of the material stack compared to the resistance due to the finite dielectric layer thickness. Time domain thermoreflectance is used to interrogate both the thermal conductivity and the thermal boundary resistance of aluminum oxide, hafnium oxide, and titanium oxide films on silicon. We calculate a representative design map of effective thermal resistances, including those of the dielectric layers and boundary resistances, as a function of dielectric layer thickness, which will be of great importance in predicting the thermal resistances of current and future devices.

  8. Tailoring the index of refraction of nanocrystalline hafnium oxide thin films

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

    Vargas, Mirella; Murphy, N. R.; Ramana, C. V., E-mail: rvchintalapalle@utep.edu

    2014-03-10

    Hafnium oxide (HfO{sub 2}) films were grown by sputter-deposition by varying the growth temperature (T{sub s} = 25–700 °C). HfO{sub 2} films grown at T{sub s} < 200 °C were amorphous, while those grown at T{sub s} ≥ 200 °C were monoclinic, nanocrystalline with (1{sup ¯}11) texturing. X-ray reflectivity (XRR) analyses indicate that the film-density (ρ) increases with increasing T{sub s}. The index of refraction (n) profiles derived from spectroscopic ellipsometry analyses follow the Cauchy dispersion relation. Lorentz-Lorenz analysis (n{sub (λ)} = 550 nm) and optical-model adopted agree well with the XRR data/analyses. A direct T{sub s}-ρ-n relationship suggests that tailoring the optical quality is possible by tuning T{sub s} and themore » microstructure of HfO{sub 2} films.« less

  9. Hafnium isotope stratigraphy of ferromanganese crusts

    PubMed

    Lee; Halliday; Hein; Burton; Christensen; Gunther

    1999-08-13

    A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in (87)Sr/(86)Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

  10. SEPARATION OF HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

    1960-05-31

    The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

  11. 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.

  12. Conduction Channel Formation and Dissolution Due to Oxygen Thermophoresis/Diffusion in Hafnium Oxide Memristors

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

    Kumar, Suhas; Wang, Ziwen; Huang, Xiaopeng

    Due to the favorable operating power, endurance, speed, and density., transition-metal-oxide memristors, or resistive random-access memory (RRAM) switches, are under intense development for storage-class memory. Their commercial deployment critically depends on predictive compact models based on understanding nanoscale physiocochemical forces, which remains elusive and controversial owing to the difficulties in directly observing atomic motions during resistive switching, Here, using scanning transmission synchrotron X-ray spectromicroscopy to study in situ switching of hafnium oxide memristors, we directly observed the formation of a localized oxygen-deficiency-derived conductive channel surrounded by a low-conductivity ring of excess oxygen. Subsequent thermal annealing homogenized the segregated oxygen, resettingmore » the cells toward their as-grown resistance state. We show that the formation and dissolution of the conduction channel are successfully modeled by radial thermophoresis and Fick diffusion of oxygen atoms driven by Joule heating. This confirmation and quantification of two opposing nanoscale radial forces that affect bipolar memristor switching are important components for any future physics-based compact model for the electronic switching of these devices.« less

  13. SEPARATING HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Lister, B.A.J.; Duncan, J.F.

    1956-08-21

    A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

  14. Pyroelectric response in crystalline hafnium zirconium oxide (Hf 1- x Zr x O 2 ) thin films

    DOE PAGES

    Smith, S. W.; Kitahara, A. R.; Rodriguez, M. A.; ...

    2017-02-13

    Pyroelectric coefficients were measured for 20 nm thick crystalline hafnium zirconium oxide (Hf 1-xZr xO 2) thin films across a composition range of 0 ≤ x ≤ 1. Pyroelectric currents were collected near room temperature under zero applied bias and a sinusoidal oscillating temperature profile to separate the influence of non-pyroelectric currents. The pyroelectric coefficient was observed to correlate with zirconium content, increased orthorhombic/tetragonal phase content, and maximum polarization response. The largest measured absolute value was 48 μCm -2K -1 for a composition with x = 0.64, while no pyroelectric response was measured for compositions which displayed no remanent polarizationmore » (x = 0, 0.91, 1).« less

  15. Etude de la nitruration carbothermique du dioxyde de hafnium par diffraction X à haute température

    NASA Astrophysics Data System (ADS)

    Pialoux, A.

    1993-03-01

    The carbothermal reduction of hafnium dioxide under atmospheric level nitrogen pressure has been investigated using a graphite resistance high temperature X-ray diffractometer up to around 2300 K. A carbon transfer reaction through the gaseous phase (N 2, CO/CO 2) is shown to precede, then to compete the direct reduction of the hafnium oxide by the graphite in pure nitrogen. A complex mechanism has been found that accounts for the formation of hafnium dioxynitride and possibly of three other hafnium oxynitrides, then of hafnium mononitride and hafnium monocarbonitride, along two different steps between 1613 and 1923 K. An evaluation has been made concerning the composition of these γ 1- HfO 2-xN x/2□ x/2 (CaF 2-type structure), γ 2- Hf 7O 11N 2, γ 3- Hf 7O 8N 4 (rhombohedral), γ 4- Hf 2ON 2 (Mn 2O 3-type structure), HfN and HfN 1-zC z (NaCl-type structure) phases, considering the variations of their lattice parameters and the available data in the literature, especially on the isomorphous compounds of zirconium. It must be emphasized the new γ 1- HfO 2-xN x/2 phase, the dilatation of which is linear ( overlineα = 12×10 -6K -1), shows a constant composition from 2158 down to 1473 K (x ≈ 0,2). But under 1473 K, inevitably, the hafnium dioxynitride disappears, and poorly crystallized monoclinic αHfO 2 and rhombohedral γ 2- Hf 7O 11N 2 are formed.

  16. Low-voltage high-performance organic thin film transistors with a thermally annealed polystyrene/hafnium oxide dielectric

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Acton, Orb; Ting, Guy; Weidner, Tobias; Ma, Hong; Castner, David G.; Jen, Alex K.-Y.

    2009-12-01

    Low-voltage pentacene-based organic thin film transistors (OTFTs) are demonstrated with polystyrene (PS)/hafnium oxide (HfOx) hybrid dielectrics. Thermal annealing of PS films on HfOx at 120 °C (PS-120) induces a flatter orientation of the phenyl groups (tilt angle 65°) at the surface compared to PS films without annealing (PS-RT) (tilt angle 31°). The flatter phenyl group orientation leads to better matching of surface energy between pentacene and PS. Pentacene deposited on PS-120 display higher quality thin films with larger grain sizes and higher crystallinity. Pentacene OTFTs with PS-120/HfOx hybrid dielectrics can operate at low-voltage (<3 V) with high field-effect mobilities (1 cm2/V s), high on/off current ratios (106), and low subthreshold slopes (100 mV/dec).

  17. Low-voltage bendable pentacene thin-film transistor with stainless steel substrate and polystyrene-coated hafnium silicate dielectric.

    PubMed

    Yun, Dong-Jin; Lee, Seunghyup; Yong, Kijung; Rhee, Shi-Woo

    2012-04-01

    The hafnium silicate and aluminum oxide high-k dielectrics were deposited on stainless steel substrate using atomic layer deposition process and octadecyltrichlorosilane (OTS) and polystyrene (PS) were treated improve crystallinity of pentacene grown on them. Besides, the effects of the pentacene deposition condition on the morphologies, crystallinities and electrical properties of pentacene were characterized. Therefore, the surface treatment condition on dielectric and pentacene deposition conditions were optimized. The pentacene grown on polystyrene coated high-k dielectric at low deposition rate and temperature (0.2-0.3 Å/s and R.T.) showed the largest grain size (0.8-1.0 μm) and highest crystallinity among pentacenes deposited various deposition conditions, and the pentacene TFT with polystyrene coated high-k dielectric showed excellent device-performance. To decrease threshold voltage of pentacene TFT, the polystyrene-thickness on high-k dielectric was controlled using different concentration of polystyrene solution. As the polystyrene-thickness on hafnium silicate decreases, the dielectric constant of polystyrene/hafnium silicate increases, while the crystallinity of pentacene grown on polystyrene/hafnium silicate did not change. Using low-thickness polystyrene coated hafnium silicate dielectric, the high-performance and low voltage operating (<5 V) pentacene thin film transistor (μ: ~2 cm(2)/(V s), on/off ratio, >1 × 10(4)) and complementary inverter (DC gains, ~20) could be fabricated.

  18. Oxidation Characterization of Hafnium-Based Ceramics Fabricated by Hot Pressing and Electric Field-Assisted Sintering

    NASA Technical Reports Server (NTRS)

    Gasch, Matt; Johnson, Sylvia; Marschall, Jochen

    2010-01-01

    Ceramic borides, such as hafnium diboride (HfB2) and zirconium diboride (ZrB2), are members of a family of materials with extremely high melting temperatures referred to as Ultra High Temperature Ceramics (UHTCs). UHTCs constitute a class of promising materials for use in high temperature applications, such as sharp leading edges on future-generation hypersonic flight vehicles, because of their high melting points. The controlled development of microstructure has become important to the processing of UHTCs, with the prospect of improving their mechanical and thermal properties. The improved oxidation resistance of HfB2 has also become important if this material is to be successfully used at temperatures above 2000 C. Furthermore, the use of UHTCs on the leading edges of vehicles traveling at hypersonic speeds will mean exposure to a mixed oxidation environment comprised of both molecular and atomic oxygen. The current study has investigated the high-temperature oxidation behavior of HfB2-based materials in a pure O2 environment, as well as in environments containing different levels of dissociated oxygen (O/O2). Materials were processed by two techniques: conventional hot pressing (HP) and electric field-assisted sintering (FAS). Their oxidation behavior was evaluated in both a tube furnace at 1250 C for 3 hours and in a simulated re-entry environment in the Advanced Heating Facility (AHF) arcjet at NASA Ames Research Center, during a 10-minute exposure to a cold wall heat flux of 250W/sq cm and stagnation pressure of 0.1-0.2 atm. The microstructure of the different materials was characterized before and after oxidation using scanning electron microscopy (SEM).

  19. Silver-hafnium braze alloy

    DOEpatents

    Stephens, Jr., John J.; Hosking, F. Michael; Yost, Frederick G.

    2003-12-16

    A binary allow braze composition has been prepared and used in a bonded article of ceramic-ceramic and ceramic-metal materials. The braze composition comprises greater than approximately 95 wt % silver, greater than approximately 2 wt % hafnium and less than approximately 4.1 wt % hafnium, and less than approximately 0.2 wt % trace elements. The binary braze alloy is used to join a ceramic material to another ceramic material or a ceramic material, such as alumina, quartz, aluminum nitride, silicon nitride, silicon carbide, and mullite, to a metal material, such as iron-based metals, cobalt-based metals, nickel-based metals, molybdenum-based metals, tungsten-based metals, niobium-based metals, and tantalum-based metals. A hermetic bonded article is obtained with a strength greater than 10,000 psi.

  20. Highly effective electronic passivation of silicon surfaces by atomic layer deposited hafnium oxide

    NASA Astrophysics Data System (ADS)

    Cui, Jie; Wan, Yimao; Cui, Yanfeng; Chen, Yifeng; Verlinden, Pierre; Cuevas, Andres

    2017-01-01

    This paper investigates the application of hafnium oxide (HfO2) thin films to crystalline silicon (c-Si) solar cells. Excellent passivation of both n- and p-type crystalline silicon surfaces has been achieved by the application of thin HfO2 films prepared by atomic layer deposition. Effective surface recombination velocities as low as 3.3 and 9.9 cm s-1 have been recorded with 15 nm thick films on n- and p-type 1 Ω cm c-Si, respectively. The surface passivation by HfO2 is activated at 350 °C by a forming gas anneal. Capacitance voltage measurement shows an interface state density of 3.6 × 1010 cm-2 eV-1 and a positive charge density of 5 × 1011 cm-2 on annealed p-type 1 Ω cm c-Si. X-ray diffraction unveils a positive correlation between surface recombination and crystallinity of the HfO2 and a dependence of the crystallinity on both annealing temperature and film thickness. In summary, HfO2 is demonstrated to be an excellent candidate for surface passivation of crystalline silicon solar cells.

  1. Hafnium-Based Contrast Agents for X-ray Computed Tomography.

    PubMed

    Berger, Markus; Bauser, Marcus; Frenzel, Thomas; Hilger, Christoph Stephan; Jost, Gregor; Lauria, Silvia; Morgenstern, Bernd; Neis, Christian; Pietsch, Hubertus; Sülzle, Detlev; Hegetschweiler, Kaspar

    2017-05-15

    Heavy-metal-based contrast agents (CAs) offer enhanced X-ray absorption for X-ray computed tomography (CT) compared to the currently used iodinated CAs. We report the discovery of new lanthanide and hafnium azainositol complexes and their optimization with respect to high water solubility and stability. Our efforts culminated in the synthesis of BAY-576, an uncharged hafnium complex with 3:2 stoichiometry and broken complex symmetry. The superior properties of this asymmetrically substituted hafnium CA were demonstrated by a CT angiography study in rabbits that revealed excellent signal contrast enhancement.

  2. 40 CFR 471.90 - Applicability; description of the zirconium-hafnium forming subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... zirconium-hafnium forming subcategory. 471.90 Section 471.90 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Zirconium-Hafnium Forming Subcategory § 471.90 Applicability; description of the zirconium-hafnium forming subcategory. This subpart applies to discharges of pollutants to waters of the...

  3. 40 CFR 421.330 - Applicability: Description of the primary zirconium and hafnium subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary zirconium and hafnium subcategory. 421.330 Section 421.330 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Zirconium and Hafnium Subcategory § 421.330 Applicability: Description of the primary zirconium and hafnium subcategory. The provisions of this subpart are applicable to discharges resulting...

  4. Ferroelectric transistors with monolayer molybdenum disulfide and ultra-thin aluminum-doped hafnium oxide

    NASA Astrophysics Data System (ADS)

    Yap, Wui Chung; Jiang, Hao; Liu, Jialun; Xia, Qiangfei; Zhu, Wenjuan

    2017-07-01

    In this letter, we demonstrate ferroelectric memory devices with monolayer molybdenum disulfide (MoS2) as the channel material and aluminum (Al)-doped hafnium oxide (HfO2) as the ferroelectric gate dielectric. Metal-ferroelectric-metal capacitors with 16 nm thick Al-doped HfO2 are fabricated, and a remnant polarization of 3 μC/cm2 under a program/erase voltage of 5 V is observed. The capability of potential 10 years data retention was estimated using extrapolation of the experimental data. Ferroelectric transistors based on embedded ferroelectric HfO2 and MoS2 grown by chemical vapor deposition are fabricated. Clockwise hysteresis is observed at low program/erase voltages due to slow bulk traps located near the 2D/dielectric interface, while counterclockwise hysteresis is observed at high program/erase voltages due to ferroelectric polarization. In addition, the endurances of the devices are tested, and the effects associated with ferroelectric materials, such as the wake-up effect and polarization fatigue, are observed. Reliable writing/reading in MoS2/Al-doped HfO2 ferroelectric transistors over 2 × 104 cycles is achieved. This research can potentially lead to advances of two-dimensional (2D) materials in low-power logic and memory applications.

  5. Metal–Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal–Organic Framework

    PubMed Central

    2017-01-01

    We report a hafnium-containing MOF, hcp UiO-67(Hf), which is a ligand-deficient layered analogue of the face-centered cubic fcu UiO-67(Hf). hcp UiO-67 accommodates its lower ligand:metal ratio compared to fcu UiO-67 through a new structural mechanism: the formation of a condensed “double cluster” (Hf12O8(OH)14), analogous to the condensation of coordination polyhedra in oxide frameworks. In oxide frameworks, variable stoichiometry can lead to more complex defect structures, e.g., crystallographic shear planes or modules with differing compositions, which can be the source of further chemical reactivity; likewise, the layered hcp UiO-67 can react further to reversibly form a two-dimensional metal–organic framework, hxl UiO-67. Both three-dimensional hcp UiO-67 and two-dimensional hxl UiO-67 can be delaminated to form metal–organic nanosheets. Delamination of hcp UiO-67 occurs through the cleavage of strong hafnium-carboxylate bonds and is effected under mild conditions, suggesting that defect-ordered MOFs could be a productive route to porous two-dimensional materials. PMID:28343394

  6. Metal-Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal-Organic Framework.

    PubMed

    Cliffe, Matthew J; Castillo-Martínez, Elizabeth; Wu, Yue; Lee, Jeongjae; Forse, Alexander C; Firth, Francesca C N; Moghadam, Peyman Z; Fairen-Jimenez, David; Gaultois, Michael W; Hill, Joshua A; Magdysyuk, Oxana V; Slater, Ben; Goodwin, Andrew L; Grey, Clare P

    2017-04-19

    We report a hafnium-containing MOF, hcp UiO-67(Hf), which is a ligand-deficient layered analogue of the face-centered cubic fcu UiO-67(Hf). hcp UiO-67 accommodates its lower ligand:metal ratio compared to fcu UiO-67 through a new structural mechanism: the formation of a condensed "double cluster" (Hf 12 O 8 (OH) 14 ), analogous to the condensation of coordination polyhedra in oxide frameworks. In oxide frameworks, variable stoichiometry can lead to more complex defect structures, e.g., crystallographic shear planes or modules with differing compositions, which can be the source of further chemical reactivity; likewise, the layered hcp UiO-67 can react further to reversibly form a two-dimensional metal-organic framework, hxl UiO-67. Both three-dimensional hcp UiO-67 and two-dimensional hxl UiO-67 can be delaminated to form metal-organic nanosheets. Delamination of hcp UiO-67 occurs through the cleavage of strong hafnium-carboxylate bonds and is effected under mild conditions, suggesting that defect-ordered MOFs could be a productive route to porous two-dimensional materials.

  7. Development and characterization of ultrathin hafnium titanates as high permittivity gate insulators

    NASA Astrophysics Data System (ADS)

    Li, Min

    High permittivity or high-kappa materials are being developed for use as gate insulators for future ultrascaled metal oxide semiconductor field effect transistors (MOSFETs). Hafnium containing compounds are the leading candidates. Due to its moderate permittivity, however, it is difficult to achieve HfO2 gate structures with an EOT well below 1.0 nm. One approach to increase HfO2 permittivity is combining it with a very high-kappa material, such as TiO2. In this thesis, we systematically studied the electrical and physical characteristics of high-kappa hafnium titanates films as gate insulators. A series of HfxTi1-xO2 films with well-controlled composition were deposited using an MOCVD system. The physical properties of the films were analyzed using a variety of characterization techniques. X-ray micro diffraction indicates that the Ti-rich thin film is more immune to crystallization. TEM analysis showed that the thick stoichiometric HfTiO 4 film has an orthorhombic structure and large anisotropic grains. The C-V curves from the devices with the hafnium titanates films displayed relatively low hysteresis. In a certain composition range, the interfacial layer (IL) EOT and permittivity of HfxTi1-x O2 increases linearly with increasing Ti. The charge is negative for HfxTi1-xO2/IL and positive for Si/IL interface, and the magnitude increases as Hf increases. For ultra-thin films (less than 2 nm EOT), the leakage current increases with increasing HE Moreover, the Hf-rich sample has weaker temperature dependence of the current. In the MOSFET devices with the hafnium titanates films, normal transistor characteristics were observed, also electron mobility degradation. Next, we investigated the effects that different pre-deposition surface treatments, including HF dipping, NH3 surface nitridation, and HfO2 deposition, have on the electrical properties of hafnium titanates. Surface nitridation shows stronger effect than the thin HfO2 layer. The nitrided samples displayed a

  8. Electron-beam-evaporated thin films of hafnium dioxide for fabricating electronic devices

    DOE PAGES

    Xiao, Zhigang; Kisslinger, Kim

    2015-06-17

    Thin films of hafnium dioxide (HfO 2) are widely used as the gate oxide in fabricating integrated circuits because of their high dielectric constants. In this paper, the authors report the growth of thin films of HfO 2 using e-beam evaporation, and the fabrication of complementary metal-oxide semiconductor (CMOS) integrated circuits using this HfO 2 thin film as the gate oxide. The authors analyzed the thin films using high-resolution transmission electron microscopy and electron diffraction, thereby demonstrating that the e-beam-evaporation-grown HfO 2 film has a polycrystalline structure and forms an excellent interface with silicon. Accordingly, we fabricated 31-stage CMOS ringmore » oscillator to test the quality of the HfO 2 thin film as the gate oxide, and obtained excellent rail-to-rail oscillation waveforms from it, denoting that the HfO 2 thin film functioned very well as the gate oxide.« less

  9. The origin of 2.7 eV luminescence and 5.2 eV excitation band in hafnium oxide

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

    Perevalov, T. V., E-mail: timson@isp.nsc.ru; Novosibirsk State University, 2 Pirogova St., 630090 Novosibirsk; Aliev, V. Sh.

    2014-02-17

    The origin of a blue luminescence band at 2.7 eV and a luminescence excitation band at 5.2 eV of hafnia has been studied in stoichiometric and non-stoichiometric hafnium oxide films. Experimental and calculated results from the first principles valence band spectra showed that the stoichiometry violation leads to the formation of the peak density of states in the band gap caused by oxygen vacancies. Cathodoluminescence in the non-stoichiometric film exhibits a band at 2.65 eV that is excited at the energy of 5.2 eV. The optical absorption spectrum calculated for the cubic phase of HfO{sub 2} with oxygen vacancies showsmore » a peak at 5.3 eV. Thus, it could be concluded that the blue luminescence band at 2.7 eV and HfO{sub x} excitation peak at 5.2 eV are due to oxygen vacancies. The thermal trap energy in hafnia was estimated.« less

  10. A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.

    1972-01-01

    A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.

  11. Hafnium(IV) chloride complexes with chelating β-ketiminate ligands: Synthesis, spectroscopic characterization and volatility study

    NASA Astrophysics Data System (ADS)

    Patil, Siddappa A.; Medina, Phillip A.; Antic, Aleks; Ziller, Joseph W.; Vohs, Jason K.; Fahlman, Bradley D.

    2015-09-01

    The synthesis and characterization of four new β-ketiminate hafnium(IV) chloride complexes dichloro-bis[4-(phenylamido)pent-3-en-2-one]-hafnium (4a), dichloro-bis[4-(4-methylphenylamido)pent-3-en-2-one]-hafnium (4b), dichloro-bis[4-(4-methoxyphenylamido)pent-3-en-2-one]-hafnium (4c), and dichloro-bis[4-(4-chlorophenylamido)pent-3-en-2-one]-hafnium (4d) are reported. All the complexes (4a-d) were characterized by spectroscopic methods (1H NMR, 13C NMR, IR), and elemental analysis while the compound 4c was further examined by single-crystal X-ray diffraction, revealing that the complex is monomer with the hafnium center in octahedral coordination environment and oxygens of the chelating N-O ligands are trans to each other and the chloride ligands are in a cis arrangement. Volatile trends are established for four new β-ketiminate hafnium(IV) chloride complexes (4a-d). Sublimation enthalpies (ΔHsub) were calculated from thermogravimetric analysis (TGA) data, which show that, the dependence of ΔHsub on the molecular weight (4a-c) and inductive effects from chlorine (4d).

  12. Processing and characterization of boron carbide-hafnium diboride ceramics

    NASA Astrophysics Data System (ADS)

    Brown-Shaklee, Harlan James

    Hafnium diboride based ceramics are promising candidate materials for advanced aerospace and nuclear reactor components. The effectiveness of boron carbide and carbon as HfB2 sintering additives was systematically evaluated. In the first stage of the research, boron carbide and carbon additives were found to improve the densification behavior of milled HfB2 powder in part by removing oxides at the HfB2 surface during processing. Boron carbide additives reduced the hot pressing temperature of HfB2 by 150°C compared to carbon, which reduced the hot pressing temperature by ˜50°C. Reduction of oxide impurities alone could not explain the difference in sintering enhancement, however, and other mechanisms of enhancement were evaluated. Boron carbides throughout the homogeneity range were characterized to understand other mechanisms of sintering enhancement in HfB2. Heavily faulted carbon rich and boron rich boron carbides were synthesized for addition to HfB2. The greatest enhancement to densification was observed in samples containing boron- and carbon-rich compositions whereas B6.5 C provided the least enhancement to densification. It is proposed that carbon rich and boron rich boron carbides create boron and hafnium point defects in HfB2, respectively, which facilitate densification. Evaluation of the thermal conductivity (kth) between room temperature and 2000°C suggested that the stoichiometry of the boron carbide additives did not significantly affect kth of HfB2-BxC composites. The improved sinterability and the high kth (˜110 W/m-K at 300K and ˜90 W/m-K at 1000°C ) of HfB2-BxC ceramics make them excellent candidates for isotopically enriched reactor control materials.

  13. Photoluminescence properties of Eu3+ doped HfO2 coatings formed by plasma electrolytic oxidation of hafnium

    NASA Astrophysics Data System (ADS)

    Stojadinović, Stevan; Tadić, Nenad; Ćirić, Aleksandar; Vasilić, Rastko

    2018-03-01

    Plasma electrolytic oxidation was used for synthesis of Eu3+ doped monoclinic HfO2 coatings on hafnium substrate. Results of photoluminescence (PL) measurements show the existence of two distinct regions: one that is related to the blue emission originating from oxygen vacancy defects in HfO2 and the other one characterized with a series of sharp orange-red emission peaks related to f-f transitions of Eu3+ from excited level 5D0 to lower levels 7FJ (J = 0, 1, 2, 3, and 4). PL peaks appearing in excitation spectra of obtained coatings are attributed either to charge transfer state of Eu3+ or to direct excitation of the Eu3+ ground state 7F0 into higher levels of the 4f-manifold. PL of formed coatings increases with PEO time due to an increase of oxygen vacancy defects and the content of Eu3+. Acquired experimental data suggest that hypersensitive electrical dipole transition is much more intense than the magnetic dipole transition, indicating that Eu3+ ions occupy a non-inversion symmetry sites.

  14. Simultaneous determination of tantalum and hafnium in silicates by neutron activation analysis

    USGS Publications Warehouse

    Greenland, L.P.

    1968-01-01

    A neutron activation procedure suitable for the routine determination of tantalum and hafnium in silicates is described. The irradiated sample is fused with sodium peroxide and leached, and the insoluble hydroxides are dissolved in dilute hydrofluoric acid-hydrochloric acid. After LaF3 and AgCl scavenges, tantalum and hafnium are separated by anion exchange. Tantalum is obtained radiochemically pure; 233Pa and 95Zr contaminants in the hafnium fraction are resolved by ??-ray spectrometry. The chemical yield of the procedure is detemined after counting by re-irradiation. Values for the 8 U.S. Geological Survey standard rocks are reported. ?? 1968.

  15. The Hot-Pressing of Hafnium Carbide (Melting Point, 7030 F)

    NASA Technical Reports Server (NTRS)

    Sanders, William A.; Grisaffe, Salvatore J.

    1960-01-01

    An investigation was undertaken to determine the effects of the hot-pressing variables (temperature, pressure, and time) on the density and grain size of hafnium carbide disks. The purpose was to provide information necessary for the production of high-density test shapes for the determination of physical and mechanical properties. Hot-pressing of -325 mesh hafnium carbide powder was accomplished with a hydraulic press and an inductively heated graphite die assembly. The ranges investigated for each variable were as follows: temperature, 3500 to 4870 F; pressure, 1000 to 6030 pounds per square inch; and time, 5 to 60 minutes. Hafnium carbide bodies of approximately 98 percent theoretical density can be produced under the following minimal conditions: 4230 F, 3500 pounds per square inch, and 15 minutes. Further increases in temperature and time resulted only in greater grain size.

  16. Zirconium and hafnium in the southeastern Atlantic States

    USGS Publications Warehouse

    Mertie, J.B.

    1958-01-01

    The principal source of zirconium and hafnium is zircon, though a minor source is baddeleyite, mined only in Brazil. Zircon is an accessory mineral in igneous, metamorphic, and sedimentary rocks, but rarely occurs in hardrock in minable quantities. The principal sources of zircon are therefore alluvial deposits, which are mined in many countries of five continents. The principal commercial deposits in the United States are in Florida, though others exist elsewhere in the southeastern Coastal Plain. The evidence indicates that conditions for the accumulation of workable deposits of heavy minerals were more favorable during the interglacial stages of the Pleistocene epoch than during Recent time. Therefore detrital ores of large volume and high tenor are more likely to be found in the terrace deposits than along the present beaches. Other concentrations of heavy minerals, however, are possible at favored sites close to the Fall Line where the Tuscaloosa formation rests upon the crystalline rocks of the Piedmont province. A score of heavy and semiheavy minerals occur in the detrital deposits of Florida, but the principal salable minerals are ilmenite, leucoxene, rutile, and zircon, though monazite and staurolite are saved at some mining plants. Commercial deposits of heavy minerals are generally required to have a tenor of 4 percent, though ores with a lower tenor can be mined at a profit if the content of monazite is notably high. The percentages of zircon in the concentrates ranges from 10 to 16 percent, and in eastern Florida from 13 to 15 percent. Thus the tenor in zircon of the ore-bearing sands ranges from 0.4 to 0.6 percent. The content of hafnium in zircon is immaterial for many uses, but for some purposes very high or very low tenors in hafnium are required. Alluvial zircon cannot be separated into such varieties, which, if needed, must be obtained from sources in bedrock. It thus becomes necessary to determine the Hf : Zr ratios in zircon from many kinds of

  17. Separation of Zirconium and Hafnium: A Review

    NASA Astrophysics Data System (ADS)

    Xu, L.; Xiao, Y.; van Sandwijk, A.; Xu, Q.; Yang, Y.

    Zirconium is an ideal material for nuclear reactors due to its low absorption cross-section for thermal neutrons, whereas the typically contained hafnium with strong neutron-absorption is very harmful for zirconium. This paper provides an overview of the processes for separating hafnium from zirconium. The separation processes are roughly classified into hydro- and pyrometallurgical routes. The current dominant zirconium production route involves pyrometallurgical ore cracking, multi-step hydrometallurgical liquid-liquid extraction for hafnium removal and the reduction of zirconium tetrachloride to the pure metal by the Kroll process. The lengthy hydrometallurgical Zr-Hf separation operations leads to high production cost, intensive labour and heavy environmental burden. Using a compact pyrometallurgical separation method can simplify the whole production flowsheet with a higher process efficiency. The known separation methods are discussed based on the following reaction features: redox characteristics, volatility, electrochemical properties and molten salt extraction. The commercially operating extractive distillation process is a significant advance in Zr-Hf separation technology but it suffers from high process maintenance cost. The recently developed new process based on molten salt-metal equilibrium for Zr-Hf separation shows a great potential for industrial application, which is compact for nuclear grade zirconium production starting from crude ore. In the present paper, the available separation technologies are compared. The advantages and disadvantages as well as future directions of research and development for nuclear grade zirconium production are discussed.

  18. High P-T phase transitions and P-V-T equation of state of hafnium

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

    Hrubiak, Rostislav; Drozd, Vadym; Karbasi, Ali

    2016-07-29

    We measured the volume of hafnium at several pressures up to 67 GPa and at temperatures between 300 to 780 K using a resistively heated diamond anvil cell with synchrotron x-ray diffraction at the Advanced Photon Source. The measured data allows us to determine the P-V-T equation of state of hafnium. The previously described [Xia et al., Phys. Rev. B 42, 6736-6738 (1990)] phase transition from hcp ({alpha}) to simple hexagonal ({omega}) phase at 38 GPa at room temperature was not observed even up to 51 GPa. The {omega} phase was only observed at elevated temperatures. Our measurements have alsomore » improved the experimental constraint on the high P-T phase boundary between the {omega} phase and high pressure bcc ({beta}) phase of hafnium. Isothermal room temperature bulk modulus and its pressure derivative for the {alpha}-phase of hafnium were measured to be B{sub 0} = 112.9{+-}0.5 GPa and B{sub 0}'=3.29{+-}0.05, respectively. P-V-T data for the {alpha}-phase of hafnium was used to obtain a fit to a thermodynamic P-V-T equation of state based on model by Brosh et al. [CALPHAD 31, 173-185 (2007)].« less

  19. Studies of Ultra High Temperature Ceramic Composite Components: Synthesis and Characterization of HfOxCy and Si Oxidation in Atomic Oxygen Containing Environments

    DTIC Science & Technology

    2008-08-01

    Andrea Hafeman and Dr Scott Guelcher for the use of the SDT analysis software. I would like to thank my committee members: Dr Clare McCabe, Dr Sharon...76 4.2: Thermogravimetric curves obtained during oxidation of hafnium...77 4.3: The thermogravimetric curves for hafnia and hafnium oxycarbide (28 mTorr) oxidized at 600°C

  20. Tensile and stress-rupture behavior of hafnium carbide dispersed molybdenum and tungsten base alloy wires

    NASA Technical Reports Server (NTRS)

    Yun, Hee Mann; Titran, Robert H.

    1993-01-01

    The tensile strain rate sensitivity and the stress-rupture strength of Mo-base and W-base alloy wires, 380 microns in diameter, were determined over the temperature range from 1200 K to 1600 K. Three molybdenum alloy wires; Mo + 1.1w/o hafnium carbide (MoHfC), Mo + 25w/o W + 1.1w/o hafnium carbide (MoHfC+25W) and Mo + 45w/o W + 1.1w/o hafnium carbide (MoHfC+45W), and a W + 0.4w/o hafnium carbide (WHfC) tungsten alloy wire were evaluated. The tensile strength of all wires studied was found to have a positive strain rate sensitivity. The strain rate dependency increased with increasing temperature and is associated with grain broadening of the initial fibrous structures. The hafnium carbide dispersed W-base and Mo-base alloys have superior tensile and stress-rupture properties than those without HfC. On a density compensated basis the MoHfC wires exhibit superior tensile and stress-rupture strengths to the WHfC wires up to approximately 1400 K. Addition of tungsten in the Mo-alloy wires was found to increase the long-term stress rupture strength at temperatures above 1400 K. Theoretical calculations indicate that the strength and ductility advantage of the HfC dispersed alloy wires is due to the resistance to recrystallization imparted by the dispersoid.

  1. Nickel aluminides and nickel-iron aluminides for use in oxidizing environments

    DOEpatents

    Liu, Chain T.

    1988-03-15

    Nickel aluminides and nickel-iron aluminides treated with hafnium or zirconium, boron and cerium to which have been added chromium to significantly improve high temperature ductility, creep resistance and oxidation properties in oxidizing environments.

  2. Stabilized tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

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

    2008-01-01

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

  3. SEPARATING HAFNIUM FROM ZIRCONIUM

    DOEpatents

    Lister, B.A.J.; Duncan, J.F.; Hutcheon, J.M.

    1956-08-21

    Substantially complete separation of zirconium from hafnium may be obtained by elution of ion exchange material, on which compounds of the elements are adsorbed, with an approximately normal solution of sulfuric acid. Preferably the acid concentration is between 0.8 N amd 1.2 N, amd should not exceed 1.5 N;. Increasing the concentration of sulfate ion in the eluting solution by addition of a soluble sulfate, such as sodium sulfate, has been found to be advantageous. The preferred ion exchange materials are sulfonated polystyrene resins such as Dowex 50,'' and are preferably arranged in a column through which the solutions are passed.

  4. Effect of cathode cooling efficiency and oxygen plasma gas pressure on the hafnium cathode wall temperature

    NASA Astrophysics Data System (ADS)

    Ashtekar, Koustubh; Diehl, Gregory; Hamer, John

    2012-10-01

    The hafnium cathode is widely used in DC plasma arc cutting (PAC) under an oxygen gas environment to cut iron and iron alloys. The hafnium erosion is always a concern which is controlled by the surface temperature. In this study, the effect of cathode cooling efficiency and oxygen gas pressure on the hafnium surface temperature are quantified. The two layer cathode sheath model is applied on the refractive hafnium surface while oxygen species (O2, O, O+, O++, e-) are considered within the thermal dis-equilibrium regime. The system of non-linear equations comprising of current density balance, heat flux balance at both the cathode surface and the sheath-ionization layer is coupled with the plasma gas composition solver. Using cooling heat flux, gas pressure and current density as inputs; the cathode wall temperature, electron temperature, and sheath voltage drop are calculated. Additionally, contribution of emitted electron current (Je) and ions current (Ji) to the total current flux are estimated. Higher gas pressure usually reduces Ji and increases Je that reduces the surface temperature by thermionic cooling.

  5. Oxide Protective Coats for Ir/Re Rocket Combustion Chambers

    NASA Technical Reports Server (NTRS)

    Fortini, Arthur; Tuffias, Robert H.

    2003-01-01

    An improved material system has been developed for rocket engine combustion chambers for burning oxygen/ hydrogen mixtures or novel monopropellants, which are highly oxidizing at operating temperatures. The baseline for developing the improved material system is a prior iridium/rhenium system for chambers burning nitrogen tetroxide/monomethyl hydrazine mixtures, which are less oxidizing. The baseline combustion chamber comprises an outer layer of rhenium that provides structural support, plus an inner layer of iridium that acts as a barrier to oxidation of the rhenium. In the improved material system, the layer of iridium is thin and is coated with a thermal fatigue-resistant refractory oxide (specifically, hafnium oxide) that serves partly as a thermal barrier to decrease the temperature and thus the rate of oxidation of the rhenium. The oxide layer also acts as a barrier against the transport of oxidizing species to the surface of the iridium. Tests in which various oxygen/hydrogen mixtures were burned in iridium/rhenium combustion chambers lined with hafnium oxide showed that the operational lifetimes of combustion chambers of the improved material system are an order of magnitude greater than those of the baseline combustion chambers.

  6. Review of anhydrous zirconium-hafnium separation techniques. Information circular/1984

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

    Skaggs, R.L.; Rogers, D.T.; Hunter, D.B.

    1983-12-01

    Sixteen nonaqueous techniques conceived to replace the current aqueous scheme for separating hafnium and zirconium tetrachlorides were reviewed and evaluated by the Bureau of Mines. The methods are divided into two classes: separation by fractional volatilization of the tetrachlorides, which takes advantage of the higher volatility of hafnium tetrachloride; and separation by chemical techniques, based on differences in chemical behavior of the two tetrachlorides. The criteria used to evaluate separation methods were temperature, pressure, separation factor per equilibrium stage, complexity, compatibility with existing technology, and potential for continuous operation. Three processes were selected as being most promising: (1) high-pressure distillation,more » (2) extractive distillation from a molten salt, and (3) preferential reduction of gaseous ZrCl4. Any of the proposed nonaqueous Hf-Zr separation schemes must be supplemented with additional purification to remove trace impurities.« less

  7. Thermomechanical and Thermochemical Behavior of a Hafnium-20 Percent Tantalum Alloy. Ph.D. Thesis - North Carolina State Univ., Raleigh

    NASA Technical Reports Server (NTRS)

    Howell, J. P.

    1971-01-01

    An investigation was conducted to determine the thermomechanical and thermochemical behavior of a high temperature, oxidation resistant, hafnium-20 percent tantalum alloy. The elastic and shear moduli of this alloy were determined in air up to 1000 C and in vacuum up to 2000 C using a mechanical resonance technique. The internal friction of the alloy was measured up to temperatures greater than 1400 C. Room temperature stress-strain behavior of the oxidized and unoxidized alloy was established. The effect of annealing on the elastic and shear moduli of the extruded rod material was investigated. The martensitic-type phase transformation occurring in the alloy was studied using hot stage metallography and electron microscopy. Static oxidation tests were conducted on the alloy at temperatures from 1000 C to 1700 C with weight gain measurements made as a function of time and temperatures. Surface morphology studies were conducted on the oxide coatings formed at the different temperatures using scanning electron microscopy and X-ray diffraction techniques.

  8. Mixed oxide solid solutions

    DOEpatents

    Magno, Scott; Wang, Ruiping; Derouane, Eric

    2003-01-01

    The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

  9. 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.

  10. Chemical precursors to non-oxide ceramics: Macro to nanoscale materials

    NASA Astrophysics Data System (ADS)

    Forsthoefel, Kersten M.

    Non-oxide ceramics exhibit a number of important properties that make them ideal for technologically important applications (thermal and chemical stability, high strength and hardness, wear-resistance, light weight, and a range of electronic and optical properties). Unfortunately, traditional methodologies to these types of materials are limited to fairly simple shapes and complex processed forms cannot be attained through these methods. The establishment of the polymeric precursor approach has allowed for the generation of advanced materials, such as refractory non-oxide ceramics, with controlled compositions, under moderate conditions, and in processed forms. The goal of the work described in this dissertation was both to develop new processible precursors to technologically important ceramics and to achieve the formation of advanced materials in processed forms. One aspect of this research exploited previously developed preceramic precursors to boron carbide, boron nitride and silicon carbide for the generation of a wide variety of advanced materials: (1) ultra-high temperature ceramic (UHTC) structural materials composed of hafnium boride and related composite materials, (2) the quaternary borocarbide superconductors, and (3) on the nanoscale, non-oxide ceramic nanotubules. The generation of the UHTC and the quaternary borocarbide materials was achieved through a method that employs a processible polymer/metal(s) dispersion followed by subsequent pyrolyses. In the case of the UHTC, hafnium oxide, hafnium, or hafnium boride powders were dispersed in a suitable precursor to afford hafnium borides or related composite materials (HfB2/HfC, HfB2/HfN, HfB2/SiC) in high yields and purities. The quaternary borocarbide superconducting materials were produced from pyrolyses of dispersions containing appropriate stoichiometric amounts of transition metal, lanthanide metal, and the polyhexenyldecaborane polymer. Both chemical vapor deposition (CVD) based routes employing a

  11. Effect of hafnium doping on density of states in dual-target magnetron co-sputtering HfZnSnO thin film transistors

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

    Huang, Chuan-Xin; Li, Jun, E-mail: SHUniverjunli@163.com; Fu, Yi-Zhou

    2015-11-23

    This study investigates the effect of hafnium doping on the density of states (DOSs) in HfZnSnO thin film transistors fabricated by dual-target magnetron co-sputtering system. The DOSs is extracted by temperature-dependent field-effect measurements, and they decrease from 1.1 × 10{sup 17} to 4.6 × 10{sup 16 }eV/cm{sup 3} with increasing the hafnium concentrations. The behavior of DOSs for the increasing hafnium concentration HfZnSnO thin film transistors can be confirmed by both the reduction of ΔV{sub T} under bias stress and the trapping charges calculated by capacitance voltage measurements. It suggests that the reduction in DOSs due to the hafnium doping is closely related with themore » bias stability and thermal stability.« less

  12. Silicon Nanowires with High-k Hafnium Oxide Dielectrics for Sensitive Detection of Small Nucleic Acid Oligomers

    PubMed Central

    Dorvel, Brian R.; Reddy, Bobby; Go, Jonghyun; Guevara, Carlos Duarte; Salm, Eric; Alam, Muhammad Ashraful; Bashir, Rashid

    2012-01-01

    Nanobiosensors based on silicon nanowire field effect transistors offer advantages of low cost, label-free detection, and potential for massive parallelization. As a result, these sensors have often been suggested as an attractive option for applications in Point-of-care (POC) medical diagnostics. Unfortunately, a number of performance issues such as gate leakage and current instability due to fluid contact, have prevented widespread adoption of the technology for routine use. High-k dielectrics, such as hafnium oxide (HfO2), have the known ability to address these challenges by passivating the exposed surfaces against destabilizing concerns of ion transport. With these fundamental stability issues addressed, a promising target for POC diagnostics and SiNWFET’s has been small oligonucleotides, more specifically microRNA (miRNA). MicroRNA’s are small RNA oligonucleotides which bind to messenger RNA’s, causing translational repression of proteins, gene silencing, and expressions are typically altered in several forms of cancer. In this paper, we describe a process for fabricating stable HfO2 dielectric based silicon nanowires for biosensing applications. Here we demonstrate sensing of single stranded DNA analogues to their microRNA cousins using miR-10b and miR-21 as templates, both known to be upregulated in breast cancer. We characterize the effect of surface functionalization on device performance using the miR-10b DNA analogue as the target sequence and different molecular weight poly-l-lysine as the functionalization layer. By optimizing the surface functionalization and fabrication protocol, we were able to achieve <100fM detection levels of miR-10b DNA analogue, with a theoretical limit of detection of 1fM. Moreover, the non-complementary DNA target strand, based on miR-21, showed very little response, indicating a highly sensitive and highly selective biosensing platform. PMID:22695179

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  14. Article having an improved platinum-aluminum-hafnium protective coating

    NASA Technical Reports Server (NTRS)

    Nagaraj, Bangalore Aswatha (Inventor); Williams, Jeffrey Lawrence (Inventor)

    2005-01-01

    An article protected by a protective coating has a substrate and a protective coating having an outer layer deposited upon the substrate surface and a diffusion zone formed by interdiffusion of the outer layer and the substrate. The protective coating includes platinum, aluminum, no more than about 2 weight percent hafnium, and substantially no silicon. The outer layer is substantially a single phase.

  15. Passivation of InP heterojunction bipolar transistors by strain controlled plasma assisted electron beam evaporated hafnium oxide

    NASA Astrophysics Data System (ADS)

    Driad, R.; Sah, R. E.; Schmidt, R.; Kirste, L.

    2012-01-01

    We present structural, stress, and electrical properties of plasma assisted e-beam evaporated hafnium dioxide (HfO2) layers on n-type InP substrates. These layers have subsequently been used for surface passivation of InGaAs/InP heterostructure bipolar transistors either alone or in combination with plasma enhanced chemical vapor deposited SiO2 layers. The use of stacked HfO2/SiO2 results in better interface quality with InGaAs/InP heterostructures, as illustrated by smaller leakage current and improved breakdown voltage. These improvements can be attributed to the reduced defect density and charge trapping at the dielectric-semiconductor interface. The deposition at room temperature makes these films suitable for sensitive devices.

  16. Hafnium-Based Bulk Metallic Glasses for Kinetic Energy Penetrators

    DTIC Science & Technology

    2004-12-01

    uranium -based (DU) and tungsten- nickel -iron (W-Ni-Fe) composite kinetic energy (KE) munitions is primarily ascribed to their high densities (U: ρ...based on an invariant point identified in the hafnium- copper- nickel ternary system. They are denser than zirconium-based glass-forming compositions...depleted- uranium penetrators. 1. INTRODUCTION 1.1 Criterion for Effective Kinetic Energy Penetrator Performance The lethality of depleted

  17. High quality transparent conducting oxide thin films

    DOEpatents

    Gessert, Timothy A.; Duenow, Joel N.; Barnes, Teresa; Coutts, Timothy J.

    2012-08-28

    A transparent conducting oxide (TCO) film comprising: a TCO layer, and dopants selected from the elements consisting of Vanadium, Molybdenum, Tantalum, Niobium, Antimony, Titanium, Zirconium, and Hafnium, wherein the elements are n-type dopants; and wherein the transparent conducting oxide is characterized by an improved electron mobility of about 42 cm.sup.2/V-sec while simultaneously maintaining a high carrier density of .about.4.4e.times.10.sup.20 cm.sup.-3.

  18. Inter-diffusion of copper and hafnium as studied by x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Pearson, Justin; Chourasia, A. R.

    The Cu/Hf interface has been characterized by x-ray photoelectron spectroscopy. Thin films (thicknesses ranging from 100 nm to 150 nm) of hafnium were deposited on a silicon substrate. About 80 nm of copper was then deposited on such samples. The e-beam method was used for the deposition. The samples were annealed for 30 min at temperatures of 100, 200, 300, 400, and 500°C. The inter-diffusion of copper and hafnium was investigated by sequential sputter depth profiling and x-ray photoelectron spectroscopy. The interdiffusion in each case was analyzed by the Matano-Boltzmann's procedure using the Fick's second law. The interdiffusion coefficients and the width of the interface as determined from the data have been correlated with the annealing temperature. Supported by Organized Research, TAMU-Commerce.

  19. Addition of oxygen to and distribution of oxides in tantalum alloy T-111 at low concentrations

    NASA Technical Reports Server (NTRS)

    Stecura, S.

    1975-01-01

    Oxygen was added at 820 and 990 C at an oxygen pressure of about .0003 torr. The technique permitted predetermined and reproducible oxygen doping of the tantalum alloy (T-111). Based on the temperature dependency of the doping reaction, it was concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the tantalum and tungsten oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and oxygen from other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C but not at 820 C. The vaporization of WO3 has no apparent effect on the doping reaction.

  20. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    DOEpatents

    Liu, W.; Flytzani-Stephanopoulos, M.

    1996-03-19

    A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  1. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    DOEpatents

    Liu, Wei; Flytzani-Stephanopoulos, Maria

    1996-01-01

    A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  2. The performance of hafnium and gadolinium self powered neutron detectors in the TREAT reactor

    NASA Astrophysics Data System (ADS)

    Imel, G. R.; Hart, P. R.

    1996-05-01

    The use of gadolinium and hafnium self powered neutron detectors in a transient reactor is described in this paper. The detectors were calibrated to the fission rate of U-235 using calibrated fission chambers; the calibration factors were tested in two reactors in steady state and found to be consistent. Calibration of the detectors in transient reactor conditions was done by using uranium wires that were analyzed by radiochemistry techniques to determine total fissions during the transient. This was correlated to the time-integrated current of the detectors during the transient. A temperature correction factor was derived to account for self-shielding effects in the hafnium and gadolinium detectors. The dynamic response of the detectors under transient conditions was studied, and found to be excellent.

  3. Oxidation resistant iron and nickel alloys for high temperature use

    NASA Technical Reports Server (NTRS)

    Hill, V. L.; Misra, S. K.; Wheaton, H. L.

    1970-01-01

    Iron-base and nickel-base alloys exhibit good oxidation resistance and improved ductility with addition of small amounts of yttrium, tantalum /or hafnium/, and thorium. They can be used in applications above the operating temperatures of the superalloys, if high strength materials are not required.

  4. The influence of interfacial defects on fast charge trapping in nanocrystalline oxide-semiconductor thin film transistors

    NASA Astrophysics Data System (ADS)

    Kim, Taeho; Hur, Jihyun; Jeon, Sanghun

    2016-05-01

    Defects in oxide semiconductors not only influence the initial device performance but also affect device reliability. The front channel is the major carrier transport region during the transistor turn-on stage, therefore an understanding of defects located in the vicinity of the interface is very important. In this study, we investigated the dynamics of charge transport in a nanocrystalline hafnium-indium-zinc-oxide thin-film transistor (TFT) by short pulse I-V, transient current and 1/f noise measurement methods. We found that the fast charging behavior of the tested device stems from defects located in both the front channel and the interface, following a multi-trapping mechanism. We found that a silicon-nitride stacked hafnium-indium-zinc-oxide TFT is vulnerable to interfacial charge trapping compared with silicon-oxide counterpart, causing significant mobility degradation and threshold voltage instability. The 1/f noise measurement data indicate that the carrier transport in a silicon-nitride stacked TFT device is governed by trapping/de-trapping processes via defects in the interface, while the silicon-oxide device follows the mobility fluctuation model.

  5. "Decarbonization" of an imino N-heterocyclic carbene via triple benzyl migration from hafnium

    USDA-ARS?s Scientific Manuscript database

    An imino N-heterocyclic carbene underwent three sequential benzyl migrations upon reaction with tetrabenzylhafnium, resulting in complete removal of the carbene carbon from the ligand. The resulting eneamido-amidinato hafnium complex showed alkene polymerization activity comparable to that of a prec...

  6. PROCESS OF RECOVERING ZIRCONIUM VALUES FROM HAFNIUM VALUES BY SOLVENT EXTRACTION WITH AN ALKYL PHOSPHATE

    DOEpatents

    Peppard, D.F.

    1960-02-01

    A process of separating hafnium nitrate from zirconium nitrate contained in a nitric acid solution by selectively. extracting the zirconium nitrate with a water-immiscible alkyl phosphate is reported.

  7. Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

    NASA Technical Reports Server (NTRS)

    Stecura, S.

    1976-01-01

    Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

  8. Raman Spectra of High-κ Dielectric Layers Investigated with Micro-Raman Spectroscopy Comparison with Silicon Dioxide

    PubMed Central

    Borowicz, P.; Taube, A.; Rzodkiewicz, W.; Latek, M.; Gierałtowska, S.

    2013-01-01

    Three samples with dielectric layers from high-κ dielectrics, hafnium oxide, gadolinium-silicon oxide, and lanthanum-lutetium oxide on silicon substrate were studied by Raman spectroscopy. The results obtained for high-κ dielectrics were compared with spectra recorded for silicon dioxide. Raman spectra suggest the similarity of gadolinium-silicon oxide and lanthanum-lutetium oxide to the bulk nondensified silicon dioxide. The temperature treatment of hafnium oxide shows the evolution of the structure of this material. Raman spectra recorded for as-deposited hafnium oxide are similar to the results obtained for silicon dioxide layer. After thermal treatment especially at higher temperatures (600°C and above), the structure of hafnium oxide becomes similar to the bulk non-densified silicon dioxide. PMID:24072982

  9. Technical Note: A simulation study on the feasibility of radiotherapy dose enhancement with calcium tungstate and hafnium oxide nano- and microparticles.

