SrZrO 3 Formation at the Interlayer/Electrolyte Interface during (La 1-xSr x) 1-δCo 1-yFe yO 3 Cathode Sintering

DOE PAGES

Lu, Zigui; Darvish, Shadi; Hardy, John; ...

2017-07-19

This work probes the formation of SrZrO 3 at the SDC/YSZ interface (Sm doped ceria, SDC; Y stabilized zirconia, YSZ) during (La 1-xSr x) 1-δCo1 -yFe yO 3 (LSCF) cathode sintering. SEM/EDS and grazing incidence X-ray diffraction results of annealed LSCF and YSZ samples reveal that even without physical contact between LSCF and YSZ, SrZrO 3 was formed on the surface of YSZ, preferentially at the grain boundaries. It was suspected that the SrZrO 3 formation is due to the Sr-containing gas species diffused through the pores of the SDC layer and reacted with the YSZ electrolyte. Computational thermodynamics wasmore » adopted to predict the gas species formed in air during sintering by using the La-Sr-Co-Fe-O-H thermodynamic database. Sr(OH) 2 is identified as the dominant Sr-containing gas species under the experimental conditions. In addition, it was found that A-site deficiency in LSCF could effectively suppress the SrZrO 3 formation while a dense and pore-free SDC interlayer is required to totally block the SrZrO 3 formation. As a result, cell performance was significantly improved for a cell with a dense SDC interlayer fabricated by pulsed laser deposition, due to elimination of SrZrO 3 formation and therefore reduced interfacial resistance.« less

SrZrO 3 Formation at the Interlayer/Electrolyte Interface during (La 1-xSr x) 1-δCo 1-yFe yO 3 Cathode Sintering

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

Lu, Zigui; Darvish, Shadi; Hardy, John

This work probes the formation of SrZrO 3 at the SDC/YSZ interface (Sm doped ceria, SDC; Y stabilized zirconia, YSZ) during (La 1-xSr x) 1-δCo1 -yFe yO 3 (LSCF) cathode sintering. SEM/EDS and grazing incidence X-ray diffraction results of annealed LSCF and YSZ samples reveal that even without physical contact between LSCF and YSZ, SrZrO 3 was formed on the surface of YSZ, preferentially at the grain boundaries. It was suspected that the SrZrO 3 formation is due to the Sr-containing gas species diffused through the pores of the SDC layer and reacted with the YSZ electrolyte. Computational thermodynamics wasmore » adopted to predict the gas species formed in air during sintering by using the La-Sr-Co-Fe-O-H thermodynamic database. Sr(OH) 2 is identified as the dominant Sr-containing gas species under the experimental conditions. In addition, it was found that A-site deficiency in LSCF could effectively suppress the SrZrO 3 formation while a dense and pore-free SDC interlayer is required to totally block the SrZrO 3 formation. As a result, cell performance was significantly improved for a cell with a dense SDC interlayer fabricated by pulsed laser deposition, due to elimination of SrZrO 3 formation and therefore reduced interfacial resistance.« less

Mesoporous titanium dioxide (TiO2) with hierarchically 3D dendrimeric architectures: formation mechanism and highly enhanced photocatalytic activity.

PubMed

Li, Xiao-Yun; Chen, Li-Hua; Rooke, Joanna Claire; Deng, Zhao; Hu, Zhi-Yi; Wang, Shao-Zhuan; Wang, Li; Li, Yu; Krief, Alain; Su, Bao-Lian

2013-03-15

Mesoporous TiO(2) with a hierarchically 3D dendrimeric nanostructure comprised of nanoribbon building units has been synthesized via a spontaneous self-formation process from various titanium alkoxides. These hierarchically 3D dendrimeric architectures can be obtained by a very facile, template-free method, by simply dropping a titanium butoxide precursor into methanol solution. The novel configuration of the mesoporous TiO(2) nanostructure in nanoribbon building units yields a high surface area. The calcined samples show significantly enhanced photocatalytic activity and degradation rates owing to the mesoporosity and their improved crystallinity after calcination. Furthermore, the 3D dendrimeric architectures can be preserved after phase transformation from amorphous TiO(2) to anatase or rutile, which occurs during calcination. In addition, the spontaneous self-formation process of mesoporous TiO(2) with hierarchically 3D dendrimeric architectures from the hydrolysis and condensation reaction of titanium butoxide in methanol has been followed by in situ optical microscopy (OM), revealing the secret on the formation of hierarchically 3D dendrimeric nanostructures. Moreover, mesoporous TiO(2) nanostructures with similar hierarchically 3D dendrimeric architectures can also be obtained using other titanium alkoxides. The porosities and nanostructures of the resultant products were characterized by SEM, TEM, XRD, and N(2) adsorption-desorption measurements. The present work provides a facile and reproducible method for the synthesis of novel mesoporous TiO(2) nanoarchitectures, which in turn could herald the fabrication of more efficient photocatalysts. Copyright © 2012 Elsevier Inc. All rights reserved.