    PubMed

    Sherck, Nicholas J; Won, You-Yeon

    2017-12-01

    To assess the radiotherapy dose enhancement (RDE) potential of calcium tungstate (CaWO 4 ) and hafnium oxide (HfO 2 ) nano- and microparticles (NPs). A Monte Carlo simulation study was conducted to gauge their respective RDE potentials relative to that of the broadly studied gold (Au) NP. The study was warranted due to the promising clinical and preclinical studies involving both CaWO 4 and HfO 2 NPs as RDE agents in the treatment of various types of cancers. The study provides a baseline RDE to which future experimental RDE trends can be compared to. All three materials were investigated in silico with the software Penetration and Energy Loss of Positrons and Electrons (PENELOPE 2014) developed by Francesc Salvat and distributed in the United States by the Radiation Safety Information Computational Center (RSICC) at Oak Ridge National Laboratory. The work utilizes the extensively studied Au NP as the "gold standard" for a baseline. The key metric used in the evaluation of the materials was the local dose enhancement factor (DEF loc ). An additional metric used, termed the relative enhancement ratio (RER), evaluates material performance at the same mass concentrations. The results of the study indicate that Au has the strongest RDE potential using the DEF loc metric. HfO 2 and CaWO 4 both underperformed relative to Au with lower DEF loc of 2-3 × and 4-100 ×, respectively. The computational investigation predicts the RDE performance ranking to be: Au > HfO 2 > CaWO 4 . © 2017 American Association of Physicists in Medicine.

  10. Hafnium nitride buffer layers for growth of GaN on silicon

    DOEpatents

    Armitage, Robert D.; Weber, Eicke R.

    2005-08-16

    Gallium nitride is grown by plasma-assisted molecular-beam epitaxy on (111) and (001) silicon substrates using hafnium nitride buffer layers. Wurtzite GaN epitaxial layers are obtained on both the (111) and (001) HfN/Si surfaces, with crack-free thickness up to 1.2 {character pullout}m. However, growth on the (001) surface results in nearly stress-free films, suggesting that much thicker crack-free layers could be obtained.

  11. Synthesis of High Symmetry Phase of Hafnium Dioxide Thin Films and Nickel Ferrite's Effect on Microstructure in Composite Heterostructure

    NASA Astrophysics Data System (ADS)

    Straka, Weston J.

    Hafnium dioxide has attracted a great deal of attention recently due to its potential use in two different electronic applications: CMOS and FeRAM. In CMOS, the usefulness of hafnia comes in due to its high dielectric constant and compatibility with current IC processing parameters. For FeRAM, hafnia's recent discovery to exhibit ferroelectricity in an orthorhombic phase makes this material attractive for replacement of the ferroelectric material in FeRAM. This study shows the feasibility of depositing thin films of hafnium oxide via chemical solution deposition for integration into these devices. The processing parameters necessary to produce this phase show how non-equilibrium processing plays a role in its synthesis. The temperature necessary to achieve the high symmetry phase was at 725 °C for 3 minutes on sapphire, silicon, and coated silicon substrates. The thermal conductivity of each was viewed as the property that allowed the hafnia formation. The dielectric constant of the hafnia films were between 30 and 32 with low dissipation factors and up to 47 with a poor dissipation factor all at 1 kHz. The formation of this phase was shown to be thickness independent with the high symmetry phase existing up to 300 nm film thickness. Interfacing the hafnia film with nickel ferrite was also studied to identify the possibility of using this composite for non-destructive reading of FeRAM. The magnetic properties showed an unchanged nickel ferrite film but the interface between the two was poor leading to the conclusion that more work must be done to successfully integrate these two films.

  12. Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago.

    PubMed

    Næraa, T; Scherstén, A; Rosing, M T; Kemp, A I S; Hoffmann, J E; Kokfelt, T F; Whitehouse, M J

    2012-05-30

    Earth's lithosphere probably experienced an evolution towards the modern plate tectonic regime, owing to secular changes in mantle temperature. Radiogenic isotope variations are interpreted as evidence for the declining rates of continental crustal growth over time, with some estimates suggesting that over 70% of the present continental crustal reservoir was extracted by the end of the Archaean eon. Patterns of crustal growth and reworking in rocks younger than three billion years (Gyr) are thought to reflect the assembly and break-up of supercontinents by Wilson cycle processes and mark an important change in lithosphere dynamics. In southern West Greenland numerous studies have, however, argued for subduction settings and crust growth by arc accretion back to 3.8 Gyr ago, suggesting that modern-day tectonic regimes operated during the formation of the earliest crustal rock record. Here we report in situ uranium-lead, hafnium and oxygen isotope data from zircons of basement rocks in southern West Greenland across the critical time period during which modern-like tectonic regimes could have initiated. Our data show pronounced differences in the hafnium isotope-time patterns across this interval, requiring changes in the characteristics of the magmatic protolith. The observations suggest that 3.9-3.5-Gyr-old rocks differentiated from a >3.9-Gyr-old source reservoir with a chondritic to slightly depleted hafnium isotope composition. In contrast, rocks formed after 3.2 Gyr ago register the first additions of juvenile depleted material (that is, new mantle-derived crust) since 3.9 Gyr ago, and are characterized by striking shifts in hafnium isotope ratios similar to those shown by Phanerozoic subduction-related orogens. These data suggest a transitional period 3.5-3.2 Gyr ago from an ancient (3.9-3.5 Gyr old) crustal evolutionary regime unlike that of modern plate tectonics to a geodynamic setting after 3.2 Gyr ago that involved juvenile crust generation by plate

  13. Growth, microstructure and electrical properties of sputter-deposited hafnium oxide (HfO2) thin films grown using HfO2 ceramic target

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

    Aguirre, B.; Vemuri, R. S.; Zubia, David

    2011-01-01

    Hafnium oxide (HfO₂) thin films have been made by radio-frequency (rf) magnetron-sputtering onto Si(100) substrates under varying growth temperature (Ts). HfO₂ ceramic target has been employed for sputtering while varying the Ts from room temperature to 500⁰C during deposition. The effect of Ts on the growth and microstructure of deposited HfO₂ films has been studied using grazing incidence x-ray diffraction (GIXRD), X-ray photoelectron spectroscopy (XPS), and high-resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive x-ray spectrometry (EDS). The results indicate that the effect of Ts is significant on the growth, surface and interface structure, morphology and chemical composition ofmore » the HfO₂ films. Structural characterization indicates that the HfO₂ films grown at Ts<200 ⁰C are amorphous while films grown at Ts>200 ⁰C are nanocrystalline. An amorphous-to-crystalline transition occurs at Ts=200 ⁰C. Nanocrystalline HfO₂ films crystallized in a monoclinic structure with a (-111) orientation. XPS measurements indicated the high surface-chemical quality and stoichiometric nature of the grown HfO₂ films. An interface layer (IL) formation occurs due to reaction at the HfO₂-Si interface for HfO₂ films deposited at Ts>200 ⁰C. The thickness of IL increases with increasing Ts. XPS and EDS at the HfO₂-Si cross-section indicate the IL is a (Hf, Si)-O compound. The electrical characterization using capacitance-voltage measurements indicate that the dielectric constant decreases from 25 to 16 with increasing Ts.« less

  14. Facing-target mid-frequency magnetron reactive sputtered hafnium oxide film: Morphology and electrical properties

    NASA Astrophysics Data System (ADS)

    Zhang, Yu; Xu, Jun; Wang, You-Nian; Choi, Chi Kyu; Zhou, Da-Yu

    2016-03-01

    Amorphous hafnium dioxide (HfO2) film was prepared on Si (100) by facing-target mid-frequency reactive magnetron sputtering under different oxygen/argon gas ratio at room temperature with high purity Hf target. 3D surface profiler results showed that the deposition rates of HfO2 thin film under different O2/Ar gas ratio remain unchanged, indicating that the facing target midfrequency magnetron sputtering system provides effective approach to eliminate target poisoning phenomenon which is generally occurred in reactive sputtering procedure. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) demonstrated that the gradual reduction of oxygen vacancy concentration and the densification of deposited film structure with the increase of oxygen/argon (O2/Ar) gas flow ratio. Atomic force microscopy (AFM) analysis suggested that the surface of the as-deposited HfO2 thin film tends to be smoother, the root-meansquare roughness (RMS) reduced from 0.876 nm to 0.333 nm while O2/Ar gas flow ratio increased from 1/4 to 1/1. Current-Voltage measurements of MOS capacitor based on Au/HfO2/Si structure indicated that the leakage current density of HfO2 thin films decreased by increasing of oxygen partial pressure, which resulted in the variations of pore size and oxygen vacancy concentration in deposited thin films. Based on the above characterization results the leakage current mechanism for all samples was discussed systematically.

  15. Thin-film transistor fabricated in single-crystalline transparent oxide semiconductor.

    PubMed

    Nomura, Kenji; Ohta, Hiromichi; Ueda, Kazushige; Kamiya, Toshio; Hirano, Masahiro; Hosono, Hideo

    2003-05-23

    We report the fabrication of transparent field-effect transistors using a single-crystalline thin-film transparent oxide semiconductor, InGaO3(ZnO)5, as an electron channel and amorphous hafnium oxide as a gate insulator. The device exhibits an on-to-off current ratio of approximately 106 and a field-effect mobility of approximately 80 square centimeters per volt per second at room temperature, with operation insensitive to visible light irradiation. The result provides a step toward the realization of transparent electronics for next-generation optoelectronics.

  16. Aminopyridinate-FI hybrids, their hafnium and titanium complexes, and their application in the living polymerization of 1-hexene.

    PubMed

    Haas, Isabelle; Dietel, Thomas; Press, Konstantin; Kol, Moshe; Kempe, Rhett

    2013-10-11

    Based on two well-established ligand systems, the aminopyridinato (Ap) and the phenoxyimine (FI) ligand systems, new Ap-FI hybrid ligands were developed. Four different Ap-FI hybrid ligands were synthesized through a simple condensation reaction and fully characterized. The reaction of hafnium tetrabenzyl with all four Ap-FI hybrid ligands exclusively led to mono(Ap-FI) complexes of the type [(Ap-FI)HfBn2 ]. The ligands acted as tetradentate dianionic chelates. Upon activation with tris(pentafluorophenyl)borane, the hafnium-dibenzyl complexes led to highly active catalysts for the polymerization of 1-hexene. Ultrahigh molecular weights and extremely narrow polydispersities support the living nature of this polymerization process. A possible deactivation product of the hafnium catalysts was characterized by single-crystal X-ray analysis and is discussed. The coordination modes of these new ligands were studied with the help of model titanium complexes. The reaction of titanium(IV) isopropoxide with ligand 1 led to a mono(Ap-FI) complex, which showed the desired fac-mer coordination mode. Titanium (IV) isopropoxide reacted with ligand 4 to give a complex of the type [(ApH-FI)2 Ti(OiPr)2 ], which featured the ligand in its monoanionic form. The two titanium complexes were characterized by X-ray crystal-structure analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pulse I-V characterization of a nano-crystalline oxide device with sub-gap density of states

    NASA Astrophysics Data System (ADS)

    Kim, Taeho; Hur, Ji-Hyun; Jeon, Sanghun

    2016-05-01

    Understanding the charge trapping nature of nano-crystalline oxide semiconductor thin film transistors (TFTs) is one of the most important requirements for their successful application. In our investigation, we employed a fast-pulsed I-V technique for understanding the charge trapping phenomenon and for characterizing the intrinsic device performance of an amorphous/nano-crystalline indium-hafnium-zinc-oxide semiconductor TFT with varying density of states in the bulk. Because of the negligible transient charging effect with a very short pulse, the source-to-drain current obtained with the fast-pulsed I-V measurement was higher than that measured by the direct-current characterization method. This is because the fast-pulsed I-V technique provides a charge-trap free environment, suggesting that it is a representative device characterization methodology of TFTs. In addition, a pulsed source-to-drain current versus time plot was used to quantify the dynamic trapping behavior. We found that the charge trapping phenomenon in amorphous/nano-crystalline indium-hafnium-zinc-oxide TFTs is attributable to the charging/discharging of sub-gap density of states in the bulk and is dictated by multiple trap-to-trap processes.

  18. Pulse I-V characterization of a nano-crystalline oxide device with sub-gap density of states.

    PubMed

    Kim, Taeho; Hur, Ji-Hyun; Jeon, Sanghun

    2016-05-27

    Understanding the charge trapping nature of nano-crystalline oxide semiconductor thin film transistors (TFTs) is one of the most important requirements for their successful application. In our investigation, we employed a fast-pulsed I-V technique for understanding the charge trapping phenomenon and for characterizing the intrinsic device performance of an amorphous/nano-crystalline indium-hafnium-zinc-oxide semiconductor TFT with varying density of states in the bulk. Because of the negligible transient charging effect with a very short pulse, the source-to-drain current obtained with the fast-pulsed I-V measurement was higher than that measured by the direct-current characterization method. This is because the fast-pulsed I-V technique provides a charge-trap free environment, suggesting that it is a representative device characterization methodology of TFTs. In addition, a pulsed source-to-drain current versus time plot was used to quantify the dynamic trapping behavior. We found that the charge trapping phenomenon in amorphous/nano-crystalline indium-hafnium-zinc-oxide TFTs is attributable to the charging/discharging of sub-gap density of states in the bulk and is dictated by multiple trap-to-trap processes.

  19. Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component

    NASA Technical Reports Server (NTRS)

    Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

    2009-01-01

    A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium diboride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

  20. Methods of repairing a substrate

    NASA Technical Reports Server (NTRS)

    Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

    2011-01-01

    A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium boride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

  1. Low-temperature fabrication of an HfO2 passivation layer for amorphous indium-gallium-zinc oxide thin film transistors using a solution process.

    PubMed

    Hong, Seonghwan; Park, Sung Pyo; Kim, Yeong-Gyu; Kang, Byung Ha; Na, Jae Won; Kim, Hyun Jae

    2017-11-24

    We report low-temperature solution processing of hafnium oxide (HfO 2 ) passivation layers for amorphous indium-gallium-zinc oxide (a-IGZO) thin-film transistors (TFTs). At 150 °C, the hafnium chloride (HfCl 4 ) precursor readily hydrolyzed in deionized (DI) water and transformed into an HfO 2 film. The fabricated HfO 2 passivation layer prevented any interaction between the back surface of an a-IGZO TFT and ambient gas. Moreover, diffused Hf 4+ in the back-channel layer of the a-IGZO TFT reduced the oxygen vacancy, which is the origin of the electrical instability in a-IGZO TFTs. Consequently, the a-IGZO TFT with the HfO 2 passivation layer exhibited improved stability, showing a decrease in the threshold voltage shift from 4.83 to 1.68 V under a positive bias stress test conducted over 10,000 s.

  2. Interactions of hydrogen with amorphous hafnium oxide

    NASA Astrophysics Data System (ADS)

    Kaviani, Moloud; Afanas'ev, Valeri V.; Shluger, Alexander L.

    2017-02-01

    We used density functional theory (DFT) calculations to study the interaction of hydrogen with amorphous hafnia (a -HfO2 ) using a hybrid exchange-correlation functional. Injection of atomic hydrogen, its diffusion towards electrodes, and ionization can be seen as key processes underlying charge instability of high-permittivity amorphous hafnia layers in many applications. Hydrogen in many wide band gap crystalline oxides exhibits negative-U behavior (+1 and -1 charged states are thermodynamically more stable than the neutral state) . Our results show that in a -HfO2 hydrogen is also negative-U, with charged states being the most thermodynamically stable at all Fermi level positions. However, metastable atomic hydrogen can share an electron with intrinsic electron trapping precursor sites [Phys. Rev. B 94, 020103 (2016)., 10.1103/PhysRevB.94.020103] forming a [etr -+O -H ] center, which is lower in energy on average by about 0.2 eV. These electron trapping sites can affect both the dynamics and thermodynamics of the interaction of hydrogen with a -HfO2 and the electrical behavior of amorphous hafnia films in CMOS devices.

  3. Metallorganic chemical vapor deposition and atomic layer deposition approaches for the growth of hafnium-based thin films from dialkylamide precursors for advanced CMOS gate stack applications

    NASA Astrophysics Data System (ADS)

    Consiglio, Steven P.

    To continue the rapid progress of the semiconductor industry as described by Moore's Law, the feasibility of new material systems for front end of the line (FEOL) process technologies needs to be investigated, since the currently employed polysilicon/SiO2-based transistor system is reaching its fundamental scaling limits. Revolutionary breakthroughs in complementary-metal-oxide-semiconductor (CMOS) technology were recently announced by Intel Corporation and International Business Machines Corporation (IBM), with both organizations revealing significant progress in the implementation of hafnium-based high-k dielectrics along with metal gates. This announcement was heralded by Gordon Moore as "...the biggest change in transistor technology since the introduction of polysilicon gate MOS transistors in the late 1960s." Accordingly, the study described herein focuses on the growth of Hf-based dielectrics and Hf-based metal gates using chemical vapor-based deposition methods, specifically metallorganic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD). A family of Hf source complexes that has received much attention recently due to their desirable properties for implementation in wafer scale manufacturing is the Hf dialkylamide precursors. These precursors are room temperature liquids and possess sufficient volatility and desirable decomposition characteristics for both MOCVD and ALD processing. Another benefit of using these sources is the existence of chemically compatible Si dialkylamide sources as co-precursors for use in Hf silicate growth. The first part of this study investigates properties of MOCVD-deposited HfO2 and HfSixOy using dimethylamido Hf and Si precursor sources using a customized MOCVD reactor. The second part of this study involves a study of wet and dry surface pre-treatments for ALD growth of HfO2 using tetrakis(ethylmethylamido)hafnium in a wafer scale manufacturing environment. The third part of this study is an investigation of

  4. Radiation Effects on the Electrical Properties of Hafnium Oxide Based MOS Capacitors

    DTIC Science & Technology

    2011-03-01

    Figures Figure Page 1. Conceptual illustration of the creation of electron-hole pairs and displacement damage in a n -type silicon metal-oxide-silicon...Illustration of the effect, in a CV plot, of oxide trapped charge for a hypothetical n -type device...8 5. Illustration of the effect, in a CV plot, of interface trapped charge for a hypothetical n -type device

  5. All-alkoxide synthesis of strontium-containing metal oxides

    DOEpatents

    Boyle, Timothy J.

    2001-01-01

    A method for making strontium-containing metal-oxide ceramic thin films from a precursor liquid by mixing a strontium neo-pentoxide dissolved in an amine solvent and at least one metal alkoxide dissolved in a solvent, said at least one metal alkoxide selected from the group consisting of alkoxides of calcium, barium, bismuth, cadmium, lead, titanium, tantalum, hafnium, tungsten, niobium, zirconium, yttrium, lanthanum, antimony, chromium and thallium, depositing a thin film of the precursor liquid on a substrate, and heating the thin film in the presence of oxygen at between 550 and 700.degree. C.

  6. Electric field cycling behavior of ferroelectric hafnium oxide.

    PubMed

    Schenk, Tony; Schroeder, Uwe; Pešić, Milan; Popovici, Mihaela; Pershin, Yuriy V; Mikolajick, Thomas

    2014-11-26

    HfO2 based ferroelectrics are lead-free, simple binary oxides with nonperovskite structure and low permittivity. They just recently started attracting attention of theoretical groups in the fields of ferroelectric memories and electrostatic supercapacitors. A modified approach of harmonic analysis is introduced for temperature-dependent studies of the field cycling behavior and the underlying defect mechanisms. Activation energies for wake-up and fatigue are extracted. Notably, all values are about 100 meV, which is 1 order of magnitude lower than for conventional ferroelectrics like lead zirconate titanate (PZT). This difference is mainly atttributed to the one to two orders of magnitude higher electric fields used for cycling and to the different surface to volume ratios between the 10 nm thin films in this study and the bulk samples of former measurements or simulations. Moreover, a new, analog-like split-up effect of switching peaks by field cycling is discovered and is explained by a network model based on memcapacitive behavior as a result of defect redistribution.

  7. Hafnium, Tungsten, and the Differentiation of the Moon and Mars

    NASA Astrophysics Data System (ADS)

    Taylor, G. J.

    2003-11-01

    Measurements of the isotopic composition of tungsten (W) show that lunar samples and Martian meteorites have an excess of W-182. This was produced by the decay of hafnium-182 (Hf-182), an isotope with a half-life of only 9 million years. Because tungsten dissolves enthusiastically in metallic iron and hafnium does not, it is possible to use the abundance of W-182 in rocks formed by melting of the silicate mantle as an indicator of the timing of core formation. However, the concentrations of Hf and W in rocky material can be affected by melting and crystallization, so we also need to know how each element concentrates in common minerals in the mantles of the Moon and Mars. The behavior of Hf has been studied experimentally, but this is not true of W. Kevin Righter (Johnson Space Center) and Charles (Chip) Shearer (University of New Mexico) have filled this knowledge void by determining how W partitions between olivine, high- and low-calcium pyroxene, plagioclase feldspar, and garnet. The new data allowed Righter and Shearer to reexamine available measurements of the isotopic composition of W in lunar samples and Martian meteorites. Their analysis suggests that the lunar magma ocean, a huge magma system that surrounded the Moon when it formed, solidified in less than 30 million years. This is shorter than many theoretical calculations suggest. Pathfinder data and chemical data from Martian meteorites suggest that the core of Mars makes up about 20% of the planet. Core formation and subsequent melting of a region of the mantle containing garnet and high-calcium pyroxene took place less than 20-30 million years after the formation of the first solids in the solar system. This type of research shows the importance of measurements of isotopic compositions of radioactive elements or their decay products and laboratory experiments on the geochemical behavior of those elements.

  8. Memory effects in a Al/Ti:HfO2/CuPc metal-oxide-semiconductor device

    NASA Astrophysics Data System (ADS)

    Tripathi, Udbhav; Kaur, Ramneek

    2016-05-01

    Metal oxide semiconductor structured organic memory device has been successfully fabricated. Ti doped hafnium oxide (Ti:HfO2) nanoparticles has been fabricated by precipitation method and further calcinated at 800 °C. Copper phthalocyanine, a hole transporting material has been utilized as an organic semiconductor. The electrical properties of the fabricated device have been studied by measuring the current-voltage and capacitance-voltage characteristics. The amount of charge stored in the nanoparticles has been calculated by using flat band condition. This simple approach for fabricating MOS memory device has opens up opportunities for the development of next generation memory devices.

  9. Composition effects on mechanical properties of tungsten-rhenium-hafnium-carbon alloys

    NASA Technical Reports Server (NTRS)

    Witzke, W. R.

    1973-01-01

    The mechanical properties of rod and sheet fabricated from arc melted W-4Re-Hf-C alloys containing up to about 0.8 mol percent hafnium carbide (HfC) were evaluated in the as-worked condition. The DBTT's of electropolished bend and tensile specimens were independent of HfC content in this range but dependent on excess Hf or C above that required for stoichiometric HfC. Low temperature ductility was a maximum at Hf contents slightly in excess of stoichiometric. Variations in high temperature strength were also dependent on excess Hf and C. Maximum creep strengthening also occurred at Hf contents in excess of stoichiometric. Analysis of extracted second phase particles indicated that creep strength was reduced by increasing WC content in the HfC particles.

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

    NASA Astrophysics Data System (ADS)

    Terauds, Kalvis

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

  11. Hafnium oxide films for application as gate dielectrics

    NASA Astrophysics Data System (ADS)

    Hsu, Shuo-Lin

    The deposition and characterization of HfO2 films for potential application as a high-kappa gate dielectric in MOS devices has been investigated. DC magnetron reactive sputtering was utilized to prepare the HfO2 films. Structural, chemical, and electrical analyses were performed to characterize the various physical, chemical and electrical properties of the sputtered HfO2 films. The sputtered HfO2 films were annealed to simulate the dopant activation process used in semiconductor processing, and to study the thermal stability of the high-kappa, films. The changes in the film properties due to the annealing are also discussed in this work. Glancing angle XRD was used to analyse the atomic scale structure of the films. The as deposited films exhibit an amorphous, regardless of the film thickness. During post-deposition annealing, the thicker films crystallized at lower temperature (< 600°C), and ultra-thin (5.8 nm) film crystallized at higher temperature (600--720°C). The crystalline phase which formed depended on the thickness of the films. The low temperature phase (monoclinic) formed in the 10--20 nm annealed films, and high temperature phase (tetragonal) formed in the ultra-thin annealed HfO2 film. TEM cross-section studies of as deposited samples show that an interfacial layer (< 1nm) exists between HfO2/Si for all film thicknesses. The interfacial layer grows thicker during heat treatment, and grows more rapidly when grain boundaries are present. XPS surface analysis shows the as deposited films are fully oxidized with an excess of oxygen. Interfacial chemistry analysis indicated that the interfacial layer is a silicon-rich silicate layer, which tends to transform to silica-like layer during heat treatment. I-V measurements show the leakage current density of the Al/as deposited-HfO 2/Si MOS diode is of the order of 10-3 A/cm 2, two orders of magnitude lower than that of a ZrO2 film with similar physical thickness. Carrier transport is dominated by Schottky

  12. Zirconium and hafnium fractionation in differentiation of alkali carbonatite magmatic systems

    NASA Astrophysics Data System (ADS)

    Kogarko, L. N.

    2016-05-01

    Zirconium and hafnium are valuable strategic metals which are in high demand in industry. The Zr and Hf contents are elevated in the final products of magmatic differentiation of alkali carbonatite rocks in the Polar Siberia region (Guli Complex) and Ukraine (Chernigov Massif). Early pyroxene fractionation led to an increase in the Zr/Hf ratio in the evolution of the ultramafic-alkali magmatic system due to a higher distribution coefficient of Hf in pyroxene with respect to Zr. The Rayleigh equation was used to calculate a quantitative model of variation in the Zr/Hf ratio in the development of the Guli magmatic system. Alkali carbonatite rocks originated from rare element-rich mantle reservoirs, in particular, the metasomatized mantle. Carbonated mantle xenoliths are characterized by a high Zr/Hf ratio due to clinopyroxene development during metasomatic replacement of orthopyroxene by carbonate fluid melt.

  13. Experimental and first-principles studies on the elastic properties of α-hafnium metal under pressure

    DOE PAGES

    Qi, Xintong; Wang, Xuebing; Chen, Ting; ...

    2016-03-30

    Compressional and shear wave velocities of the α phase of hafnium have been measured up to 10.4 GPa at room temperature using ultrasonic interferometry in a multi-anvil apparatus. A finite strain equation of state analysis yielded K s0 = 110.4 (5) GPa, G 0 = 54.7(5) GPa,K s0' = 3.7 and G 0' = 0.6 for the elastic bulk and shear moduli and their pressure derivatives at ambient conditions. Complementary to the experimental data, the single crystal elastic constants, elastic anisotropy and the unit cell axial ratio c/a of α-hafnium at high pressures were investigated by Density Functional Theory (DFT)more » based first principles calculations. A c/a value of 1.605 is predicted for α-Hf at 40 GPa, which is in excellent agreement with previous experimental results. The low-pressure derivative of the shear modulus observed in our experimental data up to 10 GPa was found to originate from the elastic constant C44 which exhibits negligible pressure dependence within the current experimental pressure range. At higher pressures (>10 GPa), C 44 was predicted to soften and the shear wave velocity ν S trended to decrease with pressure, which can be interpreted as a precursor to the α-ω transition similar to that observed in other group IV elements (titanium and zirconium). Here, the acoustic velocities, bulk and shear moduli, and the acoustic Debye temperature (θ D = 240.1 K) determined from the current experiments were all compared well with those predicted by our theoretical DFT calculations.« less

  14. Composition and method for brazing graphite to graphite

    DOEpatents

    Taylor, A.J.; Dykes, N.L.

    1982-08-10

    A brazing material is described for joining graphite structures that can be used up to 2800/sup 0/C. The brazing material is formed of a paste-like composition of hafnium carbide and uranium oxide with a thermosetting resin. The uranium oxide is converted to uranium dicarbide during the brazing operation and then the hafnium carbide and uranium dicarbide form a liquid phase at a temperature about 2600/sup 0/C with the uranium diffusing and vaporizing from the joint area as the temperature is increased to about 2800/sup 0/C so as to provide a brazed joint consisting essentially of hafnium carbide. The resulting brazed joint is chemically and thermally compatible with the graphite structures.

  15. Stress-rupture strength and microstructural stability of tungsten-hafnium-carbon-wire reinforced superalloy composites

    NASA Technical Reports Server (NTRS)

    Petrasek, D. W.; Signorelli, R. A.

    1974-01-01

    Tungsten-hafnium-carbon - superalloy composites were found to be potentially useful for turbine blade applications on the basis of stress-rupture strength. The 100- and 1000-hr rupture strengths calculated for 70 vol. % fiber composites based on test data at 1090C (2000F) were 420 and 280 MN/m2 (61,000 and 41,000 psi, respectively). The investigation indicated that, with better quality fibers, composites having 100- and 1000-hr rupture strengths of 570 and 370 MN/m2 (82,000 and 54,000 psi, respectively), may be obtained. Metallographic studies indicated sufficient fiber-matrix compatibility for 1000 hr or more at 1090C (2000F).

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

    NASA Technical Reports Server (NTRS)

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

    1997-01-01

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

  17. Work functions of hafnium nitride thin films as emitter material for field emitter arrays

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

    Gotoh, Yasuhito, E-mail: gotoh.yasuhito.5w@kyoto-u.ac.jp; Fujiwara, Sho; Tsuji, Hiroshi

    The work functions of hafnium nitride thin films prepared by radio-frequency magnetron sputtering were investigated in vacuum, before and after surface cleaning processes, with a view of improving the properties of as-fabricated field emitter arrays comprising hafnium nitride emitters. The measurement of the work function was first performed for the as-deposited films and then for films subjected to surface cleaning process, either thermal treatment or ion bombardment. Thermal treatment at a maximum temperature of 300 °C reduced the work function by 0.7 eV. Once the film was heated, the work function maintained the reduced value, even after cooling to room temperature. Amore » little change in the work function was observed for the second and third thermal treatments. The ion bombardment was conducted by exposing the sample to a thin plasma for different sample bias conditions and processing times. When the sample was biased at −10 V, the work function decreased by 0.6 eV. The work function reduction became saturated in the early stage of the ion bombardment. When the sample was biased at −50 V, the work function exhibited different behaviors, that is, first it decreased rapidly and then increased in response to the increase in processing time. The lowest attainable work function was found to be 4.00 eV. It should be noted that none of the work function values reported in this paper were obtained using surfaces that were demonstrated to be free from oxygen contamination. The present results suggest that the current–voltage characteristics of a field emitter array can be improved by a factor of 25–50 by the examined postprocesses.« less

  18. Processing development of 4 tantalum carbide-hafnium carbide and related carbides and borides for extreme environments

    NASA Astrophysics Data System (ADS)

    Gaballa, Osama Gaballa Bahig

    Carbides, nitrides, and borides ceramics are of interest for many applications because of their high melting temperatures and good mechanical properties. Wear-resistant coatings are among the most important applications for these materials. Materials with high wear resistance and high melting temperatures have the potential to produce coatings that resist degradation when subjected to high temperatures and high contact stresses. Among the carbides, Al4SiC4 is a low density (3.03 g/cm3), high melting temperature (>2000°C) compound, characterized by superior oxidation resistance, and high compressive strength. These desirable properties motivated this investigation to (1) obtain high-density Al4SiC4 at lower sintering temperatures by hot pressing, and (2) to enhance its mechanical properties by adding WC and TiC to the Al4SiC4. Also among the carbides, tantalum carbide and hafnium carbide have outstanding hardness; high melting points (3880°C and 3890°C respectively); good resistance to chemical attack, thermal shock, and oxidation; and excellent electronic conductivity. Tantalum hafnium carbide (Ta4HfC 5) is a 4-to-1 ratio of TaC to HfC with an extremely high melting point of 4215 K (3942°C), which is the highest melting point of all currently known compounds. Due to the properties of these carbides, they are considered candidates for extremely high-temperature applications such as rocket nozzles and scramjet components, where the operating temperatures can exceed 3000°C. Sintering bulk components comprised of these carbides is difficult, since sintering typically occurs above 50% of the melting point. Thus, Ta4 HfC5 is difficult to sinter in conventional furnaces or hot presses; furnaces designed for very high temperatures are expensive to purchase and operate. Our research attempted to sinter Ta4HfC5 in a hot press at relatively low temperature by reducing powder particle size and optimizing the powder-handling atmosphere, milling conditions, sintering

  19. Composition and method for brazing graphite to graphite

    DOEpatents

    Taylor, Albert J.; Dykes, Norman L.

    1984-01-01

    The present invention is directed to a brazing material for joining graphite structures that can be used at temperatures up to about 2800.degree. C. The brazing material formed of a paste-like composition of hafnium carbide and uranium oxide with a thermosetting resin. The uranium oxide is converted to uranium dicarbide during the brazing operation and then the hafnium carbide and uranium dicarbide form a liquid phase at a temperature about 2600.degree. C. with the uranium diffusing and vaporizing from the joint area as the temperature is increased to about 2800.degree. C. so as to provide a brazed joint consisting essentially of hafnium carbide. This brazing temperature for hafnium carbide is considerably less than the eutectic temperature of hafnium carbide of about 3150.degree. C. The brazing composition also incorporates the thermosetting resin so that during the brazing operation the graphite structures may be temporarily bonded together by thermosetting the resin so that machining of the structures to final dimensions may be completed prior to the completion of the brazing operation. The resulting brazed joint is chemically and thermally compatible with the graphite structures joined thereby and also provides a joint of sufficient integrity so as to at least correspond with the strength and other properties of the graphite.

  20. Hafnium-doped hydroxyapatite nanoparticles with ionizing radiation for lung cancer treatment.

    PubMed

    Chen, Min-Hua; Hanagata, Nobutaka; Ikoma, Toshiyuki; Huang, Jian-Yuan; Li, Keng-Yuan; Lin, Chun-Pin; Lin, Feng-Huei

    2016-06-01

    Recently, photodynamic therapy (PDT) is one of the new clinical options by generating cytotoxic reactive oxygen species (ROS) to kill cancer cells. However, the optical approach of PDT is limited by tissue penetration depth of visible light. In this study, we propose that a ROS-enhanced nanoparticle, hafnium-doped hydroxyapatite (Hf:HAp), which is a material to yield large quantities of ROS inside the cells when the nanoparticles are bombarded with high penetrating power of ionizing radiation. Hf:HAp nanoparticles are generated by wet chemical precipitation with total doping concentration of 15mol% Hf(4+) relative to Ca(2+) in HAp host material. The results show that the HAp particles could be successfully doped with Hf ions, resulted in the formation of nano-sized rod-like shape and with pH-dependent solubility. The impact of ionizing radiation on Hf:HAp nanoparticles is assessed by using in-vitro and in-vivo model using A549 cell line. The 2',7'-dichlorofluorescein diacetate (DCFH-DA) results reveal that after being exposed to gamma rays, Hf:HAp could significantly lead to the formation of ROS in cells. Both cell viability (WST-1) and cytotoxicity (LDH) assay show the consistent results that A549 lung cancer cell lines are damaged with changes in the cells' ROS level. The in-vivo studies further demonstrate that the tumor growth is inhibited owing to the cells apoptosis when Hf:HAp nanoparticles are bombarded with ionizing radiation. This finding offer a new therapeutic method of interacting with ionizing radiation and demonstrate the potential of Hf:HAp nanoparticles in tumor treatment, such as being used in a palliative treatment after lung surgical procedure. Photodynamic therapy (PDT) is one of the new clinical options by generating cytotoxic reactive oxygen species (ROS) to kill cancer cells. Unfortunately, the approach of PDT is usually limited to the treatment of systemic disease and deeper tumor, due to the limited tissue penetration depth of visible

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

    NASA Astrophysics Data System (ADS)

    Zamani, Davoud

    ABSTRACT Hafnium based oxides and silicates are promising high-κ dielectrics to replace SiO2 as gate material for state-of-the-art semiconductor devices. However, integrating these new high-κ materials into the existing complementary metal-oxide semiconductor (CMOS) process remains a challenge. One particular area of concern is the use of large amounts of HF during wet etching of hafnium based oxides and silicates. The patterning of thin films of these materials is accomplished by wet etching in HF solutions. The use of HF allows dissolution of hafnium as an anionic fluoride complex. Etch selectivity with respect to SiO2 is achieved by appropriately diluting the solutions and using slightly elevated temperatures. From an ESH point of view, it would be beneficial to develop methods which would lower the use of HF. The first objective of this study is to find new chemistries and developments of new wet etch methods to reduce fluoride consumption during wet etching of hafnium based high-κ materials. Another related issue with major environmental impact is the usage of large amounts of rinsing water for removal of HF in post-etch cleaning step. Both of these require a better understanding of the HF interaction with the high-κ surface during the etching, cleaning, and rinsing processes. During the rinse, the cleaning chemical is removed from the wafers. Ensuring optimal resource usage and cycle time during the rinse requires a sound understanding and quantitative description of the transport effects that dominate the removal rate of the cleaning chemicals from the surfaces. Multiple processes, such as desorption and re-adsorption, diffusion, migration and convection, all factor into the removal rate of the cleaning chemical during the rinse. Any of these processes can be the removal rate limiting process, the bottleneck of the rinse. In fact, the process limiting the removal rate generally changes as the rinse progresses, offering the opportunity to save resources

  2. Oxygen migration during resistance switching and failure of hafnium oxide memristors

    DOE PAGES

    Kumar, Suhas; Wang, Ziwen; Huang, Xiaopeng; ...

    2017-03-06

    While the recent establishment of the role of thermophoresis/diffusion-driven oxygen migration during resistance switching in metal oxide memristors provided critical insights required for memristor modeling, extended investigations of the role of oxygen migration during ageing and failure remain to be detailed. Such detailing will enable failure-tolerant design, which can lead to enhanced performance of memristor-based next-generation storage-class memory. Furthermore, we directly observed lateral oxygen migration using in-situ synchrotron x-ray absorption spectromicroscopy of HfO x memristors during initial resistance switching, wear over millions of switching cycles, and eventual failure, through which we determined potential physical causes of failure. Using this information,more » we reengineered devices to mitigate three failure mechanisms and demonstrated an improvement in endurance of about three orders of magnitude.« less

  3. Low temperature mobility in hafnium-oxide gated germanium p-channel metal-oxide-semiconductor field-effect transistors

    NASA Astrophysics Data System (ADS)

    Beer, Chris; Whall, Terry; Parker, Evan; Leadley, David; De Jaeger, Brice; Nicholas, Gareth; Zimmerman, Paul; Meuris, Marc; Szostak, Slawomir; Gluszko, Grzegorz; Lukasiak, Lidia

    2007-12-01

    Effective mobility measurements have been made at 4.2K on high performance high-k gated germanium p-type metal-oxide-semiconductor field effect transistors with a range of Ge/gate dielectric interface state densities. The mobility is successfully modelled by assuming surface roughness and interface charge scattering at the SiO2 interlayer/Ge interface. The deduced interface charge density is approximately equal to the values obtained from the threshold voltage and subthreshold slope measurements on each device. A hydrogen anneal reduces both the interface state density and the surface root mean square roughness by 20%.

  4. Synthesis of transparent nanocomposite monoliths for gamma scintillation

    NASA Astrophysics Data System (ADS)

    Liu, Chao; Hajagos, Tibor J.; Kishpaugh, David; Jin, Yunxia; Hu, Wei; Chen, Qi; Pei, Qibing

    2015-08-01

    During the past decade, inorganic nanoparticles/polymer nanocomposites have been intensively studied to provide a low cost, high performance alternative for gamma scintillation. However, the aggregation of nanoparticles often occurs even at low nanoparticle concentrations and thus deteriorates the transparency and performance of these nanocomposite scintillators. Here we report an efficient fabrication protocol of transparent nanocomposite monoliths based on surface modified hafnium oxide nanoparticles. Using hafnium oxide nanoparticles with surface-grafted methacrylate groups, highly transparent bulk-size nanocomposite monoliths (2 mm thick, transmittance at 550 nm >75%) are fabricated with nanoparticle loadings up to 40 wt% (net hafnium wt% up to 28.5%). These nanocomposite monoliths of 1 cm diameter and 2 mm thickness are capable of producing a full energy photopeak for 662 keV gamma rays, with the best deconvoluted photopeak energy resolution reaching 8%.

  5. Effect of nitrogen on tensile properties and structures of T-111 (tantalum, 8 percent tungsten, 2 percent hafnium) tubing

    NASA Technical Reports Server (NTRS)

    Buzzard, R. J.; Metroka, R. R.

    1973-01-01

    The effect of controlled nitrogen additions was evaluated on the mechanical properties of T-111 (Ta-8W-2Hf) fuel pin cladding material proposed for use in a lithium-cooled nuclear reactor concept. Additions of 80 to 1125 ppm nitrogen resulted in increased strengthening of T-111 tubular section test specimens at temperatures of 25 to 1200 C. Homogeneous distributions of up to 500 ppm nitrogen did not seriously decrease tensile ductility. Both single and two-phase microstructures, with hafnium nitride as the second phase, were evaluated in this study.

  6. Investigation to develop a method to apply diffusion barrier to high strength fibers

    NASA Technical Reports Server (NTRS)

    Veltri, R. D.; Paradis, R. D.; Douglas, F. C.

    1975-01-01

    A radio frequency powered ion plating process was used to apply the diffusion barriers of aluminum oxide, yttrium oxide, hafnium oxide and titanium carbide to a substrate tungsten fiber. Each of the coatings was examined as to its effect on both room temperature strength and tensile strength of the base tungsten fiber. The coated fibers were then overcoated with a nickel alloy to become single cell diffusion couples. These diffusion couples were exposed to 1093 C for 24 hours, cycled between room temperature and 1093 C, and given a thermal anneal for 100 hours at 1200 C. Tensile testing and metallographic examinations determined that the hafnium oxide coating produced the best high temperature diffusion barrier for tungsten of the four coatings.

  7. Alkali metal hafnium oxide scintillators

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

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Taylor, Scott Edward

    The present invention provides for a composition comprising an inorganic scintillator comprising an alkali metal hafnate, optionally cerium-doped, having the formula A 2HfO 3:Ce; wherein A is an alkali metal having a valence of 1, such as Li or Na; and the molar percent of cerium is 0% to 100%. The alkali metal hafnate are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  8. 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

  9. Alkali-resistant low-temperature atomic-layer-deposited oxides for optical fiber sensor overlays

    NASA Astrophysics Data System (ADS)

    Kosiel, K.; Dominik, M.; Ściślewska, I.; Kalisz, M.; Guziewicz, M.; Gołaszewska, K.; Niedziółka-Jonsson, J.; Bock, W. J.; Śmietana, M.

    2018-04-01

    This paper presents an investigation of properties of selected metallic oxides deposited at a low temperature (100 °C) by atomic layer deposition (ALD) technique, relating to their applicability as thin overlays for optical fiber sensors resistant in alkaline environments. Hafnium oxide (Hf x O y with y/x approx. 2.70), tantalum oxide (Ta x O y with y/x approx. 2.75) and zirconium oxide (Zr x O y with y/x approx. 2.07), which deposition was based, respectively, on tetrakis(ethylmethyl)hafnium, tantalum pentachloride and tetrakis(ethylmethyl)zirconium with deionized water, were tested as thin layers on planar Si (100) and glass substrates. Growth per cycle (GPC) in the ALD processes was 0.133-0.150 nm/cycle. Run-to-run GPC reproducibility of the ALD processes was best for Hf x O y (0.145 ± 0.001 nm/cycle) and the poorest for Ta x O y (0.133 ± 0.003 nm/cycle). Refractive indices n of the layers were 2.00-2.10 (at the wavelength λ = 632 nm), with negligible k value (at λ for 240-930 nm). The oxides examined by x-ray diffractometry proved to be amorphous, with only small addition of crystalline phases for the Zr x O y . The surfaces of the oxides had grainy but smooth topographies with root-mean square roughness ˜0.5 nm (at 10 × 10 μm2 area) according to atomic force microscopy. Ellipsometric measurements, by contrast, suggest rougher surfaces for the Zr x O y layers. The surfaces were also slightly rougher on the glass-based samples than on the Si-based ones. Nanohardness and Young modules were 4.90-8.64 GPa and 83.7-104.4 GPa, respectively. The tests of scratch resistance revealed better tribological properties for the Hf x O y and the Ta x O y than for the Zr x O y . The surfaces were hydrophilic, with wetting angles of 52.5°-62.9°. The planar oxides on Si, being resistive even to concentrated alkali (pH 14), proved to be significantly more alkali-resistive than Al2O3. The Ta x O y overlay was deposited on long-period grating sensor induced in optical

  10. Tribo-electrochemical characterization of hafnium multilayer systems deposited on nitride/vanadium nitride AISI 4140 steel

    NASA Astrophysics Data System (ADS)

    Mora, M.; Vera, E.; Aperador, W.

    2016-02-01

    In this work is presented the synergistic behaviour among corrosion/wear (tribocorrosion) of the multilayer coatings hafnium nitride/vanadium nitride [HfN/VN]n. The multilayers were deposited on AISI 4140 steel using the technique of physical vapor deposition PVD magnetron sputtering, the tests were performed using a pin-on-disk tribometer, which has an adapted potentiostat galvanostat with three-electrode electrochemical cell. Tribocorrosive parameters such as: Friction coefficient between the coating and the counter body (100 Cr6 steel ball); Polarization resistance by means of electrochemical impedance spectroscopy technique and corrosion rate by polarization curves were determined. It was observed an increase in the polarization resistance, a decrease in the corrosion rate and a low coefficient of friction in comparison with the substrate, due to an increase on the number of bilayers.

  11. Hafnium Films and Magnetic Shielding for TIME, A mm-Wavelength Spectrometer Array

    NASA Astrophysics Data System (ADS)

    Hunacek, J.; Bock, J.; Bradford, C. M.; Butler, V.; Chang, T.-C.; Cheng, Y.-T.; Cooray, A.; Crites, A.; Frez, C.; Hailey-Dunsheath, S.; Hoscheit, B.; Kim, D. W.; Li, C.-T.; Marrone, D.; Moncelsi, L.; Shirokoff, E.; Steinbach, B.; Sun, G.; Trumper, I.; Turner, A.; Uzgil, B.; Weber, A.; Zemcov, M.

    2018-04-01

    TIME is a mm-wavelength grating spectrometer array that will map fluctuations of the 157.7-μm emission line of singly ionized carbon ([CII]) during the epoch of reionization (redshift z ˜ 5-9). Sixty transition-edge sensor (TES) bolometers populate the output arc of each of the 32 spectrometers, for a total of 1920 detectors. Each bolometer consists of gold absorber on a ˜ 3 × 3 mm silicon nitride micro-mesh suspended near the corners by 1 × 1 × 500 μm silicon nitride legs targeting a photon-noise-dominated NEP ˜ 1 × 10^{-17} W/√{Hz} . Hafnium films are explored as a lower-T_c alternative to Ti (500 mK) for TIME TESs, allowing thicker support legs for improved yield. Hf T_c is shown to vary between 250 and 450 mK when varying the resident Ar pressure during deposition. Magnetic shielding designs and simulations are presented for the TIME first-stage SQUIDs. Total axial field suppression is predicted to be 5 × 10^7.

  12. Tracing the history of submarine hydrothermal inputs and the significance of hydrothermal hafnium for the seawater budget - A combined Pb-Hf-Nd isotope approach

    USGS Publications Warehouse

    van de Flierdt, T.; Frank, M.; Halliday, A.N.; Hein, J.R.; Hattendorf, B.; Gunther, D.; Kubik, P.W.

    2004-01-01

    Secular variations in the Pb isotopic composition of a mixed hydrogenous-hydrothermal ferromanganese crust from the Bauer Basin in the eastern Equatorial Pacific provide clear evidence for changes in hydrothermal contributions during the past 7 Myr. The nearby Galapagos Rise spreading center provided a strong hydrothermal flux prior to 6.5 Ma. After 6.5 Ma, the Pb became stepwise more radiogenic and more similar to Equatorial Pacific seawater, reflecting the westward shift of spreading to the presently active East Pacific Rise (EPR). A second, previously unrecognized enhanced hydrothermal period occurred between 4.4 and 2.9 Ma, which reflects either off-axis hydrothermal activity in the Bauer Basin or a late-stage pulse of hydrothermal Pb from the then active, but waning Galapagos Rise spreading center. Hafnium isotope time-series of the same mixed hydrogenous-hydrothermal crust show invariant values over the past 7 Myr. Hafnium isotope ratios, as well as Nd isotope ratios obtained for this crust, are identical to that of hydrogenous Equatorial Pacific deep water crusts and clearly indicate that hydrothermal Hf, similar to Nd, does not travel far from submarine vents. Therefore, we suggest that hydrothermal Hf fluxes do not contribute significantly to the global marine Hf budget. ?? 2004 Elsevier B.V. All rights reserved.

  13. Interfacial phenomena in high-kappa dielectrics

    NASA Astrophysics Data System (ADS)

    Mathew, Anoop

    using medium energy ion scattering (MEIS). A comparison of samples nitrided at progressively increasing temperatures in an ammonia environment shows substitution of oxygen with nitrogen atoms and increasing penetration of nitrogen into the gate stack. Trends in the binding energy of the the as-prepared hafnium silicates suggest that they are non-phase separated, and the binding energy of the hafnium and silicon track the relative composition. Upon being subject to rapid thermal annealing, the samples are observed to show behavior consistent with phase separation. There is also the evidence of charges at the oxide/Si interface that modify the expected behavior of the shifts in binding energy. In another set of experiments, a one-cycle atomic layer deposition (ALD) growth reaction on the water terminated Si(100) -- (2x1) surface is shown to lead to successful nucleation, high metal oxide coverage, and an abrupt metal-oxide/silicon interface as confirmed by photoemission, reflection high energy electron diffraction (RHEED), and Rutherford back scattering (RBS) measurements. Photoemission results confirm the coordination states of the hafnium and oxygen atoms. A Hf 4f core level shift is observed and assigned to the presence of the Si-O-Hf bonding environment with the more electronegative Si atom inducing the binding energy shift. This Hf 4f shift is smaller than that reported previously for silicates because of the difference of the semiconductor bonding environment. The subspecies *(O)2HfCl2 and *OHfCl3 are seen to be the predominant intermediate species in these reactions and photoemission results provide corroborative evidence for their presence. Experiments indicate that the hydroxyl sites bound to Si(100) are active for adsorption. The abrupt interface could be useful for aggressive Effective Oxide Thickness (EOT) scaling.

  14. Heterojunction fully depleted SOI-TFET with oxide/source overlap

    NASA Astrophysics Data System (ADS)

    Chander, Sweta; Bhowmick, B.; Baishya, S.

    2015-10-01

    In this work, a hetero-junction fully depleted (FD) Silicon-on-Insulator (SOI) Tunnel Field Effect Transistor (TFET) nanostructure with oxide overlap on the Germanium-source region is proposed. Investigations using Synopsys Technology Computer Aided Design (TCAD) simulation tools reveal that the simple oxide overlap on the Germanium-source region increases the tunneling area as well as the tunneling current without degrading the band-to-band tunneling (BTBT) and improves the device performance. More importantly, the improvement is independent of gate overlap. Simulation study shows improvement in ON current, subthreshold swing (SS), OFF current, ION/IOFF ration, threshold voltage and transconductance. The proposed device with hafnium oxide (HfO2)/Aluminium Nitride (AlN) stack dielectric material offers an average subthreshold swing of 22 mV/decade and high ION/IOFF ratio (∼1010) at VDS = 0.4 V. Compared to conventional TFET, the Miller capacitance of the device shows the enhanced performance. The impact of the drain voltage variation on different parameters such as threshold voltage, subthreshold swing, transconductance, and ION/IOFF ration are also found to be satisfactory. From fabrication point of view also it is easy to utilize the existing CMOS process flows to fabricate the proposed device.

  15. Cesium hafnium chloride: A high light yield, non-hygroscopic cubic crystal scintillator for gamma spectroscopy

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

    Burger, Arnold, E-mail: aburger@fisk.edu; Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37235; Rowe, Emmanuel

    We report on the scintillation properties of Cs{sub 2}HfCl{sub 6} (cesium hafnium chloride or CHC) as an example of a little-known class of non-hygroscopic compounds having the generic cubic crystal structure of K{sub 2}PtCl{sub 6}. The crystals are easily growable from the melt using the Bridgman method with minimal precursor treatments or purification. CHC scintillation is centered at 400 nm, with a principal decay time of 4.37 μs and a light yield of up to 54 000 photons/MeV when measured using a silicon CCD photodetector. The light yield is the highest ever reported for an undoped crystal, and CHC also exhibits excellent lightmore » yield nonproportionality. These desirable properties allowed us to build and test CHC gamma-ray spectrometers providing energy resolution of 3.3% at 662 keV.« less

  16. Atomic Layer Deposition of HfO2 and Si Nitride on Ge Substrates

    NASA Astrophysics Data System (ADS)

    Zhu, Shiyang; Nakajima, Anri

    2007-12-01

    Hafnium oxide (HfO2) thin films were deposited on Ge substrates at 300 °C using atomic layer deposition (ALD) with tetrakis(diethylamino)hafnium (termed as TDEAH) as a precursor and water as an oxidant. The deposition rate was estimated to be 0.09 nm/cycle and the deposited HfO2 films have a smooth surface and an almost stoichiometric composition, indicating that the growth follows a layer-by-layer kinetics, similarly to that on Si substrates. Si nitride thin films were also deposited on Ge by ALD using SiCl4 as a precursor and NH3 as an oxidant. Si nitride has a smaller deposition rate of about 0.055 nm/cycle and a larger gate leakage current than HfO2 deposited on Ge by ALD.

  17. New rare earth hafnium oxynitride perovskites with photocatalytic activity in water oxidation and reduction.

    PubMed

    Black, Ashley P; Suzuki, Hajime; Higashi, Masanobu; Frontera, Carlos; Ritter, Clemens; De, Chandan; Sundaresan, A; Abe, Ryu; Fuertes, Amparo

    2018-02-06

    RHfO 2 N perovskites with R = La, Nd and Sm show a GdFeO 3 -type structure and are semiconductors with band gaps of 3.35, 3.40 and 2.85 eV and relative dielectric constants of 30, 16 and 28 respectively. These compounds have adequate reduction and oxidation potentials to conduct the overall water splitting reaction, and the analogous perovskite LaZrO 2 N with a band gap of 2.8 eV shows photocatalytic activity under visible light irradiation for O 2 evolution.

  18. Isolation of tungsten and tantalum isotopes without supports from. cap alpha. -particle-irradiated hafnium targets

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

    Gasita, S.M.; Iota, B.Z.; Malachkov, A.G.

    1985-11-01

    An extraction procedure has been developed for successive isolation of tungsten (/sup 178/W and /sup 181/W) and tantalum (/sup 179/Ta and /sup 182/Ta) isotopes without supports from ..cap alpha..particle-irradiated hafnium targets. The target, irradiated on a cyclotron, is dissolved in hydrofluoric acid. Tantalum isotopes are extracted with tributyl phosphate (TBP) from 1-5 M HF and are then reextracted with a 1:1 ammonia solution, and hydrofluoric acid is removed by heating. Tungsten isotopes are extracted with a chloroform solution or N-benzoyl-N-phenylhydroxylamine (BPHA) from 11-12 M H/sub 2/SO/sub 4/ or ..cap alpha..-benzoin oxime from 4.5-5.5 M H/sub 2/SO/sub 4/ and are thenmore » reextracted with a l:l ammonia solution. The yield of tungsten isotopes is not less than 95%, and the content of radioactive impurities of other isotopes is not more than 0.1%.« less

  19. Platinum and palladium incorporation into phosphate/viologen-phosphonates of zirconium and hafnium: synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Dokoutchaev, Alexandre; Krishnan, Venkatesan V.; Thompson, Mark E.; Balasubramanian, Mahalingam

    1998-10-01

    We have continued previous efforts to synthesize and characterize a microporous metal phosphate/viologen-phosphonate compound, [(ZrF) 2(PO 4)(O 3PCH 2CH 2-4,4'-bipyridinium-CH 2CH 2PO 3)] ṡF·2H 2O, ZrPO PV. A derivative of this material has been shown to be an efficient catalyst for the production of hydrogen peroxide from hydrogen and oxygen. This paper has two objectives—one is to optimize the synthetic routes leading to the preparation of MPO PV (M=zirconium or hafnium) and the second is to characterize MPO PV and the derivatives formed by Pt or Pd incorporation by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), inductively coupled plasma-mass spectrometry (ICP-MS) and X-ray absorption fine structure analysis (XAFS). Powder XRD data have shown much higher crystallinity in MPO PV samples prepared by hydrothermal methods than those prepared by reflux methods. In the hydrothermal synthesis, the amount of mineralizer (HF) present controlled the crystallite size (as determined from TEM micrographs). The larger the quantity of HF in the bomb, the larger the size of the crystals but the lower the yield of the MPO PV material. Crystal sizes of about 2.5 μm in length and 0.15 μm in diameter have been made with very large quantities of HF as mineralizer (10 times the required stoichiometric amount). Ion exchange of the material by PdCl 42- has resulted in the incorporation of the PdCl 42- ions in place of X - in the material. This has been confirmed by XAFS studies that demonstrate the oxidation state of Pd is 2+ and show four Cl atoms bound to Pd. Upon reduction it has been confirmed (by XAFS) that the palladium exists as metal with oxidation state of zero. Ion exchange by PdCl 42- and PtCl 42- and subsequent reduction of the material suspension by hydrogen result in the formation of separate Pt and Pd colloids in the close vicinity of the crystallites. TEM micrographs show clearly that the Pt metal

  20. A COMPARISON OF EXPERIMENTS AND THREE-DIMENSIONAL ANALYSIS TECHNIQUES. PART I. UNPOISONED UNIFORM SLAB CORE WITH A PARTIALLY INSERTED HAFNIUM ROD

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

    Renzi, N.E.; Roseberry, R.J.

    >The experimental measurements and nuclear analysis of a uniformly loaded, unpoisoned slab core with a partially insented hafnium rod are described. Comparisons of experimental data with calculated results of the UFO code and flux synthesis techniques are given. It was concluded that one of the flux synthesis techniques and the UFO code are able to predict flux distributions to within approximately 5% of experiment for most cases. An error of approximately 10% was found in the synthesis technique for a channel near the partially inserted rod. The various calculations were able to predict neutron pulsed shutdowns to only approximately 30%.more » (auth)« less

  1. High-energy X-ray detection by hafnium-doped organic-inorganic hybrid scintillators prepared by sol-gel method

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

    Sun, Yan; Koshimizu, Masanori, E-mail: koshi@qpc.che.tohoku.ac.jp; Yahaba, Natsuna

    2014-04-28

    With the aim of enhancing the efficiency with which plastic scintillators detect high-energy X-rays, hafnium-doped organic-inorganic hybrid scintillators were fabricated via a sol-gel method. Transmission electron microscopy of sampled material reveals the presence of Hf{sub x}Si{sub 1−x}O{sub 2} nanoparticles, dispersed in a polymer matrix that constitutes the active material of the X-ray detector. With Hf{sub x}Si{sub 1−x}O{sub 2} nanoparticles incorporated in the polymer matrix, the absorption edge and the luminescence wavelength is shifted, which we attribute to Mie scattering. The detection efficiency for 67.4-keV X-rays in a 0.6-mm-thick piece of this material is two times better than the same thicknessmore » of a commercial plastic scintillator-NE142.« less

  2. Charge injection from gate electrode by simultaneous stress of optical and electrical biases in HfInZnO amorphous oxide thin film transistor

    NASA Astrophysics Data System (ADS)

    Kwon, Dae Woong; Kim, Jang Hyun; Chang, Ji Soo; Kim, Sang Wan; Sun, Min-Chul; Kim, Garam; Kim, Hyun Woo; Park, Jae Chul; Song, Ihun; Kim, Chang Jung; Jung, U. In; Park, Byung-Gook

    2010-11-01

    A comprehensive study is done regarding stabilities under simultaneous stress of light and dc-bias in amorphous hafnium-indium-zinc-oxide thin film transistors. The positive threshold voltage (Vth) shift is observed after negative gate bias and light stress, and it is completely different from widely accepted phenomenon which explains that negative-bias stress results in Vth shift in the left direction by bias-induced hole-trapping. Gate current measurement is performed to explain the unusual positive Vth shift under simultaneous application of light and negative gate bias. As a result, it is clearly found that the positive Vth shift is derived from electron injection from gate electrode to gate insulator.

  3. Quasiparticle energies, excitonic effects, and dielectric screening in transparent conducting oxides

    NASA Astrophysics Data System (ADS)

    Schleife, André

    Using the power of high-performance super computers, computational materials scientists nowadays employ highly accurate quantum-mechanical approaches to reliably predict materials properties. In particular, many-body perturbation theory is an excellent framework for performing theoretical spectroscopy on novel materials including transparent conducting oxides, since this framework accurately describes quasiparticle and excitonic effects.We recently used hybrid exchange-correlation functionals and an efficient implementation of the Bethe-Salpeter approach to investigate several important transparent conducting oxides. Despite their exceptional potential for applications in photovoltaics and optoelectronics their optical properties oftentimes remain poorly understood: Our calculations explain the optical spectrum of bixbyite indium oxide over a very large photon energy range, which allows us to discuss the importance of quasiparticle and excitonic effects at low photon energies around the absorption onset, but also for excitations up to 40 eV. We show that in this regime the energy dependence of the electronic self energy cannot be neglected. Furthermore, we investigated the influence of excitonic effects on optical absorption for lanthanum-aluminum oxide and hafnium oxide. Their complicated conduction band structures require an accurate description of quasiparticle energies and we find that for these strongly polar materials, a contribution of the lattice polarizability to dielectric screening needs to be taken into account. We discuss how this affects the electron-hole interaction and find a strong influence on excitonic effects.The deep understanding of electronic excitations that can be obtained using these modern first-principles techniques, eventually will allow for computational materials design, e.g. of band gaps, densities of states, and optical properties of transparent conducting oxides and other materials with societally important applications.

  4. Comparative studies of Ge and Si p-channel metal-oxide-semiconductor field-effect-transistors with HfSiON dielectric and TaN metal gate

    NASA Astrophysics Data System (ADS)

    Hu, Ai-Bin; Xu, Qiu-Xia

    2010-05-01

    Ge and Si p-channel metal-oxide-semiconductor field-effect-transistors (p-MOSFETs) with hafnium silicon oxynitride (HfSiON) gate dielectric and tantalum nitride (TaN) metal gate are fabricated. Self-isolated ring-type transistor structures with two masks are employed. W/TaN metal stacks are used as gate electrode and shadow masks of source/drain implantation separately. Capacitance-voltage curve hysteresis of Ge metal-oxide-semiconductor (MOS) capacitors may be caused by charge trapping centres in GeO2 (1 < x < 2). Effective hole mobilities of Ge and Si transistors are extracted by using a channel conductance method. The peak hole mobilities of Si and Ge transistors are 33.4 cm2/(V · s) and 81.0 cm2/(V · s), respectively. Ge transistor has a hole mobility 2.4 times higher than that of Si control sample.

  5. Measurement and Simulation of Thermal Conductivity of Hafnium-Aluminum Thermal Neutron Absorber Material

    DOE PAGES

    Guillen, Donna Post; Harris, William H.

    2016-05-11

    A metal matrix composite (MMC) material comprised of hafnium aluminide (Al3Hf) intermetallic particles in an aluminum matrix has been identified as a promising material for fast-flux irradiation testing applications. This material can filter thermal neutrons while simultaneously providing high rates of conductive cooling for experiment capsules. Our purpose is to investigate effects of Hf-Al material composition and neutron irradiation on thermophysical properties, which were measured before and after irradiation. When performing differential scanning calorimetry (DSC) on the irradiated specimens, a large exotherm corresponding to material annealment was observed. Thus, a test procedure was developed to perform DSC and laser flashmore » analysis (LFA) to obtain the specific heat and thermal diffusivity of pre- and post-annealment specimens. This paper presents the thermal properties for three states of the MMC material: (1) unirradiated, (2) as-irradiated, and (3) irradiated and annealed. Microstructure-property relationships were obtained for the thermal conductivity. These relationships are useful for designing components from this material to operate in irradiation environments. Furthermore, the ability of this material to effectively conduct heat as a function of temperature, volume fraction Al 3Hf, radiation damage and annealing is assessed using the MOOSE suite of computational tools.« less

  6. Final Technical Report for DE-SC0001878 [Theory and Simulation of Defects in Oxide Materials

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

    Chelikowsky, James R.

    2014-04-14

    We explored a wide variety of oxide materials and related problems, including materials at the nanoscale and generic problems associated with oxide materials such as the development of more efficient computational tools to examine these materials. We developed and implemented methods to understand the optical and structural properties of oxides. For ground state properties, our work is predominantly based on pseudopotentials and density functional theory (DFT), including new functionals and going beyond the local density approximation (LDA): LDA+U. To study excited state properties (quasiparticle and optical excitations), we use time dependent density functional theory, the GW approach, and GW plusmore » Bethe-Salpeter equation (GW-BSE) methods based on a many-body Green function approaches. Our work focused on the structural, electronic, optical and magnetic properties of defects (such as oxygen vacancies) in hafnium oxide, titanium oxide (both bulk and clusters) and related materials. We calculated the quasiparticle defect states and charge transition levels of oxygen vacancies in monoclinic hafnia. we presented a milestone G0W0 study of two of the crystalline phases of dye-sensitized TiO{sub 2} clusters. We employed hybrid density functional theory to examine the electronic structure of sexithiophene/ZnO interfaces. To identify the possible effect of epitaxial strain on stabilization of the ferromagnetic state of LaCoO{sub 3} (LCO), we compare the total energy of the magnetic and nonmagnetic states of the strained theoretical bulk structure.« less

  7. Development of a 30 kW Inductively Coupled Plasma Torch Facility for Advanced Aerospace Material Investigations

    DTIC Science & Technology

    2012-02-21

    passive oxidation of zirconium diboride forms zirconia and boron oxide, and the passive oxidation of silicon carbide forms silica and carbon monoxide: ZrB2... silicon carbide composites in the ICP wind tunnels. However, this concept has never been explored as an in situ diagnostic for UHTC materials systems...Process- ing, properties, and arc jet oxidation of hafnium diboride/ silicon carbide ultra high temperature ceramics. J Mater Sci 2004;39:5925–37. 12

  8. Polymer/metal oxide hybrid dielectrics for low voltage field-effect transistors with solution-processed, high-mobility semiconductors

    NASA Astrophysics Data System (ADS)

    Held, Martin; Schießl, Stefan P.; Miehler, Dominik; Gannott, Florentina; Zaumseil, Jana

    2015-08-01

    Transistors for future flexible organic light-emitting diode (OLED) display backplanes should operate at low voltages and be able to sustain high currents over long times without degradation. Hence, high capacitance dielectrics with low surface trap densities are required that are compatible with solution-processable high-mobility semiconductors. Here, we combine poly(methyl methacrylate) (PMMA) and atomic layer deposition hafnium oxide (HfOx) into a bilayer hybrid dielectric for field-effect transistors with a donor-acceptor polymer (DPPT-TT) or single-walled carbon nanotubes (SWNTs) as the semiconductor and demonstrate substantially improved device performances for both. The ultra-thin PMMA layer ensures a low density of trap states at the semiconductor-dielectric interface while the metal oxide layer provides high capacitance, low gate leakage and superior barrier properties. Transistors with these thin (≤70 nm), high capacitance (100-300 nF/cm2) hybrid dielectrics enable low operating voltages (<5 V), balanced charge carrier mobilities and low threshold voltages. Moreover, the hybrid layers substantially improve the bias stress stability of the transistors compared to those with pure PMMA and HfOx dielectrics.

  9. The controlled deposition of metal oxides onto carbon nanotubes by atomic layer deposition: examples and a case study on the application of V2O4 coated nanotubes in gas sensing.

    PubMed

    Willinger, Marc-Georg; Neri, Giovanni; Bonavita, Anna; Micali, Giuseppe; Rauwel, Erwan; Herntrich, Tobias; Pinna, Nicola

    2009-05-21

    A new atomic layer deposition (ALD) process was applied for the uniform coating of carbon nanotubes with a number of transition-metal oxide thin films (vanadium, titanium, and hafnium oxide). The presented approach is adapted from non-aqueous sol-gel chemistry and utilizes metal alkoxides and carboxylic acids as precursors. It allows the coating of the inner and outer surface of the tubes with a highly conformal film of controllable thickness and hence, the production of high surface area hybrid materials. The morphology and the chemical composition as well as the high purity of the films are evidenced through a combination of electron microscopic and electron-energy-loss spectrometric techniques. Furthermore, in order to highlight a possible application of the obtained hybrids, the electrical and sensing properties of resistive gas sensors based on hybrid vanadium oxide-coated carbon nanotubes (V2O4-CNTs) are reported and the effect of thermal treatment on the gas sensing properties is studied.

  10. IER-297 CED-2: Final Design for Thermal/Epithermal eXperiments with Jemima Plates with Polyethylene and Hafnium

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

    Nelson, A. J.; Percher, C. M.; Zywiec, W. J.

    This report presents the final design (CED-2) for IER-297, and focuses on 15 critical configurations using highly enriched uranium (HEU) Jemima plates moderated by polyethylene with and without hafnium diluent. The goal of the U.S. Nuclear Criticality Safety Program’s Thermal/Epithermal eXperiments (TEX) is to design and conduct new critical experiments to address high priority nuclear data needs from the nuclear criticality safety and nuclear data communities, with special emphasis on intermediate energy (0.625 eV – 100 keV) assemblies that can be easily modified to include various high priority diluent materials. The TEX (IER 184) CED-1 Report [1], completed in 2012,more » demonstrated the feasibility of meeting the TEX goals with two existing NCSP fissile assets, plutonium Zero Power Physics Reactor (ZPPR) plates and highly enriched uranium (HEU) Jemima plates. The first set of TEX experiments will focus on using the plutonium ZPPR plates with polyethylene moderator and tantalum diluents.« less

  11. Density of states-based design of metal oxide thin-film transistors for high mobility and superior photostability.

    PubMed

    Kim, Hyun-Suk; Park, Joon Seok; Jeong, Hyun-Kwang; Son, Kyoung Seok; Kim, Tae Sang; Seon, Jong-Baek; Lee, Eunha; Chung, Jae Gwan; Kim, Dae Hwan; Ryu, Myungkwan; Lee, Sang Yoon

    2012-10-24

    A novel method to design metal oxide thin-film transistor (TFT) devices with high performance and high photostability for next-generation flat-panel displays is reported. Here, we developed bilayer metal oxide TFTs, where the front channel consists of indium-zinc-oxide (IZO) and the back channel material on top of it is hafnium-indium-zinc-oxide (HIZO). Density-of-states (DOS)-based modeling and device simulation were performed in order to determine the optimum thickness ratio within the IZO/HIZO stack that results in the best balance between device performance and stability. As a result, respective values of 5 and 40 nm for the IZO and HIZO layers were determined. The TFT devices that were fabricated accordingly exhibited mobility values up to 48 cm(2)/(V s), which is much elevated compared to pure HIZO TFTs (∼13 cm(2)/(V s)) but comparable to pure IZO TFTs (∼59 cm(2)/(V s)). Also, the stability of the bilayer device (-1.18 V) was significantly enhanced compared to the pure IZO device (-9.08 V). Our methodology based on the subgap DOS model and simulation provides an effective way to enhance the device stability while retaining a relatively high mobility, which makes the corresponding devices suitable for ultradefinition, large-area, and high-frame-rate display applications.

  12. Oxidation Behavior of HfB2-SiC Materials in Dissociated Environments

    NASA Technical Reports Server (NTRS)

    Ellerby, Don; Irby, Edward; Johnson, Sylvia M.; Beckman, Sarah; Gusman, Michael; Gasch, Matthew

    2002-01-01

    Hafnium diboride based materials have shown promise for use in extremely high temperature applications, such as sharp leading edges on future reentry vehicles. During reentry, the oxygen and nitrogen in the atmosphere are dissociated by the shock layer ahead of the sharp leading edge such that surface reactions are determined by reactions of monatomic oxygen and nitrogen rather than O2, and N2. Simulation of the reentry environment on the ground requires the use of arc jet (plasma jet) facilities that provide monatomic species and are the closest approximation to actual flight conditions. Simple static or flowing oxidation studies under ambient pressures and atmospheres are not adequate to develop an understanding of a materials behavior in flight. Arc jet testing is required to provide the appropriate stagnation pressures, heat fluxes, enthalpies, heat loads and atmospheres encountered during flight. This work looks at the response of HfB2/SiC materials exposed to various simulated reentry environments.

  13. Nanoindentation investigation of HfO2 and Al2O3 films grown by atomic layer deposition

    Treesearch

    K. Tapily; Joseph E. Jakes; D. S. Stone; P. Shrestha; D. Gu; H. Baumgart; A. A. Elmustafa

    2008-01-01

    The challenges of reducing gate leakage current and dielectric breakdown beyond the 45 nm technology node have shifted engineers’ attention from the traditional and proven dielectric SiO2 to materials of higher dielectric constant also known as high-k materials such as hafnium oxide (HfO2) and aluminum oxide (Al2O3). These high-k materials are projected to...

  14. High Temperature Oxidation-Resistant Thruster Research

    DTIC Science & Technology

    1990-02-01

    substrates: Refractory metals, ! Ceramics, Composites and I Carbon - carbon . Rhenium and hafnium carbide were selected based on their properties I and... carbon . Rhenium was selected as the primary refractory metal candidate because of its high melting point, no ductile-to- brittle transition in the...of rhenium (Re) with those of other refractory metals. Rhenium has the second highest melting point of the elements, 3013 C, second only to tungsten

  15. Investigation of gamma radiation induced changes in local structure of borosilicate glass by TDPAC and EXAFS

    NASA Astrophysics Data System (ADS)

    Kumar, Ashwani; Nayak, C.; Rajput, P.; Mishra, R. K.; Bhattacharyya, D.; Kaushik, C. P.; Tomar, B. S.

    2016-12-01

    Gamma radiation induced changes in local structure around the probe atom (Hafnium) were investigated in sodium barium borosilicate (NBS) glass, used for immobilization of high level liquid waste generated from the reprocessing plant at Trombay, Mumbai. The (NBS) glass was doped with 181Hf as a probe for time differential perturbed angular correlation (TDPAC) spectroscopy studies, while for studies using extended X-ray absorption fine structure (EXAFS) spectroscopy, the same was doped with 0.5 and 2 % (mole %) hafnium oxide. The irradiated as well as un-irradiated glass samples were studied by TDPAC and EXAFS techniques to obtain information about the changes (if any) around the probe atom due to gamma irradiation. TDPAC spectra of unirradiated and irradiated glasses were similar and reminescent of amorphous materials, indicating negligible effect of gamma radiation on the microstructure around Hafnium probe atom, though the quaqdrupole interaction frequency ( ω Q) and asymmetry parameter ( η) did show a marginal decrease in the irradiated glass compared to that in the unirradiated glass. EXAFS measurements showed a slight decrease in the Hf-O bond distance upon gamma irradiation of Hf doped NBS glass indicating densification of the glass matrix, while the cordination number around hafnium remains unchanged.

  16. Effective Enrichment and Mass Spectrometry Analysis of Phosphopeptides Using Mesoporous Metal Oxide Nanomaterials

    PubMed Central

    Nelson, Cory A.; Szczech, Jeannine R.; Dooley, Chad J.; Xu, Qingge; Lawrence, Matthew J.; Zhu, Haoyue; Jin, Song; Ge, Ying

    2010-01-01

    Mass spectrometry (MS)-based phosphoproteomics remains challenging due to the low abundance of phosphoproteins and substoichiometric phosphorylation. This demands better methods to effectively enrich phosphoproteins/peptides prior to MS analysis. We have previously communicated the first use of mesoporous zirconium oxide (ZrO2) nanomaterials for effective phosphopeptide enrichment. Here we present the full report including the synthesis, characterization, and application of mesoporous titanium dioxide (TiO2), ZrO2, and hafnium oxide (HfO2) in phosphopeptide enrichment and MS analysis. Mesoporous ZrO2 and HfO2 are demonstrated to be superior to TiO2 for phosphopeptide enrichment from a complex mixture with high specificity (>99%), which could almost be considered as “a purification”, mainly because of the extremely large active surface area of mesoporous nanomaterials. A single enrichment and Fourier transform MS analysis of phosphopeptides digested from a complex mixture containing 7% of α-casein identified 21 out of 22 phosphorylation sites for α-casein. Moreover, the mesoporous ZrO2 and HfO2 can be reused after a simple solution regeneration procedure with comparable enrichment performance to that of fresh materials. Mesoporous ZrO2 and HfO2 nanomaterials hold great promise for applications in MS-based phosphoproteomics. PMID:20704311

  17. Process for the manufacture of an attrition resistant sorbent used for gas desulfurization

    DOEpatents

    Venkataramani, Venkat S.; Ayala, Raul E.

    2003-09-16

    This process produces a sorbent for use in desulfurization of coal gas. A zinc titanate compound and a metal oxide are mixed by milling the compounds in an aqueous medium, the resulting mixture is dried and then calcined, crushed, sleved and formed into pellets for use in a moving-bed reactor. Metal oxides suitable for use as an additive in this process include: magnesium oxide, magnesium oxide plus molybdenum oxide, calcium oxide, yttrium oxide, hafnium oxide, zirconium oxide, cupric oxide, and tin oxide. The resulting sorbent has a percentage of the original zinc or titanium ions substituted for the oxide metal of the chosen additive.

  18. Polymer/metal oxide hybrid dielectrics for low voltage field-effect transistors with solution-processed, high-mobility semiconductors

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

    Held, Martin; Schießl, Stefan P.; Gannott, Florentina

    Transistors for future flexible organic light-emitting diode (OLED) display backplanes should operate at low voltages and be able to sustain high currents over long times without degradation. Hence, high capacitance dielectrics with low surface trap densities are required that are compatible with solution-processable high-mobility semiconductors. Here, we combine poly(methyl methacrylate) (PMMA) and atomic layer deposition hafnium oxide (HfO{sub x}) into a bilayer hybrid dielectric for field-effect transistors with a donor-acceptor polymer (DPPT-TT) or single-walled carbon nanotubes (SWNTs) as the semiconductor and demonstrate substantially improved device performances for both. The ultra-thin PMMA layer ensures a low density of trap states atmore » the semiconductor-dielectric interface while the metal oxide layer provides high capacitance, low gate leakage and superior barrier properties. Transistors with these thin (≤70 nm), high capacitance (100–300 nF/cm{sup 2}) hybrid dielectrics enable low operating voltages (<5 V), balanced charge carrier mobilities and low threshold voltages. Moreover, the hybrid layers substantially improve the bias stress stability of the transistors compared to those with pure PMMA and HfO{sub x} dielectrics.« less

  19. STEM and APT characterization of scale formation on a La,Hf,Ti-doped NiCrAl model alloy.

    PubMed

    Unocic, Kinga A; Chen, Yimeng; Shin, Dongwon; Pint, Bruce A; Marquis, Emmanuelle A

    2018-06-01

    A thermally grown scale formed on a cast NiCrAl model alloy doped with lanthanum, hafnium, and titanium was examined after isothermal exposure at 1100 °C for 100 h in dry flowing O 2 to understand the dopant segregation along scale grain boundaries. The complex scale formed on the alloy surface was composed of two types of substrates: phase-dependent, thin (<250 nm) outer layers and a columnar-grained ∼3.5 μm inner alumina layer. Two types of oxides formed between the inner and outer scale layers: small (3-15 nm) La 2 O 3 and larger (≤50 nm) HfO 2 oxide precipitates. Nonuniform distributions of the hafnium, lanthanum, and titanium dopants were observed along the inner scale grain boundaries, with hafnium dominating in most of the grain boundaries of α-Al 2 O 3. The concentration of reactive elements (RE) seemed to strongly depend on the grain boundary structure. The level of titanium grain boundary segregation in the inner scale decreased toward the model alloy (substrate), confirming the fast outward diffusion of titanium. Hafnium was also observed at the metal-scale interface and in the γ' (Ni 3 Al) phase of the alloy. High-resolution scanning transmission electron microscopy (STEM) confirmed the substitution of REs for aluminum atoms at the scale grain boundaries, consistent with both the semiconducting band structure and the site-blocking models. Both STEM and atom probe tomography allowed quantification of REs along the scale grain boundaries across the scale thickness. Analysis of the scale morphology after isothermal exposure in flowing oxygen revealed a myriad of new precipitate phases, RE segregation dependence on grain boundary type, and atomic arrangement along scale grain boundaries, which is expected to influence the scale growth rate, stability, and mechanical properties. Copyright © 2018 Elsevier Ltd. All rights reserved.

  20. Efficient UV-emitting X-ray phosphors: octahedral Zr(PO 4) 6 luminescence centers in potassium hafnium-zirconium phosphates K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3

    NASA Astrophysics Data System (ADS)

    Torardi, C. C.; Miao, C. R.; Li, J.

    2003-02-01

    Potassium hafnium-zirconium phosphates, K 2Hf 1- xZr x(PO 4) 2 and KHf 2(1- x) Zr 2 x(PO 4) 3, are broad-band UV-emitting phosphors. At room temperature, they have emission peak maxima at approximately 322 and 305 nm, respectively, under 30 kV peak molybdenum X-ray excitation. Both phosphors demonstrate luminescence efficiencies that make them up to ˜60% as bright as commercially available CaWO 4 Hi-Plus. The solid-state and flux synthesis conditions, and X-ray excited UV luminescence of these two phosphors are discussed. Even though the two compounds have different atomic structures, they contain zirconium in the same active luminescence environment as that found in highly efficient UV-emitting BaHf 1- xZr x(PO 4) 2. All the three materials have hafnium and zirconium in octahedral coordination via oxygen-atom corner sharing with six separate PO 4 tetrahedra. This octahedral Zr(PO 4) 6 moiety appears to be an important structural element for efficient X-ray excited luminescence, as are the edge-sharing octahedral TaO 6 chains for tantalate emission.

  1. High-temperature fabricable nickel-iron aluminides

    DOEpatents

    Liu, Chain T.

    1988-02-02

    Nickel-iron aluminides are described that are based on Ni.sub.3 Al, and have significant iron content, to which additions of hafnium, boron, carbon and cerium are made resulting in Ni.sub.3 Al base alloys that can be fabricated at higher temperatures than similar alloys previously developed. Further addition of molybdenum improves oxidation and cracking resistance. These alloys possess the advantages of ductility, hot fabricability, strength, and oxidation resistance.

  2. What can hafnium isotope ratios arrays tell us about orogenic processes? An insight into geodynamic processes operating in the Alpine/Mediterranean region

    NASA Astrophysics Data System (ADS)

    Henderson, B.; Murphy, J.; Collins, W. J.; Hand, M. P.

    2013-12-01

    Over the last decade, technological advances in laser-ablation sampling techniques have resulted in an increase in the number of combined U-Pb-Hf zircon isotope studies used to investigate crustal evolution on a local, regional and global scale. Hafnium isotope arrays over large time scales (>500 myr) have been interpreted to track evolving plate tectonic configurations, and the geological outputs associated with changing plate boundaries. We use the Alpine-Mediterranean region as an example of how hafnium isotope arrays record the geodynamic processes associated with the complex geological evolution of a region. The geology of Alpine-Mediterranean region preserves a complex, semi-continuous tectonic history that extends from the Neoproterozoic to the present day. Major components of the Variscan and Alpine orogens are microcontinental ribbons derived from the northern Gondwanan margin, which were transferred to the Eurasian plate during the opening and closing of the Rheic and Paleo-Tethys Oceans. Convergence of the Eurasian and African plates commenced in the Mid-Late Cretaceous, following the destruction of the Alpine-Tethys Ocean during the terminal breakup of Pangea. In general, convergence occurred slowly and is characterised by northward accretion of Gondwanan fragments, interspersed with subduction of African lithosphere and intermittent roll-back events. A consequence of this geodynamic scenario was periods of granite-dominated magmatism in an arc-backarc setting. New Hf isotope data from the peri-Gondwanan terranes (Iberia, Meguma and Avalonia) and a compilation of existing Phanerozoic data from the Alpine-Mediterranean region, indicate ~500 myr (Cambrian-Recent) of reworking of peri-Gondwanan crust. The eHf array follows a typical crustal evolution pattern (Lu/Hf=0.015) and is considered to reflect reworking of juvenile peri-Gondwanan (Neoproterozoic) crust variably mixed with an older (~1.8-2.0 Ga) source component, probably Eburnian crust from the West

  3. Neutron Detection Utilizing Gadolinium Doped Hafnium Oxide Films

    DTIC Science & Technology

    2008-03-01

    2.2. Charge Carriers ................................................................................................ 2-2 2.3. Dopants and Impurities...the movement of the charge carries can be assumed to be at this drift velocity and in the direction of the electric field. 2.3. Dopants and...present even with the best purification processes. However, a material, or dopant , can be intentionally added to vary the electrical

  4. The energy landscape of glassy dynamics on the amorphous hafnium diboride surface

    NASA Astrophysics Data System (ADS)

    Nguyen, Duc; Mallek, Justin; Cloud, Andrew N.; Abelson, John R.; Girolami, Gregory S.; Lyding, Joseph; Gruebele, Martin

    2014-11-01

    Direct visualization of the dynamics of structural glasses and amorphous solids on the sub-nanometer scale provides rich information unavailable from bulk or conventional single molecule techniques. We study the surface of hafnium diboride, a conductive ultrahigh temperature ceramic material that can be grown in amorphous films. Our scanning tunneling movies have a second-to-hour dynamic range and single-point current measurements extend that to the millisecond-to-minute time scale. On the a-HfB2 glass surface, two-state hopping of 1-2 nm diameter cooperatively rearranging regions or "clusters" occurs from sub-milliseconds to hours. We characterize individual clusters in detail through high-resolution (<0.5 nm) imaging, scanning tunneling spectroscopy and voltage modulation, ruling out individual atoms, diffusing adsorbates, or pinned charges as the origin of the observed two-state hopping. Smaller clusters are more likely to hop, larger ones are more likely to be immobile. HfB2 has a very high bulk glass transition temperature Tg, and we observe no three-state hopping or sequential two-state hopping previously seen on lower Tg glass surfaces. The electronic density of states of clusters does not change when they hop up or down, allowing us to calibrate an accurate relative z-axis scale. By directly measuring and histogramming single cluster vertical displacements, we can reconstruct the local free energy landscape of individual clusters, complete with activation barrier height, a reaction coordinate in nanometers, and the shape of the free energy landscape basins between which hopping occurs. The experimental images are consistent with the compact shape of α-relaxors predicted by random first order transition theory, whereas the rapid hopping rate, even taking less confined motion at the surface into account, is consistent with β-relaxations. We make a proposal of how "mixed" features can show up in surface dynamics of glasses.

  5. Method for locating metallic nitride inclusions in metallic alloy ingots

    DOEpatents

    White, Jack C.; Traut, Davis E.; Oden, Laurance L.; Schmitt, Roman A.

    1992-01-01

    A method of determining the location and history of metallic nitride and/or oxynitride inclusions in metallic melts. The method includes the steps of labeling metallic nitride and/or oxynitride inclusions by making a coreduced metallic-hafnium sponge from a mixture of hafnium chloride and the chloride of a metal, reducing the mixed chlorides with magnesium, nitriding the hafnium-labeled metallic-hafnium sponge, and seeding the sponge to be melted with hafnium-labeled nitride inclusions. The ingots are neutron activated and the hafnium is located by radiometric means. Hafnium possesses exactly the proper metallurgical and radiochemical properties for this use.

  6. Study of the effects of gaseous environmental on the hot corrosion of superalloy materials

    NASA Technical Reports Server (NTRS)

    Smeggil, J. G.

    1981-01-01

    Studies have been conducted to examine the effect of low concentrations of NaCl(g) on the high temperature oxidation behavior of complex superalloys and potential coating formulations modified by silicon and reactive element (i.e., yttrium and hafnium) additions. Depending on alloy composition, a variety of effects were thermogravimetrically produced. Aluminum free alloys such as MAR-M509 and Hastelloy X with molybdenum and tungsten in solid solution showed accelerated (or breakaway) kinetics similar to that observed for Ni-Cr alloys. For IN-792, an alloy high in chromium and low in aluminum, molybdenum and tungsten present in solid solution does not adversely affect oxidation kinetics in the presence of NaCl(g). On the other hand, nickel-base alloys high in aluminum and molybdenum are catastrophically attacked by NaCl-bearing atmospheres. Silicon additions were, in general, observed to slightly improve the oxidation resistance of Ni, Ni-40Cr and CoCrAlY compositions in NaCl(g)-bearing atmospheres. To the degree that processes responsible for Al2O3 whisker formation deleteriously affect protective scale adherence, the addition of yttrium or hafnium can inhibit such whisker growth.

  7. Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

    PubMed

    Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

    2017-08-30

    Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

  8. Characteristics of laser produced plasmas of hafnium and tantalum in the 1-7 nm region

    NASA Astrophysics Data System (ADS)

    Li, Bowen; Otsuka, Takamitsu; Sokell, Emma; Dunne, Padraig; O'Sullivan, Gerry; Hara, Hiroyuki; Arai, Goki; Tamura, Toshiki; Ono, Yuichi; Dinh, Thanh-Hung; Higashiguchi, Takeshi

    2017-11-01

    Soft X-ray (SXR) spectra from hafnium and tantalum laser produced plasmas were recorded in the 1-7 nm region using two Nd:YAG lasers with pulse lengths of 170 ps and 10 ns, respectively, operating at a range of power densities. The maximum focused peak power density was 2. 3 × 1014 W cm-2 for 170 ps pulses and 1. 8 × 1012 W cm-2 for 10 ns pulses, respectively. Two intense quasicontinuous intensity bands resulting from n = 4 - n = 4 and n = 4 - n = 5 unresolved transition arrays (UTAs) dominate both sets of experimental spectra. Comparison with calculations performed with the Cowan suite of atomic structure codes as well as consideration of previous experimental and theoretical results aided identification of the most prominent features in the spectra. For the 10 ns spectrum, the highest ion stage that could be identified from the n = 4 - n = 5 arrays were lower than silver-like Hf25+ and Ta26+ (which has a 4 d 104 f ground configuration) indicating that the plasma temperature attained was too low to produce ions with an outermost 4 d subshell, while for the 170 ps plasmas the presence of significantly higher stages was deduced and lines due to 4 d-5 p transitions were clearly evident. Furthermore, we show an enhancement of emission from tantalum using dual laser irradiation, and the effect of pre-pulse durations and delay times between two pulses are demonstrated.

  9. Nanomechanical study of amorphous and polycrystalline ALD HfO2 thin films

    Treesearch

    K. Tapily; J.E. Jakes; D. Gu; H. Baumgart; A.A. Elmustafa

    2011-01-01

    Thin films of hafnium oxide (HfO2) were deposited by atomic layer deposition (ALD). The structural properties of the deposited films were characterised by transmission electron microscopy (TEM) and X-ray diffraction (XRD). We investigated the effect of phase transformations induced by thermal treatments on the mechanical properties of ALD HfO

  10. Silicon/HfO{sub 2} interface: Effects of gamma irradiation

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

    Maurya, Savita

    2016-05-23

    Quality of MOS devices is a strong function of substrate and oxide interface. In this work we have studied how gamma photon irradiation affects the interface of a 13 nm thick, atomic layer deposited hafnium dioxide deposited on silicon wafer. CV and GV measurements have been done for pristine and irradiated samples to quantify the effect of gamma photon irradiation. Gamma photon irradiation not only introduces positive charge in the oxide and at the interface of Si/HfO{sub 2} interface but also induce phase change of oxide layer. Maximum oxide capacitances are affected by gamma photon irradiation.

  11. Hafnium influence on the microstructure of FeCrAl alloys

    NASA Astrophysics Data System (ADS)

    Geanta, V.; Voiculescu, I.; Stanciu, E.-M.

    2016-06-01

    Due to their special properties at high temperatures, FeCrAl alloys micro-alloyed with Zr can be regarded as potential materials for use at nuclear power plants, generation 4R. These materials are resistant to oxidation at high temperatures, to corrosion, erosion and to the penetrating radiations in liquid metal environments. Also, these are able to form continuously, by the self-generation process of an oxide coating with high adhesive strength. The protective oxide layers must be textured and regenerable, with a good mechanical strength, so that crack and peeling can not appear. To improve the mechanical and chemical characteristics of the oxide layer, we introduced limited quantities of Zr, Ti, Y, Hf, Ce in the range of 1-3%wt in the FeCrAl alloy. These elements, with very high affinity to the oxygen, are capable to stabilize the alumina structure and to improve the oxide adherence to the metallic substrate. FeCrAl alloys microalloyed with Hf were prepared using VAR (Vacuum Arc Remelting) unit, under high argon purity atmosphere. Three different experimental alloys have been prepared using the same metallic matrix of Fe-14Cr-5Al, by adding of 0.5%wt Hf, 1.0%wt Hf and respectively 1.5%wt Hf. The microhardness values for the experimental alloys have been in the range 154 ... 157 HV0.2. EDAX analyses have been performed to determine chemical composition on the oxide layer and in the bulk of sample and SEM analyze has been done to determine the microstructural features. The results have shown the capacity of FeCrAl alloy to form oxide layers, with different texture and rich in elements such as Al and Hf.

  12. Materials properties of hafnium and zirconium silicates: Metal interdiffusion and dopant penetration studies

    NASA Astrophysics Data System (ADS)

    Quevedo Lopez, Manuel Angel

    Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050°C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixO y are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford Backscattering Spectroscopy (RBS), Heavy Ion RBS (HI-RBS), X-ray Photoelectron Spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM), and Time of Flight and Dynamic Secondary Ion Mass Spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling of the dopant profiles in the Si substrate. In this disseration is reported that Hf silicate films are more stable than Zr silicate films, from the metal interdiffusion point of view. On the other hand, dopant (B, As, and P) penetration is observed for HfSixO y films. However, the addition of nitrogen to the Hf - Si - O systems improves the dopant penetration properties of the resulting HfSi xOyNz films.

  13. Effect of Atomic Layer Deposition on the Quality Factor of Silicon Nanobeam Cavities

    DTIC Science & Technology

    2012-01-25

    Additionally, tuning of 2D photonic crystal systems has been shown using atomic layer deposition (ALD) of hafnium oxide [5] and titanium oxide [6] and plasma...μm. This region of the fiber is then carefully positioned across the nanobeam cavity. A tunable narrowband laser source is coupled into one end of the...fiber, and the trans- mitted power is detected at the other end. As the laser source is tuned into resonance with the cavity, some of the power is

  14. Electrical properties of radio-frequency sputtered HfO2 thin films for advanced CMOS technology

    NASA Astrophysics Data System (ADS)

    Sarkar, Pranab Kumar; Roy, Asim

    2015-08-01

    The Hafnium oxide (HfO2) high-k thin films have been deposited by radio frequency (rf) sputtering technique on p-type Si (100) substrate. The thickness, composition and phases of films in relation to annealing temperatures have been investigated by using cross sectional FE-SEM (Field Emission Scanning Electron Microscope) and grazing incidence x-ray diffraction (GI-XRD), respectively. GI-XRD analysis revealed that at annealing temperatures of 350°C, films phases change to crystalline from amorphous. The capacitance-voltage (C-V) and current-voltage (I-V) characteristics of the annealed HfO2 film have been studied employing Al/HfO2/p-Si metal-oxide-semiconductor (MOS) structures. The electrical properties such as dielectric constant, interface trap density and leakage current density have been also extracted from C-V and I-V Measurements. The value of dielectric constant, interface trap density and leakage current density of annealed HfO2 film is obtained as 23,7.57×1011eV-1 cm-2 and 2.7×10-5 Acm-2, respectively. In this work we also reported the influence of post deposition annealing onto the trapping properties of hafnium oxide and optimized conditions under which no charge trapping is observed into the dielectric stack.

  15. Effect of Brownian motion on reduced agglomeration of nanostructured metal oxide towards development of efficient cancer biosensor.

    PubMed

    Kumar, Suveen; Ashish; Kumar, Saurabh; Augustine, Shine; Yadav, Santosh; Yadav, Birendra Kumar; Chauhan, Rishi Pal; Dewan, Ajay Kumar; Malhotra, Bansi Dhar

    2018-04-15

    We report results of the studies relating to fabrication of nanostructured metal oxide (NMO) based cancer biosensor. With the help of 2D electroactive reduced graphene oxide (RGO), we successfully inhibited the Brownian motion of NMO that led to reduced agglomeration of NMO. The nanostructured hafnium oxide (nHfO 2 ) was used as a model NMO. The reduced agglomeration of nHfO 2 was achieved through controlled hydrothermal synthesis and investigated via nanoparticles tracking analysis (NTA). X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM) techniques were used for phase identification as well as morphological analysis of the synthesized nanohybrid (nHfO 2 @RGO) material. The 3-aminopropyl triethoxysilane (APTES) was used for the functionalization of nHfO 2 @RGO and electrophoretic deposition (EPD) technique was used for its deposition onto ITO coated glass electrode. Further, antibodies of cancer biomarker (anti-CYFRA-21-1) were immobilized via EDC-NHS chemistry and Bovine serum albumin (BSA) was used for blocking of the non-specific binding sites. The electrochemical response studies of fabricated immunoelectrode (BSA/anti-CYFRA-21-1/APTES/nHfO 2 @RGO/ITO) revealed higher sensitivity (18.24µAmLng -1 ), wide linear detection range (0 to 30ngmL -1 ), with remarkable lower detection limit (0.16ngmL -1 ). The obtained results showed good agreement with the concentration of CYFRA-21-1 obtained through enzyme linked immunosorbent assay (ELISA) in saliva samples of oral cancer patients. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Investigation of structural and electrical properties on substrate material for high frequency metal-oxide-semiconductor (MOS) devices

    NASA Astrophysics Data System (ADS)

    Kumar, M.; Yang, Sung-Hyun; Janardhan Reddy, K.; JagadeeshChandra, S. V.

    2017-04-01

    Hafnium oxide (HfO2) thin films were grown on cleaned P-type <1 0 0> Ge and Si substrates by using atomic layer deposition technique (ALD) with thickness of 8 nm. The composition analysis of as-deposited and annealed HfO2 films was characterized by XPS, further electrical measurements; we fabricated the metal-oxide-semiconductor (MOS) devices with Pt electrode. Post deposition annealing in O2 ambient at 500 °C for 30 min was carried out on both Ge and Si devices. Capacitance-voltage (C-V) and conductance-voltage (G-V) curves measured at 1 MHz. The Ge MOS devices showed improved interfacial and electrical properties, high dielectric constant (~19), smaller EOT value (0.7 nm), and smaller D it value as Si MOS devices. The C-V curves shown significantly high accumulation capacitance values from Ge devices, relatively when compare with the Si MOS devices before and after annealing. It could be due to the presence of very thin interfacial layer at HfO2/Ge stacks than HfO2/Si stacks conformed by the HRTEM images. Besides, from current-voltage (I-V) curves of the Ge devices exhibited similar leakage current as Si devices. Therefore, Ge might be a reliable substrate material for structural, electrical and high frequency applications.

  17. Nanotechnology Support for Memristor Nanoelectronics

    DTIC Science & Technology

    2012-03-01

    hafnium oxide; 2) investigation of a conductive atomic force microscopy (cAFM) approach for measuring nanoparticle electrical properties , which was...films; and 4) successful measurement of memristive properties of nanoparticle -loaded insulating films. These results lay the groundwork for follow-on...a cAFM strategy for measuring nanoparticle electrical properties . Our initial approach to measuring nanoparticles was to attempt electrical

  18. Cubic phase stabilization in nanoparticles of hafnia-zirconia oxides: Particle-size and annealing environment effects

    NASA Astrophysics Data System (ADS)

    Lu, Chih-Hsin; Raitano, Joan M.; Khalid, Syed; Zhang, Lihua; Chan, Siu-Wai

    2008-06-01

    Amorphous hafnia (HfO2-y), zirconia (ZrO2-y), and hafnia-zirconia (xHfO2-y-(1-x)(ZrO2-y)) nanoparticles were prepared by combining aqueous solutions of hexamethylenetetramine (HMT) with hafnium dichloride oxide (HfOCl2ṡ8H2O), zirconium dichloride oxide (ZrOCl2ṡ8H2O), or a mixture of these two salts at room temperature. For pure hafnia, transmission electron microscopy showed that the lower cation concentration (0.01M) resulted in the precipitation of smaller amorphous nanoparticles relative to higher concentrations (0.015M-0.04M). Consequently, the lower concentration preparation route coupled with a reducing environment (H2:N2=9:91) during annealing at temperatures between 650 and 850°C allowed for nanoparticles with a cubic structure to be prepared as determined by x-ray diffraction. The structurally cubic hafnia nanoparticles were 6nm or less in diameter and equiaxed. Using the same method (0.01M total metal cation concentration and reducing environment during annealing), nanoparticles of cubic structure were prepared across the entire hafnia-zirconia compositional spectrum, with a critical particle size for the cubic structure of about 6nm. Nanoparticles of tetragonal and monoclinic structure were prepared by increasing the annealing temperature and/or using a less reducing environment. The unique role of HMT in sample preparation is discussed as well.

  19. Electrical Properties and Interfacial Studies of HfxTi1–xO2 High Permittivity Gate Insulators Deposited on Germanium Substrates

    PubMed Central

    Lu, Qifeng; Mu, Yifei; Roberts, Joseph W.; Althobaiti, Mohammed; Dhanak, Vinod R.; Wu, Jingjin; Zhao, Chun; Zhao, Ce Zhou; Zhang, Qian; Yang, Li; Mitrovic, Ivona Z.; Taylor, Stephen; Chalker, Paul R.

    2015-01-01

    In this research, the hafnium titanate oxide thin films, TixHf1–xO2, with titanium contents of x = 0, 0.25, 0.9, and 1 were deposited on germanium substrates by atomic layer deposition (ALD) at 300 °C. The approximate deposition rates of 0.2 Å and 0.17 Å per cycle were obtained for titanium oxide and hafnium oxide, respectively. X-ray Photoelectron Spectroscopy (XPS) indicates the formation of GeOx and germanate at the interface. X-ray diffraction (XRD) indicates that all the thin films remain amorphous for this deposition condition. The surface roughness was analyzed using an atomic force microscope (AFM) for each sample. The electrical characterization shows very low hysteresis between ramp up and ramp down of the Capacitance-Voltage (CV) and the curves are indicative of low trap densities. A relatively large leakage current is observed and the lowest leakage current among the four samples is about 1 mA/cm2 at a bias of 0.5 V for a Ti0.9Hf0.1O2 sample. The large leakage current is partially attributed to the deterioration of the interface between Ge and TixHf1–xO2 caused by the oxidation source from HfO2. Consideration of the energy band diagrams for the different materials systems also provides a possible explanation for the observed leakage current behavior. PMID:28793705

  20. Evolution of the mechanical and tribological properties of DLC thin films doped with low-concentration hafnium on 316L steel

    NASA Astrophysics Data System (ADS)

    Qi, Meng; Xiao, Jianrong; Gong, Chenyang; Jiang, Aihua; Chen, Yong

    2018-01-01

    Low concentrations (<1 at%) of hafnium doped into diamond-like thin films (Hf-DLC) were deposited on 316L stainless steel and silicon (1 0 0) substrates by magnetron sputtering to attain superior mechanical and tribological properties. Ar and CH4 were used as source gases. The microstructure, chemical composition, and morphology of the Hf-DLC thin films in various concentrations were analyzed using x-ray diffraction, Raman spectroscopy, x-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy. Results showed that Hf species transferred from the particulate microstructure to Hf carbide phases, and the surface roughness increased monotonically with increasing Hf concentration. Moreover, the hardness and elastic modulus exhibited high values when the doped Hf concentration was 0.42 at%. Similarly, the tribological behaviors and wear life of Hf-DLC thin films had a low friction coefficient and excellent wear resistance at 0.42 at% Hf concentration. Therefore, 0.42 at% Hf is an optimal doping concentration to improve the mechanical and tribological properties of DLC thin films. Generally, the use of low-concentration Hf doping into DLC thin films is novel, and the present results provide guidance for the selection of suitable and effective concentration to optimize Hf-DLC thin films with superior performance.

  1. L2₁ and XA Ordering Competition in Hafnium-Based Full-Heusler Alloys Hf₂VZ (Z = Al, Ga, In, Tl, Si, Ge, Sn, Pb).

    PubMed

    Wang, Xiaotian; Cheng, Zhenxiang; Wang, Wenhong

    2017-10-20

    For theoretical designing of full-Heusler based spintroinc materials, people have long believed in the so-called Site Preference Rule (SPR). Very recently, according to the SPR, there are several studies on XA-type Hafnium-based Heusler alloys X₂YZ, i.e., Hf₂VAl, Hf₂CoZ (Z = Ga, In) and Hf₂CrZ (Z = Al, Ga, In). In this work, a series of Hf₂-based Heusler alloys, Hf₂VZ (Z = Al, Ga, In, Tl, Si, Ge, Sn, Pb), were selected as targets to study the site preferences of their atoms by first-principle calculations. It has been found that all of them are likely to exhibit the L2₁-type structure instead of the XA one. Furthermore, we reveal that the high values of spin-polarization of XA-type Hf₂VZ (Z = Al, Ga, In, Tl, Si, Ge, Sn, Pb) alloys have dropped dramatically when they form the L2₁-type structure. Also, we prove that the electronic, magnetic, and physics nature of these alloys are quite different, depending on the L2₁-type or XA-type structures.

  2. Structure and properties of a model conductive filament/host oxide interface in HfO2-based ReRAM

    NASA Astrophysics Data System (ADS)

    Padilha, A. C. M.; McKenna, K. P.

    2018-04-01

    Resistive random-access memory (ReRAM) is a promising class of nonvolatile memory capable of storing information via its resistance state. In the case of hafnium oxide-based devices, experimental evidence shows that a conductive oxygen-deficient filament is formed and broken inside of the device by oxygen migration, leading to switching of its resistance state. However, little is known about the nature of this conductive phase, its interface with the host oxide, or the associated interdiffusion of oxygen, presenting a challenge to understanding the switching mechanism and device properties. To address these problems, we present atomic-scale first-principles simulations of a prototypical conductive phase (HfO), the electronic properties of its interface with HfO2, as well as stability with respect to oxygen diffusion across the interface. We show that the conduction-band offset between HfO and HfO2 is 1.3 eV, smaller than typical electrode-HfO2 band offsets, suggesting that positive charging and band bending should occur at the conductive filament-HfO2 interface. We also show that transfer of oxygen across the interface, from HfO2 into HfO, costs around 1.2 eV per atom and leads to a gradual opening of the HfO band gap, and hence disruption of the electrical conductivity. These results provide invaluable insights into understanding the switching mechanism for HfO2-based ReRAM.