Thermal decomposition of FC(O)OCH3 and FC(O)OCH2CH3.

PubMed

Berasategui, M; Argüello, G A; Burgos Paci, M A

2018-05-09

The thermal decomposition of methyl and ethyl formates has been extensively studied due to their importance in the oxidation of several fuels, pesticidal properties and their presence in interstellar space. We hitherto present the study of the thermal decomposition of methyl and ethyl fluoroformates, which could help in the elucidation of the reaction mechanisms. The reaction mechanisms were studied using FTIR spectroscopy in the temperature range of 453-733 K in the presence of different pressures of N2 as bath gas. For FC(O)OCH3 two different channels were observed; the unimolecular decomposition which is favored at higher temperatures and has a rate constant kFC(O)OCH3 = (5.3 ± 0.5) × 1015 exp[-(246 ± 10 kJ mol-1/RT)] (in units of s-1) and a bimolecular channel with a rate constant kFC(O)OCH3 = (1.6 ± 0.5) × 1011 exp[-(148 ± 10 kJ mol-1/RT)] (in units of s-1 (mol L)-1). However for ethyl formate, only direct elimination of CO2, HF and ethylene operates. The rate constants of the homogeneous first-order process fit the Arrhenius equation kFC(O)OCH2CH3 = (2.06 ± 0.09) × 1013 exp[-(169 ± 6 kJ mol-1/RT)] (in units of s-1). The difference between the mechanisms of the two fluoroformates relies on the stabilization of a six-centered transition state that only exists for ethyl formate. First principles calculations for the different channels were carried out to understand the dynamics of the decomposition.

Formation mechanisms of Fe3−xSnxO4 by a chemical vapor transport (CVT) process

PubMed Central

Su, Zijian; Zhang, Yuanbo; Liu, Bingbing; Chen, Yingming; Li, Guanghui; Jiang, Tao

2017-01-01

Our former study reported that Fe-Sn spinel (Fe3−xSnxO4) was easily formed when SnO2 and Fe3O4 were roasted under CO-CO2 atmosphere at 900–1100 °C. However, the formation procedure is still unclear and there is a lack of theoretical research on the formation mechanism of the Fe-Sn spinel. In this work, the reaction mechanisms between SnO2 and Fe3O4 under CO-CO2 atmosphere were determined using XRD, VSM, SEM-EDS, XPS, etc. The results indicated that the formation of Fe3−xSnxO4 could be divided into four steps: reduction of SnO2 to solid phase SnO, volatilization of gaseous SnO, adsorption of gaseous SnO on the surface of Fe3O4, and redox reaction between SnO and Fe3O4. During the roasting process, part of Fe3+ in Fe3O4 was reduced to Fe2+ by gaseous SnO, and meanwhile Sn2+ was oxidized to Sn4+ and entered into Fe3−xSnxO4. The reaction between SnO2 and Fe3O4 could be summarized as Fe3O4 + xSnO(g) → Fe3−xSnxO4 (x = 0–1.0). PMID:28262673

Strain dynamics during La{sub 2}O{sub 3}/Lu{sub 2}O{sub 3} superlattice and alloy formation

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

Proessdorf, André; Niehle, Michael; Grosse, Frank

The dynamics of strain relaxation and intermixing during molecular beam epitaxy of La{sub 2}O{sub 3} and Lu{sub 2}O{sub 3} superlattices and alloys consisting of both binaries on Si(111) have been studied by real-time in situ grazing incidence x-ray diffraction and high resolution transmission electron microscopy. The presence of both hexagonal and cubic polymorphs of La{sub 2}O{sub 3} influences the epitaxial formation within the superlattice. The process of strain relaxation is closely related to the presence of a (La,Lu){sub 2}O{sub 3} alloy adopting a cubic symmetry. It is formed by interdiffusion of La and Lu atoms reducing internal lattice mismatch withinmore » the superlattice. An interface thickness dominated by interdiffusion regions of about 3 monolayers is determined by high-angle annular dark field scanning transmission electron microscopy.« less

Hemoglobin as a nitrite anhydrase: modeling methemoglobin-mediated N2O3 formation.