  3. A COMPARISON OF EXPERIMENTS AND THREE-DIMENSIONAL ANALYSIS TECHNIQUES. PART II. UNPOISONED UNIFORM SLAB CORE WITH A PARTIALLY INSERTED HAFNIUM ROD AND A PARTIALLY INSERTED WATER GAP

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

    Roseberry, R.J.

    The experimental measurements and nuclear analysis of a uniformly loaded, unpoisoned slab core with a partially inserted hafnium rod and/or a partially inserted water gap are described. Comparisons of experimental data with calculated results of the UFO core and flux synthesis techniques are given. It is concluded that one of the flux synthesis techniques and the UFO code are able to predict flux distributions to within approximately -5% of experiment for most cases, with a maximum error of approximately -10% for a channel at the core- reflector boundary. The second synthesis technique failed to give comparable agreement with experiment evenmore » when various refinements were used, e.g. increasing the number of mesh points, performing the flux synthesis technique of iteration, and spectrum-weighting the appropriate calculated fluxes through the use of the SWAKRAUM code. These results are comparable to those reported in Part I of this study. (auth)« less

  4. Biologically Self-Assembled Memristive Circuit Elements

    DTIC Science & Technology

    2010-01-01

    hydrothermal approach, TiO2 nanoparticles were synthesized by slowly stirring a 1:3 volumetric ratio mixture of titanium isopropoxide (TTIP) and isopropyl...Synthesis of TiO2 nanoparticles by hydrolysis and peptization of titanium isopropoxide solution. Journal of Materials Processing Technology 2007, 189...important role interfacing with group IV metal oxides such as hafnium, providing a stable linkage to the surface [3]. Titanium dioxide (TiO2), which is

  5. Interplay between ferroelectric and resistive switching in doped crystalline HfO2

    NASA Astrophysics Data System (ADS)

    Max, Benjamin; Pešić, Milan; Slesazeck, Stefan; Mikolajick, Thomas

    2018-04-01

    Hafnium oxide is widely used for resistive switching devices, and recently it has been discovered that ferroelectricity can be established in (un-)doped hafnium oxide as well. Previous studies showed that both switching mechanisms are influenced by oxygen vacancies. For resistive switching, typically amorphous oxide layers with an asymmetric electrode configuration are used to create a gradient of oxygen vacancies. On the other hand, ferroelectric switching is performed by having symmetric electrodes and requires crystalline structures. The coexistence of both effects has recently been demonstrated. In this work, a detailed analysis of the reversible interplay of both switching mechanisms within a single capacitor cell is investigated. First, ferroelectric switching cycles were applied in order to drive the sample into the fatigued stage characterized by increased concentration of oxygen vacancies in the oxide layer. Afterwards, a forming step that is typical for the resistive switching devices was utilized to achieve a soft breakdown. In the next step, twofold alternation between the high and low resistance state is applied to demonstrate the resistive switching behavior of the device. Having the sample in the high resistance state with a ruptured filament, ferroelectric switching behavior is again shown within the same stack. Interestingly, the same endurance as before was observed without a hard breakdown of the device. Therefore, an effective sequence of ferroelectric—resistive—ferroelectric switching is realized. Additionally, the dependence of the forming, set, and reset voltage on the ferroelectric cycling stage (pristine, woken-up and fatigued) is analyzed giving insight into the physical device operation.

  6. Standard specification for nuclear grade hafnium oxide pellets. ASTM standard

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

    NONE

    This specification is under the jurisdiction of ASTM Committee C-26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.03 on Neutron Absorber Materials Specifications. Current edition approved May 10, 1997. Published May 1998. Originally published as C 1076-87. Last previous edition C 1076-92.

  7. Method for the melting of metals

    DOEpatents

    White, Jack C.; Traut, Davis E.

    1992-01-01

    A method of quantitatively determining the molten pool configuration in melting of metals. The method includes the steps of introducing hafnium metal seeds into a molten metal pool at intervals to form ingots, neutron activating the ingots and determining the hafnium location by radiometric means. Hafnium possesses exactly the proper metallurgical and radiochemical properties for this use.

  8. Thin Films of Reduced Hafnium Oxide with Excess Carbon for High-Temperature Oxidation Protection

    DTIC Science & Technology

    2010-02-01

    Cho, N. V. Nguyen, C. A. Richter, J. R. Ehrstein, B . H. Lee, and J. C. Lee, "Spectroscopic Ellipsometry Characterization of High- k Dielectric Hf02...34 Canadian Journal of Chemistry, 61 850-55 (1983). I6D. B . Chrisey and G. K . Hubler (Eds.), "Pulsed Laser Deposition of Thin Films." John Wiley...smaller than b rim. It was shown that high carbon content in the films inhibits crystaliization of HtO( at temperatures at least up to 333 C. Study ot

  9. 6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion: [M6(O2)6(OH)6(gamma-SiW10O36)3]18- (M = Zr, Hf).

    PubMed

    Bassil, Bassem S; Mal, Sib Sankar; Dickman, Michael H; Kortz, Ulrich; Oelrich, Holger; Walder, Lorenz

    2008-05-28

    We have synthesized and structurally characterized the unprecedented peroxo-zirconium(IV) containing [Zr6(O2)6(OH)6(gamma-SiW10O36)3]18- (1). Polyanion 1 comprises a cyclic 6-peroxo-6-zirconium core stabilized by three decatungstosilicate units. We have also prepared the isostructural hafnium(IV) analogue [Hf6(O2)6(OH)6(gamma-SiW10O36)3]18- (2). We investigated the acid/base and redox properties of 1 by UV-vis spectroscopy and electrochemistry studies. Polyanion 1 represents the first structurally characterized Zr-peroxo POM with side-on, bridging peroxo units. The simple, one-pot synthesis of 1 and 2 involving dropwise addition of aqueous hydrogen peroxide could represent a general procedure for incorporating peroxo groups into a large variety of transition metal and lanthanide containing POMs.

  10. 40 CFR 471.91 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... million off-pounds) of zirconium-hafnium extruded Chromium 0.104 0.043 Cyanide 0.069 0.029 Nickel 0.455 0... million off-pounds) of zirconium-hafnium heat treated Chromium 0.151 0.062 Cyanide 0.100 0.041 Nickel 0...-hafnium surface treated Chromium 0.150 0.61 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20...

  11. 40 CFR 471.91 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... million off-pounds) of zirconium-hafnium extruded Chromium 0.104 0.043 Cyanide 0.069 0.029 Nickel 0.455 0... million off-pounds) of zirconium-hafnium heat treated Chromium 0.151 0.062 Cyanide 0.100 0.041 Nickel 0...-hafnium surface treated Chromium 0.150 0.61 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20...

  12. A STUDY OF THE STABILITY OF ZIRCONIUM AND HAFNIUM TETRAHALIDES ON HITTING A HOT SURFACE IN VACUUM (in Russian)

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

    Tsirel'nikov, V.I.; Komissarova, L.N.; Spitsyn, V.I.

    1962-09-01

    The decomposition coefficients of the chlorides, bromides, and iodides of Zr and Hf were determined as a function of the temperature of a hot surface. The tetrahalides were carefully purified in an inert atmosphere of argon. The halide compound in a quartz ampoule was heated by a removable heater. The vapors passed through a capillary opening and struck a tungsten foil 0.5 mm thick and 12 to 15 mm wide. The Mo foil was heated electrically to control the surface temperature which was measured by an optical pyrometer. The tetrahalide decomposed according to the following reaction: Me(Hal)/sub 4/ yields Memore » + 2(Hal)/sub 2/. The lower halides dissociated completely to metal and free halides, since the temperature was >600 deg C. The Mo backing was dissolved in nitric acid, and the unsupported metal deposit of Zr or Hf was weighed, The decomposition coefficient was calcuweight of metal evaporated. Zrl/sub 4/ decomposed completely (100%) at 1500 deg C, while only 96% of the HfI/sub 4/ was decomposed at this temperature. The ZrBr/sub 4/ and HfBr/sub 4/ were decomposed by 68 and 61% respectively. The ZrCl/sub 4/ and HfCl/sub 4/ were stable at l500 deg C (5% of the ZrCl/sub 4/ was decomposed at l500 deg C). In all cases, the hafnium halide was more stable than the zirconium halide, especially in the case of the iodides. The decomposition was directly proportional to the temperature of the molybdenum target. (TTT)« less

  13. Optimization of the Energy Level Alignment between the Photoactive Layer and the Cathode Contact Utilizing Solution-Processed Hafnium Acetylacetonate as Buffer Layer for Efficient Polymer Solar Cells.

    PubMed

    Yu, Lu; Li, Qiuxiang; Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Wang, Fuzhi; Zhang, Bing; Dai, Songyuan; Lin, Jun; Tan, Zhan'ao

    2016-01-13

    The insertion of an appropriate interfacial buffer layer between the photoactive layer and the contact electrodes makes a great impact on the performance of polymer solar cells (PSCs). Ideal interfacial buffer layers could minimize the interfacial traps and the interfacial barriers caused by the incompatibility between the photoactive layer and the electrodes. In this work, we utilized solution-processed hafnium(IV) acetylacetonate (Hf(acac)4) as an effective cathode buffer layer (CBL) in PSCs to optimize the energy level alignment between the photoactive layer and the cathode contact, with the short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) all simultaneously improved with Hf(acac)4 CBL, leading to enhanced power conversion efficiencies (PCEs). Ultraviolet photoemission spectroscopy (UPS) and scanning Kelvin probe microscopy (SKPM) were performed to confirm that the interfacial dipoles were formed with the same orientation direction as the built-in potential between the photoactive layer and Hf(acac)4 CBL, benefiting the exciton separation and electron transport/extraction. In addition, the optical characteristics and surface morphology of the Hf(acac)4 CBL were also investigated.

  14. Nanostructured microtubes based on TiO2 doped by Zr and Hf oxides with the anatase structure

    NASA Astrophysics Data System (ADS)

    Zheleznov, VV; Voit, EI; Sushkov, YV; Sarin, SA; Kuryavyi, VG; Opra, DP; Gnedenkov, SV; Sinebryukhov, SL; Sokolov, AA

    2016-01-01

    The nanostructured microtubes based on TiO2 have been prepared on the carbon fiber template using the sol-gel method. The microtubes consist of nanoparticles of metal oxides: TiO2/ZrO2 and TiO2/HfO2. The dependence of microtubes morphology and nanoparticles structure on the synthesis conditions has been studied using the methods of SEM, SAXS, and Raman spectroscopy. It has been demonstrated that at the stoichiometric ratio of up to 0.04 for Zr/Ti and up to 0.06 for Hf/Ti microtubes consist of uniform nanoparticles with the anatase structure. Along with further increase of the dopants content in the microtubes composition, nanoparticles acquire the core-shell structure. It has been suggested that nanoparticles have a core composed of the solid solutions Ti1-xZrxO2 or Ti1-xHfxO2 and a shell consisting of zirconium or hafnium titanate. The fabricated Zr- and Hf-doped TiO2 materials were investigated in view of their possible use as anode materials for Li-ion batteries. Charge- discharge measurements showed that the doped samples manifested significantly higher reversibility in comparison with the undoped TiO2. The method opens new prospects in synthesis of nanostructured materials for Li-ion batteries application.

  15. Understanding the Structure of High-K Gate Oxides - Oral Presentation

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

    Miranda, Andre

    2015-08-25

    Hafnium Oxide (HfO 2) amorphous thin films are being used as gate oxides in transistors because of their high dielectric constant (κ) over Silicon Dioxide. The present study looks to find the atomic structure of HfO 2 thin films which hasn’t been done with the technique of this study. In this study, two HfO 2 samples were studied. One sample was made with thermal atomic layer deposition (ALD) on top of a Chromium and Gold layer on a silicon wafer. The second sample was made with plasma ALD on top of a Chromium and Gold layer on a Silicon wafer.more » Both films were deposited at a thickness of 50nm. To obtain atomic structure information, Grazing Incidence X-ray diffraction (GIXRD) was carried out on the HfO 2 samples. Because of this, absorption, footprint, polarization, and dead time corrections were applied to the scattering intensity data collected. The scattering curves displayed a difference in structure between the ALD processes. The plasma ALD sample showed the broad peak characteristic of an amorphous structure whereas the thermal ALD sample showed an amorphous structure with characteristics of crystalline materials. This appears to suggest that the thermal process results in a mostly amorphous material with crystallites within. Further, the scattering intensity data was used to calculate a pair distribution function (PDF) to show more atomic structure. The PDF showed atom distances in the plasma ALD sample had structure up to 10 Å, while the thermal ALD sample showed the same structure below 10 Å. This structure that shows up below 10 Å matches the bond distances of HfO 2 published in literature. The PDF for the thermal ALD sample also showed peaks up to 20 Å, suggesting repeating atomic spacing outside the HfO 2 molecule in the sample. This appears to suggest that there is some crystalline structure within the thermal ALD sample.« less

  16. Effects of anode material on arcjet performance

    NASA Technical Reports Server (NTRS)

    Sankovic, John M.; Curran, Frank M.; Larson, C. A.

    1992-01-01

    Anodes fabricated from four different materials were tested in a modular arcjet thruster at 1 kW power level on nitrogen/hydrogen mixtures. A two-percent thoriated tungsten anode served as the control. Graphite was chosen for its ease in fabrication, but experienced severe erosion in the constrictor and diverging side. Hafnium carbide and lanthanum hexaboride were chosen for their low work functions but failed due to thermal stress and reacted with the propellant. When compared to the thoriated tungsten nozzle, thruster performance was significantly lower for the lanthanum hexaboride insert and the graphite nozzle, but was slightly higher for the hafnium carbide nozzle. Both the lanthanum hexaboride and hafnium carbide nozzle operated at higher voltages. An attempt was made to duplicate higher performance hafnium carbide results, but repeated attempts at machining a second anode insert were unsuccessful. Graphite, hafnium carbide, and lanthanum hexaboride do not appear viable anode materials for low power arcjet thrusters.

  17. 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

  18. 40 CFR 471.94 - Pretreatment standards for existing sources (PSES).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-hafnium extruded Chromium 0.104 0.043 Cyanide 0.069 0.029 Nickel 0.455 0.301 Ammonia 31.6 13.9 Fluoride 14...-hafnium heat treated Chromium 0.015 0.006 Cyanide 0.010 0.004 Nickel 0.066 0.044 Ammonia 4.57 2.01...-hafnium surface treated Chromium 0.150 0.061 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20.0...

  19. 40 CFR 471.94 - Pretreatment standards for existing sources (PSES).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-hafnium extruded Chromium 0.104 0.043 Cyanide 0.069 0.029 Nickel 0.455 0.301 Ammonia 31.6 13.9 Fluoride 14...-hafnium heat treated Chromium 0.015 0.006 Cyanide 0.010 0.004 Nickel 0.066 0.044 Ammonia 4.57 2.01...-hafnium surface treated Chromium 0.150 0.061 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20.0...

  20. Three dimensional graphene transistor for ultra-sensitive pH sensing directly in biological media.

    PubMed

    Ameri, Shideh Kabiri; Singh, Pramod K; Sonkusale, Sameer R

    2016-08-31

    In this work, pH sensing directly in biological media using three dimensional liquid gated graphene transistors is presented. The sensor is made of suspended network of graphene coated all around with thin layer of hafnium oxide (HfO2), showing high sensitivity and sensing beyond the Debye-screening limit. The performance of the pH sensor is validated by measuring the pH of isotonic buffered, Dulbecco's phosphate buffered saline (DPBS) solution, and of blood serum derived from Sprague-Dawley rat. The pH sensor shows high sensitivity of 71 ± 7 mV/pH even in high ionic strength media with molarities as high as 289 ± 1 mM. High sensitivity of this device is owing to suspension of three dimensional graphene in electrolyte which provides all around liquid gating of graphene, leading to higher electrostatic coupling efficiency of electrolyte to the channel and higher gating control of transistor channel by ions in the electrolyte. Coating graphene with hafnium oxide film (HfO2) provides binding sites for hydrogen ions, which results in higher sensitivity and sensing beyond the Debye-screening limit. The 3D graphene transistor offers the possibility of real-time pH measurement in biological media without the need for desaltation or sample preparation. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Oxidation Resitant HfC-TaC Rocket Thruster for High Performance Propellants

    NASA Technical Reports Server (NTRS)

    Patterson, Mark

    1999-01-01

    The purpose of this reasearch effort was to develop high temperature, oxidation resistant thrusters which would lessen the thruster cooling requirements, resulting in increased performance and longer life for onboard propulsion systems for spacecraft. This research effort focussed on developing ceramic matrix composites (CMCs) for this application, and specifically investigated the use of HfC stabilized with TaC. This material composition can potentially operate in a stoichiometric oxygen to hydrogen ratio at a temperature of 5000 deg F (2760 deg C) in a radiatively cooled mode. Various compositions of Hafnium Carbide (HfC) and Tantalum Carbide (TaC) were deposited by chemical vapor deposition (CVD) and tested, in an attempt to identify the composition which offered the best oxidation resistance. Although it was identified that small amounts of TaC appeared to offer improved oxidation resistance over HfC alone, an optimal composition was not identified. A 251bf thruster was fabricated from a novel CMC sandwich construction with a HfC-TaC matrix, and survived two test firings, each of 5 seconds before a failure in the injector caused the run to be aborted. It was not possible to control the relative stoichiometry of the HfC and TaC composition throughout the reactor due to the large difference in the thermodynamics of the HfC and TaC formation from their respective chlorides. This also resulted in an inability to infiltrate TaC into the preform under the experimental conditions investigated. Other material compositions were fabricated and tested and two material systems; HfC-SiC functionally graded to C(sub f)/C and Re functionally graded to C(sub f)/C were selected for further testing. These functionally graded composites have use in a number of propulsion applications presently of interest to NASA and the defense industry. Their ability to withstand extremely hostile thermal environments and the light-weight and high-strength exhibited from the C(sub f

  2. Restorative effect of oxygen annealing on device performance in HfIZO thin-film transistors

    NASA Astrophysics Data System (ADS)

    Ha, Tae-Jun

    2015-03-01

    Metal-oxide based thin-film transistors (oxide-TFTs) are very promising for use in next generation electronics such as transparent displays requiring high switching and driving performance. In this study, we demonstrate an optimized process to secure excellent device performance with a favorable shift of the threshold voltage toward 0V in amorphous hafnium-indium-zinc-oxide (a-HfIZO) TFTs by using post-treatment with oxygen annealing. This enhancement results from the improved interfacial characteristics between gate dielectric and semiconductor layers due to the reduction in the density of interfacial states related to oxygen vacancies afforded by oxygen annealing. The device statistics confirm the improvement in the device-to-device and run-to-run uniformity. We also report on the photo-induced stability in such oxide-TFTs against long-term UV irradiation, which is significant for transparent displays.

  3. The solar photospheric abundance of hafnium and thorium. Results from CO5BOLD 3D hydrodynamic model atmospheres

    NASA Astrophysics Data System (ADS)

    Caffau, E.; Sbordone, L.; Ludwig, H.-G.; Bonifacio, P.; Steffen, M.; Behara, N. T.

    2008-05-01

    Context: The stable element hafnium (Hf) and the radioactive element thorium (Th) were recently suggested as a suitable pair for radioactive dating of stars. The applicability of this elemental pair needs to be established for stellar spectroscopy. Aims: We aim at a spectroscopic determination of the abundance of Hf and Th in the solar photosphere based on a CO5BOLD 3D hydrodynamical model atmosphere. We put this into a wider context by investigating 3D abundance corrections for a set of G- and F-type dwarfs. Methods: High-resolution, high signal-to-noise solar spectra were compared to line synthesis calculations performed on a solar CO5BOLD model. For the other atmospheres, we compared synthetic spectra of CO5BOLD 3D and associated 1D models. Results: For Hf we find a photospheric abundance A(Hf) = 0.87 ± 0.04, in good agreement with a previous analysis, based on 1D model atmospheres. The weak Th II 401.9 nm line constitutes the only Th abundance indicator available in the solar spectrum. It lies in the red wing of a Ni-Fe blend exhibiting a non-negligible convective asymmetry. Accounting for the asymmetry-related additional absorption, we obtain A(Th) = 0.08 ± 0.03, consistent with the meteoritic abundance, and about 0.1 dex lower than obtained in previous photospheric abundance determinations. Conclusions: Only for the second time, to our knowledge, has a non-negligible effect of convective line asymmetries on an abundance derivation been highlighted. Three-dimensional hydrodynamical simulations should be employed to measure Th abundances in dwarfs if similar blending is present, as in the solar case. In contrast, 3D effects on Hf abundances are small in G- to mid F-type dwarfs and sub-giants, and 1D model atmospheres can be conveniently used.

  4. Advanced High Temperature Coating Systems Beyond Current State of the Art Systems.

    DTIC Science & Technology

    1986-04-15

    cobalt and chromium rich oxides. The A120 3 scales developed on the NiCrAl and CoCrAI alloys doped with yttrium or hafnium were relatively flat and...third element such as Cr is present in the alloy. Chromium acts as a getter which prevents oxygen from entering the alloy, so A12 0 3 tends to develop...or Cr doped alumina. Yttrium is isovalent with aluminum so it is not expected to alter the intrinsic defect structure of alumina, however

  5. Corrosion resistant surface for vanadium nitride and hafnium nitride layers as function of grain size

    NASA Astrophysics Data System (ADS)

    Escobar, C. A.; Caicedo, J. C.; Aperador, W.

    2014-01-01

    In this research it was studied vanadium nitride (VN) and hafnium nitride (HfN) film, which were deposited onto silicon (Si (100)) and AISI 4140 steel substrates via r.f. magnetron sputtering technique in Ar/N2 atmosphere with purity at 99.99% for both V and Hf metallic targets. Both films were approximately 1.2±0.1 μm thick. The crystallography structures that were evaluated via X-ray diffraction analysis (XRD) showed preferential orientations in the Bragg planes VN (200) and HfN (111). The chemical compositions for both films were characterized by EDX. Atomic Force Microscopy (AFM) was used to study the morphology; the results reveal grain sizes of 78±2 nm for VN and 58±2 nm for HfN and roughness values of 4.2±0.1 nm for VN and 1.5±0.1 nm for HfN films. The electrochemical performance in VN and HfN films deposited onto steel 4140 were studied by Tafel polarization curves and impedance spectroscopy methods (EIS) under contact with sodium chloride at 3.5 wt% solution, therefore, it was found that the corrosion rate decreased about 95% in VN and 99% for HfN films in relation to uncoated 4140 steel, thus demonstrating, the protecting effect of VN and HfN films under a corrosive environment as function of morphological characteristics (grain size). VN(grain size)=78±2.0 nm, VN(roughness)=4.2±0.1 nm, VN(corrosion rate)=40.87 μmy. HfN(grain size)=58±2.0 nm, HfN(roughness)=1.5±0.1 nm, HfN(corrosion rate)=0.205 μmy. It was possible to analyze that films with larger grain size, can be observed smaller grain boundary thus generating a higher corrosion rate, therefore, in this work it was found that the HfN layer has better corrosion resistance (low corrosion rate) in relation to VN film which presents a larger grain size, indicating that the low grain boundary in (VN films) does not restrict movement of the Cl- ion and in this way the corrosion rate increases dramatically.

  6. Low-Voltage Electrowetting on a Lipid Bilayer Formed on Hafnium Oxide

    DTIC Science & Technology

    2011-06-01

    currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES...exceeding 10 V [9-10]. Here we report the development of electrowetting systems that do not contain solid organic dielectrics such as fluoropolymers, but...and the effective thickness ( T 𔃺 : :) of the bilayer in response to applied voltage are plotted in Fig. 3(b). The capacitance per area increased with

  7. Investigation of Hafnium oxide/Copper resistive memory for advanced encryption applications

    NASA Astrophysics Data System (ADS)

    Briggs, Benjamin D.

    The Advanced Encryption Standard (AES) is a widely used encryption algorithm to protect data and communications in today's digital age. Modern AES CMOS implementations require large amounts of dedicated logic and must be tuned for either performance or power consumption. A high throughput, low power, and low die area AES implementation is required in the growing mobile sector. An emerging non-volatile memory device known as resistive memory (ReRAM) is a simple metal-insulator-metal capacitor device structure with the ability to switch between two stable resistance states. Currently, ReRAM is targeted as a non-volatile memory replacement technology to eventually replace flash. Its advantages over flash include ease of fabrication, speed, and lower power consumption. In addition to memory, ReRAM can also be used in advanced logic implementations given its purely resistive behavior. The combination of a new non-volatile memory element ReRAM along with high performance, low power CMOS opens new avenues for logic implementations. This dissertation will cover the design and process implementation of a ReRAM-CMOS hybrid circuit, built using IBM's 10LPe process, for the improvement of hardware AES implementations. Further the device characteristics of ReRAM, specifically the HfO2/Cu memory system, and mechanisms for operation are not fully correlated. Of particular interest to this work is the role of material properties such as the stoichiometry, crystallinity, and doping of the HfO2 layer and their effect on the switching characteristics of resistive memory. Material properties were varied by a combination of atomic layer deposition and reactive sputtering of the HfO2 layer. Several studies will be discussed on how the above mentioned material properties influence switching parameters, and change the underlying physics of device operation.

  8. Nuclear-grade zirconium prepared by combining combustion synthesis with molten-salt electrorefining technique

    NASA Astrophysics Data System (ADS)

    Li, Hui; Nersisyan, Hayk H.; Park, Kyung-Tae; Park, Sung-Bin; Kim, Jeong-Guk; Lee, Jeong-Min; Lee, Jong-Hyeon

    2011-06-01

    Zirconium has a low absorption cross-section for neutrons, which makes it an ideal material for use in nuclear reactor applications. However, hafnium typically contained in zirconium causes it to be far less useful for nuclear reactor materials because of its high neutron-absorbing properties. In the present study, a novel effective method has been developed for the production of hafnium-free zirconium. The process includes two main stages: magnesio-thermic reduction of ZrSiO 4 under a combustion mode, to produce zirconium silicide (ZrSi), and recovery of hafnium-free zirconium by molten-salt electrorefining. It was found that, depending on the electrorefining procedure, it is possible to produce zirconium powder with a low hafnium content: 70 ppm, determined by ICP-AES analysis.

  9. Electronic structure and relative stability of the coherent and semi-coherent HfO2/III-V interfaces

    NASA Astrophysics Data System (ADS)

    Lahti, A.; Levämäki, H.; Mäkelä, J.; Tuominen, M.; Yasir, M.; Dahl, J.; Kuzmin, M.; Laukkanen, P.; Kokko, K.; Punkkinen, M. P. J.

    2018-01-01

    III-V semiconductors are prominent alternatives to silicon in metal oxide semiconductor devices. Hafnium dioxide (HfO2) is a promising oxide with a high dielectric constant to replace silicon dioxide (SiO2). The potentiality of the oxide/III-V semiconductor interfaces is diminished due to high density of defects leading to the Fermi level pinning. The character of the harmful defects has been intensively debated. It is very important to understand thermodynamics and atomic structures of the interfaces to interpret experiments and design methods to reduce the defect density. Various realistic gap defect state free models for the HfO2/III-V(100) interfaces are presented. Relative energies of several coherent and semi-coherent oxide/III-V semiconductor interfaces are determined for the first time. The coherent and semi-coherent interfaces represent the main interface types, based on the Ga-O bridges and As (P) dimers, respectively.

  10. Impact of metal gates on remote phonon scattering in titanium nitride/hafnium dioxide n-channel metal-oxide-semiconductor field effect transistors-low temperature electron mobility study

    NASA Astrophysics Data System (ADS)

    Maitra, Kingsuk; Frank, Martin M.; Narayanan, Vijay; Misra, Veena; Cartier, Eduard A.

    2007-12-01

    We report low temperature (40-300 K) electron mobility measurements on aggressively scaled [equivalent oxide thickness (EOT)=1 nm] n-channel metal-oxide-semiconductor field effect transistors (nMOSFETs) with HfO2 gate dielectrics and metal gate electrodes (TiN). A comparison is made with conventional nMOSFETs containing HfO2 with polycrystalline Si (poly-Si) gate electrodes. No substantial change in the temperature acceleration factor is observed when poly-Si is replaced with a metal gate, showing that soft optical phonons are not significantly screened by metal gates. A qualitative argument based on an analogy between remote phonon scattering and high-resolution electron energy-loss spectroscopy (HREELS) is provided to explain the underlying physics of the observed phenomenon. It is also shown that soft optical phonon scattering is strongly damped by thin SiO2 interface layers, such that room temperature electron mobility values at EOT=1 nm become competitive with values measured in nMOSFETs with SiON gate dielectrics used in current high performance processors.

  11. Electrical characterization of doped strontium titanate thin films for semiconductor memories

    NASA Astrophysics Data System (ADS)

    Han, Jeong Hee

    2002-08-01

    Doped strontium titanate (ST) thin films were investigated for high-density memory applications. ST has become a promising candidate to replace conventional silicon oxide due to its high inherent dielectric constant, superior leakage characteristics, and good chemical stability. However, oxygen vacancies and the problems that arise as a result are one of the main drawbacks against this material. Resistance degradation is a serious reliability issue in perovskite titanate films and may be a result of oxygen vacancies. In this dissertation, an attempt to reduce the resistance degradation was made by doping the ST films with both niobium and lanthanum. Niobium is a B-site donor in the perovskite, whereas lanthanum is an A-site donor. Both have an extra valence charge than the atom which it replaces in the crystal structure. With a higher valence charge, the number of oxygen vacancies is hoped to be reduced and result in better electrical performance. Experimental results showed that the degradation rate is reduced by doping with either niobium or lanthanum. A bi-layer study was also performed to optimize the dielectric with the strengths of both doped and undoped strontium titanate and to distinguish the source of the oxygen vacancies. A study on the conduction mechanisms and dielectric dispersion was also performed. An additional study was made on the effect of iridium as a possible gate electrode for a MOS capacitor. Hafnium oxide was used as the high-permittivity oxide. The results observed showed that the capacitance was higher for iridium electrodes than those for platinum electrodes. However, both electrodes showed unacceptable frequency dispersion which may be caused by crude patterning techniques. A hysteresis review was also done for hafnium and zirconium oxides. It was observed that the hysteresis measured in the high-permittivity oxides are dependent on the accumulation sweep voltage due to the trapping and de-trapping of charge at the dielectric

  12. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  13. Light-Immune pH Sensor with SiC-Based Electrolyte-Insulator-Semiconductor Structure

    NASA Astrophysics Data System (ADS)

    Lin, Yi-Ting; Huang, Chien-Shiang; Chow, Lee; Lan, Jyun-Ming; Yang, Chia-Ming; Chang, Liann-Be; Lai, Chao-Sung

    2013-12-01

    An electrolyte-insulator-semiconductor (EIS) structure with high-band-gap semiconductor of silicon carbide is demonstrated as a pH sensor in this report. Two different sensing membranes, i.e., gadolinium oxide (Gd2O3) and hafnium oxide (HfO2), were investigated. The HfO2 film deposited by atomic layer deposition (ALD) at low temperature shows high pH sensing properties with a sensitivity of 52.35 mV/pH and a low signal of 4.95 mV due to light interference. The EIS structures with silicon carbide can provide better visible light immunity due to its high band gap that allows pH detection in an outdoor environment without degradation of pH sensitivity.

  14. CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

    NASA Technical Reports Server (NTRS)

    Nagaraj, Bangalore A. (Inventor); Williams, Jeffrey L. (Inventor)

    2003-01-01

    A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

  15. Method for fabricating hafnia films

    DOEpatents

    Hu, Michael Z [Knoxville, TN

    2007-08-21

    The present invention comprises a method for fabricating hafnia film comprising the steps of providing a substrate having a surface that allows formation of a self-assembled monolayer thereon via covalent bonding; providing an aqueous solution that provides homogeneous hafnium ionic complexes and hafnium nanoclusters wherein the aqueous solution is capable of undergoing homogeneous precipitation under controlled conditions for a desired period of time at a controlled temperature and controlled solution acidity for desired nanocluster nucleation and growth kinetics, desired nanocluster size, desired growth rate of film thickness and desired film surface characteristics. The method further comprising forming the self-assembled monolayer on the surface of the substrate wherein the self-assembled monolayer comprises a plurality of hydrocarbon chains cross-linked together along the surface of the substrate, the hydrocarbon chains being uniformly spaced from one another and wherein each of the hydrocarbon chains having a functional anchoring group at a first end of the chain covalently bonded with the surface of the substrate and each of the hydrocarbon chains having a functional terminating group projected away from the surface wherein the functional terminating group provides a bonding site for the hafnium film to grow; and exposing the substrate to the aqueous solution for a desired period of time at a controlled temperature wherein the hafnium ionic complexes and the hafnium nanoclusters are deposited on the bonding site of the functional terminating group thereby forming the hafnia film wherein the hafnium bonded to the hydrocarbons and to one another provide a uniform ordered arrangement defined by the uniform arrangement of the hydrocarbons.

  16. High Temperature Oxidation Behavior of gamma-Ni+gamma'-Ni3Al Alloys and Coatings Modified with Pt and Reactive Elements

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

    Mu, Nan

    2007-12-01

    Materials for high-pressure turbine blades must be able to operate in the high-temperature gases (above 1000 C) emerging from the combustion chamber. Accordingly, the development of nickel-based superalloys has been constantly motivated by the need to have improved engine efficiency, reliability and service lifetime under the harsh conditions imposed by the turbine environment. However, the melting point of nickel (1455 C) provides a natural ceiling for the temperature capability of nickel-based superalloys. Thus, surface-engineered turbine components with modified diffusion coatings and overlay coatings are used. Theses coatings are capable of forming a compact and adherent oxide scale, which greatly impedesmore » the further transport of reactants between the high-temperature gases and the underlying metal and thus reducing attack by the atmosphere. Typically, these coatings contain β-NiAl as a principal constituent phase in order to have sufficient aluminum content to form an Al 2O 3 scale at elevated temperatures. The drawbacks to the currently-used {beta}-based coatings, such as phase instabilities, associated stresses induced by such phase instabilities, and extensive coating/substrate interdiffusion, are major motivations in this study to seek next-generation coatings. The high-temperature oxidation resistance of novel Pt + Hf-modified γ-Ni + γ-Ni 3Al-based alloys and coatings were investigated in this study. Both early-stage and 4-days isothermal oxidation behavior of single-phase γ-Ni and γ'-Ni 3Al alloys were assessed by examining the weight changes, oxide-scale structures, and elemental concentration profiles through the scales and subsurface alloy regions. It was found that Pt promotes Al 2O 3 formation by suppressing the NiO growth on both γ-Ni and γ'Ni 3Al single-phase alloys. This effect increases with increasing Pt content. Moreover, Pt exhibits this effect even at lower temperatures (~970 C) in the very early stage of oxidation. It was

  17. PRODUCTION OF METALS AND THEIR COMPOUNDS

    DOEpatents

    Arden, T.V.; Burstall, F.H.; Davies, G.R.; Linstead, R.P.; Wells, R.A.

    1958-11-18

    Zirconium nitrate can be separated from hafnium nitrate by mixing the nitrates with ethyl cellulose pulp, eluting the mass with diethyl ether containing nitric acid, and passing the eluent through a column of cellulose pulp the outflow of which is substantially free of hafnium.

  18. Effects of alloy composition in alleviating embrittlement problems associated with the tantalum alloy T-111

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.

    1975-01-01

    The causes of aging embrittlement in T-111 (Ta-8W-2Hf) and the effect of alloy modification were investigated. Results show that T-111 possesses a critical combination of tungsten and hafnium that leads to loss in ductility at -196 C after aging near 1040 C. It was found that this occurs because tungsten enhances hafnium segregation to grain boundaries, which also leads to increased susceptibility to hydrogen embrittlement. Aging embrittlement was not observed in tantalum alloys with reduced tungsten or hafnium contents; most of the alloys studied have lower strengths than T-111 and exhibit susceptibility to hydrogen embrittlement.

  19. Structure and Optical Properties of Nanocrystalline Hafnium Oxide Thin Films (PostPrint)

    DTIC Science & Technology

    2014-09-01

    sputter-deposition. A large band gap coupled with low absorption provide optical transparency over a broad range in the electromagnetic spectrum; HfO2...k) in the middle of the visible spec- trum, and C influences n(k) to a greater extent in shorter wave - lengths [31]. Note that this principle behind...Approved for publicnanocrystalline HfO2 films crystallize in monoclinic structure. Fur - thermore, increasing Ts results in improved structural order and

  20. Assessing the impact of atomic oxygen in the damage threshold and stress of Hafnia films grown by ion beam sputter deposition

    NASA Astrophysics Data System (ADS)

    Patel, D.; Wang, Y.; Larotonda, M.; Lovewell, J.; Jensen, J.; Hsiao, K. J.; Krous, E.; Rocca, J. J.; Menoni, C. S.; Tomasel, F.; Kholi, S.; McCurdy, P.

    2007-01-01

    Hafnium oxide (HfO II) is undoubtedly one of the most desirable high-index optical coatings for high power laser applications. One of the key goals in the fabrication of oxide films with high Laser Induced Damage Threshold (LIDT) is to minimize the number of film imperfections, in particular stoichiometric defects. For HfO II films deposited by ion beam (reactive) sputtering (IBS) of a hafnium metal target, stoichiometry is controlled by the injection of molecular oxygen, either close to the substrate or mixed with the sputtering gas or some other combination. Good stoichiometry is important to reduce the density of unoxidized particles buried in the coatings, which affect the LIDT. This work evaluates the potential advantages of using pre-activation of oxygen in the IBS of HfO II, with special emphasis on its impact on LIDT and film stress. For the experiments, oxygen was activated by an independent plasma source and then introduced into a commercial IBS chamber. The optical properties of the films were characterized using spectrophotometry and ellipsometry. Their structural quality and composition were determined from x-ray diffraction and x-ray photoelectron emission spectroscopy. The stress was determined from interferometer measurements. For optimized conditions, 2.5 J/cm2 LIDT was measured on HfO II films at λ=800 nm with 1 ps and 25 mJ pulses from a chirped amplification Ti:Sapphire laser. In the range of oxygen variations under consideration the effects on LIDT are shown to be minimal.

  1. Highly stable thin film transistors using multilayer channel structure

    NASA Astrophysics Data System (ADS)

    Nayak, Pradipta K.; Wang, Zhenwei; Anjum, D. H.; Hedhili, M. N.; Alshareef, H. N.

    2015-03-01

    We report highly stable gate-bias stress performance of thin film transistors (TFTs) using zinc oxide (ZnO)/hafnium oxide (HfO2) multilayer structure as the channel layer. Positive and negative gate-bias stress stability of the TFTs was measured at room temperature and at 60 °C. A tremendous improvement in gate-bias stress stability was obtained in case of the TFT with multiple layers of ZnO embedded between HfO2 layers compared to the TFT with a single layer of ZnO as the semiconductor. The ultra-thin HfO2 layers act as passivation layers, which prevent the adsorption of oxygen and water molecules in the ZnO layer and hence significantly improve the gate-bias stress stability of ZnO TFTs.

  2. Variable angle spectroscopic ellipsometric characterization of HfO2 thin film

    NASA Astrophysics Data System (ADS)

    Kumar, M.; Kumari, N.; Karar, V.; Sharma, A. L.

    2018-02-01

    Hafnium Oxide film was deposited on BK7 glass substrate using reactive oxygenated E-Beam deposition technique. The film was deposited using in-situ quartz crystal thickness monitoring to control the film thickness and rate of evaporation. The thin film was grown with a rate of deposition of 0.3 nm/s. The coated substrate was optically characterized using spectrophotometer to determine its transmission spectra. The optical constants as well as film thickness of the hafnia film were extracted by variable angle spectroscopic ellipsometry with Cauchy fitting at incidence angles of 65˚, 70˚ and 75˚.

  3. Grindability of cast Ti-Hf alloys.

    PubMed

    Kikuchi, Masafumi; Takahashi, Masatoshi; Sato, Hideki; Okuno, Osamu; Nunn, Martha E; Okabe, Toru

    2006-04-01

    As part of our systematic studies characterizing the properties of titanium alloys, we investigated the grindability of a series of cast Ti-Hf alloys. Alloy buttons with hafnium concentrations up to 40 mass% were made using an argon-arc melting furnace. Each button was cast into a magnesia-based mold using a dental titanium casting machine; three specimens were made for each metal. Prior to testing, the hardened surface layer was removed. The specimens were ground at five different speeds for 1 min at 0.98 N using a carborundum wheel on an electric dental handpiece. Grindability was evaluated as the volume of metal removed per minute (grinding rate) and the volume ratio of metal removed compared to the wheel material lost (grinding ratio). The data were analyzed using ANOVA. A trend of increasing grindability was found with increasing amounts of hafnium, although there was no statistical difference in the grindability with increasing hafnium contents. We also found that hafnium may be used to harden or strengthen titanium without deteriorating the grindability.

  4. 40 CFR 471.93 - New source performance standards (NSPS).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... monthly average mg/off-kg (pounds per million off-pounds) of zirconium-hafnium extruded Chromium 0.104 0... monthly average mg/off-kg (pounds per million off-pounds) of zirconium-hafnium heat treated Chromium 0.015... Chromium 0.150 0.061 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20.0 Fluoride 20.0 8.98 Oil and...

  5. 40 CFR 471.93 - New source performance standards (NSPS).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... monthly average mg/off-kg (pounds per million off-pounds) of zirconium-hafnium extruded Chromium 0.104 0... monthly average mg/off-kg (pounds per million off-pounds) of zirconium-hafnium heat treated Chromium 0.015... Chromium 0.150 0.061 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20.0 Fluoride 20.0 8.98 Oil and...

  6. Radioisotopic heat source

    DOEpatents

    Jones, G.J.; Selle, J.E.; Teaney, P.E.

    1975-09-30

    Disclosed is a radioisotopic heat source and method for a long life electrical generator. The source includes plutonium dioxide shards and yttrium or hafnium in a container of tantalum-tungsten-hafnium alloy, all being in a nickel alloy outer container, and subjected to heat treatment of from about 1570$sup 0$F to about 1720$sup 0$F for about one h. (auth)

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

    Nayak, Pradipta K.; Wang, Zhenwei; Anjum, D. H.

    We report highly stable gate-bias stress performance of thin film transistors (TFTs) using zinc oxide (ZnO)/hafnium oxide (HfO{sub 2}) multilayer structure as the channel layer. Positive and negative gate-bias stress stability of the TFTs was measured at room temperature and at 60 °C. A tremendous improvement in gate-bias stress stability was obtained in case of the TFT with multiple layers of ZnO embedded between HfO{sub 2} layers compared to the TFT with a single layer of ZnO as the semiconductor. The ultra-thin HfO{sub 2} layers act as passivation layers, which prevent the adsorption of oxygen and water molecules in the ZnOmore » layer and hence significantly improve the gate-bias stress stability of ZnO TFTs.« less

  8. Enhancement of thermoelectric figure-of-merit at low temperatures by titanium substitution for hafnium in n-type half-Heuslers Hf0.75-xTixZr0.25NiSn0.99Sb0.01

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

    Joshi, Giri; Dahal, Tulashi; Chen, Shuo

    The effect of titanium (Ti) substitution for hafnium (Hf) on thermoelectric properties of (Hf, Zr)-based n-type half-Heuslers: Hf0.75-xTixZr0.25NiSn0.99Sb0.01, has been studied. The samples are made by arc melting followed by ball milling and hot pressing via the nanostructuring approach. A peak thermoelectric figure-of-merit (ZT) of ~1.0 is achieved at 500 °C in samples with a composition of Hf0.5Zr0.25Ti0.25NiSn0.99Sb0.01 due to a slight increase in carrier concentration and also a lower thermal conductivity caused by Ti. The ZT values below 500 °C of hot pressed Hf0.5Zr0.25Ti0.25NiSn0.99Sb0.01 samples are significantly higher than those of the same way prepared Hf0.75Zr0.25NiSn0.99Sb0.01 samples at eachmore » temperature, which are very much desired for mid-range temperature applications such as waste heat recovery in automobiles.« less

  9. Enhancement of thermoelectric figure-of-merit at low temperatures by titanium substitution for hafnium in n-type half-Heuslers Hf0.75-xTixZr0.25NiSn0.99Sb0.01

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

    Joshi, Giri; Dahal, Tulashi; Chen, Shuo

    The effect of titanium (Ti) substitution for hafnium (Hf) on thermoelectric properties of (Hf, Zr)-based n-type half-Heuslers: Hf 0.75-xTi xZr 0.25NiSn 0.99Sb 0.01, has been studied. The samples are made by arc melting followed by ball milling and hot pressing via the nanostructuring approach. A peak thermoelectric figure-of-merit (ZT) of ~1.0 is achieved at 500 °C in samples with a composition of Hf 0.5Zr 0.25Ti 0.25NiSn 0.99Sb 0.01 due to a slight increase in carrier concentration and also a lower thermal conductivity caused by Ti. TheZT values below 500 °C of hot pressed Hf 0.5Zr 0.25Ti 0.25NiSn 0.99Sb 0.01 samplesmore » are significantly higher than those of the same way prepared Hf 0.75Zr 0.25NiSn 0.99Sb 0.01samples at each temperature, which are very much desired for mid-range temperature applications such as waste heat recovery in automobiles.« less

  10. Evolution of E 2 transition strength in deformed hafnium isotopes from new measurements on 172Hf,174Hf, and 176Hf

    NASA Astrophysics Data System (ADS)

    Rudigier, M.; Nomura, K.; Dannhoff, M.; Gerst, R.-B.; Jolie, J.; Saed-Samii, N.; Stegemann, S.; Régis, J.-M.; Robledo, L. M.; Rodríguez-Guzmán, R.; Blazhev, A.; Fransen, Ch.; Warr, N.; Zell, K. O.

    2015-04-01

    Background: The available data for E 2 transition strengths in the region between neutron-deficient hafnium and platinum isotopes are far from complete. More and precise data are needed to enhance the picture of structure evolution in this region and to test state-of-the-art nuclear models. In a simple model, the maximum collectivity is expected at the middle of the major shell. However, for actual nuclei, particularly in heavy-mass regions, which should be highly complex, this picture may no longer be the case, and one should use a more realistic nuclear-structure model. We address this point by studying the spectroscopy of Hf as a representative case. Purpose: We remeasure the 21+ half-lives of 172,174,176Hf, for which there is some disagreement in the literature. The main goal is to measure, for the first time, the half-lives of higher-lying states of the rotational band. The new results are compared to a theoretical calculation for absolute transition strengths. Method: The half-lives were measured using γ -γ and conversion-electron-γ delayed coincidences with the fast timing method. For the determination of half-lives in the picosecond region, the generalized centroid difference method was applied. For the theoretical calculation of the spectroscopic properties, the interacting boson model is employed, whose Hamiltonian is determined based on microscopic energy-density functional calculations. Results: The measured 21+ half-lives disagree with results from earlier γ -γ fast timing measurements, but are in agreement with data from Coulomb excitation experiments and other methods. Half-lives of the 41+ and 61+ states were measured, as well as a lower limit for the 81+ states. Conclusions: This work shows the importance of a mass-dependent effective boson charge in the interacting boson model for the description of E 2 transition rates in chains of nuclei. It encourages further studies of the microscopic origin of this mass dependence. New experimental

  11. CHARACTERISTICS OF ANODIC AND CORROSION FILMS ON ZIRCONIUM

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

    Misch, R.D.

    1960-05-01

    Zirconium anodizes similarly to tungsten in respect to the change of interference colors with applied voltage. However, the oxide layer on tungsten cannot reach as great a thickness. Hafnium does not anodize in the same way as zirconium but is similar to tantalum. By measuring the interference color and capacitative thicknesses on zirconium (Grades I and III) and a 2.5 wt.% tin ailoy, the film was found to grow less rapidly in terms of capacitance than in terms of iaterference colors. This was interpreted to mean that cracks develop in the oxide as it thickens. The effect was most pronouncedmore » on Grade III zirconium and least pronounced on the tin alloy. The reduction in capacitative thickness was especially noticeable when white oxide appeared. Comparative measurements on Grade I zirconium and 2.5 wt.% tin alloy indicated that the thickness of the oxide film on the tin alloy (after 16 hours in water) increased more rapidly with temperature than the film on zirconium. Tin is believed to act in ways to counteract the tendency of the oxide to form cracks, and to produce vacancies which promote ionic diffusion. (auth)« less

  12. Effect of native defects and Co doping on ferromagnetism in HfO2: first-principles calculations.

    PubMed

    Han, Chong; Yan, Shi-Shen; Lin, Xue-Ling; Hu, Shu-Jun; Zhao, Ming-Wen; Yao, Xin-Xin; Chen, Yan-Xue; Liu, Guo-Lei; Mei, Liang-Mo

    2011-05-01

    First-principles calculations of undoped HfO(2) and cobalt-doped HfO(2) have been carried out to study the magnetic properties of the dielectric material. In contrast to previous reports, it was found that the native defects in HfO(2) could not induce strong ferromagnetism. However, the cobalt substituting hafnium is the most stable defect under oxidation condition, and the ferromagnetic (FM) coupling between the cobalt substitutions is favorable in various configurations. We found that the FM coupling is mediated by the threefold-coordinated oxygen atoms in monoclinic HfO(2) and could be further enhanced in electron-rich condition. Copyright © 2010 Wiley Periodicals, Inc.

  13. 40 CFR 471.95 - Pretreatment standards for new sources (PSNS).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... extruded Chromium 0.104 0.043 Cyanide 0.069 0.029 Nickel 0.455 0.301 Ammonia 31.6 13.9 Fluoride 14.1 6.26...-hafnium heat treated Chromium 0.015 0.006 Cyanide 0.010 0.004 Nickel 0.066 0.044 Ammonia 4.57 2.01...-hafnium surface treated Chromium 0.150 0.061 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20...

  14. 40 CFR 471.95 - Pretreatment standards for new sources (PSNS).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... extruded Chromium 0.104 0.043 Cyanide 0.069 0.029 Nickel 0.455 0.301 Ammonia 31.6 13.9 Fluoride 14.1 6.26...-hafnium heat treated Chromium 0.015 0.006 Cyanide 0.010 0.004 Nickel 0.066 0.044 Ammonia 4.57 2.01...-hafnium surface treated Chromium 0.150 0.061 Cyanide 0.099 0.041 Nickel 0.653 0.432 Ammonia 45.3 20...

  15. Precipitation hardening austenitic superalloys

    DOEpatents

    Korenko, Michael K.

    1985-01-01

    Precipitation hardening, austenitic type superalloys are described. These alloys contain 0.5 to 1.5 weight percent silicon in combination with about 0.05 to 0.5 weight percent of a post irradiation ductility enhancing agent selected from the group of hafnium, yttrium, lanthanum and scandium, alone or in combination with each other. In addition, when hafnium or yttrium are selected, reductions in irradiation induced swelling have been noted.

  16. High temperature oxidation behavior of gamma-nickel+gamma'-nickel aluminum alloys and coatings modified with platinum and reactive elements

    NASA Astrophysics Data System (ADS)

    Mu, Nan

    was also inferred that Pt enhances the diffusive flux of aluminum from the substrate to the scale/alloy interface. Relatively low levels of hafnium addition to Pt-free gamma'-Ni 3Al increased the extent of external NiO formation due to non-protective HfO2 formation. Accordingly, this effect intensified with increasing Hf content from 0.2 to 0.5at.%. The synergistic effect of Pt and Hf co-addition was realized by examining Pt+Hf-modified gamma'-Ni3Al alloys. It was inferred that Pt decreases the chemical activity of Hf so that HfO2 formation could be suppressed with increasing Pt content. Thus, the early-stage Al2O3 formation facilitated by Pt additions and NiO development assisted by Hf additions are the competing scale growth processes that are influenced by the relative contents of Pt and Hf. Large interfacial voids were observed on the gamma'-Ni 3Al alloy after 4-days isothermal oxidation at 1150°C, which could be attributed to the Kirkendall effect. Platinum addition was also found to improve Al2O3-scale adhesion. Pt and Hf effects on two-phase gamma-Ni+gamma'-Ni3Al alloys of compositions Ni-20Al-20Pt-xHf (x ranges from 0 to 0.91) were examined by both thermal gravimetric analyses and cyclic oxidation tests. Scale microstructures were characterized by confocal photo-stimulated microspectroscopy (CPSM), in-lens SEM, and FIB-TEM. Hafnium additions up to about 0.48at.% markedly decreased the weight change of isothermally oxidized Pt-modified gamma+gamma' alloys by forming thinner oxide scales than that on the Hf-free Ni-20Al-20Pt base alloy. This could be attributed to an Al2O3 grain boundary blocking effect imparted by the segregated Hf. However, an over-doped alloy with 0.91at.% Hf exhibited detrimental effect by forming internal HfO 2. It was observed that Hf additions altered the Al2O3 scale microstructure. The most remarkable difference was that the columnar width of the Al2O3 scale grains formed on Ni-20Al-20Pt was much larger than it was on Ni-20Al-20Pt-0

  17. Ternary boride product and process

    NASA Technical Reports Server (NTRS)

    Clougherty, Edward V. (Inventor)

    1976-01-01

    A hard, tough, strong ceramic body is formed by hot pressing a mixture of a powdered metal and a powdered metal diboride. The metal employed is zirconium, titanium or hafnium and the diboride is the diboride of a different member of the same group of zirconium, titanium or hafnium to form a ternary composition. During hot pressing at temperatures above about 2,000.degree.F., a substantial proportion of acicular ternary monoboride is formed.

  18. Oxidative shielding or oxidative stress?

    PubMed

    Naviaux, Robert K

    2012-09-01

    In this review I report evidence that the mainstream field of oxidative damage biology has been running fast in the wrong direction for more than 50 years. Reactive oxygen species (ROS) and chronic oxidative changes in membrane lipids and proteins found in many chronic diseases are not the result of accidental damage. Instead, these changes are the result of a highly evolved, stereotyped, and protein-catalyzed "oxidative shielding" response that all eukaryotes adopt when placed in a chemically or microbially hostile environment. The machinery of oxidative shielding evolved from pathways of innate immunity designed to protect the cell from attack and limit the spread of infection. Both oxidative and reductive stress trigger oxidative shielding. In the cases in which it has been studied explicitly, functional and metabolic defects occur in the cell before the increase in ROS and oxidative changes. ROS are the response to disease, not the cause. Therefore, it is not the oxidative changes that should be targeted for therapy, but rather the metabolic conditions that create them. This fresh perspective is relevant to diseases that range from autism, type 1 diabetes, type 2 diabetes, cancer, heart disease, schizophrenia, Parkinson's disease, and Alzheimer disease. Research efforts need to be redirected. Oxidative shielding is protective and is a misguided target for therapy. Identification of the causal chemistry and environmental factors that trigger innate immunity and metabolic memory that initiate and sustain oxidative shielding is paramount for human health.

  19. Nickel aluminide alloy suitable for structural applications

    DOEpatents

    Liu, Chain T.

    1998-01-01

    Alloys for use in structural applications based upon NiAl to which are added selected elements to enhance room temperature ductility and high temperature strength. Specifically, small additions of molybdenum produce a beneficial alloy, while further additions of boron, carbon, iron, niobium, tantalum, zirconium and hafnium further improve performance of alloys at both room temperature and high temperatures. A preferred alloy system composition is Ni--(49.1.+-.0.8%)Al--(1.0.+-.0.8%)Mo--(0.7.+-.0.5%)Nb/Ta/Zr/Hf--(nearly zero to 0.03%)B/C, where the % is at. % in each of the concentrations. All alloys demonstrated good oxidation resistance at the elevated temperatures. The alloys can be fabricated into components using conventional techniques.

  20. Creep and Oxidation of Hafnium Diboride Based Ultra High Temperature Ceramics at 1500C

    DTIC Science & Technology

    2015-12-01

    through experimentation. Although the Literature Review showed that some theories and models have been developed based on extensive experimental results...of Some Refractory Metals & Ceramics [Fahrenholtz] ........... 14 Figure 4: Creep Strain vs Time Based on Burgers Model ...

  1. 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

  2. High Atomic Number Contrast Media Offer Potential for Radiation Dose Reduction in Contrast-Enhanced Computed Tomography.

    PubMed

    Roessler, Ann-Christin; Hupfer, Martin; Kolditz, Daniel; Jost, Gregor; Pietsch, Hubertus; Kalender, Willi A

    2016-04-01

    Spectral optimization of x-ray computed tomography (CT) has led to substantial radiation dose reduction in contrast-enhanced CT studies using standard iodinated contrast media. The purpose of this study was to analyze the potential for further dose reduction using high-atomic-number elements such as hafnium and tungsten. As in previous studies, spectra were determined for which the patient dose necessary to provide a given contrast-to-noise ratio (CNR) is minimized. We used 2 different quasi-anthropomorphic phantoms representing the liver cross-section of a normal adult and an obese adult patient with the lateral widths of 360 and 460 mm and anterior-posterior heights of 200 and 300 mm, respectively. We simulated and measured on 2 different scanners with x-ray spectra from 80 to 140 kV and from 70 to 150 kV, respectively. We determined the contrast for iodine-, hafnium-, and tungsten-based contrast media, the noise, and 3-dimensional dose distributions at all available tube voltages by measurements and by simulations. The dose-weighted CNR was determined as optimization parameter. Simulations and measurements were in good agreement regarding their dependence on energy for all parameters investigated. Hafnium provided the best performance for normal and for obese patient phantoms, indicating a dose reduction potential of 30% for normal and 50% for obese patients at 120 kV compared with iodine; this advantage increased further with higher kV values. Dose-weighted CNR values for tungsten were always slightly below the hafnium results. Iodine proved to be the superior choice at voltage values of 80 kV and below. Hafnium and tungsten both seem to be candidates for contrast-medium-enhanced CT of normal and obese adult patients with strongly reduced radiation dose at unimpaired image quality. Computed tomography examinations of obese patients will decrease in dose for higher kV values.

  3. 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.

  4. Nanocontainers made of Various Materials with Tunable Shape and Size

    NASA Astrophysics Data System (ADS)

    Zhao, Xianglong; Meng, Guowen; Han, Fangming; Li, Xiangdong; Chen, Bensong; Xu, Qiaoling; Zhu, Xiaoguang; Chu, Zhaoqin; Kong, Mingguang; Huang, Qing

    2013-07-01

    Nanocontainers have great potentials in targeted drug delivery and nanospace-confined reactions. However, the previous synthetic approaches exhibited limited control over the morphology, size and materials of the nanocontainers, which are crucial in practical applications. Here, we present a synthetic approach to multi-segment linear-shaped nanopores with pre-designed morphologies inside anodic aluminium oxide (AAO), by tailoring the anodizing duration after a rational increase of the applied anodizing voltage and the number of voltage increase during Al foil anodization. Then, we achieve nanocontainers with designed morphologies, such as nanofunnels, nanobottles, nano-separating-funnels and nanodroppers, with tunable sizes and diverse materials of carbon, silicon, germanium, hafnium oxide, silica and nickel/carbon magnetic composite, by depositing a thin layer of materials on the inner walls of the pre-designed AAO nanopores. The strategy has far-reaching implications in the designing and large-scale fabrication of nanocontainers, opening up new opportunities in nanotechnology applications.

  5. Nanocontainers made of Various Materials with Tunable Shape and Size

    PubMed Central

    Zhao, Xianglong; Meng, Guowen; Han, Fangming; Li, Xiangdong; Chen, Bensong; Xu, Qiaoling; Zhu, Xiaoguang; Chu, Zhaoqin; Kong, Mingguang; Huang, Qing

    2013-01-01

    Nanocontainers have great potentials in targeted drug delivery and nanospace-confined reactions. However, the previous synthetic approaches exhibited limited control over the morphology, size and materials of the nanocontainers, which are crucial in practical applications. Here, we present a synthetic approach to multi-segment linear-shaped nanopores with pre-designed morphologies inside anodic aluminium oxide (AAO), by tailoring the anodizing duration after a rational increase of the applied anodizing voltage and the number of voltage increase during Al foil anodization. Then, we achieve nanocontainers with designed morphologies, such as nanofunnels, nanobottles, nano-separating-funnels and nanodroppers, with tunable sizes and diverse materials of carbon, silicon, germanium, hafnium oxide, silica and nickel/carbon magnetic composite, by depositing a thin layer of materials on the inner walls of the pre-designed AAO nanopores. The strategy has far-reaching implications in the designing and large-scale fabrication of nanocontainers, opening up new opportunities in nanotechnology applications. PMID:23867836

  6. Nitric oxide scavengers differentially inhibit ammonia oxidation in ammonia-oxidizing archaea and bacteria.

    PubMed

    Sauder, Laura A; Ross, Ashley A; Neufeld, Josh D

    2016-04-01

    Differential inhibitors are important for measuring the relative contributions of microbial groups, such as ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA), to biogeochemical processes in environmental samples. In particular, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO) represents a nitric oxide scavenger used for the specific inhibition of AOA, implicating nitric oxide as an intermediate of thaumarchaeotal ammonia oxidation. This study investigated four alternative nitric oxide scavengers for their ability to differentially inhibit AOA and AOB in comparison to PTIO. Caffeic acid, curcumin, methylene blue hydrate and trolox were tested onNitrosopumilus maritimus, two unpublished AOA representatives (AOA-6f and AOA-G6) as well as the AOB representative Nitrosomonas europaea All four scavengers inhibited ammonia oxidation by AOA at lower concentrations than for AOB. In particular, differential inhibition of AOA and AOB by caffeic acid (100 μM) and methylene blue hydrate (3 μM) was comparable to carboxy-PTIO (100 μM) in pure and enrichment culture incubations. However, when added to aquarium sponge biofilm microcosms, both scavengers were unable to inhibit ammonia oxidation consistently, likely due to degradation of the inhibitors themselves. This study provides evidence that a variety of nitric oxide scavengers result in differential inhibition of ammonia oxidation in AOA and AOB, and provides support to the proposed role of nitric oxide as a key intermediate in the thaumarchaeotal ammonia oxidation pathway. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  7. Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

    NASA Astrophysics Data System (ADS)

    Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

    2017-06-01

    The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

  8. Powerful Oxidizing Agents for the Oxidative Deintercalation of Lithium from Transition Metal Oxides

    DTIC Science & Technology

    1989-08-16

    22217 11 TITLE dnrcluae Sec’.r/ 2 ’als.rit,catC Powerful Oxidizing Agents for the Oxidative Deintercalation of Lithium from Transition Metal Oxides...0 d dlentity by block number) FIELD GROUP SUB GROUP Oxidizing Agents, Lithium Oxides I - Deintercalation 19 AbS*RA?, trne on-tsxes~e it necessary...anid enit’y oy 010ck .1Uf~oer. N02+ andMoF6 are shown to be powerful oxidizing agents for the deintercalation of lithium from Li~oO2 an 62Ct . The

  9. Hybrid nuclear reactor grey rod to obtain required reactivity worth

    DOEpatents

    Miller, John V.; Carlson, William R.; Yarbrough, Michael B.

    1991-01-01

    Hybrid nuclear reactor grey rods are described, wherein geometric combinations of relatively weak neutron absorber materials such as stainless steel, zirconium or INCONEL, and relatively strong neutron absorber materials, such as hafnium, silver-indium cadmium and boron carbide, are used to obtain the reactivity worths required to reach zero boron change load follow. One embodiment includes a grey rod which has combinations of weak and strong neutron absorber pellets in a stainless steel cladding. The respective pellets can be of differing heights. A second embodiment includes a grey rod with a relatively thick stainless steel cladding receiving relatively strong neutron absorber pellets only. A third embodiment includes annular relatively weak netron absorber pellets with a smaller diameter pellet of relatively strong absorber material contained within the aperture of each relatively weak absorber pellet. The fourth embodiment includes pellets made of a homogeneous alloy of hafnium and a relatively weak absorber material, with the percentage of hafnium chosen to obtain the desired reactivity worth.

  10. Evaluation of T-111 forced-convection loop tested with lithium at 1370 C. [free convection

    NASA Technical Reports Server (NTRS)

    Devan, J. H.; Long, E. L., Jr.

    1975-01-01

    A T-111 alloy (Ta-8% W-2% Hf) forced-convection loop containing molten lithium was operated 3000 hr at a maximum temperature of 1370 C. Flow velocities up to 6.3 m/sec were used, and the results of this forced-convection loop are very similar to those observed in lower velocity thermal-convection loops of T-111 containing lithium. Weight changes were determined at 93 positions around the loop. The maximum dissolution rate occurred at the maximum wall temperature of the loop and was less than 1.3 microns/year. Mass transfer of hafnium, nitrogen, and, to a lesser extent, carbon occurred from the hotter to cooler regions. Exposed surfaces in the highest temperature region were found to be depleted in hafnium to a depth of 60 microns with no detectable change in tungsten content. There was some loss in room-temperature tensile strength for specimens exposed to lithium at 1370 C, attributable to depletion of hafnium and nitrogen and to attendant grain growth.

  11. Silver(II) Oxide or Silver(I,III) Oxide?

    ERIC Educational Resources Information Center

    Tudela, David

    2008-01-01

    The often called silver peroxide and silver(II) oxide, AgO or Ag[subscript 2]O[subscript 2], is actually a mixed oxidation state silver(I,III) oxide. A thermochemical cycle, with lattice energies calculated within the "volume-based" thermodynamic approach, explain why the silver(I,III) oxide is more stable than the hypothetical silver(II) oxide.…

  12. Solid oxide fuel cells fueled with reducible oxides

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

    Chuang, Steven S.; Fan, Liang Shih

    A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing themore » solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.« less

  13. Hysteresis-free high rate reactive sputtering of niobium oxide, tantalum oxide, and aluminum oxide

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

    Särhammar, Erik, E-mail: erik.sarhammar@angstrom.uu.se; Berg, Sören; Nyberg, Tomas

    2014-07-01

    This work reports on experimental studies of reactive sputtering from targets consisting of a metal and its oxide. The composition of the targets varied from pure metal to pure oxide of Al, Ta, and Nb. This combines features from both the metal target and oxide target in reactive sputtering. If a certain relation between the metal and oxide parts is chosen, it may be possible to obtain a high deposition rate, due to the metal part, and a hysteresis-free process, due to the oxide part. The aim of this work is to quantify the achievable boost in oxide deposition ratemore » from a hysteresis-free process by using a target consisting of segments of a metal and its oxide. Such an increase has been previously demonstrated for Ti using a homogeneous substoichiometric target. The achievable gain in deposition rate depends on transformation mechanisms from oxide to suboxides due to preferential sputtering of oxygen. Such mechanisms are different for different materials and the achievable gain is therefore material dependent. For the investigated materials, the authors have demonstrated oxide deposition rates that are 1.5–10 times higher than what is possible from metal targets in compound mode. However, although the principle is demonstrated for oxides of Al, Ta, and Nb, a similar behavior is expected for most oxides.« less

  14. Efficient and self-adaptive in-situ learning in multilayer memristor neural networks.

    PubMed

    Li, Can; Belkin, Daniel; Li, Yunning; Yan, Peng; Hu, Miao; Ge, Ning; Jiang, Hao; Montgomery, Eric; Lin, Peng; Wang, Zhongrui; Song, Wenhao; Strachan, John Paul; Barnell, Mark; Wu, Qing; Williams, R Stanley; Yang, J Joshua; Xia, Qiangfei

    2018-06-19

    Memristors with tunable resistance states are emerging building blocks of artificial neural networks. However, in situ learning on a large-scale multiple-layer memristor network has yet to be demonstrated because of challenges in device property engineering and circuit integration. Here we monolithically integrate hafnium oxide-based memristors with a foundry-made transistor array into a multiple-layer neural network. We experimentally demonstrate in situ learning capability and achieve competitive classification accuracy on a standard machine learning dataset, which further confirms that the training algorithm allows the network to adapt to hardware imperfections. Our simulation using the experimental parameters suggests that a larger network would further increase the classification accuracy. The memristor neural network is a promising hardware platform for artificial intelligence with high speed-energy efficiency.

  15. Effect of growth rate on crystallization of HfO{sub 2} thin films deposited by RF magnetron sputtering

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

    Dhanunjaya, M.; Manikanthababu, N.; Pathak, A. P.

    2016-05-23

    Hafnium oxide (HfO{sub 2}) is the potentially useful dielectric material in both; electronics to replace the conventional SiO{sub 2} as gate dielectric and in Optics as anti-reflection coating material. In this present work we have synthesized polycrystalline HfO{sub 2} thin films by RF magnetron sputtering deposition technique with varying target to substrate distance. The deposited films were characterized by X-ray Diffraction, Rutherford Backscattering Spectrometry (RBS) and transmission and Reflection (T&R) measurements to study the growth behavior, microstructure and optical properties. XRD measurement shows that the samples having mixed phase of monoclinic, cubic and tetragonal crystal structure. RBS measurements suggest themore » formation of Inter Layer (IL) in between Substrate and film.« less

  16. Nickel aluminide alloy suitable for structural applications

    DOEpatents

    Liu, C.T.

    1998-03-10

    Alloys are disclosed for use in structural applications based upon NiAl to which are added selected elements to enhance room temperature ductility and high temperature strength. Specifically, small additions of molybdenum produce a beneficial alloy, while further additions of boron, carbon, iron, niobium, tantalum, zirconium and hafnium further improve performance of alloys at both room temperature and high temperatures. A preferred alloy system composition is Ni--(49.1{+-}0.8%)Al--(1.0{+-}0.8%)Mo--(0.7 + 0.5%)Nb/Ta/Zr/Hf--(nearly zero to 0.03%)B/C, where the % is at. % in each of the concentrations. All alloys demonstrated good oxidation resistance at the elevated temperatures. The alloys can be fabricated into components using conventional techniques. 4 figs.

  17. Deep-ocean ferromanganese crusts and nodules

    USGS Publications Warehouse

    Hein, James R.; Koschinsky, Andrea

    2014-01-01

    Ferromanganese crusts and nodules may provide a future resource for a large variety of metals, including many that are essential for emerging high- and green-technology applications. A brief review of nodules and crusts provides a setting for a discussion on the latest (past 10 years) research related to the geochemistry of sequestration of metals from seawater. Special attention is given to cobalt, nickel, titanium, rare earth elements and yttrium, bismuth, platinum, tungsten, tantalum, hafnium, tellurium, molybdenum, niobium, zirconium, and lithium. Sequestration from seawater by sorption, surface oxidation, substitution, and precipitation of discrete phases is discussed. Mechanisms of metal enrichment reflect modes of formation of the crusts and nodules, such as hydrogenetic (from seawater), diagenetic (from porewaters), and mixed diagenetic–hydrogenetic processes.

  18. Experimental Observations of Nuclear Activity in Deuterated Materials Subjected to a Low-Energy Photon Beam

    NASA Technical Reports Server (NTRS)

    Steinetz, Bruce M.; Benyo, Theresa L.; Pines, Vladimir; Pines, Marianna; Forsley, Lawrence P.; Westmeyer, Paul A.; Chait, Arnon; Becks, Michael D.; Martin, Richard E.; Hendricks, Robert C.; hide

    2017-01-01

    Exposure of highly deuterated materials to a low-energy (nom. 2 MeV) photon beam resulted in nuclear activity of both the parent metals of hafnium and erbium and a witness material (molybdenum) mixed with the reactants. Gamma spectral analysis of all deuterated materials, ErD2.8+C36D74+Mo and HfD2+C36D74+Mo, showed that nuclear processes had occurred as shown by unique gamma signatures. For the deuterated erbium specimens, posttest gamma spectra showed evidence of radioisotopes of erbium ((163)Er and (171)Er) and of molybdenum ((99)Mo and (101)Mo) and by beta decay, technetium (99mTc and 101Tc). For the deuterated hafnium specimens, posttest gamma spectra showed evidence of radioisotopes of hafnium (180mHf and 181Hf) and molybdenum ((99)Mo and (101)Mo), and by beta decay, technetium ((99m)Tc and (101)Tc). In contrast, when either the hydrogenated or non-gas-loaded erbium or hafnium materials were exposed to the gamma flux, the gamma spectra revealed no new isotopes. Neutron activation materials showed evidence of thermal and epithermal neutrons. CR-39 solid-state nuclear track detectors showed evidence of fast neutrons with energies between 1.4 and 2.5 MeV and several instances of triple tracks, indicating (is) greater than 10 MeV neutrons. Further study is required to determine the mechanism causing the nuclear activity.

  19. Highly oxidized graphene oxide and methods for production thereof

    DOEpatents

    Tour, James M.; Kosynkin, Dmitry V.

    2016-08-30

    A highly oxidized form of graphene oxide and methods for production thereof are described in various embodiments of the present disclosure. In general, the methods include mixing a graphite source with a solution containing at least one oxidant and at least one protecting agent and then oxidizing the graphite source with the at least one oxidant in the presence of the at least one protecting agent to form the graphene oxide. Graphene oxide synthesized by the presently described methods is of a high structural quality that is more oxidized and maintains a higher proportion of aromatic rings and aromatic domains than does graphene oxide prepared in the absence of at least one protecting agent. Methods for reduction of graphene oxide into chemically converted graphene are also disclosed herein. The chemically converted graphene of the present disclosure is significantly more electrically conductive than is chemically converted graphene prepared from other sources of graphene oxide.

  20. Advanced materials for radiation-cooled rockets

    NASA Technical Reports Server (NTRS)

    Reed, Brian; Biaglow, James; Schneider, Steven

    1993-01-01

    The most common material system currently used for low thrust, radiation-cooled rockets is a niobium alloy (C-103) with a fused silica coating (R-512A or R-512E) for oxidation protection. However, significant amounts of fuel film cooling are usually required to keep the material below its maximum operating temperature of 1370 C, degrading engine performance. Also the R-512 coating is subject to cracking and eventual spalling after repeated thermal cycling. A new class of high-temperature, oxidation-resistant materials are being developed for radiation-cooled rockets, with the thermal margin to reduce or eliminate fuel film cooling, while still exceeding the life of silicide-coated niobium. Rhenium coated with iridium is the most developed of these high-temperature materials. Efforts are on-going to develop 22 N, 62 N, and 440 N engines composed of these materials for apogee insertion, attitude control, and other functions. There is also a complimentary NASA and industry effort to determine the life limiting mechanisms and characterize the thermomechanical properties of these materials. Other material systems are also being studied which may offer more thermal margin and/or oxidation resistance, such as hafnium carbide/tantalum carbide matrix composites and ceramic oxide-coated iridium/rhenium chambers.

  1. Optically reversible electrical soft-breakdown in wide-bandgap oxides—A factorial study

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Ang, D. S.; Kalaga, P. S.

    2018-04-01

    In an earlier work, we found that an electrical soft-breakdown region in wide-bandgap oxides, such as hafnium dioxide, silicon dioxide, etc., could be reversed when illuminated by white light. The effect is evidenced by a decrease in the breakdown leakage current, termed as a negative photoconductivity response. This finding raises the prospect for optical sensing applications based on these traditionally non-photo-responsive but ubiquitous oxide materials. In this study, we examine the statistical distribution for the rate of breakdown reversal as well as the influence of factors such as wavelength, light intensity, oxide stoichiometry (or oxygen content) and temperature on the reversal rate. The rate of breakdown reversal is shown to be best described by the lognormal distribution. Light in the range of ˜400-700 nm is found to have relatively little influence on the reversal rate. On the other hand, light intensity, oxygen content and temperature, each of them has a clear impact; a stronger light intensity, an oxide that is richer in oxygen content and a reduced temperature all speed up the reversal process substantially. These experimental results are consistent with the proposed phenomenological redox model involving photo-assisted recombination of the surrounding oxygen interstitials with vacancy defects in the breakdown path.

  2. Realization of the Switching Mechanism in Resistance Random Access Memory™ Devices: Structural and Electronic Properties Affecting Electron Conductivity in a Hafnium Oxide-Electrode System Through First-Principles Calculations

    NASA Astrophysics Data System (ADS)

    Aspera, Susan Meñez; Kasai, Hideaki; Kishi, Hirofumi; Awaya, Nobuyoshi; Ohnishi, Shigeo; Tamai, Yukio

    2013-01-01

    The resistance random access memory (RRAM™) device, with its electrically induced nanoscale resistive switching capacity, has attracted considerable attention as a future nonvolatile memory device. Here, we propose a mechanism of switching based on an oxygen vacancy migration-driven change in the electronic properties of the transition-metal oxide film stimulated by set pulse voltages. We used density functional theory-based calculations to account for the effect of oxygen vacancies and their migration on the electronic properties of HfO2 and Ta/HfO2 systems, thereby providing a complete explanation of the RRAM™ switching mechanism. Furthermore, computational results on the activation energy barrier for oxygen vacancy migration were found to be consistent with the set and reset pulse voltage obtained from experiments. Understanding this mechanism will be beneficial to effectively realizing the materials design in these devices.

  3. Preparation of refractory cermet structures for lithium compatibility testing

    NASA Technical Reports Server (NTRS)

    Heestand, R. L.; Jones, R. A.; Wright, T. R.; Kizer, D. E.

    1973-01-01

    High-purity nitride and carbide cermets were synthesized for compatability testing in liquid lithium. A process was developed for the preparation of high-purity hafnium nitride powder, which was subsequently blended with tungsten powder or tantalum nitride and tungsten powders and fabricated into 3 in diameter billets by uniaxial hot pressing. Specimens were then cut from the billets for compatability testing. Similar processing techniques were applied to produce hafnium carbide and zirconium carbide cermets for use in the testing program. All billets produced were characterized with respect to chemistry, structure, density, and strength properties.

  4. Sol-gel-derived double-layered nanocrystal memory

    NASA Astrophysics Data System (ADS)

    Ko, Fu-Hsiang; You, Hsin-Chiang; Lei, Tan-Fu

    2006-12-01

    The authors have used the sol-gel spin-coating method to fabricate a coexisting hafnium silicate and zirconium silicate double-layered nanocrystal (NC) memories. From transmission electron microscopic and x-ray photoelectron spectroscopic analyses, the authors determined that the hafnium silicate and zirconium silicate NCs formed after annealing at 900°C for 1min. When using channel hot electron injection for charging and band-to-band tunneling-induced hot hole injection for discharging, the NC memories exhibited superior Vth shifting because of the higher probability for trapping the charge carrier.

  5. Lipid oxidation induced oxidative degradation of cereal beta-glucan.

    PubMed

    Wang, Yu-Jie; Mäkelä, Noora; Maina, Ndegwa Henry; Lampi, Anna-Maija; Sontag-Strohm, Tuula

    2016-04-15

    In food systems, lipid oxidation can cause oxidation of other molecules. This research for the first time investigated oxidative degradation of β-glucan induced by lipid oxidation using an oil-in-water emulsion system which simulated a multi-phased aqueous food system containing oil and β-glucan. Lipid oxidation was monitored using peroxide value and hexanal production while β-glucan degradation was evaluated by viscosity and molecular weight measurements. The study showed that while lipid oxidation proceeded, β-glucan degradation occurred. Emulsions containing β-glucan, oil and ferrous ion showed significant viscosity and molecular weight decrease after 1 week of oxidation at room temperature. Elevated temperature (40°C) enhanced the oxidation reactions causing higher viscosity drop. In addition, the presence of β-glucan appeared to retard the hexanal production in lipid oxidation. The study revealed that lipid oxidation may induce the degradation of β-glucan in aqueous food systems where β-glucan and lipids co-exist. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. High Temperature Materials for Chemical Propulsion Applications

    NASA Technical Reports Server (NTRS)

    Elam, Sandra; Hickman, Robert; O'Dell, Scott

    2007-01-01

    Radiation or passively cooled thrust chambers are used for a variety of chemical propulsion functions including apogee insertion, reaction control for launch vehicles, and primary propulsion for planetary spacecraft. The performance of these thrust chambers is limited by the operating temperature of available materials. Improved oxidation resistance and increased operating temperatures can be achieved with the use of thermal barrier coatings such as zirconium oxide (ZrO2) and hafnium oxide (HfO2). However, previous attempts to include these materials showed cracking and spalling of the oxide layer due to poor bonding. Current research at NASA's Marshall Space Flight Center (MSFC) has generated unique, high temperature material options for in-space thruster designs that are capable of up to 2500 C operating temperatures. The research is focused on fabrication technologies to form low cost Iridium,qF_.henium (Ir/Re) components with a ceramic hot wall created as an integral, functionally graded material (FGM). The goal of this effort is to further de?celop proven technologies for embedding a protective ceramic coating within the Ir/Re liner to form a robust functional gradient material. Current work includes the fabrication and testing of subscale samples to evaluate tensile, creep, thermal cyclic/oxidation, and thermophysical material properties. Larger test articles have also being fabricated and hot-fire tested to demonstrate the materials in prototype thrusters at 1O0 lbf thrust levels.

  7. Interface Engineering with MoS2 -Pd Nanoparticles Hybrid Structure for a Low Voltage Resistive Switching Memory.

    PubMed

    Wang, Xue-Feng; Tian, He; Zhao, Hai-Ming; Zhang, Tian-Yu; Mao, Wei-Quan; Qiao, Yan-Cong; Pang, Yu; Li, Yu-Xing; Yang, Yi; Ren, Tian-Ling

    2018-01-01

    Metal oxide-based resistive random access memory (RRAM) has attracted a lot of attention for its scalability, temperature robustness, and potential to achieve machine learning. However, a thick oxide layer results in relatively high program voltage while a thin one causes large leakage current and a small window. Owing to these fundamental limitations, by optimizing the oxide layer itself a novel interface engineering idea is proposed to reduce the programming voltage, increase the uniformity and on/off ratio. According to this idea, a molybdenum disulfide (MoS 2 )-palladium nanoparticles hybrid structure is used to engineer the oxide/electrode interface of hafnium oxide (HfO x )-based RRAM. Through its interface engineering, the set voltage can be greatly lowered (from -3.5 to -0.8 V) with better uniformity under a relatively thick HfO x layer (≈15 nm), and a 30 times improvement of the memory window can be obtained. Moreover, due to the atomic thickness of MoS 2 film and high transmittance of ITO, the proposed RRAM exhibits high transparency in visible light. As the proposed interface-engineering RRAM exhibits good transparency, low SET voltage, and a large resistive switching window, it has huge potential in data storage in transparent circuits and wearable electronics with relatively low supply voltage. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Oxidizing action of purine N-oxide esters.

    PubMed

    Stöhrer, G; Salemnick, G

    1975-01-01

    A technique involving O-acetylation of purine N-oxide derivatives in buffered aqueous solutions has permitted studies of the reactivity of many compounds for which the O-acetyl derivatives are not otherwise available. The oxidizing properties of a variety of N-acetoxypurines have been measured through their ability to oxidize iodide ion ot iodine, a reaction which is representative of a more general oxidizing ability. Those esters that oxidize iodide ion also catalyze the autoxidation of sulfite, a property characteristic of radicals. The same esters also oxidize cysteine to cysteic acid and tryptophan, tyrosine, and uric acid to yet uncharacterized products. Their oxidizing reactivity was compared with the ability of the same esters to react as electrophiles in another assay that measured the rate of formation of pyridine substitution products. The sulfate ester of 3-hydroxyxanthine has been synthesized. Its reactivity is qualitatively the same as that of 3-acetoxyxanthine but proceeds at a higher rate. Syntheses of S-(8-xanthyl)-N-acetylcysteine, 8-(2-hydroxyethylthio)xanthine, and 1-methyl-8-mehtylmercaptoguanine are also described.

  9. Oxidative Stress, Nitric Oxide, and Diabetes

    PubMed Central

    Pitocco, Dario; Zaccardi, Francesco; Di Stasio, Enrico; Romitelli, Federica; Santini, Stefano A.; Zuppi, Cecilia; Ghirlanda, Giovanni

    2010-01-01

    In the recent decades, oxidative stress has become focus of interest in most biomedical disciplines and many types of clinical research. Increasing evidence from research on several diseases show that oxidative stress is associated with the pathogenesis of diabetes, obesity, cancer, ageing, inflammation, neurodegenerative disorders, hypertension, apoptosis, cardiovascular diseases, and heart failure. Based on this research, the emerging concept is that oxidative stress is the “final common pathway”, through which risk factors of several diseases exert their deleterious effects. Oxidative stress causes a complex dysregulation of cell metabolism and cell-cell homeostasis. In this review, we discuss the role of oxidative stress in the pathogenesis of insulin resistance and beta-cell dysfunction. These are the two most relevant mechanisms in the pathophysiology of type 2 diabetes, and in the pathogenesis of diabetic vascular complications, the leading cause of death in diabetic patients. PMID:20703435

  10. Single-Phase Rare-Earth Oxide/Aluminum Oxide Glasses

    NASA Technical Reports Server (NTRS)

    Weber, J. K. Richard; Abadie, John G.; Hixson, April D.; Nordine, Paul C.

    2006-01-01

    Glasses that comprise rare-earth oxides and aluminum oxide plus, optionally, lesser amounts of other oxides, have been invented. The other oxide(s) can include SiO2, B2O3, GeO2, and/or any of a variety of glass-forming oxides that have been used heretofore in making a variety of common and specialty glasses. The glasses of the invention can be manufactured in bulk single-phase forms to ensure near uniformity in optical and mechanical characteristics, as needed for such devices as optical amplifiers, lasers, and optical waveguides (including optical fibers). These glasses can also be formulated to have high indices of refraction, as needed in some of such devices.

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

    NASA Astrophysics Data System (ADS)

    Francillon, Wesley

    This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is

  12. Metabolism of Nitrogen Oxides in Ammonia-Oxidizing Bacteria

    NASA Astrophysics Data System (ADS)

    Kozlowski, J.; Stein, L. Y.

    2014-12-01

    Ammonia-oxidizing bacteria (AOB) are key microorganisms in the transformation of nitrogen intermediates in most all environments. Until recently there was very little work done to elucidate the physiology of ammonia-oxidizing bacteria cultivated from variable trophic state environments. With a greater variety of ammonia-oxidizers now in pure culture the importance of comparative physiological and genomic analysis is crucial. Nearly all known physiology of ammonia-oxidizing bacteria lies within the Nitrosomonas genus with Nitrosomonas europaea strain ATCC 19718 as the model. To more broadly characterize and understand the nature of obligate ammonia chemolithotrophy and the contribution of AOB to production of nitrogen oxides, Nitrosomonas spp. and Nitrosospira spp. isolated from variable trophic states and with sequenced genomes, were utilized. Instantaneous ammonia- and hydroxylamine-oxidation kinetics as a function of oxygen and substrate concentration were measured using an oxygen micro-sensor. The pathway intermediates nitric oxide and nitrous oxide were measured in real time using substrate-specific micro-sensors to elucidate whether production of these molecules is stoichiometric with rates of substrate oxidation. Genomic inventory was compared among the strains to identify specific pathways and modules to explain physiological differences in kinetic rates and production of N-oxide intermediates as a condition of their adaptation to different ammonium concentrations. This work provides knowledge of how nitrogen metabolism is differentially controlled in AOB that are adapted to different concentrations of ammonium. Overall, this work will provide further insight into the control of ammonia oxidizing chemolithotrophy across representatives of the Nitrosomonas and Nitrosospira genus, which can then be applied to examine additional genome-sequenced AOB isolates.

  13. Chromium(iii) oxidation by biogenic manganese oxides with varying structural ripening.

    PubMed

    Tang, Yuanzhi; Webb, Samuel M; Estes, Emily R; Hansel, Colleen M

    2014-09-20

    Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions. Yet the influence of Mn biooxide mineral structural evolution on Cr(iii) oxidation under varying geochemical conditions is unknown. In this study we examined the role of light, organic carbon, pH, and the structure of biogenic Mn oxides on Cr(iii) oxidation. Aging of Mn oxides produced by a marine bacterium within the widespread Roseobacter clade resulted in structural ripening from a colloidal hexagonal to a particulate triclinic birnessite phase. The structurally diverse Mn oxides were then reacted with aqueous Cr(iii) within artificial seawater in the presence or absence of carbon and light. Here we found that Cr(iii) oxidation capacity was highest at near neutral pH and in the combined presence of carbon and light. Mn oxide ripening from a hexagonal to a triclinic birnessite phase led to decreased Cr(iii) oxidation in the presence of carbon and light, whereas no change in reactivity was observed in the absence of carbon and/or in the dark. As only minimal Cr(iii) oxidation was observed in the absence of Mn oxides, these results strongly point to coupled Mn oxide- and photo-induced generation of organic and/or oxygen radicals involved in Cr(iii) oxidation. Based on Mn oxide concentration and structural trends, we postulate that Mn(ii) produced from the oxidation of Cr(iii) by the primary Mn oxide is recycled in the presence of organics and light conditions, (re)generating secondary hexagonal birnessite and thereby allowing for continuous oxidation of Cr(iii). In the absence of this Mn oxide regeneration, Cr(iii) induced structural ripening of the hexagonal birnessite precludes further Cr(iii) oxidation. These results highlight the complexity of reactions involved in Mn oxide mediated Cr(iii) oxidation and suggest that photochemical carbon reactions are requisite for sustained Cr(iii) oxidation

  14. Antibacterial activity of graphite, graphite oxide, graphene oxide, and reduced graphene oxide: membrane and oxidative stress.

    PubMed

    Liu, Shaobin; Zeng, Tingying Helen; Hofmann, Mario; Burcombe, Ehdi; Wei, Jun; Jiang, Rongrong; Kong, Jing; Chen, Yuan

    2011-09-27

    Health and environmental impacts of graphene-based materials need to be thoroughly evaluated before their potential applications. Graphene has strong cytotoxicity toward bacteria. To better understand its antimicrobial mechanism, we compared the antibacterial activity of four types of graphene-based materials (graphite (Gt), graphite oxide (GtO), graphene oxide (GO), and reduced graphene oxide (rGO)) toward a bacterial model-Escherichia coli. Under similar concentration and incubation conditions, GO dispersion shows the highest antibacterial activity, sequentially followed by rGO, Gt, and GtO. Scanning electron microscope (SEM) and dynamic light scattering analyses show that GO aggregates have the smallest average size among the four types of materials. SEM images display that the direct contacts with graphene nanosheets disrupt cell membrane. No superoxide anion (O(2)(•-)) induced reactive oxygen species (ROS) production is detected. However, the four types of materials can oxidize glutathione, which serves as redox state mediator in bacteria. Conductive rGO and Gt have higher oxidation capacities than insulating GO and GtO. Results suggest that antimicrobial actions are contributed by both membrane and oxidation stress. We propose that a three-step antimicrobial mechanism, previously used for carbon nanotubes, is applicable to graphene-based materials. It includes initial cell deposition on graphene-based materials, membrane stress caused by direct contact with sharp nanosheets, and the ensuing superoxide anion-independent oxidation. We envision that physicochemical properties of graphene-based materials, such as density of functional groups, size, and conductivity, can be precisely tailored to either reducing their health and environmental risks or increasing their application potentials. © 2011 American Chemical Society

  15. Oxidation behaviour and electrical properties of cobalt/cerium oxide composite coatings for solid oxide fuel cell interconnects

    NASA Astrophysics Data System (ADS)

    Harthøj, Anders; Holt, Tobias; Møller, Per

    2015-05-01

    This work evaluates the performance of cobalt/cerium oxide (Co/CeO2) composite coatings and pure Co coatings to be used for solid oxide fuel cell (SOFC) interconnects. The coatings are electroplated on the ferritic stainless steels Crofer 22 APU and Crofer 22H. Coated and uncoated samples are exposed in air at 800 °C for 3000 h and oxidation rates are measured and oxide scale microstructures are investigated. Area-specific resistances (ASR) in air at 850 °C of coated and uncoated samples are also measured. A dual layered oxide scale formed on all coated samples. The outer layer consisted of Co, Mn, Fe and Cr oxide and the inner layer consisted of Cr oxide. The CeO2 was present as discrete particles in the outer oxide layer after exposure. The Cr oxide layer thicknesses and oxidations rates were significantly reduced for Co/CeO2 coated samples compared to for Co coated and uncoated samples. The ASR of all Crofer 22H samples increased significantly faster than of Crofer 22 APU samples which was likely due to the presence of SiO2 in the oxide/metal interface of Crofer 22H.

  16. Microsomal oxidation of tribromoethylene and reactions of tribromoethylene oxide.

    PubMed

    Yoshioka, Tadao; Krauser, Joel A; Guengerich, F Peter

    2002-11-01

    Halogenated olefins are of interest because of their widespread use in industry and their potential toxicity to humans. Epoxides are among the enzymatic oxidation products and have been studied in regard to their toxicity. Most of the attention has been given to chlorinated epoxides, and we have previously studied the reactions of the mono-, di-, tri-, and tetrachloroethylene oxides. To further test some hypotheses concerning the reactivity of these compounds, we prepared tribromoethylene (TBE) oxide and compared it to trichloroethylene (TCE) oxide and other chlorinated epoxides. TBE oxide reacted with H(2)O about 3 times faster than did TCE oxide. Several hydrolysis products of TBE oxide were the same as formed from TCE oxide, i.e., glyoxylic acid, CO, and HCO(2)H. Br(2)CHCO(2)H was formed from TBE oxide; the yield was higher than for Cl(2)CHCO(2)H formed in the hydrolysis of TCE oxide. The yield of tribromoacetaldehyde was < 0.4% in aqueous buffer (pH 7.4). In rat liver microsomal incubations containing TBE and NADPH, Br(2)CHCO(2)H was a major product, and tribromoacetaldehyde was a minor product. These results are consistent with schemes previously developed for halogenated epoxides, with migration of bromine being more favorable than for chlorine. Reaction of TBE oxide with lysine yielded relatively more N-dihaloacetyllysine and less N-formyllysine than in the case of TCE oxide. This same pattern was observed in the products of the reaction of TBE oxide with the lysine residues in bovine serum albumin. We conclude that the proposed scheme of hydrolysis of halogenated epoxides follows the expected halide order and that this can be used to rationalize patterns of hydrolysis and reactivity of other halogenated epoxides.

  17. Effects of Oxidation on Oxidation-Resistant Graphite

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

    Windes, William; Smith, Rebecca; Carroll, Mark

    2015-05-01

    The Advanced Reactor Technology (ART) Graphite Research and Development Program is investigating doped nuclear graphite grades that exhibit oxidation resistance through the formation of protective oxides on the surface of the graphite material. In the unlikely event of an oxygen ingress accident, graphite components within the VHTR core region are anticipated to oxidize so long as the oxygen continues to enter the hot core region and the core temperatures remain above 400°C. For the most serious air-ingress accident which persists over several hours or days the continued oxidation can result in significant structural damage to the core. Reducing the oxidationmore » rate of the graphite core material during any air-ingress accident would mitigate the structural effects and keep the core intact. Previous air oxidation testing of nuclear-grade graphite doped with varying levels of boron-carbide (B4C) at a nominal 739°C was conducted for a limited number of doped specimens demonstrating a dramatic reduction in oxidation rate for the boronated graphite grade. This report summarizes the conclusions from this small scoping study by determining the effects of oxidation on the mechanical strength resulting from oxidation of boronated and unboronated graphite to a 10% mass loss level. While the B4C additive did reduce mechanical strength loss during oxidation, adding B4C dopants to a level of 3.5% or more reduced the as-fabricated compressive strength nearly 50%. This effectively minimized any benefits realized from the protective film formed on the boronated grades. Future work to infuse different graphite grades with silicon- and boron-doped material as a post-machining conditioning step for nuclear components is discussed as a potential solution for these challenges in this report.« less

  18. CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

    NASA Technical Reports Server (NTRS)

    Herz, Richard K.

    1990-01-01

    Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

  19. Superoxide Production by a Manganese-Oxidizing Bacterium Facilitates Iodide Oxidation

    PubMed Central

    Li, Hsiu-Ping; Daniel, Benjamin; Creeley, Danielle; Grandbois, Russell; Zhang, Saijin; Xu, Chen; Ho, Yi-Fang; Schwehr, Kathy A.; Kaplan, Daniel I.; Santschi, Peter H.; Hansel, Colleen M.

    2014-01-01

    The release of radioactive iodine (i.e., iodine-129 and iodine-131) from nuclear reprocessing facilities is a potential threat to human health. The fate and transport of iodine are determined primarily by its redox status, but processes that affect iodine oxidation states in the environment are poorly characterized. Given the difficulty in removing electrons from iodide (I−), naturally occurring iodide oxidation processes require strong oxidants, such as Mn oxides or microbial enzymes. In this study, we examine iodide oxidation by a marine bacterium, Roseobacter sp. AzwK-3b, which promotes Mn(II) oxidation by catalyzing the production of extracellular superoxide (O2−). In the absence of Mn2+, Roseobacter sp. AzwK-3b cultures oxidized ∼90% of the provided iodide (10 μM) within 6 days, whereas in the presence of Mn(II), iodide oxidation occurred only after Mn(IV) formation ceased. Iodide oxidation was not observed during incubations in spent medium or with whole cells under anaerobic conditions or following heat treatment (boiling). Furthermore, iodide oxidation was significantly inhibited in the presence of superoxide dismutase and diphenylene iodonium (a general inhibitor of NADH oxidoreductases). In contrast, the addition of exogenous NADH enhanced iodide oxidation. Taken together, the results indicate that iodide oxidation was mediated primarily by extracellular superoxide generated by Roseobacter sp. AzwK-3b and not by the Mn oxides formed by this organism. Considering that extracellular superoxide formation is a widespread phenomenon among marine and terrestrial bacteria, this could represent an important pathway for iodide oxidation in some environments. PMID:24561582

  20. Superoxide production by a manganese-oxidizing bacterium facilitates iodide oxidation.

    PubMed

    Li, Hsiu-Ping; Daniel, Benjamin; Creeley, Danielle; Grandbois, Russell; Zhang, Saijin; Xu, Chen; Ho, Yi-Fang; Schwehr, Kathy A; Kaplan, Daniel I; Santschi, Peter H; Hansel, Colleen M; Yeager, Chris M

    2014-05-01

    The release of radioactive iodine (i.e., iodine-129 and iodine-131) from nuclear reprocessing facilities is a potential threat to human health. The fate and transport of iodine are determined primarily by its redox status, but processes that affect iodine oxidation states in the environment are poorly characterized. Given the difficulty in removing electrons from iodide (I(-)), naturally occurring iodide oxidation processes require strong oxidants, such as Mn oxides or microbial enzymes. In this study, we examine iodide oxidation by a marine bacterium, Roseobacter sp. AzwK-3b, which promotes Mn(II) oxidation by catalyzing the production of extracellular superoxide (O2(-)). In the absence of Mn(2+), Roseobacter sp. AzwK-3b cultures oxidized ∼90% of the provided iodide (10 μM) within 6 days, whereas in the presence of Mn(II), iodide oxidation occurred only after Mn(IV) formation ceased. Iodide oxidation was not observed during incubations in spent medium or with whole cells under anaerobic conditions or following heat treatment (boiling). Furthermore, iodide oxidation was significantly inhibited in the presence of superoxide dismutase and diphenylene iodonium (a general inhibitor of NADH oxidoreductases). In contrast, the addition of exogenous NADH enhanced iodide oxidation. Taken together, the results indicate that iodide oxidation was mediated primarily by extracellular superoxide generated by Roseobacter sp. AzwK-3b and not by the Mn oxides formed by this organism. Considering that extracellular superoxide formation is a widespread phenomenon among marine and terrestrial bacteria, this could represent an important pathway for iodide oxidation in some environments.

  1. Surface modifications of steels to improve corrosion resistance in sulfidizing-oxidizing environments

    NASA Astrophysics Data System (ADS)

    Behrani, Vikas

    Industrial and power generation processes employ units like boilers and gasifiers to burn sulfur containing fuels to produce steam and syn gas (H 2 and CO), which can generate electricity using turbines and fuel cells. These units often operate under environments containing gases such as H 2S, SO2, O2 etc, which can attack the metallic structure and impose serious problems of corrosion. Corrosion control in high temperature sulfur bearing environments is a challenging problem requiring information on local gaseous species at the surface of alloy and mechanisms of degradation in these environments. Coatings have proved to be a better alternative for improving corrosion resistance without compromising the bulk mechanical properties. Changes in process conditions may result in thermal and/or environment cycling between oxidizing and sulfidizing environments at the alloy surface, which can damage the protective scale formed on the alloy surface, leading to increase in corrosion rates. Objective of this study was to understand the effect of fluctuating environments on corrosion kinetics of carbon steels and develop diffusion based coatings to mitigate the high temperatures corrosion under these conditions. More specifically, the focus was: (1) to characterize the local gaseous environments at the surface of alloys in boilers; (2) optimizing diffusion coatings parameters for carbon steel; (3) understand the underlying failure mechanisms in cyclic environments; (4) to improve aluminide coating behavior by co-deposition of reactive elements such as Yttrium and Hafnium; (5) to formulate a plausible mechanism of coating growth and effects of alloying elements on corrosion; and (6) to understand the spallation behavior of scale by measuring stresses in the scales. The understanding of coating mechanism and effects of fluctuating gaseous environments provides information for designing materials with more reliable performance. The study also investigates the mechanism behind

  2. Nanoparticle radio-enhancement: principles, progress and application to cancer treatment

    NASA Astrophysics Data System (ADS)

    Kuncic, Zdenka; Lacombe, Sandrine

    2018-01-01

    Enhancement of radiation effects by high-atomic number nanoparticles (NPs) has been increasingly studied for its potential to improve radiotherapeutic efficacy. The underlying principle of NP radio-enhancement is the potential to release copious electrons into a nanoscale volume, thereby amplifying radiation-induced biological damage. While the vast majority of studies to date have focused on gold nanoparticles with photon radiation, an increasing number of experimental, theoretical and simulation studies have explored opportunities offered by other NPs (e.g. gadolinium, platinum, iron oxide, hafnium) and other therapeutic radiation sources such as ion beams. It is thus of interest to the research community to consolidate findings from the different studies and summarise progress to date, as well as to identify strategies that offer promising opportunities for clinical translation. This is the purpose of this Topical Review.

  3. Light Water Breeder Reactor fuel rod design and performance characteristics (LWBR Development Program)

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

    Campbell, W.R.; Giovengo, J.F.

    1987-10-01

    Light Water Breeder Reactor (LWBR) fuel rods were designed to provide a reliable fuel system utilizing thorium/uranium-233 mixed-oxide fuel while simultaneously minimizing structural material to enhance fuel breeding. The fuel system was designed to be capable of operating successfully under both load follow and base load conditions. The breeding objective required thin-walled, low hafnium content Zircaloy cladding, tightly spaced fuel rods with a minimum number of support grid levels, and movable fuel rod bundles to supplant control rods. Specific fuel rod design considerations and their effects on performance capability are described. Successful completion of power operations to over 160 percentmore » of design lifetime including over 200 daily load follow cycles has proven the performance capability of the fuel system. 68 refs., 19 figs., 44 tabs.« less

  4. The 2016 oxide electronic materials and oxide interfaces roadmap

    NASA Astrophysics Data System (ADS)

    Lorenz, M.; Ramachandra Rao, M. S.; Venkatesan, T.; Fortunato, E.; Barquinha, P.; Branquinho, R.; Salgueiro, D.; Martins, R.; Carlos, E.; Liu, A.; Shan, F. K.; Grundmann, M.; Boschker, H.; Mukherjee, J.; Priyadarshini, M.; DasGupta, N.; Rogers, D. J.; Teherani, F. H.; Sandana, E. V.; Bove, P.; Rietwyk, K.; Zaban, A.; Veziridis, A.; Weidenkaff, A.; Muralidhar, M.; Murakami, M.; Abel, S.; Fompeyrine, J.; Zuniga-Perez, J.; Ramesh, R.; Spaldin, N. A.; Ostanin, S.; Borisov, V.; Mertig, I.; Lazenka, V.; Srinivasan, G.; Prellier, W.; Uchida, M.; Kawasaki, M.; Pentcheva, R.; Gegenwart, P.; Miletto Granozio, F.; Fontcuberta, J.; Pryds, N.

    2016-11-01

    Oxide electronic materials provide a plethora of possible applications and offer ample opportunity for scientists to probe into some of the exciting and intriguing phenomena exhibited by oxide systems and oxide interfaces. In addition to the already diverse spectrum of properties, the nanoscale form of oxides provides a new dimension of hitherto unknown phenomena due to the increased surface-to-volume ratio. Oxide electronic materials are becoming increasingly important in a wide range of applications including transparent electronics, optoelectronics, magnetoelectronics, photonics, spintronics, thermoelectrics, piezoelectrics, power harvesting, hydrogen storage and environmental waste management. Synthesis and fabrication of these materials, as well as processing into particular device structures to suit a specific application is still a challenge. Further, characterization of these materials to understand the tunability of their properties and the novel properties that evolve due to their nanostructured nature is another facet of the challenge. The research related to the oxide electronic field is at an impressionable stage, and this has motivated us to contribute with a roadmap on ‘oxide electronic materials and oxide interfaces’. This roadmap envisages the potential applications of oxide materials in cutting edge technologies and focuses on the necessary advances required to implement these materials, including both conventional and novel techniques for the synthesis, characterization, processing and fabrication of nanostructured oxides and oxide-based devices. The contents of this roadmap will highlight the functional and correlated properties of oxides in bulk, nano, thin film, multilayer and heterostructure forms, as well as the theoretical considerations behind both present and future applications in many technologically important areas as pointed out by Venkatesan. The contributions in this roadmap span several thematic groups which are represented by

  5. Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

    DOEpatents

    Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

    2013-09-24

    A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

  6. Volatilization of oxides during oxidation of some superalloys at 1200 C

    NASA Technical Reports Server (NTRS)

    Zaplatynsky, I.

    1977-01-01

    Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541 chromium was found to be the main metallic element in the oxide scales.

  7. Volatilization of oxides during oxidation of some superalloys at 1200 C

    NASA Technical Reports Server (NTRS)

    Zaplatynsky, I.

    1977-01-01

    Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541, chromium was found to be the main metallic element in the oxide scales.

  8. Study of gas tungsten arc welding procedures for tantalum alloy T-111 (Ta-8 W-2Hf) plate

    NASA Technical Reports Server (NTRS)

    Gold, R. E.; Kesterson, R. L.

    1973-01-01

    Methods of eliminating or reducing underbread cracking in multipass GTA welds in thick T-111 plate were studied. Single V butt welds prepared using experimental filler metal compositions and standard weld procedures resulted in only moderate success in reducing underbread cracking. Subsequent procedural changes incorporating manual welding, slower weld speeds, and three or fewer fill passes resulted in crack-free single V welds only when the filler metal was free of hafnium. The double V joint design with successive fill passes on opposite sides of the joint produced excellent welds. The quality of each weld was determined metallographically since the cracking, when present, was very slight and undetectable using standard NDT techniques. Tensile and bend tests were performed on selected weldments. The inherent filler metal strength and the joint geometry determined the strength of the weldment. Hardness and electron beam microprobe traverses were made on selected specimens with the result that significant filler metal-base metal dilution as well as hafnium segregation was detected. A tentative explanation of T-111 plate underbread cracking is presented based on the intrinsic effects of hafnium in the weldment.

  9. PRODUCTION OF HAFNIUM METAL

    DOEpatents

    Elger, G.W.; Boubel, R.W.

    1963-01-01

    This patent deals with a process of producing pure Hf metal from oxygen- contaminated gaseous Hf chloride. The oxygen compounds in the chioride gas are halogenated by contacting the gas at elevated temperature with Cl/sub 2/ in the presence of C. The Hf chloride, still in gaseous form, is contacted with molten Mg whereby Hf metal is formed and condensed on the Mg. (AEC)

  10. Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

    PubMed

    Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2014-07-28

    Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.

  11. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts.

    PubMed

    Rizo, Hanika; Walker, Richard J; Carlson, Richard W; Horan, Mary F; Mukhopadhyay, Sujoy; Manthos, Vicky; Francis, Don; Jackson, Matthew G

    2016-05-13

    How much of Earth's compositional variation dates to processes that occurred during planet formation remains an unanswered question. High-precision tungsten isotopic data from rocks from two large igneous provinces, the North Atlantic Igneous Province and the Ontong Java Plateau, reveal preservation to the Phanerozoic of tungsten isotopic heterogeneities in the mantle. These heterogeneities, caused by the decay of hafnium-182 in mantle domains with high hafnium/tungsten ratios, were created during the first ~50 million years of solar system history, indicating that portions of the mantle that formed during Earth's primary accretionary period have survived to the present. Copyright © 2016, American Association for the Advancement of Science.

  12. Lateral amorphous selenium metal-insulator-semiconductor-insulator-metal photodetectors using ultrathin dielectric blocking layers for dark current suppression

    NASA Astrophysics Data System (ADS)

    Chang, Cheng-Yi; Pan, Fu-Ming; Lin, Jian-Siang; Yu, Tung-Yuan; Li, Yi-Ming; Chen, Chieh-Yang

    2016-12-01

    We fabricated amorphous selenium (a-Se) photodetectors with a lateral metal-insulator-semiconductor-insulator-metal (MISIM) device structure. Thermal aluminum oxide, plasma-enhanced chemical vapor deposited silicon nitride, and thermal atomic layer deposited (ALD) aluminum oxide and hafnium oxide (ALD-HfO2) were used as the electron and hole blocking layers of the MISIM photodetectors for dark current suppression. A reduction in the dark current by three orders of magnitude can be achieved at electric fields between 10 and 30 V/μm. The effective dark current suppression is primarily ascribed to electric field lowering in the dielectric layers as a result of charge trapping in deep levels. Photogenerated carriers in the a-Se layer can be transported across the blocking layers to the Al electrodes via Fowler-Nordheim tunneling because a high electric field develops in the ultrathin dielectric layers under illumination. Since the a-Se MISIM photodetectors have a very low dark current without significant degradation in the photoresponse, the signal contrast is greatly improved. The MISIM photodetector with the ALD-HfO2 blocking layer has an optimal signal contrast more than 500 times the contrast of the photodetector without a blocking layer at 15 V/μm.

  13. Oxidized limonene and oxidized linalool - concomitant contact allergy to common fragrance terpenes.

    PubMed

    Bråred Christensson, Johanna; Karlberg, Ann-Therese; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Giménez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

    2016-05-01

    Limonene and linalool are common fragrance terpenes. Both oxidized R-limonene and oxidized linalool have recently been patch tested in an international setting, showing contact allergy in 5.2% and 6.9% of dermatitis patients, respectively. To investigate concomitant reactions between oxidized R-limonene and oxidized linalool in consecutive dermatitis patients. Oxidized R-limonene 3.0% (containing limonene hydroperoxides 0.33%) and oxidized linalool 6% (linalool hydroperoxides 1%) in petrolatum were tested in 2900 consecutive dermatitis patients in Australia, Denmark, Singapore, Spain, Sweden, and the United Kingdom. A total of 281 patients reacted to either oxidized R-limonene or oxidized linalool. Of these, 25% had concomitant reactions to both compounds, whereas 29% reacted only to oxidized R-limonene and 46% only to oxidized linalool. Of the 152 patients reacting to oxidized R-limonene, 46% reacted to oxidized linalool, whereas 35% of the 200 patients reacting to oxidized linalool also reacted to oxidized R-limonene. The majority of the patients (75%) reacted to only one of the oxidation mixtures, thus supporting the specificity of the reactions. The concomitant reactions to the two fragrance allergens suggest multiple sensitizations, which most likely reflect the exposure to the different fragrance materials in various types of consumer products. This is in accordance with what is generally seen for patch test reactions to fragrance materials. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  14. Oxidation of silicon nitride sintered with rare-earth oxide additions

    NASA Technical Reports Server (NTRS)

    Mieskowski, D. M.; Sanders, W. A.

    1985-01-01

    The effects of rare-earth oxide additions on the oxidation of sintered Si3N4 were examined. Insignificant oxidation occurred at 700 and 1000 C, with no evidence of phase instability. At 1370 C, the oxidation rate was lowest for Y2O3 and increased for additions of La2O3, Sm2O3, and CeO2, in that order. Data obtained from X-ray diffraction, electron microprobe analysis, and scanning electron microscopy indicate that oxidation occurs via diffusion of cationic species from Si3N4 grain boundaries.

  15. Charge Trapping in Low Temperature MOS (Metal-Oxide-Silicon) Oxides.

    DTIC Science & Technology

    1984-08-24

    high pressure thermal oxidation (HIPOX). The LPCVD process involved reaction of dichlorosilane with nitrous oxide. The HIPOX process involved dry...oxygen. The LPCVD and HIPOX films were subjected to a variety of annealing treatments. We have systematically investigated the effects of these treatments...systematically altered by annealing treatments. In general, the electron traps in LPCVD oxide films produced by the nitrous oxide- dichlorosilane

  16. Structural, electronic and chemical properties of metal/oxide and oxide/oxide interfaces and thin film structures

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

    Lad, Robert J.

    1999-12-14

    This project focused on three different aspects of oxide thin film systems: (1) Model metal/oxide and oxide/oxide interface studies were carried out by depositing ultra-thin metal (Al, K, Mg) and oxide (MgO, AlO{sub x}) films on TiO{sub 2}, NiO and {alpha}-Al{sub 2}O{sub 3} single crystal oxide substrates. (2) Electron cyclotron resonance (ECR) oxygen plasma deposition was used to fabricate AlO{sub 3} and ZrO{sub 2} films on sapphire substrates, and film growth mechanisms and structural characteristics were investigated. (3) The friction and wear characteristics of ZrO{sub 2} films on sapphire substrates in unlubricated sliding contact were studied and correlated with filmmore » microstructure. In these studies, thin film and interfacial regions were characterized using diffraction (RHEED, LEED, XRD), electron spectroscopies (XPS, UPS, AES), microscopy (AFM) and tribology instruments (pin-on-disk, friction microprobe, and scratch tester). By precise control of thin film microstructure, an increased understanding of the structural and chemical stability of interface regions and tribological performance of ultra-thin oxide films was achieved in these important ceramic systems.« less

  17. Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

    NASA Astrophysics Data System (ADS)

    Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

    2016-12-01

    Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be

  18. New insight of high temperature oxidation on self-exfoliation capability of graphene oxide.

    PubMed

    Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

    2018-05-04

    The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

  19. New insight of high temperature oxidation on self-exfoliation capability of graphene oxide

    NASA Astrophysics Data System (ADS)

    Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

    2018-05-01

    The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

  20. Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

    PubMed

    Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

    2012-11-20

    A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

  1. Photo-oxidation catalysts

    DOEpatents

    Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  2. Separate Nitrite, Nitric Oxide, and Nitrous Oxide Reducing Fractions from Pseudomonas perfectomarinus

    PubMed Central

    Payne, W. J.; Riley, P. S.; Cox, C. D.

    1971-01-01

    Pseudomonas perfectomarinus was found to grow anaerobically at the expense of nitrate, nitrite, or nitrous oxide but not chlorate or nitric oxide. In several repetitive experiments, anaerobic incubation in culture media containing nitrate revealed that an average of 82% of the cells in aerobically grown populations were converted to the capacity for respiration of nitrate. Although they did not form colonies under these conditions, the bacteria synthesized the denitrifying enzymes within 3 hr in the absence of oxygen or another acceptable inorganic oxidant. This was demonstrated by the ability, after anaerobic incubation, of cells and of extracts to reduce nitrite, nitric oxide, and nitrous oxide to nitrogen. From crude extracts of cells grown on nitrate, nitrite, or nitrous oxide, separate complex fractions were obtained that utilized reduced nicotinamide adenine dinucleotide as the source of electrons for the reduction of (i) nitrite to nitric oxide, (ii) nitric oxide to nitrous oxide, and (iii) nitrous oxide to nitrogen. Gas chromatographic analyses revealed that each of these fractions reduced only one of the nitrogenous oxides. PMID:4324803

  3. X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

    PubMed

    Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

    2014-08-14

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  5. Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

    DOEpatents

    Clay, David T.; Lynn, Scott

    1976-10-19

    A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

  6. Structural Characterization of Oxidized Glycerophosphatidylserine: Evidence of Polar Head Oxidation

    NASA Astrophysics Data System (ADS)

    Maciel, Elisabete; da Silva, Raquel Nunes; Simões, Cláudia; Domingues, Pedro; Domingues, M. Rosário M.

    2011-10-01

    Non-oxidized phosphatidylserine (PS) is known to play a key role in apoptosis but there is considerable research evidence suggesting that oxidized PS also plays a role in this event, leading to the increasing interest in studying PS oxidative modifications. In this work, different PS (1-palmitoyl-2-linoleoyl-sn-glycero-3-phospho-L-serine (PLPS), 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-L-serine (POPS), and 1,2-dipalmitoyl-sn-glycero-3-phospho-L-serine (DPPS) were oxidized in vitro by hydroxyl radical, generated under Fenton reaction conditions, and the reactions were monitored by ESI-MS in negative mode. Oxidation products were then fractionated by thin layer chromatography (TLC) and characterized by tandem mass spectrometry (MS/MS). This approach allowed the identification of hydroxyl, peroxy, and keto derivatives due to oxidation of unsaturated fatty acyl chains. Oxidation products due to oxidation of serine polar head were also identified. These products, with lower molecular weight than the non-modified PS, were identified as [M - 29 - H]- (terminal acetic acid), [M - 30 - H]- (terminal acetamide), [M - 13 - H]- (terminal hydroperoxyacetaldehyde), and [M - 13 - H]- (terminal hydroxyacetaldehyde plus hydroxy fatty acyl chain). Phosphatidic acid was also formed in these conditions. These findings confirm the oxidation of the serine polar head induced by the hydroxyl radical. The identification of these modifications may be a valuable tool to evaluate phosphatidylserine alteration under physiopathologic conditions and also to help understand the biological role of phosphatidylserine oxidation in the apoptotic process and other biological functions.

  7. 21 CFR 172.808 - Copolymer condensates of ethylene oxide and propylene oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Copolymer condensates of ethylene oxide and... ethylene oxide and propylene oxide. Copolymer condensates of ethylene oxide and propylene oxide may be... percent aqueous solution. (2) α-Hydro-omega-hydroxy-poly (oxy-ethylene)poly(oxypropylene)-(53-59 moles...

  8. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks

    PubMed Central

    Jones, J. Graham; Warner, C. G.

    1972-01-01

    Graham Jones, J., and Warner, C. G. (1972).Brit. J. industr. Med.,29, 169-177. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks. Occupational and medical histories, smoking habits, respiratory symptoms, chest radiographs, and ventilatory capacities were studied in 14 steelworkers employed as deseamers of steel ingots for periods of up to 16 years. The men were exposed for approximately five hours of each working shift to fume concentrations ranging from 1·3 to 294·1 mg/m3 made up mainly of iron oxide with varying proportions of chromium oxide and nickel oxide. Four of the men, with 14 to 16 years' exposure, showed radiological evidence of pneumoconiosis classified as ILO categories 2 or 3. Of these, two had pulmonary function within the normal range and two had measurable loss of function, moderate in one case and mild in the other. Many observers would diagnose these cases as siderosis but the authors consider that this term should be reserved for cases exposed to pure iron compounds. The correct diagnosis is mixed-dust pneumoconiosis and the loss of pulmonary function is caused by the effects of the mixture of metallic oxides. It is probable that inhalation of pure iron oxide does not cause fibrotic pulmonary changes, whereas the inhalation of iron oxide plus certain other substances obviously does. Images PMID:5021996

  9. Oxidation resistant alloys, method for producing oxidation resistant alloys

    DOEpatents

    Dunning, John S.; Alman, David E.

    2002-11-05

    A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800 C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800 C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700 C. at a low cost

  10. 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.

  11. 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

  12. Investigation of Mixed Oxide Catalysts for NO Oxidation

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

    Szanyi, Janos; Karim, Ayman M.; Pederson, Larry R.

    2014-12-09

    The oxidation of engine-generated NO to NO2 is an important step in the reduction of NOx in lean engine exhaust because NO2 is required for the performance of the LNT technology [2], and it enhances the activities of ammonia selective catalytic reduction (SCR) catalysts [1]. In particular, for SCR catalysts an NO:NO2 ratio of 1:1 is most effective for NOx reduction, whereas for LNT catalysts, NO must be oxidized to NO2 before adsorption on the storage components. However, NO2 typically constitutes less than 10% of NOx in lean exhaust, so catalytic oxidation of NO is essential. Platinum has been foundmore » to be especially active for NO oxidation, and is widely used in DOC and LNT catalysts. However, because of the high cost and poor thermal durability of Pt-based catalysts, there is substantial interest in the development of alternatives. The objective of this project, in collaboration with partner General Motors, is to develop mixed metal oxide catalysts for NO oxidation, enabling lower precious metal usage in emission control systems. [1] M. Koebel, G. Madia, and M. Elsener, Catalysis Today 73, 239 (2002). [2] C. H. Kim, G. S. Qi, K. Dahlberg, and W. Li, Science 327, 1624 (2010).« less

  13. Oxidation of artificial sweetener sucralose by advanced oxidation processes: a review.

    PubMed

    Sharma, Virender K; Oturan, Mehmet; Kim, Hyunook

    2014-01-01

    Sucralose, a chlorinated carbohydrate, has shown its increased use as an artificial sweetener and persistently exists in wastewater treatment plant effluents and aquatic environment. This paper aims to review possible degradation of sucralose and related carbohydrates by biological, electrochemical, chemical, and advanced oxidation processes. Biodegradation of sucralose in waterworks did not occur significantly. Electrochemical oxidation of carbohydrates may be applied to seek degradation of sucralose. The kinetics of the oxidation of sucralose and the related carbohydrates by different oxidative species is compared. Free chlorine, ozone, and ferrate did not show any potential to degrade sucralose in water. Advanced oxidation processes, generating highly strong oxidizing agent hydroxyl radicals ((•)OH), have demonstrated effectiveness in transforming sucralose in water. The mechanism of oxidation of sucralose by (•)OH is briefly discussed.

  14. Improved Understanding of In Situ Chemical Oxidation Contaminant Oxidation Kinetics

    DTIC Science & Technology

    2007-12-01

    natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE perchloroethylene HSO5− peroxymonosulfate PNDA p...properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and stability in the subsurface, and develop a standardized natural...chlorinated ethenes For contaminant oxidation by activated S2O82−, it is more difficult to develop a general description of kobs vs. T because there are

  15. Oxidation of nitroxyl anion to nitric oxide by copper ions

    PubMed Central

    Nelli, Silvia; Hillen, Mark; Buyukafsar, Kansu; Martin, William

    2000-01-01

    This study made use of a nitric oxide-sensitive electrode to examine possible means of generating nitric oxide from nitroxyl anion (NO−) released upon the decomposition of Angeli's salt. Our results show that copper ions (from CuSO4) catalyze the rapid and efficient oxidation of nitroxyl to nitric oxide. Indeed, the concentrations of copper required to do so (0.1–100 μM) are roughly 100-times lower than those required to generate equivalent amounts of nitric oxide from S-nitroso-N-acetyl-D,L-penicillamine (SNAP). Experiments with ascorbate (1 mM), which reduces Cu2+ ions to Cu+, and with the Cu2+ chelators, EDTA and cuprizone, and the Cu+ chelator, neocuproine, each at 1 mM, suggest that the oxidation is catalyzed by copper ions in both valency states. Some compounds containing other transition metals, i.e. methaemoglobin, ferricytochrome c and Mn(III)TMPyP, were much less efficient than CuSO4 in catalyzing the formation of nitric oxide from nitroxyl, while FeSO4, FeCl3, MnCl2, and ZnSO4 were inactive. Of the copper containing enzymes examined, Cu-Zn superoxide dismutase and ceruloplasmin were weak generators of nitric oxide from nitroxyl, even at concentrations (2500 and 30 u ml−1, respectively) vastly greater than are present endogenously. Two others, ascorbate oxidase (10 u ml−1) and tyrosinase (250 u ml−1) were inactive. Our findings suggest that a copper-containing enzyme may be responsible for the rapid oxidation of nitroxyl to nitric oxide by cells, but the identity of such an enzyme remains elusive. PMID:10991931

  16. Reproductive Benefit of Oxidative Damage: An Oxidative Stress “Malevolence”?

    PubMed Central

    Poljsak, B.; Milisav, I.; Lampe, T.; Ostan, I.

    2011-01-01

    High levels of reactive oxygen species (ROS) compared to antioxidant defenses are considered to play a major role in diverse chronic age-related diseases and aging. Here we present an attempt to synthesize information about proximate oxidative processes in aging (relevant to free radical or oxidative damage hypotheses of aging) with an evolutionary scenario (credited here to Dawkins hypotheses) involving tradeoffs between the costs and benefits of oxidative stress to reproducing organisms. Oxidative stress may be considered a biological imperfection; therefore, the Dawkins' theory of imperfect adaptation of beings to environment was applied to the role of oxidative stress in processes like famine and infectious diseases and their consequences at the molecular level such as mutations and cell signaling. Arguments are presented that oxidative damage is not necessarily an evolutionary mistake but may be beneficial for reproduction; this may prevail over its harmfulness to health and longevity in evolution. Thus, Dawkins' principle of biological “malevolence” may be an additional biological paradigm for explaining the consequences of oxidative stress. PMID:21969876

  17. Influence of dielectric protective layer on laser damage resistance of gold coated gratings

    NASA Astrophysics Data System (ADS)

    Wu, Kepeng; Ma, Ping; Pu, Yunti; Xia, Zhilin

    2016-03-01

    Aiming at the problem that the damage threshold of gold coated grating is relatively low, a dielectric film is considered on the gold coated gratings as a protective layer. The thickness range of the protective layer is determined under the prerequisite that the diffraction efficiency of the gold coated grating is reduced to an acceptable degree. In this paper, the electromagnetic field, the temperature field and the stress field distribution in the grating are calculated when the silica and hafnium oxide are used as protective layers, under the preconditions of the electromagnetic field distribution of the gratings known. The results show that the addition of the protective layer changes the distribution of the electromagnetic field, temperature field and stress field in the grating, and the protective layer with an appropriate thickness can improve the laser damage resistance of the grating.

  18. Stable tetragonal phase and magnetic properties of Fe-doped HfO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Sales, T. S. N.; Cavalcante, F. H. M.; Bosch-Santos, B.; Pereira, L. F. D.; Cabrera-Pasca, G. A.; Freitas, R. S.; Saxena, R. N.; Carbonari, A. W.

    2017-05-01

    In this paper, the effect in structural and magnetic properties of iron doping with concentration of 20% in hafnium dioxide (HfO2) nanoparticles is investigated. HfO2 is a wide band gap oxide with great potential to be used as high-permittivity gate dielectrics, which can be improved by doping. Nanoparticle samples were prepared by sol-gel chemical method and had their structure, morphology, and magnetic properties, respectively, investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) with electron back scattering diffraction (EBSD), and magnetization measurements. TEM and SEM results show size distribution of particles in the range from 30 nm to 40 nm with small dispersion. Magnetization measurements show the blocking temperature at around 90 K with a strong paramagnetic contribution. XRD results show a major tetragonal phase (94%).

  19. Nanostructured transition metal oxides useful for water oxidation catalysis

    DOEpatents

    Frei, Heinz M; Jiao, Feng

    2013-12-24

    The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

  20. Oxidation resistant alloys, method for producing oxidation resistant alloys

    DOEpatents

    Dunning, John S.; Alman, David E.

    2002-11-05

    A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800.degree. C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800.degree. C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700.degree. C. at a low cost

  1. UV Induced Oxidation of Nitric Oxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde, F. (Inventor); Luecke, Dale E. (Inventor)

    2007-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated at least in part using in situ UV radiation sources. The sources of the oxidizing species include oxygen and/or hydrogen peroxide. The oxygen may be a component of the gaseous stream or added to the gaseous stream, preferably near a UV radiation source, and is converted to ozone by the UV irradiation. The hydrogen peroxide is decomposed through a combination of vaporization and UV irradiation. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50% by volume and increased in concentration in a continuous process preceding vaporization within the flow channel of the gaseous stream and in the presence of the UV radiation sources.

  2. Some Properties of Beryllium Oxide and Beryllium Oxide - Columbium Ceramals

    NASA Technical Reports Server (NTRS)

    Robards, C F; Gangler, J J

    1951-01-01

    High-temperature tensile and thermal-shock investigations were conducted on beryllium oxide and beryllium oxide plus columbium metal additions. X-ray diffraction and metallographic results are given. The tensile strength of 6150 pounds per square inch for beryllium oxide at 1800 degrees F compared favorably with the zirconia bodies previously tested. Additions of 2, 5, 8, 10, 12, and 15 percent by weight of columbium metal failed to improve the shock resistance over that of pure beryllium oxide.

  3. Partial oxidation catalyst

    DOEpatents

    Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

    2000-01-01

    A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

  4. Growth control of the oxidation state in vanadium oxide thin films

    DOE PAGES

    Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; ...

    2014-12-05

    Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metalinsulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V₂⁺²O₃, V⁺⁴O₂, and V₂⁺⁵O₅. A well pronounced MIT was only observed in VO₂ films grown in a very narrow range of oxygen partial pressure P(O₂). The films grown either in lower (< 10 mTorr) or higher P(O₂) (> 25 mTorr) result in V₂O₃ and V₂O₅ phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO₂ thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an 3 improved MIT behavior.« less

  5. Growth control of the oxidation state in vanadium oxide thin films

    NASA Astrophysics Data System (ADS)

    Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; Egami, Takeshi; Lee, Ho Nyung

    2014-12-01

    Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V2 + 3 O 3 , V + 4 O 2 , and V2 + 5 O 5 . A well pronounced MIT was only observed in VO2 films grown in a very narrow range of oxygen partial pressure P(O2). The films grown either in lower (<10 mTorr) or higher P(O2) (>25 mTorr) result in V2O3 and V2O5 phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO2 thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.

  6. Oxidation stress evolution and relaxation of oxide film/metal substrate system

    NASA Astrophysics Data System (ADS)

    Dong, Xuelin; Feng, Xue; Hwang, Keh-Chih

    2012-07-01

    Stresses in the oxide film/metal substrate system are crucial to the reliability of the system at high temperature. Two models for predicting the stress evolution during isothermal oxidation are proposed. The deformation of the system is depicted by the curvature for single surface oxidation. The creep strain of the oxide and metal, and the lateral growth strain of the oxide are considered. The proposed models are compared with the experimental results in literature, which demonstrates that the elastic model only considering for elastic strain gives an overestimated stress in magnitude, but the creep model is consistent with the experimental data and captures the stress relaxation phenomenon during oxidation. The effects of the parameter for the lateral growth strain rate are also analyzed.

  7. Role of oxidative stress and nitric oxide in atherothrombosis

    PubMed Central

    Lubos, Edith; Handy, Diane E.; Loscalzo, Joseph

    2008-01-01

    During the last decade basic and clinical research has highlighted the central role of reactive oxygen species (ROS) in cardiovascular disease. Enhanced production or attenuated degradation of ROS leads to oxidative stress, a process that affects endothelial and vascular function, and contributes to vascular disease. Nitric oxide (NO), a product of the normal endothelium, is a principal determinant of normal endothelial and vascular function. In states of inflammation, NO production by the vasculature increases considerably and, in conjunction with other ROS, contributes to oxidative stress. This review examines the role of oxidative stress and NO in mechanisms of endothelial and vascular dysfunction with an emphasis on atherothrombosis. PMID:18508590

  8. A change in the geodynamics of continental growth 3 billion years ago.

    PubMed

    Dhuime, Bruno; Hawkesworth, Chris J; Cawood, Peter A; Storey, Craig D

    2012-03-16

    Models for the growth of continental crust rely on knowing the balance between the generation of new crust and the reworking of old crust throughout Earth's history. The oxygen isotopic composition of zircons, for which uranium-lead and hafnium isotopic data provide age constraints, is a key archive of crustal reworking. We identified systematic variations in hafnium and oxygen isotopes in zircons of different ages that reveal the relative proportions of reworked crust and of new crust through time. Growth of continental crust appears to have been a continuous process, albeit at variable rates. A marked decrease in the rate of crustal growth at ~3 billion years ago may be linked to the onset of subduction-driven plate tectonics.

  9. Oxidized film structure and method of making epitaxial metal oxide structure

    DOEpatents

    Gan, Shupan [Richland, WA; Liang, Yong [Richland, WA

    2003-02-25

    A stable oxidized structure and an improved method of making such a structure, including an improved method of making an interfacial template for growing a crystalline metal oxide structure, are disclosed. The improved method comprises the steps of providing a substrate with a clean surface and depositing a metal on the surface at a high temperature under a vacuum to form a metal-substrate compound layer on the surface with a thickness of less than one monolayer. The compound layer is then oxidized by exposing the compound layer to essentially oxygen at a low partial pressure and low temperature. The method may further comprise the step of annealing the surface while under a vacuum to further stabilize the oxidized film structure. A crystalline metal oxide structure may be subsequently epitaxially grown by using the oxidized film structure as an interfacial template and depositing on the interfacial template at least one layer of a crystalline metal oxide.

  10. Oxidation resistance of silicon ceramics

    NASA Technical Reports Server (NTRS)

    Yasutoshi, H.; Hirota, K.

    1984-01-01

    Oxidation resistance, and examples of oxidation of SiC, Si3N4 and sialon are reviewed. A description is given of the oxidation mechanism, including the oxidation product, oxidation reaction and the bubble size. The oxidation reactions are represented graphically. An assessment is made of the oxidation process, and an oxidation example of silicon ceramics is given.

  11. Growth control of the oxidation state in vanadium oxide thin films

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

    Lee, Shinbuhm; Meyer, Tricia L.; Lee, Ho Nyung, E-mail: hnlee@ornl.gov

    2014-12-01

    Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V{sub 2}{sup +3}O{sub 3}, V{sup +4}O{sub 2}, and V{sub 2}{sup +5}O{sub 5}. A well pronounced MIT was only observed in VO{sub 2} films grown in a very narrow range of oxygen partial pressure P(O{sub 2}). The films grown either in lower (<10 mTorr) or higher P(O{sub 2}) (>25 mTorr) result in V{sub 2}O{sub 3} and V{sub 2}O{sub 5} phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO{sub 2} thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.« less

  12. Liquid-phase oxidation of cyclohexanone over cerium oxide catalyst

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

    Shen, H.C.; Weng, H.S.

    Catalytic oxidation of cyclohexanone in the liquid phase with glacial acetic acid as the solvent over cerium oxide was studied between 5 and 15 atm and 98 and 118 {degrees} C in a batch reactor. The products were adipic acid, glutaric acid, succinic acid, caprolactone, carbon oxides, etc. The reaction undergoes a short induction period prior to a rapid reaction regime. In both regimes, the reaction is independent of oxygen pressure when the system pressure is above 10 atm. The induction period is inversely proportional to both of the catalyst weight and cyclohexanone concentration.During the rapid reaction regime, the reactionmore » rate was found to be proportional to the 0.5 power of the catalyst weight and to the 1.5 power of the cyclohexanone concentration. Reaction mechanisms and rate expressions are proposed. The carbon oxides produced in this study were much lower than those previously reported. The cerium oxide catalyst is stable during the reaction.« less

  13. Electrospinning of ceramic nanofibers

    NASA Astrophysics Data System (ADS)

    Eick, Benjamin M.

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

  14. Niche differentiation of ammonia oxidizers and nitrite oxidizers in rice paddy soil.

    PubMed

    Ke, Xiubin; Angel, Roey; Lu, Yahai; Conrad, Ralf

    2013-08-01

    The dynamics of populations and activities of ammonia-oxidizing and nitrite-oxidizing microorganisms were investigated in rice microcosms treated with two levels of nitrogen. Different soil compartments (surface, bulk, rhizospheric soil) and roots (young and old roots) were collected at three time points (the panicle initiation, heading and maturity periods) of the season. The population dynamics of bacterial (AOB) and archaeal (AOA) ammonia oxidizers was assayed by determining the abundance (using qPCR) and composition (using T-RFLP and cloning/sequencing) of their amoA genes (coding for a subunit of ammonia monooxygenase), that of nitrite oxidizers (NOB) by quantifying the nxrA gene (coding for a subunit of nitrite oxidase of Nitrobacter spp.) and the 16S rRNA gene of Nitrospira spp. The activity of the nitrifiers was determined by measuring the rates of potential ammonia oxidation and nitrite oxidation and by quantifying the copy numbers of amoA and nxrA transcripts. Potential nitrite oxidation activity was much higher than potential ammonia oxidation activity and was not directly affected by nitrogen amendment demonstrating the importance of ammonia oxidizers as pace makers for nitrite oxidizer populations. Marked differences in the distribution of bacterial and archaeal ammonia oxidizers, and of Nitrobacter-like and Nitrospira-like nitrite oxidizers were found in the different compartments of planted paddy soil indicating niche differentiation. In bulk soil, ammonia-oxidizing bacteria (Nitrosospira and Nitrosomonas) were at low abundance and displayed no activity, but in surface soil their activity and abundance was high. Nitrite oxidation in surface soil was dominated by Nitrospira spp. By contrast, ammonia-oxidizing Thaumarchaeota and Nitrobacter spp. seemed to dominate nitrification in rhizospheric soil and on rice roots. In contrast to soil compartment, the level of N fertilization and the time point of sampling had only little effect on the abundance

  15. Oxidation of Haynes 230 alloy in reduced temperature solid oxide fuel cell environments

    NASA Astrophysics Data System (ADS)

    Jian, Li; Jian, Pu; Jianzhong, Xiao; Xiaoliang, Qian

    Haynes 230 alloy was exposed to reducing and oxidizing environments at 750 °C for 1000 h, simulating the conditions in a reduced temperature solid oxide fuel cell (SOFC). The oxidized specimens were characterized in terms of the oxide morphology, composition and crystal structure. The oxide scale in each environment was identified as Cr 2O 3 with the existence of Cr 2MnO 4. Ni remained metallic in the reducing atmosphere, and NiO was detected in the sample exposed to air. The oxide scale is around 1 μm thick after 1000 h of oxidation in both situations. The area specific resistance (ASR) contributed by the oxide scale is expected less than 0.1 Ω cm 2 after 40,000 h of exposure when a parabolic oxide growth rate is assumed, demonstrating the suitability of the interconnect application of this alloy in the reduced temperature SOFCs.

  16. Improved Understanding of In Situ Chemical Oxidation. Technical Objective I: Contaminant Oxidation Kinetics Contaminant Oxidation Kinetics

    DTIC Science & Technology

    2009-05-01

    methyl tert butyl ether NAPL non-aqueous phase liquid NOD natural oxidant demand •OH hydroxide radical Ox oxidant O3 ozone PCE...and persulfate; and Technical Objective 2, assess how soil properties (e.g., soil mineralogy , natural carbon content) affect oxidant mobility and...to develop a general description of kobs vs. T because there are many reactions that can contribute to the concentration of the reactive intermediate

  17. Ambient temperature NO oxidation over Cr-based amorphous mixed oxide catalysts: effects from the second oxide components

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

    Wang, Aiyong; Lin, Bo; Zhang, Hanlei

    2017-01-01

    Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures were synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. The best performing catalysts achieve 100% NO conversion for ~30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure was found to be critical for these catalysts to maintain high activity and durability. Control of Cr/M (M=Co, Fe andmore » Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature was key to the synthesis of these highly active catalysts.« less

  18. Diversity of Mn oxides produced by Mn(II)-oxidizing fungi

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

    Santelli, Cara M.; Webb, Samuel M.; Dohnalkova, Alice

    Manganese (Mn) oxides are environmentally abundant, highly reactive mineral phases that mediate the biogeochemical cycling of nutrients, contaminants, carbon, and numerous other elements. Despite the belief that microorganisms (specifically bacteria and fungi) are responsible for the majority of Mn oxide formation in the environment, the impact of microbial species, physiology, and growth stage on Mn oxide formation is largely unresolved. Here, we couple microscopic and spectroscopic techniques to characterize the Mn oxides produced by four different species of Mn(II)-oxidizing Ascomycete fungi (Plectosphaerella cucumerina strain DS2psM2a2, Pyrenochaeta sp. DS3sAY3a, Stagonospora sp. SRC1lsM3a, and Acremonium strictum strain DS1bioAY4a) isolated from acid minemore » drainage treatment systems in central Pennsylvania. The site of Mn oxide formation varies greatly among the fungi, including deposition on hyphal surfaces, at the base of reproductive structures (e.g., fruiting bodies), and on envisaged extracellular polymers adjacent to the cell. The primary product of Mn(II) oxidation for all species growing under the same chemical and physical conditions is a nanoparticulate, poorly-crystalline hexagonal birnessite-like phase resembling synthetic d-MnO2. The phylogeny and growth conditions (planktonic versus surface-attached) of the fungi, however, impact the conversion of the initial phyllomanganate to more ordered phases, such as todorokite (A. strictum strain DS1bioAY4a) and triclinic birnessite (Stagonospora sp. SRC1lsM3a). Our findings reveal that the species of Mn(II)-oxidizing fungi impacts the size, morphology, and structure of Mn biooxides, which will likely translate to large differences in the reactivity of the Mn oxide phases.« less

  19. Oxidizer Scoping Studies

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

    Chancellor, Christopher John

    2016-11-07

    The purpose of this report is to present the results of the acceptable knowledge (AK) review of oxidizers present in active waste streams, provide a technical analysis of the oxidizers, and report the results of the scoping study testing. This report will determine the fastest burning oxidizer to be used in the development of a Test Plan for Preparation and Testing of Sorbents Mixed with Oxidizer found in Transuranic Waste (DWT-TP-001). The companion report, DWT-RPT-002, Sorbent Scoping Studies, contains similar information for sorbents identified during the AK review of TRU waste streams. The results of the oxidizer and sorbent scopingmore » studies will be used to inform the QL1 test plan. The QL1 test results will support the development of a basis of knowledge document that will evaluate oxidizing chemicals and sorbents in TRU waste and provide guidance for treatment.« less

  20. Metal oxide-polymer composites

    NASA Technical Reports Server (NTRS)

    Wellinghoff, Stephen T. (Inventor)

    1997-01-01

    A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

  1. Metal oxide-polymer composites

    NASA Technical Reports Server (NTRS)

    Wellinghoff, Stephen T. (Inventor)

    1994-01-01

    A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

  2. Interfacial structure and electrical properties of ultrathin HfO2 dielectric films on Si substrates by surface sol-gel method

    NASA Astrophysics Data System (ADS)

    Gong, You-Pin; Li, Ai-Dong; Qian, Xu; Zhao, Chao; Wu, Di

    2009-01-01

    Ultrathin HfO2 films with about ~3 nm thickness were deposited on n-type (1 0 0) silicon substrates using hafnium chloride (HfCl4) source by the surface sol-gel method and post-deposition annealing (PDA). The interfacial structure and electrical properties of ultrathin HfO2 films were investigated. The HfO2 films show amorphous structures and smooth surface morphologies with a very thin interfacial oxide layer of ~0.5 nm and small surface roughness (~0.45 nm). The 500 °C PDA treatment forms stronger Hf-O bonds, leading to passivated traps, and the interfacial layer is mainly Hf silicate (HfxSiyOz). Equivalent oxide thickness of around 0.84 nm of HfO2/Si has been obtained with a leakage current density of 0.7 A cm-2 at Vfb + 1 V after 500 °C PDA. It was found that the current conduction mechanism of HfO2/Si varied from Schottky-Richardson emission to Fowler-Nordheim tunnelling at an applied higher positive voltage due to the activated partial traps remaining in the ultrathin HfO2 films.

  3. Evaluation of thermal stability in spectrally selective few-layer metallo-dielectric structures for solar thermophotovoltaics

    NASA Astrophysics Data System (ADS)

    Shimizu, Makoto; Kohiyama, Asaka; Yugami, Hiroo

    2018-06-01

    The thermal stability of spectrally selective few-layer metallo-dielectric structures is evaluated to analyze their potential as absorber and emitter materials in solar thermophotovoltaic (STPV) systems. High-efficiency (e.g., STPV) systems require materials with spectrally selective properties, especially at high temperatures (>1273 K). Aiming to develop such materials for high-temperature applications, we propose a few-layer structure composed of a refractory metal (i.e., Mo) nanometric film sandwiched between the layers of a dielectric material (i.e., hafnium oxide, HfO2) deposited on a Mo bulk substrate. In vacuum conditions (<5 × 10-2 Pa), the few-layer structure shows thermal stability at 1423 K for at least 1 h. At 1473 K, the spectral selectivity was degraded. This could have been caused by the oxidation of the Mo thin film by the residual oxygen through the grain boundaries of the upper HfO2 layer. This experiment showed the potential stability of few-layer structures for applications working at temperatures greater than 1273 K as well as the degradation mechanism of the few-layer structure. This characteristic is expected to help improve the thermal stability in few-layer structures further.

  4. Surface Passivation of Silicon Using HfO2 Thin Films Deposited by Remote Plasma Atomic Layer Deposition System.

    PubMed

    Zhang, Xiao-Ying; Hsu, Chia-Hsun; Lien, Shui-Yang; Chen, Song-Yan; Huang, Wei; Yang, Chih-Hsiang; Kung, Chung-Yuan; Zhu, Wen-Zhang; Xiong, Fei-Bing; Meng, Xian-Guo

    2017-12-01

    Hafnium oxide (HfO 2 ) thin films have attracted much attention owing to their usefulness in equivalent oxide thickness scaling in microelectronics, which arises from their high dielectric constant and thermodynamic stability with silicon. However, the surface passivation properties of such films, particularly on crystalline silicon (c-Si), have rarely been reported upon. In this study, the HfO 2 thin films were deposited on c-Si substrates with and without oxygen plasma pretreatments, using a remote plasma atomic layer deposition system. Post-annealing was performed using a rapid thermal processing system at different temperatures in N 2 ambient for 10 min. The effects of oxygen plasma pretreatment and post-annealing on the properties of the HfO 2 thin films were investigated. They indicate that the in situ remote plasma pretreatment of Si substrate can result in the formation of better SiO 2 , resulting in a better chemical passivation. The deposited HfO 2 thin films with oxygen plasma pretreatment and post-annealing at 500 °C for 10 min were effective in improving the lifetime of c-Si (original lifetime of 1 μs) to up to 67 μs.

  5. A molecular catalyst for water oxidation that binds to metal oxide surfaces

    PubMed Central

    Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich; Crabtree, Robert H.; Brudvig, Gary W.; Schmuttenmaer, Charles A.

    2015-01-01

    Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425

  6. Alkali oxide-tantalum, niobium and antimony oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Brower, W. S.; Parker, H. S.; Minor, D. B.; Waring, J. L.

    1975-01-01

    The phase equilibrium relations of four systems were investigated in detail. These consisted of sodium and potassium antimonates with antimony oxide and tantalum and niobium oxide with rubidium oxide as far as the ratio 4Rb2O:llB2O5 (B=Nb, Ta). The ternary system NaSbO3-Sb2O4-NaF was investigated extensively to determine the actual composition of the body centered cubic sodium antimonate. Various other binary and ternary oxide systems involving alkali oxides were examined in lesser detail. The phases synthesized were screened by ion exchange methods to determine mobility of the mobility of the alkali ion within the niobium, tantalum or antimony oxide (fluoride) structural framework. Five structure types warranted further investigation; these structure types are (1) hexagonal tungsten bronze (HTB), (2) pyrochlore, (3) the hybrid HTB-pyrochlore hexagonal ordered phases, (4) body centered cubic antimonates and (5) 2K2O:3Nb2O5. Although all of these phases exhibit good ion exchange properties only the pyrochlore was prepared with Na(+) ions as an equilibrium phase and as a low porosity ceramic. Sb(+3) in the channel interferes with ionic conductivity in this case, although relatively good ionic conductivity was found for the metastable Na(+) ion exchanged analogs of RbTa2O5F and KTaWO6 pyrochlore phases.

  7. Synthesis of graphene oxide through different oxidation degrees for solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoshan; Wang, Huan; Huang, Tianjiao; Wen, Lingling; Zhou, Liya

    2018-03-01

    Graphene is known as an electro-chemical material and widely used in electro-chemical devices, especially in solar cell. Decreasing the thickness of the layer is a critical way to improve the electrochemical property of solar cells as far as possible. Among the various oxidation approaches, presented herein is a facile approach, which is easier, less cost and more effective, environmental benign with the greener processing and without any requirement for post purification, towards the synthesis of graphene oxide (GO) with different oxidation degrees by potassium ferrate (K2FeO4). A modified method using less amount of oxidizing agent is reported herein. It is the pretreatment of the synthesis of graphite, which maintains the thermal cycle of the system. This novel reports to compound GO with controlled oxidation degrees can not only increase the quantity of oxygen-containing functional groups on GO surface, increase space between graphene oxide layer and facilitate the dispersion of graphene in aqueous solution. Thus, the modified method shows prospect for large-scale production of graphene oxide and its novel application, in addition to its derivative and market potential for solar cells.

  8. Characterization of Graphite Oxide and Reduced Graphene Oxide Obtained from Different Graphite Precursors and Oxidized by Different Methods Using Raman Spectroscopy.

    PubMed

    Muzyka, Roksana; Drewniak, Sabina; Pustelny, Tadeusz; Chrubasik, Maciej; Gryglewicz, Grażyna

    2018-06-21

    In this paper, the influences of the graphite precursor and the oxidation method on the resulting reduced graphene oxide (especially its composition and morphology) are shown. Three types of graphite were used to prepare samples for analysis, and each of the precursors was oxidized by two different methods (all samples were reduced by the same method of thermal reduction). Each obtained graphite oxide and reduced graphene oxide was analysed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy (RS).

  9. Electrolytic oxidation of anthracite

    USGS Publications Warehouse

    Senftle, F.E.; Patton, K.M.; Heard, I.

    1981-01-01

    An anthracite slurry can be oxidized only with difficulty by electrolytic methods in which aqueous electrolytes are used if the slurry is confined to the region of the anode by a porous pot or diaphragm. However, it can be easily oxidized if the anthracite itself is used as the anode. No porous pot or diaphragm is needed. Oxidative consumption of the coal to alkali-soluble compounds is found to proceed preferentially at the edges of the aromatic planes. An oxidation model is proposed in which the chief oxidants are molecular and radical species formed by the electrolytic decomposition of water at the coal surface-electrolyte interface. The oxidation reactions proposed account for the opening of the aromatic rings and the subsequent formation of carboxylic acids. The model also explains the observed anisotropic oxidation and the need for the porous pot or diaphragm used in previous studies of the oxidation of coal slurries. ?? 1981.

  10. Catalytic process for formaldehyde oxidation

    NASA Technical Reports Server (NTRS)

    Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

    1996-01-01

    Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  11. Ethylene Oxide

    Cancer.gov

    Learn about ethylene oxide, which can raise your risk of lymphoma and leukemia. Exposure may occur through industrial emissions, tobacco smoke, and the use of products sterilized with ethylene oxide, such as certain medical products or cosmetics.

  12. Partial oxidation of methane (POM) assisted solid oxide co-electrolysis

    DOEpatents

    Chen, Fanglin; Wang, Yao

    2017-02-21

    Methods for simultaneous syngas generation by opposite sides of a solid oxide co-electrolysis cell are provided. The method can comprise exposing a cathode side of the solid oxide co-electrolysis cell to a cathode-side feed stream; supplying electricity to the solid oxide co-electrolysis cell such that the cathode side produces a product stream comprising hydrogen gas and carbon monoxide gas while supplying oxygen ions to an anode side of the solid oxide co-electrolysis cell; and exposing the anode side of the solid oxide co-electrolysis cell to an anode-side feed stream. The cathode-side feed stream comprises water and carbon dioxide, and the anode-side feed stream comprises methane gas such that the methane gas reacts with the oxygen ions to produce hydrogen and carbon monoxide. The cathode-side feed stream can further comprise nitrogen, hydrogen, or a mixture thereof.

  13. Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level.

    PubMed

    Javanaud, Cedric; Michotey, Valerie; Guasco, Sophie; Garcia, Nicole; Anschutz, Pierre; Canton, Mathieu; Bonin, Patricia

    2011-11-01

    Nitrite and (29)N(2) productions in slurry incubations of anaerobically sediment after (15)NO(3) or (15)NH(4) labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH(4) amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by (29)N(2) production in the presence of (15)NO(3) and (14)NH(4) under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

  14. Thermally exfoliated graphite oxide

    NASA Technical Reports Server (NTRS)

    Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

    2011-01-01

    A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

  15. Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

    NASA Astrophysics Data System (ADS)

    Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

    2018-05-01

    In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

  16. An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Sarvi, Bahram; Haghighi, Behzad

    2015-09-14

    Synthesis of new efficient catalysts inspired by Nature is a key goal in the production of clean fuel. Different compounds based on manganese oxide have been investigated in order to find their water-oxidation activity. Herein, we introduce a novel engineered polypeptide containing tyrosine around nano-sized manganese-calcium oxide, which was shown to be a highly active catalyst toward water oxidation at low overpotential (240 mV), with high turnover frequency of 1.5 × 10(-2) s(-1) at pH = 6.3 in the Mn(III)/Mn(IV) oxidation range. The compound is a novel structural and efficient functional model for the water-oxidizing complex in Photosystem II. A new proposed clever strategy used by Nature in water oxidation is also discussed. The new model of the water-oxidizing complex opens a new perspective for synthesis of efficient water-oxidation catalysts.

  17. [Immobilization of pectawamorine G10x on silichromes].

    PubMed

    Bogatskiĭ, A V; Davidenko, T I; Gren', T A

    1980-01-01

    Immobilization of pectawamorine G10x on silochromes, using cyanuric chloride, 2,4-toluylene diisocyanate, glutaric dialdehyde, thionyl chloride, phosphorus tribromide, titanium tetrachloride, zirconium oxychloride and hafnium oxychloride was studied. The use of glutaric dialdehyde assured the strongest binding and the preatest stability of activity. Properties of the native pectawamorine G10x and immobilized preparations were studied on a comparative basis. Pectawamorine G10x immobilized by means of hafnium oxychloride showed increased stability when stored at 5 degrees C and used repeatedly. In every case, except for cyanuric chloride and glutaric dialdehyde, maximum activity was at a temperature 10 degrees C higher than for the native enzyme, and optimum pH varied for the preparations with different binding reagents.

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

  19. Synthesis of Hf 8O 7, a new binary hafnium oxide, at high pressures and high temperatures

    DOE PAGES

    Bayarjargal, L.; Morgenroth, W.; Schrodt, N.; ...

    2017-01-23

    In this paper, two binary phases in the system Hf-O have been synthesized at pressures between 12 and 34 GPa and at temperatures up to 3000 K by reacting Hf with HfO 2 using a laser-heated diamond anvil cell. In situ X-ray diffraction in conjunction with density functional theory calculations has been employed to characterize a previously unreported tetragonal Hf 8O 7 phase. This phase has a structure which is based on an fcc Hf packing with oxygen atoms occupying octahedral interstitial positions. Its predicted bulk modulus is 223(1) GPa. The second phase has a composition close to Hf 6O,more » where oxygen atoms occupy octahedral interstitial sites in an hcp Hf packing. Its experimentally determined bulk modulus is 128(30) GPa. Finally, the phase diagram of Hf metal was further constrained at high pressures and temperatures, where we show that α-Hf transforms to β-Hf around 2160(150) K and 18.2 GPa and β-Hf remains stable up to at least 2800 K at this pressure.« less

  20. Laccase-Functionalized Graphene Oxide Assemblies as Efficient Nanobiocatalysts for Oxidation Reactions

    PubMed Central

    Patila, Michaela; Kouloumpis, Antonios; Gournis, Dimitrios; Rudolf, Petra; Stamatis, Haralambos

    2016-01-01

    Multi-layer graphene oxide-enzyme nanoassemblies were prepared through the multi-point covalent immobilization of laccase from Trametes versicolor (TvL) on functionalized graphene oxide (fGO). The catalytic properties of the fGO-TvL nanoassemblies were found to depend on the number of the graphene oxide-enzyme layers present in the nanostructure. The fGO-TvL nanoassemblies exhibit an enhanced thermal stability at 60 °C, as demonstrated by a 4.7-fold higher activity as compared to the free enzyme. The multi-layer graphene oxide-enzyme nanoassemblies can efficiently catalyze the oxidation of anthracene, as well as the decolorization of an industrial dye, pinacyanol chloride. These materials retained almost completely their decolorization activity after five reaction cycles, proving their potential as efficient nano- biocatalysts for various applications. PMID:26927109

  1. Platinum Electrodeposition at Unsupported Electrochemically Reduced Nanographene Oxide for Enhanced Ammonia Oxidation

    PubMed Central

    2015-01-01

    The electrochemical reduction of highly oxidized unsupported graphene oxide nanosheets and its platinum electrodeposition was done by the rotating disk slurry electrode technique. Avoiding the use of a solid electrode, graphene oxide was electrochemically reduced in a slurry solution with a scalable process without the use of a reducing agent. Graphene oxide nanosheets were synthesized from carbon platelet nanofibers to obtain highly hydrophilic layers of less than 250 nm in width. The graphene oxide and electrochemically reduced graphene oxide/Pt (erGOx/Pt) hybrid materials were characterized through different spectroscopy and microscopy techniques. Pt nanoparticles with 100 facets, clusters, and atoms at erGOx were identified by high resolution transmission electron microscopy (HRTEM). Cyclic voltammetry was used to characterize the electrocatalytic activity of the highly dispersed erGOx/Pt hybrid material toward the oxidation of ammonia, which showed a 5-fold current density increase when compared with commercially available Vulcan/Pt 20%. This is in agreement with having Pt (100) facets present in the HRTEM images of the erGOx/Pt material. PMID:24417177

  2. Mild Oxidation Promotes and Advanced Oxidation Impairs Remodeling of Human High-Density Lipoprotein in vitro

    PubMed Central

    Gao, Xuan; Jayaraman, Shobini; Gursky, Olga

    2008-01-01

    SUMMARY High-density lipoproteins (HDL) prevent atherosclerosis by removing cholesterol from macrophages and by exerting anti-oxidant and anti-inflammatory effects. Oxidation is thought to impair HDL functions, yet certain oxidative modifications may be advantageous; thus, mild oxidation reportedly enhances cell cholesterol uptake by HDL whereas extensive oxidation impairs it. To elucidate the underlying energetic and structural basis, we analyzed the effects of copper and hypochlorite (that preferentially oxidize lipids and proteins, respectively) on thermal stability of plasma spherical HDL. Circular dichroism, light scattering, calorimetry, gel electrophoresis and electron microscopy showed that mild oxidation destabilizes HDL and accelerates protein dissociation and lipoprotein fusion, while extensive oxidation inhibits these reactions; this inhibition correlates with massive protein cross-linking and lipolysis. We propose that mild oxidation lowers kinetic barriers for HDL remodeling due to diminished apolipoprotein affinity for lipids resulting from oxidation of methionine and aromatic residues in apolipoproteins A-I and A-II followed by protein cross-linking into dimers and/or trimers. In contrast, advanced oxidation inhibits protein dissociation and HDL fusion due to lipid re-distribution from core to surface upon lipolysis and to massive protein cross-linking. Our results help reconcile the apparent controversy in the studies of oxidized HDL and suggest that mild oxidation may benefit HDL functions. PMID:18190928

  3. Transition metal-catalyzed oxidation of sulfur(IV) oxides. Atmospheric-relevant processes and mechanisms

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

    Brandt, C.; Eldik, R. van

    1995-01-01

    The transition metal-catalyzed oxidation of sulfur(IV) oxides has been known for more than 100 years. There is a significant lack of information on the actual role of the transition metal-catalyzed reactions, and much of the earlier work was performed without a detailed knowledge of the chemical system. For this reason attention is focused on the role of transition metal ions in the oxidation of sulfur(IV) oxides in terms of the coordination chemistry involved, as well as the stability and chemical behavior of the various participating species. The oxidation process of sulfur(IV) oxides plays an important role in atmospheric chemistry (e.g.more » acid rain formation) as well as industrial processes (e.g. desulfurization of plume gases and ore). The present report deals with the mechanism of the transition metal-catalyzed oxidation of sulfur(IV) oxides with the aim to discuss this in terms of atmospheric and chemical processes. In addition, the authors would like to emphasize the key role of oxygen in these processes. 1,076 refs.« less

  4. Synthesis of Graphene Oxide by Oxidation of Graphite with Ferrate(VI) Compounds: Myth or Reality?

    PubMed

    Sofer, Zdeněk; Luxa, Jan; Jankovský, Ondřej; Sedmidubský, David; Bystroň, Tomáš; Pumera, Martin

    2016-09-19

    It is well established that graphene oxide can be prepared by the oxidation of graphite using permanganate or chlorate in an acidic environment. Recently, however, the synthesis of graphene oxide using potassium ferrate(VI) ions has been reported. Herein, we critically replicate and evaluate this new ferrate(VI) oxidation method. In addition, we test the use of potassium ferrate(VI) for the synthesis of graphene oxide under various experimental routes. The synthesized materials are analyzed by a number of analytical methods in order to confirm or disprove the possibility of synthesizing graphene oxide by the ferrate(VI) oxidation route. Our results confirm the unsuitability of using ferrate(VI) for the oxidation of graphite on graphene oxide because of its high instability in an acidic environment and low oxidation power in neutral and alkaline environments. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. Oxidation of Octopus vulgaris hemocyanin by nitrogen oxides

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

    Salvato, B.; Giacometti, G.M.; Beltramini, M.

    1989-01-24

    The reaction of Octopus vulgaris hemocyanin with nitrite was studied under a variety of conditions in which the green half-met derivative is formed. Analytical evidence shows that the amount of chemically detectable nitrite in various samples of the derivative is not proportional to the cupric copper detected by EPR. The kinetics of oxidation of hemocyanin as a function of protein concentration and pH, in the presence of nitrite and ascorbate, is consistent with a scheme in which NO/sub 2/ is the reactive oxidant. We suggest that the green half-methemocyanin contains a metal center with one cuprous and one cupric coppermore » without an exogenous nitrogen oxide ligand.« less

  7. SELECTIVE OXIDATION OF ALCOHOLS OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

    EPA Science Inventory

    Oxidation of various alcohols is studied in liquid phase under nitrogen atmosphere over vanadium phosphorus oxide catalyst in an environmentally friendly protocol using hydrogen peroxide. The catalyst and the method are found to be suitable for the selective oxidation of a variet...

  8. Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

    NASA Astrophysics Data System (ADS)

    Renaud, Gilles

    Experimental determinations of the atomic structure of insulating oxide surfaces and metal/oxide interfaces are scarce, because surface science techniques are often limited by the insulating character of the substrate. Grazing incidence X-ray scattering (GIXS), which is not subject to charge effects, can provide very precise information on the atomic structure of oxide surfaces: roughness, relaxation and reconstruction. It is also well adapted to analyze the atomic structure, the registry, the misfit relaxation, elastic or plastic, the growth mode and the morphology of metal/oxide interfaces during their growth, performed in situ. GIXS also allows the analysis of thin films and buried interfaces, in a non-destructive way, yielding the epitaxial relationships, and, by variation of the grazing incidence angle, the lattice parameter relaxation along the growth direction. On semi-coherent interfaces, the existence of an ordered network of interfacial misfit dislocations can be demonstrated, its Burger's vector determined, its ordering during in situ annealing cycles followed, and sometimes even its atomic structure can be addressed. Careful analysis during growth allows the modeling of the dislocation nucleation process. This review emphasizes the new information that GIXS can bring to oxide surfaces and metal/oxide interfaces by comparison with other surface science techniques. The principles of X-ray diffraction by surfaces and interfaces are recalled, together with the advantages and properties of grazing angles. The specific experimental requirements are discussed. Recent results are presented on the determination of the atomic structure of relaxed or reconstructed oxide surfaces. A description of results obtained during the in situ growth of metal on oxide surfaces is also given, as well as investigations of thick metal films on oxide surfaces, with lattice parameter misfit relaxed by an array of dislocations. Recent work performed on oxide thin films having

  9. Simultaneous effect of temperature, cyanide and ammonia-oxidizing bacteria concentrations on ammonia oxidation.

    PubMed

    Do, Hyojin; Lim, Juntaek; Shin, Seung Gu; Wu, Yi-Ju; Ahn, Johng-Hwa; Hwang, Seokhwan

    2008-11-01

    For biological nitrification, a set of experiments were carried out to approximate the response of lag period along with ammonia oxidation rate with respect to different concentrations of cyanide (CN-) and ammonia-oxidizing bacteria (AOB), and temperature variation in laboratory-scale batch reactors. The effects of simultaneous changes in these three factors on ammonia oxidation were quantitatively estimated and modeled using response surface analysis. The lag period and the ammonia oxidation rate responded differently to changes in the three factors. The lag period and the ammonia oxidation rate were significantly affected by the CN- and AOB concentrations, while temperature changes only affected the ammonia oxidation rate. The increase of AOB concentration and temperature alleviated the inhibition effect of cyanide on ammonia oxidation. The statistical method used in this study can be extended to estimate the quantitative effects of other environmental factors that can change simultaneously.

  10. 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

  11. 40 CFR 471.95 - Pretreatment standards for new sources (PSNS).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... I—PSNS. There shall be no discharge of process wastewater pollutants. (p) Molten salt rinse. Subpart... (pounds per million off-pounds) of zirconium-hafnium rinsed following molten salt treatment Chromium 0.333...

  12. 40 CFR 471.95 - Pretreatment standards for new sources (PSNS).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... I—PSNS. There shall be no discharge of process wastewater pollutants. (p) Molten salt rinse. Subpart... (pounds per million off-pounds) of zirconium-hafnium rinsed following molten salt treatment Chromium 0.333...

  13. 40 CFR 471.95 - Pretreatment standards for new sources (PSNS).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... I—PSNS. There shall be no discharge of process wastewater pollutants. (p) Molten salt rinse. Subpart... (pounds per million off-pounds) of zirconium-hafnium rinsed following molten salt treatment Chromium 0.333...

  14. In Situ Electrochemical Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation

    DOE PAGES

    Chen, Wei; Wang, Haotian; Li, Yuzhang; ...

    2015-07-15

    The development of catalysts with earth-abundant elements for efficient oxygen evolution reactions is of paramount significance for clean and sustainable energy storage and conversion devices. Our group demonstrated recently that the electrochemical tuning of catalysts via lithium insertion and extraction has emerged as a powerful approach to improve catalytic activity. Here we report a novel in situ electrochemical oxidation tuning approach to develop a series of binary, ternary, and quaternary transition metal (e.g., Co, Ni, Fe) oxides from their corresponding sulfides as highly active catalysts for much enhanced water oxidation. The electrochemically tuned cobalt–nickel–iron oxides grown directly on the three-dimensionalmore » carbon fiber electrodes exhibit a low overpotential of 232 mV at current density of 10 mA cm –2, small Tafel slope of 37.6 mV dec –1, and exceptional long-term stability of electrolysis for over 100 h in 1 M KOH alkaline medium, superior to most non-noble oxygen evolution catalysts reported so far. The materials evolution associated with the electrochemical oxidation tuning is systematically investigated by various characterizations, manifesting that the improved activities are attributed to the significant grain size reduction and increase of surface area and electroactive sites. This work provides a promising strategy to develop electrocatalysts for large-scale water-splitting systems and many other applications.« less

  15. Highly Conductive One-Dimensional Manganese Oxide Wires by Coating with Graphene Oxides

    NASA Astrophysics Data System (ADS)

    Tojo, Tomohiro; Shinohara, Masaki; Fujisawa, Kazunori; Muramatsu, Hiroyuki; Hayashi, Takuya; Ahm Kim, Yoong; Endo, Morinobu

    2012-10-01

    Through coating with graphene oxides, we have developed a chemical route to the bulk production of long, thin manganese oxide (MnO2) nanowires that have high electrical conductivity. The average diameter of these hybrid nanowires is about 25 nm, and their average length is about 800 nm. The high electrical conductivity of these nanowires (ca. 189.51+/-4.51 µS) is ascribed to the homogeneous coating with conductive graphene oxides as well as the presence of non-bonding manganese atoms. The growth mechanism of the nanowires is theoretically supported by the initiation of morphological conversion from graphene oxide to wrapped structures through the formation of covalent bonds between manganese and oxygen atoms at the graphene oxide edge.

  16. 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.

  17. Oxidative Stress and Nucleic Acid Oxidation in Patients with Chronic Kidney Disease

    PubMed Central

    Sung, Chih-Chien; Hsu, Yu-Chuan; Lin, Yuh-Feng

    2013-01-01

    Patients with chronic kidney disease (CKD) have high cardiovascular mortality and morbidity and a high risk for developing malignancy. Excessive oxidative stress is thought to play a major role in elevating these risks by increasing oxidative nucleic acid damage. Oxidative stress results from an imbalance between reactive oxygen/nitrogen species (RONS) production and antioxidant defense mechanisms and can cause vascular and tissue injuries as well as nucleic acid damage in CKD patients. The increased production of RONS, impaired nonenzymatic or enzymatic antioxidant defense mechanisms, and other risk factors including gene polymorphisms, uremic toxins (indoxyl sulfate), deficiency of arylesterase/paraoxonase, hyperhomocysteinemia, dialysis-associated membrane bioincompatibility, and endotoxin in patients with CKD can inhibit normal cell function by damaging cell lipids, arachidonic acid derivatives, carbohydrates, proteins, amino acids, and nucleic acids. Several clinical biomarkers and techniques have been used to detect the antioxidant status and oxidative stress/oxidative nucleic acid damage associated with long-term complications such as inflammation, atherosclerosis, amyloidosis, and malignancy in CKD patients. Antioxidant therapies have been studied to reduce the oxidative stress and nucleic acid oxidation in patients with CKD, including alpha-tocopherol, N-acetylcysteine, ascorbic acid, glutathione, folic acid, bardoxolone methyl, angiotensin-converting enzyme inhibitor, and providing better dialysis strategies. This paper provides an overview of radical production, antioxidant defence, pathogenesis and biomarkers of oxidative stress in patients with CKD, and possible antioxidant therapies. PMID:24058721

  18. Nitric Oxide as a Mediator of Oxidant Lung Injury Due to Paraquat

    NASA Astrophysics Data System (ADS)

    Berisha, Hasan I.; Pakbaz, Hedayatollah; Absood, Afaf; Said, Sami I.

    1994-08-01

    At low concentrations, nitric oxide is a physiological transmitter, but in excessive concentrations it may cause cell and tissue injury. We report that in acute oxidant injury induced by the herbicide paraquat in isolated guinea pig lungs, nitric oxide synthesis was markedly stimulated, as evidenced by increased levels of cyclic GMP in lung perfusate and of nitrite and L-citrulline production in lung tissue. All signs of injury, including increased airway and perfusion pressures, pulmonary edema, and protein leakage into the airspaces, were dose-dependently attenuated or totally prevented by either N^G-nitro-L-arginine methyl ester or N^ω-nitro-L-arginine, selective and competitive inhibitors of nitric oxide synthase. Protection was reversed by excess L-arginine but not by its enantiomer D-arginine. When blood was added to the lung perfusate, the paraquat injury was moderated or delayed as it was when paraquat was given to anesthetized guinea pigs. The rapid onset of injury and its failure to occur in the absence of Ca2+ suggest that constitutive rather than inducible nitric oxide synthase was responsible for the stimulated nitric oxide synthesis. The findings indicate that nitric oxide plays a critical role in the production of lung tissue injury due to paraquat, and it may be a pathogenetic factor in other forms of oxidant tissue injury.

  19. Nitric oxide: a physiologic messenger.

    PubMed

    Lowenstein, C J; Dinerman, J L; Snyder, S H

    1994-02-01

    To review the physiologic role of nitric oxide, an unusual messenger molecule that mediates blood vessel relaxation, neurotransmission, and pathogen suppression. A MEDLINE search of articles published from 1987 to 1993 that addressed nitric oxide and the enzyme that synthesizes it, nitric oxide synthase. Animal and human studies were selected from 3044 articles to analyze the clinical importance of nitric oxide. Descriptions of the structure and function of nitric oxide synthase were selected to show how nitric oxide acts as a biological messenger molecule. Biochemical and physiologic studies were analyzed if the same results were found by three or more independent observers. Two major classes of nitric oxide synthase enzymes produce nitric oxide. The constitutive isoforms found in endothelial cells and neurons release small amounts of nitric oxide for brief periods to signal adjacent cells, whereas the inducible isoform found in macrophages releases large amounts of nitric oxide continuously to eliminate bacteria and parasites. By diffusing into adjacent cells and binding to enzymes that contain iron, nitric oxide plays many important physiologic roles. It regulates blood pressure, transmits signals between neurons, and suppresses pathogens. Excess amounts, however, can damage host cells, causing neurotoxicity during strokes and causing the hypotension associated with sepsis. Nitric oxide is a simple molecule with many physiologic roles in the cardiovascular, neurologic, and immune systems. Although the general principles of nitric oxide synthesis are known, further research is necessary to determine what role it plays in causing disease.

  20. Improving Thermo-Oxidative Stability of Nitrile Rubber Composites by Functional Graphene Oxide.

    PubMed

    Zhong, Rui; Zhang, Zhao; Zhao, Hongguo; He, Xianru; Wang, Xin; Zhang, Rui

    2018-05-30

    Graphene oxide (GO), modified with anti-aging agent p -phenylenediamine (PPD), was added into nitrile rubber (NBR) in order to improve the thermo-oxidative stability of NBR. The modification of GO and the transformation of functional groups were characterized by Fourier transform infrared spectroscopy (FTIR), Raman, and X-ray diffraction (XRD). Mechanical performances of NBR composites before and after the thermo-oxidative aging were recorded. The results of dynamic mechanical analysis (DMA) show an increased storage modulus (G') and a decreased value of area of tan δ peak after introducing modified GO into NBR. It indicates that filler particles show positive interaction with molecular chains. The thermo-oxidative stability of composites was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Then, the thermo-oxidative aging kinetic parameters were obtained by the Flynn⁻Wall⁻Ozawa (FWO) equation. The results of aging tests show that the thermo-oxidative stability of rubber matrix increases obviously after introducing GO⁻PPD. In addition, mechanical properties (tensile strength and elongation at break) of both before and after aged NBR/GO⁻PPD composites were superior to that of NBR. This work provides meaningful guidance for achieving multifunction thermo-oxidative aging resistance rubber composites.

  1. Oxidant/Antioxidant Balance in Animal Nutrition and Health: The Role of Protein Oxidation

    PubMed Central

    Celi, Pietro; Gabai, Gianfranco

    2015-01-01

    This review examines the role that oxidative stress (OS), and protein oxidation in particular, plays in nutrition, metabolism, and health of farm animals. The route by which redox homeostasis is involved in some important physiological functions and the implications of the impairment of oxidative status on animal health and diseases is also examined. Proteins have various and, at the same time, unique biological functions and their oxidation can result in structural changes and various functional modifications. Protein oxidation seems to be involved in pathological conditions, such as respiratory diseases and parasitic infection; however, some studies also suggest that protein oxidation plays a crucial role in the regulation of important physiological functions, such as reproduction, nutrition, metabolism, lactation, gut health, and neonatal physiology. As the characterization of the mechanisms by which OS may influence metabolism and health is attracting considerable scientific interest, the aim of this review is to present veterinary scientists and clinicians with various aspects of oxidative damage to proteins. PMID:26664975

  2. Design of thermoelectrically highly efficient Heusler compounds using phase separations and nano-composites under an economic point of view

    NASA Astrophysics Data System (ADS)

    Balke, Benjamin

    Half-Heusler (HH) compounds are one of the most promising candidates for thermoelectric materials for automotive and industrial waste heat recovery applications. In this talk, I will give an overview about our recent investigations of phase separations in HH thermoelectrics, focusing on the ternary system TiNiSn-ZrNiSn-HfNiSn. I will show how we adapted this knowledge to design a p-type HH compound which exhibits a ZT that is increased by 130% compared to the best published bulk p-type Heusler. I will also present how we used the phase separation to design thermoelectric highly efficient nano-composites of different single-phase materials. Since the price for Hafnium doubled within the last year, our research focused on the design of HH compounds without Hafnium. I will present a very recent calculation on ZT per Euro and efficiency per Euro for various materials followed by our latest very promising results for n-type Heusler compunds without Hafnium resulting in 20 times higher ZT/Euro values. These results strongly underline the importance of phase separations as a powerful tool for designing highly efficient materials for thermoelectric applications that fulfill the industrial demands for a thermoelectric converter. The author gratefully acknowledges financial support by the thermoHEUSLER2 Project (Project No. 19U15006F) of the German Federal Ministry of Economics and Technology (BMWi).

  3. Exceptionally Active and Stable Spinel Nickel Manganese Oxide Electrocatalysts for Urea Oxidation Reaction.

    PubMed

    Periyasamy, Sivakumar; Subramanian, Palaniappan; Levi, Elena; Aurbach, Doron; Gedanken, Aharon; Schechter, Alex

    2016-05-18

    Spinel nickel manganese oxides, widely used materials in the lithium ion battery high voltage cathode, were studied in urea oxidation catalysis. NiMn2O4, Ni1.5Mn1.5O4, and MnNi2O4 were synthesized by a simple template-free hydrothermal route followed by a thermal treatment in air at 800 °C. Rietveld analysis performed on nonstoichiometric nickel manganese oxide-Ni1.5Mn1.5O4 revealed the presence of three mixed phases: two spinel phases with different lattice parameters and NiO unlike the other two spinels NiMn2O4 and MnNi2O4. The electroactivity of nickel manganese oxide materials toward the oxidation of urea in alkaline solution is evaluated using cyclic voltammetric measurements. Ni1.5Mn1.5O4 exhibits excellent redox characteristics and lower charge transfer resistances in comparison with other compositions of nickel manganese oxides and nickel oxide prepared under similar conditions.The Ni1.5Mn1.5O4modified electrode oxidizes urea at 0.29 V versus Ag/AgCl with a corresponding current density of 6.9 mA cm(-2). At a low catalyst loading of 50 μg cm(-2), the urea oxidation current density of Ni1.5Mn1.5O4 in alkaline solution is 7 times higher than that of nickel oxide and 4 times higher than that of NiMn2O4 and MnNi2O4, respectively.

  4. PREFACE: Semiconducting oxides Semiconducting oxides

    NASA Astrophysics Data System (ADS)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for

  5. Facile Access to Graphene Oxide from Ferro-Induced Oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Chao; Wang, Cai-Feng; Chen, Su

    2016-01-01

    Methods allowing the oxidation of graphite to graphene oxide (GO) are vital important for the production of graphene from GO. This oxidation reaction has mainly relied on strong acid strategy for 174 years, which circumvents issues associated with toxicity of reagent and product, complex post-treatment, high cost and waste generation. Here, we report a green route for performing this oxidization reaction via a ferro-induced strategy, with use of water, potassium ferrate (Fe(VI)) and hydrogen peroxide (H2O2) as reagents, to produce about 65% yield of GO (vs. 40% for Hummers’ method, the most commonly used concentrated acid strategy) and non-toxic by-products. Moreover, GO produced from this new method shows equivalent performance to those reported previously. This H2SO4-free strategy makes it possible to process graphite into GO in a safe, low-cost, time-saving, energy-efficient and eco-friendly pathway, opening a promising avenue for the large-scale production of GO and GO-based materials.

  6. Facile Access to Graphene Oxide from Ferro-Induced Oxidation.

    PubMed

    Yu, Chao; Wang, Cai-Feng; Chen, Su

    2016-01-28

    Methods allowing the oxidation of graphite to graphene oxide (GO) are vital important for the production of graphene from GO. This oxidation reaction has mainly relied on strong acid strategy for 174 years, which circumvents issues associated with toxicity of reagent and product, complex post-treatment, high cost and waste generation. Here, we report a green route for performing this oxidization reaction via a ferro-induced strategy, with use of water, potassium ferrate (Fe(VI)) and hydrogen peroxide (H2O2) as reagents, to produce about 65% yield of GO (vs. 40% for Hummers' method, the most commonly used concentrated acid strategy) and non-toxic by-products. Moreover, GO produced from this new method shows equivalent performance to those reported previously. This H2SO4-free strategy makes it possible to process graphite into GO in a safe, low-cost, time-saving, energy-efficient and eco-friendly pathway, opening a promising avenue for the large-scale production of GO and GO-based materials.

  7. Facile Access to Graphene Oxide from Ferro-Induced Oxidation

    PubMed Central

    Yu, Chao; Wang, Cai-Feng; Chen, Su

    2016-01-01

    Methods allowing the oxidation of graphite to graphene oxide (GO) are vital important for the production of graphene from GO. This oxidation reaction has mainly relied on strong acid strategy for 174 years, which circumvents issues associated with toxicity of reagent and product, complex post-treatment, high cost and waste generation. Here, we report a green route for performing this oxidization reaction via a ferro-induced strategy, with use of water, potassium ferrate (Fe(VI)) and hydrogen peroxide (H2O2) as reagents, to produce about 65% yield of GO (vs. 40% for Hummers’ method, the most commonly used concentrated acid strategy) and non-toxic by-products. Moreover, GO produced from this new method shows equivalent performance to those reported previously. This H2SO4-free strategy makes it possible to process graphite into GO in a safe, low-cost, time-saving, energy-efficient and eco-friendly pathway, opening a promising avenue for the large-scale production of GO and GO-based materials. PMID:26818784

  8. Oxidation of Structural Fe(II) in Biotite by Lithotrophic Fe(II)-oxidizing microorganisms

    NASA Astrophysics Data System (ADS)

    Shelobolina, E.; Blöthe, M.; Xu, H.; Konishi, H.; Roden, E.

    2008-12-01

    The potential for microbial involvement in the oxidation of Fe(II)-bearing phyllosilicates is an understudied aspect of soil/sediment Fe biogeochemistry. An important property of structural Fe in Fe-bearing smectites is their ability to undergo multiple redox cycles without being mobilized. An obvious choice of mineral substrate for enumeration/isolation of Fe(II)-oxidizing microorganisms would be reduced smectite. But reduced smectite is readily oxidized by air. That is why biotite was chosen as a substrate for this study. In contrast to smectite, biotite is more stable in the presence of air, but incapable of redox cycling. Once Fe(II) is oxidized, biotite is weathered to expendable 2:1 phyllosilicates or kaolinite. First, we evaluated the ability of a neutral-pH lithoautotrophic nitrate-reducing enrichment culture (MPI culture), recovered by Straub et al (Appl. Environ. Microbiol., 1996, 62:1458-1460) from a freshwater ditch, to oxidize two different specimens of biotite. The culture was capable of multiple transfers in anaerobic nitrate-containing biotite suspensions. The growth of MPI culture resulted in decrease of 0.5 N HCl-extractable Fe(II) content and simultaneous nitrate reduction. Cell yields were comparable to those observed for other neutral-pH lithoautotrophic Fe(II)-oxidizing bacteria. High resolution TEM examination revealed structural and chemical changes at the edges of oxidized biotite and formation of reddish amorphous precipitates dominated by Si and Fe. To further evaluate efficiency of biotite for recovery of oxygen- and nitrate-dependent Fe(II) oxidizing cultures microbial enumeration study was performed using subsoil from a site near Madison, WI. The soil is rich in Fe-bearing smectite and shows evidence of redoximorphic features. The enumeration of Fe(II) oxidizing organisms from this sediment showed 10-fold higher efficiency of biotite over soluble Fe(II) for recovery of Fe(II)-oxidizers. Isolation and identification of both aerobic and

  9. Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides.

    PubMed

    Najafpour, Mohamad Mahdi; Heidari, Sima; Balaghi, S Esmael; Hołyńska, Małgorzata; Sadr, Moayad Hossaini; Soltani, Behzad; Khatamian, Maasoumeh; Larkum, Anthony W; Allakhverdiev, Suleyman I

    2017-02-01

    Plants, algae and cyanobacteria capture sunlight, extracting electrons from H 2 O to reduce CO 2 into sugars while releasing O 2 in the oxygenic photosynthetic process. Because of the important role of water oxidation in artificial photosynthesis and many solar fuel systems, understanding the structure and function of this unique biological catalyst forms a requisite research field. Herein the structure of the water-oxidizing complex and its ligand environment are described with reference to the 1.9Å resolution X-ray-derived crystallographic model of the water-oxidizing complex from the cyanobacterium Thermosynechococcus vulcanus. Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides are also reviewed and discussed in the paper. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

    NASA Astrophysics Data System (ADS)

    Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

    1984-04-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

  11. Grain boundary oxidation and an analysis of the effects of oxidation on fatigue crack nucleation life

    NASA Technical Reports Server (NTRS)

    Oshida, Y.; Liu, H. W.

    1988-01-01

    The effects of preoxidation on subsequent fatigue life were studied. Surface oxidation and grain boundary oxidation of a nickel-base superalloy (TAZ-8A) were studied at 600 to 1000 C for 10 to 1000 hours in air. Surface oxides were identified and the kinetics of surface oxidation was discussed. Grain boundary oxide penetration and morphology were studied. Pancake type grain boundary oxide penetrates deeper and its size is larger, therefore, it is more detrimental to fatigue life than cone-type grain boundary oxide. Oxide penetration depth, a (sub m), is related to oxidation temperature, T, and exposure time, t, by an empirical relation of the Arrhenius type. Effects of T and t on statistical variation of a (sub m) were analyzed according to the Weibull distribution function. Once the oxide is cracked, it serves as a fatigue crack nucleus. Statistical variation of the remaining fatigue life, after the formation of an oxide crack of a critical length, is related directly to the statistical variation of grain boundary oxide penetration depth.

  12. Oxidation mechanism of T91 steel in liquid lead-bismuth eutectic: with consideration of internal oxidation

    PubMed Central

    Ye, Zhongfei; Wang, Pei; Dong, Hong; Li, Dianzhong; Zhang, Yutuo; Li, Yiyi

    2016-01-01

    Clarification of the microscopic events that occur during oxidation is of great importance for understanding and consequently controlling the oxidation process. In this study the oxidation product formed on T91 ferritic/martensitic steel in oxygen saturated liquid lead-bismuth eutectic (LBE) at 823 K was characterized at the nanoscale using focused-ion beam and transmission electron microscope. An internal oxidation zone (IOZ) under the duplex oxide scale has been confirmed and characterized systematically. Through the microscopic characterization of the IOZ and the inner oxide layer, the micron-scale and nano-scale diffusion of Cr during the oxidation in LBE has been determined for the first time. The micron-scale diffusion of Cr ensures the continuous advancement of IOZ and inner oxide layer, and nano-scale diffusion of Cr gives rise to the typical appearance of the IOZ. Finally, a refined oxidation mechanism including the internal oxidation and the transformation of IOZ to inner oxide layer is proposed based on the discussion. The proposed oxidation mechanism succeeds in bridging the gap between the existing models and experimental observations. PMID:27734928

  13. Grain boundary oxidation and an analysis of the effects of pre-oxidation on subsequent fatigue life

    NASA Technical Reports Server (NTRS)

    Oshida, Y.; Liu, H. W.

    1986-01-01

    The effects of preoxidation on subsequent fatigue life were studied. Surface oxidation and grain boundary oxidation of a nickel-base superalloy (TAZ-8A) were studied at 600 to 1000 C for 10 to 1000 hours in air. Surface oxides were identified and the kinetics of surface oxidation was discussed. Grain boundary oxide penetration and morphology were studied. Pancake type grain boundary oxide penetrates deeper and its size is larger, therefore, it is more detrimental to fatigue life than cone-type grain boundary oxide. Oxide penetration depth, a (sub m), is related to oxidation temperature, T, and exposure time, t, by an empirical relation of the Arrhenius type. Effects of T and t on statistical variation of a (sub m) were analyzed according to the Weibull distribution function. Once the oxide is cracked, it serves as a fatigue crack nucleus. Statistical variation of the remaining fatigue life, after the formation of an oxide crack of a critical length, is related directly to the statistical variation of grain boundary oxide penetration depth.

  14. Cathodoluminescence of Irradiated Hafnium Dioxide

    DTIC Science & Technology

    2011-03-01

    d allows for a smaller A for a given C, but the insulator can only become so thin before tunneling occurs, which causes high power consumption and... coefficient is given by 4 Inπα λ = , (2.7) where λ is the vacuum wavelength of the light [11]. Luminescence is the general term for the...between localized states in the band tails, while the 4.2 eV feature is excited due to the interband absorption. Strzhemechny et al., 2008, studied

  15. Staged membrane oxidation reactor system

    DOEpatents

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2014-05-20

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  16. Staged membrane oxidation reactor system

    DOEpatents

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2013-04-16

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  17. Staged membrane oxidation reactor system

    DOEpatents

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2012-09-11

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  18. METAL OXIDE NANOPARTICLES

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

    FERNANDEZ-GARCIA,M.; RODGRIGUEZ, J.A.

    2007-10-01

    This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

  19. The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

    PubMed

    Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

    2016-05-01

    Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. 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.

  1. Photo-electrochemical Oxidation of Organic C1 Molecules over WO3 Films in Aqueous Electrolyte: Competition Between Water Oxidation and C1 Oxidation.

    PubMed

    Reichert, Robert; Zambrzycki, Christian; Jusys, Zenonas; Behm, R Jürgen

    2015-11-01

    To better understand organic-molecule-assisted photo-electrochemical water splitting, photo-electrochemistry and on-line mass spectrometry measurements are used to investigate the photo-electrochemical oxidation of the C1 molecules methanol, formaldehyde, and formic acid over WO3 film anodes in aqueous solution and its competition with O2 evolution from water oxidation O2 (+) and CO2 (+) ion currents show that water oxidation is strongly suppressed by the organic species. Photo-electro-oxidation of formic acid is dominated by formation of CO2 , whereas incomplete oxidation of formaldehyde and methanol prevails, with the selectivity for CO2 formation increasing with increasing potential and light intensity. The mechanistic implications for the photo-electro-oxidation of the organic molecules and its competition with water oxidation, which could be derived from this novel approach, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Oxidation-resistant cermet

    NASA Technical Reports Server (NTRS)

    Phillips, W. M.

    1977-01-01

    Chromium metal alloys and chromium oxide ceramic are combined to produce cermets with oxidation-resistant properties. Application of cermets includes use in hot corrosive environments requiring strong resistive materials.

  3. 40 CFR 471.94 - Pretreatment standards for existing sources (PSES).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... I—PSES. There shall be no discharge of process wastewater pollutants. (p) Molten salt rinse. Subpart... (pounds per million off-pounds) of zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide...

  4. 40 CFR 471.94 - Pretreatment standards for existing sources (PSES).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... I—PSES. There shall be no discharge of process wastewater pollutants. (p) Molten salt rinse. Subpart... (pounds per million off-pounds) of zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide...

  5. 40 CFR 471.94 - Pretreatment standards for existing sources (PSES).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... I—PSES. There shall be no discharge of process wastewater pollutants. (p) Molten salt rinse. Subpart... (pounds per million off-pounds) of zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide...

  6. A Study of Oxides for Solid Oxide Cells

    NASA Astrophysics Data System (ADS)

    Comets, Olivier

    As the world energy consumption increases, it is a question of global health to increase energy production efficiency and to reduce CO2 emissions. In that respect, solid oxide cells are solid state devices that convert directly fuel into electricity, or vice versa. In fact, when run in fuel cell mode, such devices produce electricity with efficiency up to twice that of current natural gas power plants. However, systems equipped with them have only seen limited commercialization owing to issues of cost, durability, and performance. In this thesis, three different aspects of solid oxide cells are studied. First, the effects of stress on the properties of mixed ionic electronic conducting oxides are considered. Such oxides can be used as electrode materials, where they are often subject to large stresses, which can, in turn, affect their performance. Hence, understanding the relationship between stress and properties in such materials is crucial. Non-stoichiometry in strontium substituted lanthanum cobaltite is found to increase under tension and to decrease under compression. Then, degradation taking place when the cell is run in electrolysis mode is discussed. A high current allows for a high production rate of hydrogen gas. However, this can also lead to oxygen bubble nucleating in the electrolyte and subsequent degradation of the cell. The analysis conducted here shows that such nucleation phenomenon can be avoided by keeping the overpotential at the oxygen electrode below a critical value. Finally, the growth and coarsening of catalyst nanoparticles at the surface of an oxide is studied. Scientists have developed new oxides for anodes in which a catalyst material is dissolved and exsolves under operating conditions. As the performance of the cell is controlled by the surface area of the catalyst phase, understanding the kinetics of the growth is critical to predict the performance of the cell. An approach is developed to study the growth of one particle, in the

  7. OXIDATION-REDUCTION POTENTIAL MEASUREMENTS OF IMPORTANT OXIDANTS IN DRINKING WATER

    EPA Science Inventory

    Oxidation-reduction (redox) reactions are important in drinking water treatment and distribution. Oxidation-reduction potential (ORP) measurements of water reflect the tendency of major constituents in the water to accept or lose electrons. Although ORP measurements are valuable...

  8. 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.

  9. Microbial Hydrocarbon Co-oxidation

    PubMed Central

    Raymond, R. L.; Jamison, V. W.; Hudson, J. O.

    1967-01-01

    Nocardia cultures, isolated from soil by use of n-paraffins as the sole carbon source, have been shown to bring about significant oxidation of several methyl-substituted mono- and dicyclic aromatic hydrocarbons. Oxygen uptake by washed cell suspensions was not a reliable indicator of oxidation. Under co-oxidation conditions in shaken flasks, o- and p-xylenes were oxidized to their respective mono-aromatic acids, o-toluic and p-toluic acids. In addition, a new fermentation product, 2, 3-dihydroxy-p-toluic acid, was found in the p-xylene oxidation system. Of 10 methyl-substituted naphthalenes tested (1-methyl, 2-methyl, 1, 3-dimethyl, 1, 4-dimethyl, 1, 5-dimethyl, 1, 8-dimethyl, 1, 6-dimethyl, 2, 3-dimethyl, 2, 6-dimethyl, 2, 7-dimethyl), only those containing a methyl group in the β position were oxidized at this position to the mono acid. PMID:6049305

  10. Wet-cupping removes oxidants and decreases oxidative stress.

    PubMed

    Tagil, Suleyman Murat; Celik, Huseyin Tugrul; Ciftci, Sefa; Kazanci, Fatmanur Hacievliyagil; Arslan, Muzeyyen; Erdamar, Nazan; Kesik, Yunus; Erdamar, Husamettin; Dane, Senol

    2014-12-01

    Wet-cupping therapy is one of the oldest known medical techniques. Although it is widely used in various conditions such as acute\\chronic inflammation, infectious diseases, and immune system disorders, its mechanism of action is not fully known. In this study, we investigated the oxidative status as the first step to elucidate possible mechanisms of action of wet cupping. Wet cupping therapy is implemented to 31 healthy volunteers. Venous blood samples and Wet cupping blood samples were taken concurrently. Serum nitricoxide, malondialdehyde levels and activity of superoxide dismutase and myeloperoxidase were measured spectrophotometrically. Wet cupping blood had higher activity of myeloperoxidase, lower activity of superoxide dismutase, higher levels of malondialdehyde and nitricoxide compared to the venous blood. Wet cupping removes oxidants and decreases oxidative stress. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Low temperature processed complementary metal oxide semiconductor (CMOS) device by oxidation effect from capping layer.

    PubMed

    Wang, Zhenwei; Al-Jawhari, Hala A; Nayak, Pradipta K; Caraveo-Frescas, J A; Wei, Nini; Hedhili, M N; Alshareef, H N

    2015-04-20

    In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190 °C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

  12. Compatibility of refractory materials for nuclear reactor poison control systems

    NASA Technical Reports Server (NTRS)

    Sinclair, J. H.

    1974-01-01

    Metal-clad poison rods have been considered for the control system of an advanced space power reactor concept studied at the NASA Lewis Research Center. Such control rods may be required to operate at temperatures of about 140O C. Selected poison materials (including boron carbide and the diborides of zirconium, hafnium, and tantalum) were subjected to 1000-hour screening tests in contact with candidate refractory metal cladding materials (including tungsten and alloys of tantalum, niobium, and molybdenum) to assess the compatibility of these materials combinations at the temperatures of interest. Zirconium and hafnium diborides were compatible with refractory metals at 1400 C, but boron carbide and tantalum diboride reacted with the refractory metals at this temperature. Zirconium diboride also showed promise as a reaction barrier between boron carbide and tungsten.

  13. Development of Advanced Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites: Path Toward 2700 F Temperature Capability and Beyond

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Harder, Bryan; Hurst, Janet B.; Good, Brian; Costa, Gustavo; Bhatt, Ramakrishna T.; Fox, Dennis S.

    2017-01-01

    Advanced environmental barrier coating systems for SiC-SiC Ceramic Matrix Composite (CMC) turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant coating development challenges is to achieve prime-reliant environmental barrier coating systems to meet the future 2700F EBC-CMC temperature stability and environmental durability requirements. This presentation will emphasize recent NASA environmental barrier coating system testing and down-selects, particularly the development path and properties towards 2700-3000F durability goals by using NASA hafnium-hafnia-rare earth-silicon-silicate composition EBC systems for the SiC-SiC CMC turbine component applications. Advanced hafnium-based compositions for enabling next generation EBC and CMCs capabilities towards ultra-high temperature ceramic coating systems will also be briefly mentioned.

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

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

    Treesearch

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

    2001-01-01

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

  16. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  17. Fatty acid oxidation promotes reprogramming by enhancing oxidative phosphorylation and inhibiting protein kinase C.

    PubMed

    Lin, Zhaoyu; Liu, Fei; Shi, Peiliang; Song, Anying; Huang, Zan; Zou, Dayuan; Chen, Qin; Li, Jianxin; Gao, Xiang

    2018-02-26

    Changes in metabolic pathway preferences are key events in the reprogramming process of somatic cells to induced pluripotent stem cells (iPSCs). The optimization of metabolic conditions can enhance reprogramming; however, the detailed underlying mechanisms are largely unclear. By comparing the gene expression profiles of somatic cells, intermediate-phase cells, and iPSCs, we found that carnitine palmitoyltransferase (Cpt)1b, a rate-limiting enzyme in fatty acid oxidation, was significantly upregulated in the early stage of the reprogramming process. Mouse embryonic fibroblasts isolated from transgenic mice carrying doxycycline (Dox)-inducible Yamanaka factor constructs were used for reprogramming. Various fatty acid oxidation-related metabolites were added during the reprogramming process. Colony counting and fluorescence-activated cell sorting (FACS) were used to calculate reprogramming efficiency. Fatty acid oxidation-related metabolites were measured by liquid chromatography-mass spectrometry. Seahorse was used to measure the level of oxidative phosphorylation. We found that overexpression of cpt1b enhanced reprogramming efficiency. Furthermore, palmitoylcarnitine or acetyl-CoA, the primary and final products of Cpt1-mediated fatty acid oxidation, also promoted reprogramming. In the early reprogramming process, fatty acid oxidation upregulated oxidative phosphorylation and downregulated protein kinase C activity. Inhibition of protein kinase C also promoted reprogramming. We demonstrated that fatty acid oxidation promotes reprogramming by enhancing oxidative phosphorylation and inhibiting protein kinase C activity in the early stage of the reprogramming process. This study reveals that fatty acid oxidation is crucial for the reprogramming efficiency.

  18. In situ arsenic oxidation and sorption by a Fe-Mn binary oxide waste in soil.

    PubMed

    McCann, Clare M; Peacock, Caroline L; Hudson-Edwards, Karen A; Shrimpton, Thomas; Gray, Neil D; Johnson, Karen L

    2018-01-15

    The ability of a Fe-Mn binary oxide waste to adsorb arsenic (As) in a historically contaminated soil was investigated. Initial laboratory sorption experiments indicated that arsenite [As(III)] was oxidized to arsenate [As(V)] by the Mn oxide component, with concurrent As(V) sorption to the Fe oxide. The binary oxide waste had As(III) and As(V) adsorption capacities of 70mgg -1 and 32mgg -1 respectively. X-ray Absorption Near-Edge Structure and Extended X-ray Absorption Fine Structure at the As K-edge confirmed that all binary oxide waste surface complexes were As(V) sorbed by mononuclear bidentate corner-sharing, with 2 Fe at ∼3.27Ǻ. The ability of the waste to perform this coupled oxidation-sorption reaction in real soils was investigated with a 10% by weight addition of the waste to an industrially As contaminated soil. Electron probe microanalysis showed As accumulation onto the Fe oxide component of the binary oxide waste, which had no As innately. The bioaccessibility of As was also significantly reduced by 7.80% (p<0.01) with binary oxide waste addition. The results indicate that Fe-Mn binary oxide wastes could provide a potential in situ remediation strategy for As and Pb immobilization in contaminated soils. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  19. Modeling Thin Film Oxide Growth

    NASA Astrophysics Data System (ADS)

    Sherman, Quentin

    Thin film oxidation is investigated using two modeling techniques in the interest of better understanding the roles of space charge and non-equilibrium effects. An electrochemical phase-field model of an oxide-metal interface is formulated in one dimension and studied at equilibrium and during growth. An analogous sharp interface model is developed to validate the phase-field model in the thick film limit. Electrochemical profiles across the oxide are shown to deviate from the sharp interface prediction when the oxide film is thin compared to the Debye length, however no effect on the oxidation kinetics is found. This is attributed to the simple thermodynamic and kinetic models used therein. The phase-field model provides a framework onto to which additional physics can be added to better model thin film oxidation. A model for solute trapping during the oxidation of binary alloys is developed to study non-equilibrium effects during the early stages of oxide growth. The model is applied to NiCr alloys, and steady-state interfacial composition maps are presented for the growth of an oxide with the rock salt structure. No detailed experimental data is available to verify the predictions of the solute trapping model, however it is shown to be consistent with the trends observed during the early stages of NiCr oxidation. Lastly, experimental studies of the wet infiltration technique for decorating solid oxide fuel cell anodes with nickel nanoparticles are presented. The effect of nickel nitrate calcination parameters on the resulting nickel oxide microstructures are studied on both porous and planar substrates. Decreasing the calcination temperature and dwell time, as well as a dehydration step after nickel nitrate infiltration, are all shown to decrease the initial nickel oxide particle size, but other factors such as geometry and nickel loading per unit area also affected the final nickel particle size and morphology upon reduction.

  20. Method of producing homogeneous mixed metal oxides and metal-metal oxide mixtures

    DOEpatents

    Quinby, Thomas C.

    1978-01-01

    Metal powders, metal oxide powders, and mixtures thereof of controlled particle size are provided by reacting an aqueous solution containing dissolved metal values with excess urea. Upon heating, urea reacts with water from the solution leaving a molten urea solution containing the metal values. The molten urea solution is heated to above about 180.degree. C. whereupon metal values precipitate homogeneously as a powder. The powder is reduced to metal or calcined to form oxide particles. One or more metal oxides in a mixture can be selectively reduced to produce metal particles or a mixture of metal and metal oxide particles.

  1. Graphene-supported metal oxide monolith

    DOEpatents

    Worsley, Marcus A.; Baumann, Theodore F.; Biener, Juergen; Biener, Monika A.; Wang, Yinmin; Ye, Jianchao; Tylski, Elijah

    2017-01-10

    A composition comprising at least one graphene-supported metal oxide monolith, said monolith comprising a three-dimensional structure of graphene sheets crosslinked by covalent carbon bonds, wherein the graphene sheets are coated by at least one metal oxide such as iron oxide or titanium oxide. Also provided is an electrode comprising the aforementioned graphene-supported metal oxide monolith, wherein the electrode can be substantially free of any carbon-black and substantially free of any binder.

  2. Mechanical properties of graphene oxides.

    PubMed

    Liu, Lizhao; Zhang, Junfeng; Zhao, Jijun; Liu, Feng

    2012-09-28

    The mechanical properties, including the Young's modulus and intrinsic strength, of graphene oxides are investigated by first-principles computations. Structural models of both ordered and amorphous graphene oxides are considered and compared. For the ordered graphene oxides, the Young's modulus is found to vary from 380 to 470 GPa as the coverage of oxygen groups changes, respectively. The corresponding variations in the Young's modulus of the amorphous graphene oxides with comparable coverage are smaller at 290-430 GPa. Similarly, the ordered graphene oxides also possess higher intrinsic strength compared with the amorphous ones. As coverage increases, both the Young's modulus and intrinsic strength decrease monotonically due to the breaking of the sp(2) carbon network and lowering of the energetic stability for the ordered and amorphous graphene oxides. In addition, the band gap of the graphene oxide becomes narrower under uniaxial tensile strain, providing an efficient way to tune the electronic properties of graphene oxide-based materials.

  3. Zinc oxide varistors and/or resistors

    DOEpatents

    Arnold, Jr., Wesley D.; Bond, Walter D.; Lauf, Robert J.

    1993-01-01

    Varistors and/or resistors that includes doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.

  4. 40 CFR 471.93 - New source performance standards (NSPS).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... of process wastewater pollutants (p) Molten salt rinse. Subpart I—NSPS Pollutant or pollutant... zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide 0.220 0.091 Nickel 1.45 0.960...

  5. 40 CFR 471.92 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... of process wastewater pollutants. (p) Molten salt rinse. Subpart I—BAT Pollutant or pollutant... zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide 0.220 0.091 Nickel 1.45 0.960...

  6. 40 CFR 471.92 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... of process wastewater pollutants. (p) Molten salt rinse. Subpart I—BAT Pollutant or pollutant... zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide 0.220 0.091 Nickel 1.45 0.960...

  7. 40 CFR 471.91 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...) Degreasing rinse—subpart I—BPT. There shall be no discharge or process wastewater pollutants. (p) Molten salt.../off-kg (pounds per million off pounds) of zirconium-hafnium treated with molten salt Chromium 3.33 1...

  8. 40 CFR 471.93 - New source performance standards (NSPS).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... of process wastewater pollutants (p) Molten salt rinse. Subpart I—NSPS Pollutant or pollutant... zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide 0.220 0.091 Nickel 1.45 0.960...

  9. 40 CFR 471.93 - New source performance standards (NSPS).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... of process wastewater pollutants (p) Molten salt rinse. Subpart I—NSPS Pollutant or pollutant... zirconium-hafnium treated with molten salt Chromium 0.333 0.136 Cyanide 0.220 0.091 Nickel 1.45 0.960...

  10. 40 CFR 471.91 - Effluent limitations representing the degree of effluent reduction attainable by the application...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) Degreasing rinse—subpart I—BPT. There shall be no discharge or process wastewater pollutants. (p) Molten salt.../off-kg (pounds per million off pounds) of zirconium-hafnium treated with molten salt Chromium 3.33 1...

  11. Supported versus colloidal zinc oxide for advanced oxidation processes

    NASA Astrophysics Data System (ADS)

    Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

    2017-07-01

    Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

  12. Oxidative stress inhibition and oxidant activity by fibrous clays.

    PubMed

    Cervini-Silva, Javiera; Nieto-Camacho, Antonio; Gómez-Vidales, Virginia

    2015-09-01

    Fibrous clays (sepiolite, palygorskite) are produced at 1.2m tonnes per year and have a wide range of industrial applications needing to replace long-fibre length asbestos. However, information on the beneficial effects of fibrous clays on health remains scarce. This paper reports on the effect of sepiolite (Vallecas, Spain) and palygorskite (Torrejón El Rubio, Spain) on cell damage via oxidative stress (determined as the progress of lipid peroxidation, LP). The extent of LP was assessed using the Thiobarbituric Acid Reactive Substances assay. The oxidant activity by fibrous clays was quantified using Electron-Paramagnetic Resonance. Sepiolite and palygorskite inhibited LP, whereby corresponding IC50 values were 6557±1024 and 4250±289μgmL(-1). As evidenced by dose-response experiments LP inhibition by palygorskite was surface-controlled. Fibrous clay surfaces did not stabilize HO species, except for suspensions containing 5000μgmL(-1). A strong oxidant (or weak anti-oxidant) activity favours the inhibition of LP by fibrous clays. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    PubMed Central

    Wang, Zhenwei; Al-Jawhari, Hala A.; Nayak, Pradipta K.; Caraveo-Frescas, J. A.; Wei, Nini; Hedhili, M. N.; Alshareef, H. N.

    2015-01-01

    In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field. PMID:25892711

  14. Nitric oxide ameliorates the damaging effects of oxidative stress induced by iron deficiency in cyanobacterium Anabaena 7120.

    PubMed

    Kaushik, Manish Singh; Srivastava, Meenakshi; Srivastava, Alka; Singh, Anumeha; Mishra, Arun Kumar

    2016-11-01

    In cyanobacterium Anabaena 7120, iron deficiency leads to oxidative stress with unavoidable consequences. Nitric oxide reduces pigment damage and supported the growth of Anabaena 7120 in iron-deficient conditions. Elevation in nitric oxide accumulation and reduced superoxide radical production justified the role of nitric oxide in alleviating oxidative stress in iron deficiency. Increased activities of antioxidative enzymes and higher levels of ROS scavengers (ascorbate, glutathione and thiol) in iron deficiency were also observed in the presence of nitric oxide. Nitric oxide also supported the membrane integrity of Anabaena cells and reduces protein and DNA damage caused by oxidative stress induced by iron deficiency. Results suggested that nitric oxide alleviates the damaging effects of oxidative stress induced by iron deficiency in cyanobacterium Anabaena 7120.

  15. HYDROCARBON OXIDATION OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

    EPA Science Inventory

    Selective oxidation of hydrocarbons is one of the very important and challenging areas in industrial chemistry due to the wide ranging utility of the resulting oxygenates in fine chemical synthesis. Most of the existing processes for their oxidations employ toxic and often stoich...

  16. Effect of magnesium oxide content on oxidation behavior of some superalloy-base cermets

    NASA Technical Reports Server (NTRS)

    Zaplatynsky, I.

    1975-01-01

    The effect of increasing magnesium oxide (MgO) content on the cyclic oxidation resistance of hot-pressed cermets of MgO in NiCrAlY, MgO in Hoskins-875, MgO in Inconel-702, and MgO in Hastelloy-X was investigated. The cermets with magnesium oxide levels of 5, 10, 20, and 40 vol percent were examined. The cyclic oxidation behavior of these cermets at 1100 and 1200 C in still air was determined by a thermogravimetric method supplemented by X-ray diffraction analysis and light and electron microscopy. In all instances, MgO prevented grain growth in the metallic phase. No evidence of oxidation along interphase boundaries was detected. Cermets of MgO in NiCrAlY and MgO in Hoskins-875 were superior to cermets of MgO in Inconel-702 and MgO in Hastelloy-X. Their oxidation resistance was degraded only when the MgO content was 40 vol percent. The oxidation behavior of MgO-in-Inconel-702 powder cermets containing 5- and 10-vol percent MgO was approximately similar to that of pure Inconel-702 compacts. The 20- and 40-vol percent MgO content reduced the oxidation resistance of MgO-in-Inconel-702 powder cermets relative to that of pure Inconel-702.

  17. A novel hydrogen oxidizer amidst the sulfur-oxidizing Thiomicrospira lineage

    PubMed Central

    Hansen, Moritz; Perner, Mirjam

    2015-01-01

    Thiomicrospira species are ubiquitously found in various marine environments and appear particularly common in hydrothermal vent systems. Members of this lineage are commonly classified as sulfur-oxidizing chemolithoautotrophs. Although sequencing of Thiomicrospira crunogena's genome has revealed genes that encode enzymes for hydrogen uptake activity and for hydrogenase maturation and assembly, hydrogen uptake ability has so far not been reported for any Thiomicrospira species. We isolated a Thiomicrospira species (SP-41) from a deep sea hydrothermal vent and demonstrated that it can oxidize hydrogen. We show in vivo hydrogen consumption, hydrogen uptake activity in partially purified protein extracts and transcript abundance of hydrogenases during different growth stages. The ability of this strain to oxidize hydrogen opens up new perspectives with respect to the physiology of Thiomicrospira species that have been detected in hydrothermal vents and that have so far been exclusively associated with sulfur oxidation. PMID:25226028

  18. Influence of oxidation temperature on the oxide scale formation of NiCoCrAl coatings

    NASA Astrophysics Data System (ADS)

    Sugiarti, E.; Zaini, K. A.; Sundawa, R.; Wang, Y.; Ohnuki, S.; Hayashi, S.

    2017-04-01

    Intermetalic coatings of NiCoCrAl have been successfully developed on low carbon steel substrate to improve oxidation resistance in extreme environments. The influence of oxidation temperature on the oxide scale formation was studied in the temperature range of 600-1000 °C. The measurements were made in air under isothermal oxidation test for 100 h. The surface morphology showed that a cauliflower like structure developed entire the oxide scale of sample oxidized at 800 °C and 1000 °C, while partly distributed on the surface of sample oxidized at 600 °C. The XRD analysis identified Cr2O3 phase predominantly formed on the oxidized sample at 600 °C and meta-stable Al2O3 with several polymorphs crystalline structures: η, δ, θ, κ, and α-Al2O3 at relatively high temperatures, i.e. 800 °C and 1000 °C. A Cross-sectional microstructure showed that complex and porous structures formed on the top surface of 600 °C and 1000 °C samples. In contrast, a very thin oxide scale formed on 800 °C oxidized samples and it appeared to act as a diffusion barrier of oxygen to diffuse inward, hence could increase in the service life of carbon steel substrate.

  19. Oxidation of anthracene using waste Mn oxide minerals: the importance of wetting and drying sequences.

    PubMed

    Clarke, Catherine; Tourney, Janette; Johnson, Karen

    2012-02-29

    PAHs are a common problem in contaminated urban soils due to their recalcitrance. This study presents results on the oxidation of anthracene on synthetic and natural Mn oxide surfaces. Evaporation of anthracene spiked Mn oxide slurries in air results in the oxidation of 30% of the anthracene to anthraquinone. Control minerals, quartz and calcite, also oxidised a small but significant proportion of the anthracene (4.5% and 14% conversion, respectively) when spiked mineral slurries were evaporated in air. However, only Mn oxide minerals showed significant anthracene oxidation (5-10%) when evaporation took place in the absence of oxygen (N2 atmosphere). In the fully hydrated systems where no drying took place, natural Mn oxides showed an increase in anthracene oxidation with decreasing pH, with a conversion of 75% anthracene at pH 4. These results show both acidification and drying favor the oxidation of anthracene on Mn oxide mineral surfaces. It has also been demonstrated that non-redox active mineral surfaces, such as calcite, may play a role in contaminant breakdown during wetting and drying sequences. Given that climate changes suggest that wetting and drying sequences are likely to become more significant these results have important implications for contaminated land remediation technologies. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Zinc oxide overdose

    MedlinePlus

    Zinc oxide is an ingredient in many products. Some of these are certain creams and ointments used ... prevent or treat minor skin burns and irritation. Zinc oxide overdose occurs when someone eats one of ...

  1. Zinc oxide varistors and/or resistors

    DOEpatents

    Arnold, W.D. Jr.; Bond, W.D.; Lauf, R.J.

    1993-07-27

    Varistors and/or resistors are described that include doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.

  2. Synergistic effect of graphene oxide on the methanol oxidation for fuel cell application

    NASA Astrophysics Data System (ADS)

    Siwal, Samarjeet; Ghosh, Sarit; Nandi, Debkumar; Devi, Nishu; Perla, Venkata K.; Barik, Rasmita; Mallick, Kaushik

    2017-09-01

    Aromatic polypyrene was synthesized by the oxidative polymerization of pyrene with potassium tetrachloropalladate (II), as oxidant. During the polymerization process the palladium salt was reduced to metallic palladium and forms the metal-polymer composite material. Polypyrene stabilized palladium nanoparticles showed electrocatalytic activity toward the oxidation of methanol. The performance of the electrocatalytic activity was substantially improved with the incorporation of graphene oxide to the palladium-polypyrene composite and the synergistic performance was attributed to the electronic and structural properties of the system.

  3. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

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

    Jernigan, Glenn Geoffrey

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu 2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu 2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/molmore » < Cu 2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N 2 and CO 2. At the end of each reaction, the catalyst was found to be Cu 2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.« less

  4. Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps

    DOE PAGES

    Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V.; ...

    2014-09-22

    Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with 13C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organicmore » carbon oxidation or in diffusive sedimentary sulfate–methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. Furthermore, these results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling.« less

  5. W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

    NASA Astrophysics Data System (ADS)

    Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

    2017-11-01

    W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

  6. Metal/oxide interfacial effects on the selective oxidation of primary alcohols

    PubMed Central

    Zhao, Guofeng; Yang, Fan; Chen, Zongjia; Liu, Qingfei; Ji, Yongjun; Zhang, Yi; Niu, Zhiqiang; Mao, Junjie; Bao, Xinhe; Hu, Peijun; Li, Yadong

    2017-01-01

    A main obstacle in the rational development of heterogeneous catalysts is the difficulty in identifying active sites. Here we show metal/oxide interfacial sites are highly active for the oxidation of benzyl alcohol and other industrially important primary alcohols on a range of metals and oxides combinations. Scanning tunnelling microscopy together with density functional theory calculations on FeO/Pt(111) reveals that benzyl alcohol enriches preferentially at the oxygen-terminated FeO/Pt(111) interface and undergoes readily O–H and C–H dissociations with the aid of interfacial oxygen, which is also validated in the model study of Cu2O/Ag(111). We demonstrate that the interfacial effects are independent of metal or oxide sizes and the way by which the interfaces were constructed. It inspires us to inversely support nano-oxides on micro-metals to make the structure more stable against sintering while the number of active sites is not sacrificed. The catalyst lifetime, by taking the inverse design, is thereby significantly prolonged. PMID:28098146

  7. The Role of Citric Acid in the Stabilization of Nanoparticles and Colloidal Particles in the Environment: Measurement of Surface Forces between Hafnium Oxide Surfaces in the Presence of Citric Acid.

    PubMed

    Shinohara, Shuhei; Eom, Namsoon; Teh, E-Jen; Tamada, Kaoru; Parsons, Drew; Craig, Vincent S J

    2018-02-27

    The interactions between colloidal particles and nanoparticles determine solution stability and the structures formed when the particles are unstable to flocculation. Therefore, knowledge of the interparticle interactions is important for understanding the transport, dissolution, and fate of particles in the environment. The interactions between particles are governed by the surface properties of the particles, which are altered when species adsorb to the surface. The important interactions in the environment are almost never those between the bare particles but rather those between particles that have been modified by the adsorption of natural organic materials. Citric acid is important in this regard not only because it is present in soil but also as a model of humic and fulvic acids. Here we have studied the surface forces between the model metal oxide surface hafnia in the presence of citric acid in order to understand the stability of colloidal particles and nanoparticles. We find that citric acid stabilizes the particles over a wide range of pH at low to moderate ionic strength. At high ionic strength, colloidal particles will flocculate due to a secondary minimum, resulting in aggregates that are dense and easily redispersed. In contrast, nanoparticles stabilized by citric acid remain stable at high ionic strengths and therefore exist in solution as individual particles; this will contribute to their dispersion in the environment and the uptake of nanoparticles by mammalian cells.

  8. The influence of oxidation time on the properties of oxidized zinc films

    NASA Astrophysics Data System (ADS)

    Rambu, A. P.

    2012-09-01

    The effect of oxidation time on the structural characteristics and electronic transport mechanism of zinc oxide thin films prepared by thermal oxidation, have been investigated. Zinc metallic films were deposited by thermal evaporation under vacuum, the subsequent oxidation of Zn films being carried out in open atmosphere. XRD and AFM analysis indicate that obtained films posses a polycrystalline structure, the crystallites having a preferential orientation. Structural analysis reveals that microstructure of the films (crystallite size, surface roughness, internal stress) is depending on the oxidation time of metallic films. The electrical behavior of ZnO films was investigated, during a heat treatment (two heating/cooling cycles). It was observed that after the first heating, the temperature dependences of electrical conductivity become reversible. Mott variable range hopping model was proposed to analyze the temperature dependence of the electrical conductivity, in low temperature ranges. Values of some characteristic parameters were calculated.

  9. Oxide film on metal substrate reduced to form metal-oxide-metal layer structure

    NASA Technical Reports Server (NTRS)

    Youngdahl, C. A.

    1967-01-01

    Electrically conductive layer of zirconium on a zirconium-oxide film residing on a zirconium substrate is formed by reducing the oxide in a sodium-calcium solution. The reduced metal remains on the oxide surface as an adherent layer and seems to form a barrier that inhibits further reaction.

  10. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

    PubMed

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

    2013-05-28

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

  11. Characterization of oxide nanoparticles in Al-free and Al-containing oxide dispersion strengthened ferritic steels.

    PubMed

    Lee, Jae Hoon; Kim, Jeoung Han

    2013-09-01

    Oxide nanoparticles in oxide dispersion strengthened (ODS) ferritic steels with and without Al have been characterized by transmission electron microscopy. It is confirmed that most of the complex oxide particles consist of Y2TiO5 for 18Cr-ODS steel and YAlO3 or YAl5O12 for 18Cr5Al-ODS steel, respectivley. The addition of 5% Al in 18Cr-ODS steel leads to the formation of larger oxide particles and the reduction in their number density. For 18Cr-ODS steel, 87% of the oxide particles are coherent. The misfit strain of the coherent particles and a few semi-coherent particles is about 0.034 and 0.056, respectively. For 18Cr5Al-ODS steel, 75% of the oxide particles are semi-coherent, of which the misfit strain is 0.091 and 0.125, respectively. These results suggest that for the Al-containing ODS steel the Al addition accelerates the formation of semi-coherent oxide particles and its larger coherent and semi-coherent particles result in the larger misfit strain between the oxide particle and alloy matrix, indicating that the coherence of oxide nanoparticles in ODS steels is size-dependent.

  12. Is Oxidized Thioredoxin a Major Trigger for Cysteine Oxidation? Clues from a Redox Proteomics Approach

    PubMed Central

    García-Santamarina, Sarela; Boronat, Susanna; Calvo, Isabel A.; Rodríguez-Gabriel, Miguel; Ayté, José; Molina, Henrik

    2013-01-01

    Abstract Cysteine oxidation mediates oxidative stress toxicity and signaling. It has been long proposed that the thioredoxin (Trx) system, which consists of Trx and thioredoxin reductase (Trr), is not only involved in recycling classical Trx substrates, such as ribonucleotide reductase, but it also regulates general cytoplasmic thiol homeostasis. To investigate such a role, we have performed a proteome-wide analysis of cells expressing or not the two components of the Trx system. We have compared the reversibly oxidized thiol proteomes of wild-type Schizosaccharomyces pombe cells with mutants lacking Trx or Trr. Specific Trx substrates are reversibly-oxidized in both strain backgrounds; however, in the absence of Trr, Trx can weakly recycle its substrates at the expense of an alternative electron donor. A massive thiol oxidation occurs only in cells lacking Trr, with 30% of all cysteine-containing peptides being reversibly oxidized; this oxidized cysteine proteome depends on the presence of Trxs. Our observations lead to the hypothesis that, in the absence of its reductase, the natural electron donor Trx becomes a powerful oxidant and triggers general thiol oxidation. Antioxid. Redox Signal. 18, 1549–1556. PMID:23121505

  13. Nitrate-Dependent Ferrous Iron Oxidation by Anaerobic Ammonium Oxidation (Anammox) Bacteria

    PubMed Central

    Oshiki, M.; Ishii, S.; Yoshida, K.; Fujii, N.; Ishiguro, M.; Satoh, H.

    2013-01-01

    We examined nitrate-dependent Fe2+ oxidation mediated by anaerobic ammonium oxidation (anammox) bacteria. Enrichment cultures of “Candidatus Brocadia sinica” anaerobically oxidized Fe2+ and reduced NO3− to nitrogen gas at rates of 3.7 ± 0.2 and 1.3 ± 0.1 (mean ± standard deviation [SD]) nmol mg protein−1 min−1, respectively (37°C and pH 7.3). This nitrate reduction rate is an order of magnitude lower than the anammox activity of “Ca. Brocadia sinica” (10 to 75 nmol NH4+ mg protein−1 min−1). A 15N tracer experiment demonstrated that coupling of nitrate-dependent Fe2+ oxidation and the anammox reaction was responsible for producing nitrogen gas from NO3− by “Ca. Brocadia sinica.” The activities of nitrate-dependent Fe2+ oxidation were dependent on temperature and pH, and the highest activities were seen at temperatures of 30 to 45°C and pHs ranging from 5.9 to 9.8. The mean half-saturation constant for NO3− ± SD of “Ca. Brocadia sinica” was determined to be 51 ± 21 μM. Nitrate-dependent Fe2+ oxidation was further demonstrated by another anammox bacterium, “Candidatus Scalindua sp.,” whose rates of Fe2+ oxidation and NO3− reduction were 4.7 ± 0.59 and 1.45 ± 0.05 nmol mg protein−1 min−1, respectively (20°C and pH 7.3). Co-occurrence of nitrate-dependent Fe2+ oxidation and the anammox reaction decreased the molar ratios of consumed NO2− to consumed NH4+ (ΔNO2−/ΔNH4+) and produced NO3− to consumed NH4+ (ΔNO3−/ΔNH4+). These reactions are preferable to the application of anammox processes for wastewater treatment. PMID:23624480

  14. Technology and characterization of Thin-Film Transistors (TFTs) with a-IGZO semiconductor and high-k dielectric layer

    NASA Astrophysics Data System (ADS)

    Mroczyński, R.; Wachnicki, Ł.; Gierałtowska, S.

    2016-12-01

    In this work, we present the design of the technology and fabrication of TFTs with amorphous IGZO semiconductor and high-k gate dielectric layer in the form of hafnium oxide (HfOx). In the course of this work, the IGZO fabrication was optimized by means of Taguchi orthogonal tables approach in order to obtain an active semiconductor with reasonable high concentration of charge carriers, low roughness and relatively high mobility. The obtained Thin-Film Transistors can be characterized by very good electrical parameters, i.e., the effective mobility (μeff ≍ 12.8 cm2V-1s-1) significantly higher than that for a-Si TFTs (μeff ≍ 1 cm2V-1s-1). However, the value of sub-threshold swing (i.e., 640 mV/dec) points that the interfacial properties of IGZO/HfOx stack is characterized by high value of interface states density (Dit) which, in turn, demands further optimization for future applications of the demonstrated TFT structures.

  15. Wide band antireflective coatings Al2O3 / HfO2 / MgF2 for UV region

    NASA Astrophysics Data System (ADS)

    Winkowski, P.; Marszałek, Konstanty W.

    2013-07-01

    Deposition technology of the three layers antireflective coatings consists of hafnium compound are presented in this paper. Oxide films were deposited by means of e-gun evaporation in vacuum of 5x10-5 mbar in presence of oxygen and fluoride films by thermal evaporation. Substrate temperature was 250°C. Coatings were deposited onto optical lenses made from quartz glass (Corning HPFS). Thickness and deposition rate were controlled by thickness measuring system Inficon XTC/2. Simulations leading to optimization of thickness and experimental results of optical measurements carried during and after deposition process were presented. Physical thickness measurements were made during deposition process and were equal to 43 nm/74 nm/51 nm for Al2O3 / HfO2 / MgF2 respectively. Optimization was carried out for ultraviolet region from 230nm to the beginning of visible region 400 nm. In this region the average reflectance of the antireflective coating was less than 0.5% in the whole range of application.

  16. CATALYTIC OXIDATION OF ALCOHOLS AND EPOXIDATION OF OLEFINS WITH HYDROGEN PEROXIDE AS OXIDANT

    EPA Science Inventory

    Hydrogen peroxide (H2O2) is an ideal oxidant of choice for these oxidations due to economic and environmental reasons by giving water as a by-product. Two catalysts used are vanadium phosphorus oxide (VPO) and Fe3+/montmorillonite-K10 catalyst prepared by ion-exchange method at a...

  17. Oxidative desulfurization of benzene fraction on transition metal oxides

    NASA Astrophysics Data System (ADS)

    Boikov, E. B.; Vishnetskaya, M. V.

    2013-02-01

    It is established that molecular oxygen is able to oxidize thiophene selectively in a mixture with benzene on V2O5 · MoO3. The introduction of thiophene inhibits the oxidation of benzene. It is shown that the conversion of thiophene during operation of the catalyst is reduced at first and then increases until it reaches its initial value.

  18. Genetic resistance to malaria, oxidative stress and hemoglobin oxidation.

    PubMed

    Destro Bisol, G

    1999-09-01

    I describe a model which posits the molecular basis of some malaria-resistance genes in the interaction between oxidized hemoglobin and membrane components. The model is supported by a considerable body of evidence which indicates that erythrocytes of genetically protected individuals (carriers of sickle cell trait, alpha- and beta-thalassemia, and G6PD deficiency) are susceptible to the increase of oxidation of hemoglobin following H2O2 release in the host cell by Plasmodium falciparum. I suggest that the irreversible interaction between oxidized hemoglobin and the red cell membrane could trigger mechanisms that: (i) reduce invasion of erythrocytes by the falciparum parasite; (ii) impair parasite survival and development within the cell; (iii) accelerate infected erythrocyte clearance by phagocytosis.

  19. Does oxidative stress shorten telomeres?

    PubMed

    Boonekamp, Jelle J; Bauch, Christina; Mulder, Ellis; Verhulst, Simon

    2017-05-01

    Oxidative stress shortens telomeres in cell culture, but whether oxidative stress explains variation in telomere shortening in vivo at physiological oxidative stress levels is not well known. We therefore tested for correlations between six oxidative stress markers and telomere attrition in nestling birds (jackdaws Corvus monedula ) that show a high rate of telomere attrition in early life. Telomere attrition was measured between ages 5 and 30 days, and was highly variable (average telomere loss: 323 bp, CV = 45%). Oxidative stress markers were measured in blood at age 20 days and included markers of oxidative damage (TBARS, dROMs and GSSG) and markers of antioxidant protection (GSH, redox state, uric acid). Variation in telomere attrition was not significantly related to these oxidative stress markers (| r | ≤ 0.08, n = 87). This finding raises the question whether oxidative stress accelerates telomere attrition in vivo The accumulation of telomere attrition over time depends both on the number of cell divisions and on the number of base pairs lost per DNA replication and, based on our findings, we suggest that in a growing animal cell proliferation, dynamics may be more important for explaining variation in telomere attrition than oxidative stress. © 2017 The Author(s).

  20. Oxidative stress in Alzheimer disease

    PubMed Central

    Durany, Nuria

    2009-01-01

    Alzheimer disease (AD) is a progressive dementia affecting a large proportion of the aging population. The histopathological changes in AD include neuronal cell death, formation of amyloid plaques and neurofibrillary tangles. There is also evidence that brain tissue in patients with AD is exposed to oxidative stress (e.g., protein oxidation, lipid oxidation, DNA oxidation and glycoxidation) during the course of the disease. Advanced glycation endproducts (AGEs) are present in amyloid plaques in AD, and its extracellular accumulation may be caused by an accelerated oxidation of glycated proteins. AGEs participate in neuronal death causing direct (chemical) and indirect (cellular) free radical production and consequently increase oxidative stress. The development of drugs for the treatment of AD that breaks the vicious cycles of oxidative stress and neurodegeneration offer new opportunities. These approaches include AGE-inhibitors, antioxidants and anti-inflammatory substances, which prevent free radical production. PMID:19372765

  1. Oxidative stress in Alzheimer disease.

    PubMed

    Gella, Alejandro; Durany, Nuria

    2009-01-01

    Alzheimer disease (AD) is a progressive dementia affecting a large proportion of the aging population. The histopathological changes in AD include neuronal cell death, formation of amyloid plaques and neurofibrillary tangles. There is also evidence that brain tissue in patients with AD is exposed to oxidative stress (e.g., protein oxidation, lipid oxidation, DNA oxidation and glycoxidation) during the course of the disease. Advanced glycation endproducts (AGEs) are present in amyloid plaques in AD, and its extracellular accumulation may be caused by an accelerated oxidation of glycated proteins. AGEs participate in neuronal death causing direct (chemical) and indirect (cellular) free radical production and consequently increase oxidative stress. The development of drugs for the treatment of AD that breaks the vicious cycles of oxidative stress and neurodegeneration offer new opportunities. These approaches include AGE-inhibitors, antioxidants and anti-inflammatory substances, which prevent free radical production.

  2. The oxidative hypothesis of senescence.

    PubMed

    Gilca, M; Stoian, I; Atanasiu, V; Virgolici, B

    2007-01-01

    The oxidative hypothesis of senescence, since its origin in 1956, has garnered significant evidence and growing support among scientists for the notion that free radicals play an important role in ageing, either as "damaging" molecules or as signaling molecules. Age-increasing oxidative injuries induced by free radicals, higher susceptibility to oxidative stress in short-lived organisms, genetic manipulations that alter both oxidative resistance and longevity and the anti-ageing effect of caloric restriction and intermittent fasting are a few examples of accepted scientific facts that support the oxidative theory of senescence. Though not completely understood due to the complex "network" of redox regulatory systems, the implication of oxidative stress in the ageing process is now well documented. Moreover, it is compatible with other current ageing theories (e.g, those implicating the mitochondrial damage/mitochondrial-lysosomal axis, stress-induced premature senescence, biological "garbage" accumulation, etc). This review is intended to summarize and critically discuss the redox mechanisms involved during the ageing process: sources of oxidant agents in ageing (mitochondrial -electron transport chain, nitric oxide synthase reaction- and non-mitochondrial- Fenton reaction, microsomal cytochrome P450 enzymes, peroxisomal beta -oxidation and respiratory burst of phagocytic cells), antioxidant changes in ageing (enzymatic- superoxide dismutase, glutathione-reductase, glutathion peroxidase, catalase- and non-enzymatic glutathione, ascorbate, urate, bilirubine, melatonin, tocopherols, carotenoids, ubiquinol), alteration of oxidative damage repairing mechanisms and the role of free radicals as signaling molecules in ageing.

  3. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    PubMed Central

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  4. High temperature oxidation resistant cermet compositions

    NASA Technical Reports Server (NTRS)

    Phillips, W. M. (Inventor)

    1976-01-01

    Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

  5. Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)

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

    Cooper, J.F.; Krueger, R.; Farmer, J.C.

    1995-10-11

    Chemical warfare agents may be completely destroyed (converted to H{sub 2}O, CO{sub 2}, salts) by oxidation at 90--100 C using acidified ammonium peroxydisulfate, with recycle of NH{sub 4}SO{sub 4} byproduct. The process requires no toxic or expended catalysts and produces no secondary wastes other than the precipitated inorganic content of the agents. To determine oxidative capability of peroxydisulfate at low reductant contents, we measured rate data for oxidation of 20 diverse compounds with diverse functional groups; 4 of these have bonds similar to those found in VX, HD, and GB. On an equivalence basis, integral first-order rate constants for 100more » C oxidation are 0.012{plus_minus}0.005 min{sup {minus}1} for di-isopropyl-methyl-phosphonate, methyl phosphonic acid, triethylamine, and 2,2{prime}-thiodiethanol at low initial concentrations of 50 ppM(as carbon) and pH 1.5. To provide scale-up equations for a bulk chemical agent destruction process, we measured time-dependent oxidation of bulk model chemicals at high concentrations (0.5 N) and developed and tested a quantitative model. A practical process for bulk VX destruction would begin with chemical detoxification by existing techniques (eg, hydrolysis or mild oxidation using oxone), followed by mineralization of the largely detoxified products by peroxydisulfate. Secondary wastes would be avoided by use of commercial electrolysis equipment to regenerate the oxidant. Reagent requirements, mass balance and scaleup parameters are given for VX destruction, using peroxydisulfate alone, or supplemented with hydrogen peroxide. For the use of 2.5 N peroxydisulfate as the oxidant, a 1 m{sup 3} digester will process about 200 kg (as C) per day. The process may be extended to total destruction of HD and hydrolysis products of G agents.« less

  6. Rheological characterization of thermal, thermo-oxidative and photo-oxidative degradation of LDPE

    NASA Astrophysics Data System (ADS)

    Rolón-Garrido, Víctor Hugo; Wagner, Manfred Hermann

    2015-04-01

    Rheology has been used to study thermal degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011), thermo-oxidative degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011; V. H. Rolón-Garrido et al., J. Rheol. 57, 105-129, 2013) and photo-oxidative degradation (V. H. Rolón-Garrido and M. H. Wagner, Polym. Degrad. Stab. 99, 136-145, 2014; V. H. Rolón-Garrido and M. H. Wagner, J. Rheol. 58, 199-22 2, 2014; V. H. Rolón-Garrido et al., Polym. Degrad. Stab. 111, 46-54, 2015) of low-density polyethylene (LDPE). This contribution presents the analogies and differences between these types of degradations of LDPE on the linear (by use of van-Gurp Palmen plots) and non-linear viscoelastic properties (by use of the parameters of the MSF model, fmax2 and β), as well as on the failure mode of the samples (through the maximum strain and stress achieved experimentally). In contrast to thermal and thermo-oxidative degradation, the linear viscoelastic properties of photo-oxidated samples were more affected by degradation. In the non-linear regime, for thermal and thermo-oxidative treated samples, the elongational measurements elucidated the role of chain scission and long-chain branching (LCB) formation, while for photo-oxidated LDPE even the competition between chain scission, LCB formation, and gel formation was demonstrated. The failure behavior was found to be determined by a constant maximum strain in thermo-oxidative degradation, if the LDPE has high content in branching points, or in photo-oxidative degraded LDPE, if a considerable portion of gel structure is present. Otherwise, either the maximum strain or stress measured was found to be strain-rate dependent.

  7. The Moraxella catarrhalis nitric oxide reductase is essential for nitric oxide detoxification.

    PubMed

    Wang, Wei; Kinkel, Traci; Martens-Habbena, Willm; Stahl, David A; Fang, Ferric C; Hansen, Eric J

    2011-06-01

    Moraxella catarrhalis is a Gram-negative obligate aerobe that is an important cause of human respiratory tract infections. The M. catarrhalis genome encodes a predicted truncated denitrification pathway that reduces nitrate to nitrous oxide. We have previously shown that expression of both the M. catarrhalis aniA (encoding a nitrite reductase) and norB (encoding a putative nitric oxide reductase) genes is repressed by the transcriptional regulator NsrR under aerobic conditions and that M. catarrhalis O35E nsrR mutants are unable to grow in the presence of low concentrations of nitrite (W. Wang, et al., J. Bacteriol. 190:7762-7772, 2008). In this study, we constructed an M. catarrhalis norB mutant and showed that planktonic growth of this mutant is inhibited by low levels of nitrite, whether or not an nsrR mutation is present. To determine the importance of NorB in this truncated denitrification pathway, we analyzed the metabolism of nitrogen oxides by norB, aniA norB, and nsrR norB mutants. We found that norB mutants are unable to reduce nitric oxide and produce little or no nitrous oxide from nitrite. Furthermore, nitric oxide produced from nitrite by the AniA protein is bactericidal for a Moraxella catarrhalis O35E norB mutant but not for wild-type O35E bacteria under aerobic growth conditions in vitro, suggesting that nitric oxide catabolism in M. catarrhalis is accomplished primarily by the norB gene product. Measurement of bacterial protein S-nitrosylation directly implicates nitrosative stress resulting from AniA-dependent nitric oxide formation as a cause of the growth inhibition of norB and nsrR mutants by nitrite.

  8. Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms.

    PubMed

    Ivarsson, Magnus; Broman, Curt; Holm, Nils G

    2011-06-03

    Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts.

  9. Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms

    PubMed Central

    2011-01-01

    Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts. PMID:21639896

  10. Characteristics of oxide scale formed on Cu-bearing austenitic stainless steel during early stages of high temperature oxidation

    NASA Astrophysics Data System (ADS)

    Swaminathan, Srinivasan; Krishna, Nanda Gopala; Kim, Dong-Ik

    2015-10-01

    Oxide scale evolution on Cu-bearing austenitic stainless steel 304H at 650 °C, in ambient air, for exposure times 100, 300, 500 and 1000 h, has been investigated. Surface morphology and chemistry of the oxide scale grown were examined using SEM/EDX and XPS. The oxidation kinetics was determined by measuring the weight change using an electronic balance. At the initial stage, up to 500 h of exposure time, the oxidation rate was rapid due to surface reactions governed primarily by oxygen ingress, and then, dropped to a low rate after prolonged oxidation for 1000 h. The diffusion of reactants through the initially formed oxide scale limits the oxidation rate at longer times, thus, the progress of reaction followed the parabolic kinetics. The formed oxide scale was enriched significantly with segregation and subsequent oxidation of Nb, and finely dispersed metallic Cu particles. Within the time frame of oxidation, the oxide scale was mainly composed of mixed oxides such as FeCr2O4 and MnCr2O4 along with the binary oxides of Fe, Cr and Mn. Moreover, the precipitation fraction of Cu-rich particles on the oxide scale increased markedly with increase of exposure times. The chemical heterogeneity of oxide scale suggests that the oxidation occurred in a non-selective manner.

  11. Conduction mechanism change with transport oxide layer thickness in oxide hetero-interface diode

    NASA Astrophysics Data System (ADS)

    Nam, Bu-il; Park, Jong Seo; Lim, Keon-Hee; Ahn, Yong-keon; Lee, Jinwon; Park, Jun-woo; Cho, Nam-Kwang; Lee, Donggun; Lee, Han-Bo-Ram; Kim, Youn Sang

    2017-07-01

    An effective and facile strategy is proposed to demonstrate an engineered oxide hetero-interface of a thin film diode with a high current density and low operating voltage. The electrical characteristics of an oxide hetero-interface thin film diode are governed by two theoretical models: the space charge-limited current model and the Fowler-Nordheim (F-N) tunneling model. Interestingly, the dominant mechanism strongly depends on the insulator thickness, and the mechanism change occurs at a critical thickness. This paper shows that conduction mechanisms of oxide hetero-interface thin film diodes depend on thicknesses of transport oxide layers and that current densities of these can be exponentially increased through quantum tunneling in the diodes with the thicknesses less than 10 nm. These oxide hetero-interface diodes have great potential for low-powered transparent nanoscale applications.

  12. Homology of vanadium oxide

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

    Vasyutinskii, N.A.

    1987-05-01

    The authors examine the homology of vanadium oxide and note that data on the existence of phases and homogeneity limits in the V-O system are very contradictory. A graphical illustration shows the homologous series of vanadium oxides. The predominant part of the discrete formations in the system V-O is characterized by integral stoichiometry and forms six homologous series. It is found that homologous series of vanadium oxides are not only a basis for systematization of such oxides, but also may serve as a means for predicting the composition of new phases, limits of homogeneity, their structure, and properties.

  13. Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.

    PubMed

    Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles

    2013-03-06

    Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface.

  14. The oxidation of carbon monoxide using tin oxide based catalysts

    NASA Technical Reports Server (NTRS)

    Sampson, Christopher F.; Jorgensen, Norman

    1990-01-01

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

  15. Oxidative Weathering of Archean Sulfides: Implications for the Great Oxidation Event

    NASA Astrophysics Data System (ADS)

    Johnson, A.; Romaniello, S. J.; Reinhard, C.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

    2015-12-01

    The first widely accepted evidence for oxidation of Earth's atmosphere and oceans occurs ~2.45 Ga immediately prior to the Great Oxidation Event (GOE). A major line of evidence for this transition includes the abundances and isotopic variations of redox-sensitive transition metals in marine sediments (e.g., Fe, Mo, Re, Cr, and U). It is often assumed that oxidative weathering is required to liberate these redox-sensitive elements from sulfide minerals in the crust, and hence that their presence in early Archean marine sediments signifies that oxidative weathering was stimulated by small and/or transient "whiffs" of O2 in the environment.1 However, studies of crustal sulfide reactivity have not been conducted at O2 concentrations as low as those that would have prevailed when O2 began its rise during the late Archean (estimated at <10-5 present atmospheric O2).2 As a result, it is difficult to quantify O2 concentrations implied by observed trace metal variations. As a first step toward providing more quantitative constraints on late Archean pO2, we conducted laboratory studies of pyrite and molybdenite oxidation kinetics at the nanomolar O2 concentrations that are relevant to late Archean environments. These measurements were made using recently developed, highly sensitive optical O2 sensors to monitor the rates at which the powdered minerals consumed dissolved O2 in a range of pH-buffered solutions.3Our data extend the range of experimental pyrite oxidation rates in the literature by three orders of magnitude from ~10-3 present atmospheric O2 to ~10-6. We find that molybdenite and pyrite oxidation continues to <1 nM O2 (4 x 10-6 present atmospheric O2). This implies that oxidative weathering of sulfides could occur under conditions which preserve MIF S fractionation. Furthermore, our results indicate that the rate law and reaction order of pyrite oxidation kinetics change significantly at nanomolar concentrations of O2 when compared to previous compilations.2 Our

  16. Metal oxide nanorod arrays on monolithic substrates

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

    Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

    A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can includemore » a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.« less

  17. Characterization of a transient +2 sulfur oxidation state intermediate from the oxidation of aqueous sulfide

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

    Vairavmurthy, M.A.; Zhou, Weiqing

    1995-04-01

    The oxidation H{sub 2}S to sulfate involves a net transfer of eight electrons and occurs through the formation of several partially oxidized intermediates with oxidation states ranging from {minus}1 to +5. Known intermediates include elemental sulfur (oxidation state 0), polysulfides (outer sulfur: {minus}1, inner sulfur: 0), sulfite (+4) and thiosulfate (outer sulfur: {minus}1, inner sulfur: +5). A noticeable gap in this series of intermediates is that of a +2 sulfur oxidation state oxoacid/oxoanion species, which was never detected experimentally. Here, we present evidence of the transient existence of +2 oxidation state intermediate in the Ni(II)-catalyzed oxidation of aqueous sulfide. X-raymore » absorption near-edge structure (XANES) spectroscopy and Fourier-transform-infrared (FT-IR) spectroscopy were used to characterize this species; they suggest that it has a sulfoxylate ion (SO{sub 2}{sup 2{minus}}) structure.« less

  18. Resistive and Capacitive Memory Effects in Oxide Insulator/ Oxide Conductor Hetero-Structures

    NASA Astrophysics Data System (ADS)

    Meyer, Rene; Miao, Maosheng; Wu, Jian; Chevallier, Christophe

    2013-03-01

    We report resistive and capacitive memory effects observed in oxide insulator/ oxide conductor hetero-structures. Electronic transport properties of Pt/ZrO2/PCMO/Pt structures with ZrO2 thicknesses ranging from 20A to 40A are studied before and after applying short voltage pulses of positive and negative polarity for set and reset operation. As processed devices display a non-linear IV characteristic which we attribute to trap assisted tunneling through the ZrO2 tunnel oxide. Current scaling with electrode area and tunnel oxide thickness confirms uniform conduction. The set/reset operation cause an up/down shift of the IV characteristic indicating that the conduction mechanism of both states is still dominated by tunneling. A change in the resistance is associated with a capacitance change of the device. An exponential relation between program voltages and set times is found. A model based on electric field mediated non-linear transport of oxygen ions across the ZrO2/PCMO interface is proposed. The change in the tunnel current is explained by ionic charge transfer between tunnel oxide and conductive metal oxide changing both tunnel barrier height and PCMO conductivity. DFT techniques are employed to explain the conductivity change in the PCMO interfacial layer observed through capacitance measurements.

  19. Method of fabricating conducting oxide-silicon solar cells utilizing electron beam sublimation and deposition of the oxide

    DOEpatents

    Feng, Tom; Ghosh, Amal K.

    1979-01-01

    In preparing tin oxide and indium tin oxide-silicon heterojunction solar cells by electron beam sublimation of the oxide and subsequent deposition thereof on the silicon, the engineering efficiency of the resultant cell is enhanced by depositing the oxide at a predetermined favorable angle of incidence. Typically the angle of incidence is between 40.degree. and 70.degree. and preferably between 55.degree. and 65.degree. when the oxide is tin oxide and between 40.degree. and 70.degree. when the oxide deposited is indium tin oxide. gi The Government of the United States of America has rights in this invention pursuant to Department of Energy Contract No. EY-76-C-03-1283.

  20. Reduction of graphene oxide by aniline with its concomitant oxidative polymerization.

    PubMed

    Xu, Li Qun; Liu, Yi Liang; Neoh, Koon-Gee; Kang, En-Tang; Fu, Guo Dong

    2011-04-19

    Graphene oxide (GO) nanosheets are readily reduced by aniline above room temperature in an aqueous acid medium, with the aniline simultaneously undergoing oxidative polymerization to produce the reduced graphene oxide-polyaniline nanofiber (RGO-PANi) composites. The resulting RGO-PANi composites and RGO (after dissolution of PANi) were characterized by XPS, XRD analysis, TGA, UV-visible absorption spectroscopy, and TEM. It was also found that the RGO-PANi composites exhibit good specific capacitance during galvanostatic charging-discharging when used as capacitor electrodes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Lipid oxidation. Part 2. Oxidation products of olive oil methyl esters.

    PubMed

    Pokorný, J; Tài, P; Parízková, H; Smidrkalová, E; El-Tarras, M F; Janícek, G

    1976-01-01

    Olive oil was converted into methyl esters which were autoxidized at 60 degrees C. The composition of oxidized products was determined by the comparison of infrared spectra and NMR spectra of the original and acetylated samples, the sample reduced with potassium iodide and the acetylated reduced sample. Oxidized products were separated by preparative thin layer chromatography on silica gel and characterized by selective detection and by infrared spectrometry of the fractions. The oxidation products consisted of hydroperoxido butyl oleate, substituted hydroperoxides, mono- and disubstituted monomeric derivatives and a small amount of oligomers.

  2. Pro-Oxidant Biological Effects of Inorganic Component of Petroleum: Vanadium and Oxidative Stress

    DTIC Science & Technology

    1996-08-01

    independent existence. Pro-Oxidant Chemicals and Free Radicals Involved in Oxidative Stress Pro-Oxidant Chemicals Chemical and Metabolic Generation... metabolic reactions may generate primary free radicals (Fig. 1). Then, in an avalanche-type process, secondary free radicals and reactive oxygen species...vanadium absorption, distribution, metabolism , and disposition, and no pharmacokinetic model is available describing comparative kinetics and toxicity

  3. HfO2 Gate Dielectric on (NH4)2S Passivated (100) GaAs Grown by Atomic Layer Deposition

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

    Chen, P.T.; /Stanford U., Materials Sci. Dept.; Sun, Y.

    2007-09-28

    The interface between hafnium oxide grown by atomic layer deposition and (100) GaAs treated with HCl cleaning and (NH{sub 4}){sub 2}S passivation has been characterized. Synchrotron radiation photoemission core level spectra indicated successful removal of the native oxides and formation of passivating sulfides on the GaAs surface. Layer-by-layer removal of the hafnia film revealed a small amount of As{sub 2}O{sub 3} formed at the interface during the dielectric deposition. Traces of arsenic and sulfur out-diffusion into the hafnia film were observed after a 450 C post-deposition anneal, and may be the origins for the electrically active defects. Transmission electron microscopymore » cross section images showed thicker HfO{sub 2} films for a given precursor exposure on S-treated GaAs versus the non-treated sample. In addition, the valence-band and the conduction-band offsets at the HfO{sub 2}/GaAs interface were deduced to be 3.18 eV and a range of 0.87-0.97 eV, respectively. It appears that HCl+(NH{sub 4})2{sub S} treatments provide a superior chemical passivation for GaAs and initial surface for ALD deposition.« less

  4. Steep-slope hysteresis-free negative capacitance MoS2 transistors

    NASA Astrophysics Data System (ADS)

    Si, Mengwei; Su, Chun-Jung; Jiang, Chunsheng; Conrad, Nathan J.; Zhou, Hong; Maize, Kerry D.; Qiu, Gang; Wu, Chien-Ting; Shakouri, Ali; Alam, Muhammad A.; Ye, Peide D.

    2018-01-01

    The so-called Boltzmann tyranny defines the fundamental thermionic limit of the subthreshold slope of a metal-oxide-semiconductor field-effect transistor (MOSFET) at 60 mV dec-1 at room temperature and therefore precludes lowering of the supply voltage and overall power consumption1,2. Adding a ferroelectric negative capacitor to the gate stack of a MOSFET may offer a promising solution to bypassing this fundamental barrier3. Meanwhile, two-dimensional semiconductors such as atomically thin transition-metal dichalcogenides, due to their low dielectric constant and ease of integration into a junctionless transistor topology, offer enhanced electrostatic control of the channel4-12. Here, we combine these two advantages and demonstrate a molybdenum disulfide (MoS2) two-dimensional steep-slope transistor with a ferroelectric hafnium zirconium oxide layer in the gate dielectric stack. This device exhibits excellent performance in both on and off states, with a maximum drain current of 510 μA μm-1 and a sub-thermionic subthreshold slope, and is essentially hysteresis-free. Negative differential resistance was observed at room temperature in the MoS2 negative-capacitance FETs as the result of negative capacitance due to the negative drain-induced barrier lowering. A high on-current-induced self-heating effect was also observed and studied.

  5. Evolution of Near-Surface Internal and External Oxide Morphology During High-Temperature Selective Oxidation of Steels

    NASA Astrophysics Data System (ADS)

    Story, Mary E.; Webler, Bryan A.

    2018-05-01

    In this work we examine some observations made using high-temperature confocal scanning laser microscopy (HT-CSLM) during selective oxidation experiments. A plain carbon steel and advanced high-strength steel (AHSS) were selectively oxidized at high temperature (850-900°C) in either low oxygen or water vapor atmospheres. Surface evolution, including thermal grooving along grain boundaries and oxide growth, was viewed in situ during heating. Experiments investigated the influence of the microstructure and oxidizing atmosphere on selective oxidation behavior. Sequences of CSLM still frames collected during the experiment were processed with ImageJ to obtain histograms that showed a general darkening trend indicative of oxidation over time with all samples. Additional ex situ scanning electron microscopy and energy dispersive spectroscopy analysis supported in situ observations. Distinct oxidation behavior was observed for each case. Segregation, grain orientation, and extent of internal oxidation were all found to strongly influence surface evolution.

  6. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION POTENTIAL, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  7. Hafnium and neodymium isotopes and REY distribution in the truly dissolved, nanoparticulate/colloidal and suspended loads of rivers in the Amazon Basin, Brazil

    NASA Astrophysics Data System (ADS)

    Merschel, Gila; Bau, Michael; Schmidt, Katja; Münker, Carsten; Dantas, Elton L.

    2017-09-01

    Radiogenic isotopes in river sediments and river waters have been widely used in provenance studies, as these samples naturally integrate the geology/chemistry of the entire catchment. While the Hf and Nd isotope systems are coupled during igneous processes, they are decoupled during supergene processes at the Earth's surface, which is reflected by the isotope composition of riverine sediments. We present the first data for both Hf and Nd isotope compositions of the dissolved (0.2 μm-filtrates rich in nanoparticles and colloids, NPCs) and the truly dissolved (1 kDa-ultrafiltrates) load of rivers. Hafnium and Nd isotope compositions and concentrations of the Rare Earths and Yttrium (REY) and Hf were determined for suspended particles (>0.2 μm) as well as for the dissolved and the truly dissolved load of the Rio Solimões, the Amazon's largest tributary draining the Andes, and of the Rio Negro, an organic NPC- and particle-rich river draining the rainforest of northern Amazonia. We also analyzed the Nd isotope compositions of suspended sediments and 0.2 μm-filtered water samples from the Amazon River and its tributaries Rio Tapajos, Rio Xingu and Rio Jari. Our novel results clearly show that the decoupling of the Hf and Nd isotope systems is related to incongruent weathering processes on the continent, as this decoupling can already be observed in the different Hf and Nd pools, i.e. in the particulate, the NPC-dominated dissolved and the truly dissolved load of rivers. In the Rio Negro and Rio Solimões, a strong particle size-dependent difference in Hf isotope composition is observed. Values of εHf become more radiogenic as filter poresize decreases, which can be related to the density- and size-dependent distribution of Hf-rich minerals, e.g. zircons, and their absence from the truly dissolved pool. In contrast, the Nd isotope composition of Amazonian river waters reflects that of their catchment geology. Tributaries draining the Precambrian Brazilian and

  8. Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

    NASA Astrophysics Data System (ADS)

    Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

    2015-12-01

    Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

  9. Cordierite-supported metal oxide for non-methane hydrocarbon oxidation in cooking oil fumes.

    PubMed

    Huang, Yonghai; Yi, Honghong; Tang, Xiaolong; Zhao, Shunzheng; Gao, Fengyu; Wang, Jiangen; Yang, Zhongyu

    2018-05-21

    Cooking emission is an important reason for the air quality deterioration in the metropolitan area in China. Transition metal oxide and different loading of manganese oxide supported on cordierite were prepared by incipient wetness impregnation method and were used for non-methane hydrocarbon (NMHC) oxidation in cooking oil fumes (COFs). The effects of different calcination temperature and different Mn content were also studied. The SEM photographs and CO 2 temperature-programmed desorption revealed 5 wt% Mn/cordierite had the best pore structure and the largest number of the weak and moderate basic sites so it showed the best performance for NMHC oxidation. XRD analysis exhibited 5 wt% Mn/cordierite had the best dispersion of active phase and the active phase was MnO 2 when the calcination temperature was 400℃ which were good for the catalytic oxidation of NMHC.

  10. 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.

  11. Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates.

    PubMed

    Zhang, Miao; Frei, Heinz

    2017-05-05

    Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. Combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

  12. [Increasing oxidative stress in aging].

    PubMed

    Shimosawa, Tatsuo

    2005-06-01

    The balance between reactive oxigen species (ROS) production and degradation is important in defining oxidative stress. In aging process, ROS production increases and degradation is impaired and thus oxidative stress is accumulated. Oxidative stress damages organs both directly and indirectly. Protein, lipid, as well as DNA are directly react with ROS, more over, ROS interact with intracellular signaling system. It is reported that several transcription factors such as NF-kappaB, AP-1 and ASK-1 and also it interferes MAPK activity. Besides these signaling, we recently showed that insulin resistance is induced by accumulated oxidative stress in aged mice. Adrenomedullin deficient mice accumulate higher oxidative stress and insulin resistance developed in aging. Oxidative stress in aging relates not only direct organ damage but also induce risk factors for vascular damage such as metabolic syndrome.

  13. Fabrication of cermet bearings for the control system of a high temperature lithium cooled nuclear reactor

    NASA Technical Reports Server (NTRS)

    Yacobucci, H. G.; Heestand, R. L.; Kizer, D. E.

    1973-01-01

    The techniques used to fabricate cermet bearings for the fueled control drums of a liquid metal cooled reference-design reactor concept are presented. The bearings were designed for operation in lithium for as long as 5 years at temperatures to 1205 C. Two sets of bearings were fabricated from a hafnium carbide - 8-wt. % molybdenum - 2-wt. % niobium carbide cermet, and two sets were fabricated from a hafnium nitride - 10-wt. % tungsten cermet. Procedures were developed for synthesizing the material in high purity inert-atmosphere glove boxes to minimize oxygen content in order to enhance corrosion resistance. Techniques were developed for pressing cylindrical billets to conserve materials and to reduce machining requirements. Finishing was accomplished by a combination of diamond grinding, electrodischarge machining, and diamond lapping. Samples were characterized in respect to composition, impurity level, lattice parameter, microstructure and density.

  14. Aspirin increases mitochondrial fatty acid oxidation

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

    Uppala, Radha; Dudiak, Brianne; Beck, Megan E.

    The metabolic effects of salicylates are poorly understood. This study investigated the effects of aspirin on fatty acid oxidation. Aspirin increased mitochondrial long-chain fatty acid oxidation, but inhibited peroxisomal fatty acid oxidation, in two different cell lines. Aspirin increased mitochondrial protein acetylation and was found to be a stronger acetylating agent in vitro than acetyl-CoA. However, aspirin-induced acetylation did not alter the activity of fatty acid oxidation proteins, and knocking out the mitochondrial deacetylase SIRT3 did not affect the induction of long-chain fatty acid oxidation by aspirin. Aspirin did not change oxidation of medium-chain fatty acids, which can freely traverse themore » mitochondrial membrane. Together, these data indicate that aspirin does not directly alter mitochondrial matrix fatty acid oxidation enzymes, but most likely exerts its effects at the level of long-chain fatty acid transport into mitochondria. The drive on mitochondrial fatty acid oxidation may be a compensatory response to altered mitochondrial morphology and inhibited electron transport chain function, both of which were observed after 24 h incubation of cells with aspirin. These studies provide insight into the pathophysiology of Reye Syndrome, which is known to be triggered by aspirin ingestion in patients with fatty acid oxidation disorders. - Highlights: • Aspirin increases mitochondrial—but inhibits peroxisomal—fatty acid oxidation. • Aspirin acetylates mitochondrial proteins including fatty acid oxidation enzymes. • SIRT3 does not influence the effect of aspirin on fatty acid oxidation. • Increased fatty acid oxidation is likely due to altered mitochondrial morphology and respiration.« less

  15. OXIDATION OF TRANSURANIC ELEMENTS

    DOEpatents

    Moore, R.L.

    1959-02-17

    A method is reported for oxidizing neptunium or plutonium in the presence of cerous values without also oxidizing the cerous values. The method consists in treating an aqueous 1N nitric acid solution, containing such cerous values together with the trivalent transuranic elements, with a quantity of hydrogen peroxide stoichiometrically sufficient to oxidize the transuranic values to the hexavalent state, and digesting the solution at room temperature.

  16. Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

    USGS Publications Warehouse

    Wang, Bronwen; Burau, Richard G.

    1995-01-01

    Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

  17. X-ray detection capabilities of plastic scintillators incorporated with hafnium oxide nanoparticles surface-modified with phenyl propionic acid

    NASA Astrophysics Data System (ADS)

    Hiyama, Fumiyuki; Noguchi, Takio; Koshimizu, Masanori; Kishimoto, Shunji; Haruki, Rie; Nishikido, Fumihiko; Yanagida, Takayuki; Fujimoto, Yutaka; Aida, Tsutomu; Takami, Seiichi; Adschiri, Tadafumi; Asai, Keisuke

    2018-01-01

    We synthesized plastic scintillators incorporated with HfO2 nanoparticles as detectors for X-ray synchrotron radiation. Nanoparticles with sizes of less than 10 nm were synthesized with the subcritical hydrothermal method. The detection efficiency of high-energy X-ray photons improved by up to 3.3 times because of the addition of the nanoparticles. Nanosecond time resolution was successfully achieved for all the scintillators. These results indicate that this method is applicable for the preparation of plastic scintillators to detect X-ray synchrotron radiation.

  18. The development of latent fingerprints by zinc oxide and tin oxide nanoparticles prepared by precipitation technique

    NASA Astrophysics Data System (ADS)

    Luthra, Deepali; Kumar, Sacheen

    2018-05-01

    Fingerprints are the very important evidence at the crime scene which must be developed clearly with shortest duration of time to solve the case. Metal oxide nanoparticles could be the mean to develop the latent fingerprints. Zinc oxide and Tin Oxide Nanoparticles were prepared by using chemical precipitation technique which were dried and characterized by X-ray diffraction, UV-Visible spectroscopy and FTIR. The size of zinc oxide crystallite was found to be 14.75 nm with minimum reflectance at 360 nm whereas tin oxide have the size of 90 nm and reflectance at minimum level 321 nm. By using these powdered samples on glass, plastic and glossy cardboard, latent fingerprints were developed. Zinc oxide was found to be better candidate than tin oxide for the fingerprint development on all the three types of substrates.

  19. Understanding complete oxidation of methane on spinel oxides at a molecular level

    DOE PAGES

    Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; ...

    2015-08-04

    It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo 2O 4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo 2O 4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo 2Omore » 4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH 3O with a following dehydrogenation to -CH 2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.« less

  20. Biogeochemistry of Fe(II) oxidation in a photosynthetic microbial mat: Implications for Precambrian Fe(II) oxidation

    NASA Astrophysics Data System (ADS)

    Trouwborst, Robert E.; Johnston, Anne; Koch, Gretchen; Luther, George W.; Pierson, Beverly K.

    2007-10-01

    We studied the role of microbial photosynthesis in the oxidation of Fe(II) to Fe(III) in a high Fe(II) and high Mn(II) hot spring devoid of sulfide and atmospheric oxygen in the source waters. In situ light and dark microelectrode measurements of Fe(II), Mn(II) and O 2 were made in the microbial mat consisting of cyanobacteria and anoxygenic photosynthetic Chloroflexus sp. We show that Fe(II) oxidation occurred when the mat was exposed to varying intensities of sunlight but not near infrared light. We did not observe any Mn(II) oxidation under any light or dark condition over the pH range 5-7. We observed the impact of oxygenic photosynthesis on Fe(II) oxidation, distinct from the influence of atmospheric O 2 and anoxygenic photosynthesis. In situ Fe(II) oxidation rates in the mats and cell suspensions exposed to light are consistent with abiotic oxidation by O 2. The oxidation of Fe(II) to form primary Fe(III) phases contributed to banded iron-formations (BIFs) during the Precambrian. Both oxygenic photosynthesis, which produces O 2 as an oxidizing waste product, and anoxygenic photosynthesis in which Fe(II) is used to fix CO 2 have been proposed as Fe(II) oxidation mechanisms. Although we do not know the specific mechanisms responsible for all Precambrian Fe(II) oxidation, we assessed the relative importance of both mechanisms in this modern hot spring environment. In this environment, cyanobacterial oxygen production accounted for all the observed Fe(II) oxidation. The rate data indicate that a modest population of cyanobacteria could have mediated sufficient Fe(II) oxidation for some BIFs.