PubMed

Hopmann, Kathrin H; Cardey, Bruno; Gladwin, Mark T; Kim-Shapiro, Daniel B; Ghosh, Abhik

2011-05-27

Nitrite has recently been recognized as a storage form of NO in blood and as playing a key role in hypoxic vasodilation. The nitrite ion is readily reduced to NO by hemoglobin in red blood cells, which, as it happens, also presents a conundrum. Given NO's enormous affinity for ferrous heme, a key question concerns how it escapes capture by hemoglobin as it diffuses out of the red cells and to the endothelium, where vasodilation takes place. Dinitrogen trioxide (N(2)O(3)) has been proposed as a vehicle that transports NO to the endothelium, where it dissociates to NO and NO(2). Although N(2)O(3) formation might be readily explained by the reaction Hb-Fe(3+)+NO(2)(-)+NO⇌Hb-Fe(2+)+N(2)O(3), the exact manner in which methemoglobin (Hb-Fe(3+)), nitrite and NO interact with one another is unclear. Both an "Hb-Fe(3+)-NO(2)(-)+NO" pathway and an "Hb-Fe(3+)-NO+NO(2)(-) " pathway have been proposed. Neither pathway has been established experimentally. Nor has there been any attempt until now to theoretically model N(2)O(3) formation, the so-called nitrite anhydrase reaction. Both pathways have been examined here in a detailed density functional theory (DFT, B3LYP/TZP) study and both have been found to be feasible based on energetics criteria. Modeling the "Hb-Fe(3+)-NO(2)(-)+NO" pathway proved complex. Not only are multiple linkage-isomeric (N- and O-coordinated) structures conceivable for methemoglobin-nitrite, multiple isomeric forms are also possible for N(2)O(3) (the lowest-energy state has an N-N-bonded nitronitrosyl structure, O(2)N-NO). We considered multiple spin states of methemoglobin-nitrite as well as ferromagnetic and antiferromagnetic coupling of the Fe(3+) and NO spins. Together, the isomerism and spin variables result in a diabolically complex combinatorial space of reaction pathways. Fortunately, transition states could be successfully calculated for the vast majority of these reaction channels, both M(S)=0 and M(S)=1. For a six-coordinate Fe(3+)-O

Magnetic order and polaron formation in hole-doped LaMnO_3

NASA Astrophysics Data System (ADS)

Terashita, Hirotoshi; Neumeier, John J.; Mitchell, J. F.

2003-03-01

We report the magnetic properties of hole-doped La_1-xCa_xMnO3 (0 <= x <= 0.14). A ferromagnetic saturation moment M_sat develops linearly with Mn^4+ concentration. The slope of M_sat versus Mn^4+ concentration is 27 μ_B/(Mn-ion) per substututed Mn^4+, which is about 3 times larger in magnitude than that of electron-doped CaMnO3 [1]. This result suggests differences in the formation of magnetic polarons of the A-type antiferromagnet LaMnO3 versus that of the G-type antiferromagnet CaMnO_3. Supported by NSF Grant DMR9982834 and the USDOE under contract W-31-109-ENG-38. [1] J. J. Neumeier and J. L. Cohn, Phys. Rev. B 61, 14319 (2000).

Heating rate effects in simulated liquid Al2O_3

NASA Astrophysics Data System (ADS)

van Hoang, Vo

2006-01-01

The heating rate effects in simulated liquid Al{2}O{3} have been investigated by Molecular Dynamics (MD) method. Simulations were done in the basic cube under periodic boundary conditions containing 3000 ions with Born-Mayer type pair potentials. The temperature of the system was increasing linearly in time from the zero temperature as T(t)=T0 +γ t, where γ is the heating rate. The heating rate dependence of density and enthalpy of the system was found. Calculations show that static properties of the system such as the coordination number distributions and bond-angle distributions slightly depend on γ . Structure of simulated amorphous Al{2}O{3} model with the real density at the ambient pressure is in good agreement with Lamparter's experimental data. The heating rate dependence of dynamics of the system has been studied through the diffusion constant, mean-squared atomic displacement and comparison of partial radial distribution functions (PRDFs) for 10% most mobile and immobile particles with the corresponding mean ones. Finally, the evolution of diffusion constant of Al and O particles and structure of the system upon heating for the smallest heating rate was studied and presented. And we find that the temperature dependence of self-diffusion constant in the high temperature region shows a crossover to one which can be described well by a power law, D∝ (T-Tc )^γ . The critical temperature Tc is about 3500 K and the exponent γ is close to 0.941 for Al and to 0.925 for O particles. The glass phase transition temperature Tg for the Al{2}O{3} system is at anywhere around 2000 K.

Estimation of total rate of formation of nitric oxide in the rat.

PubMed Central

Sakinis, A; Wennmalm, A

1998-01-01

Nitric oxide (NO) is a powerful mediator with important actions in several organ systems. NO is synthesized during the enzymatic conversion of l-arginine and molecular oxygen to L-citrulline. About 90% of the NO formed is degraded to nitrate. Utilizing this information we have developed a method for assessment of the total rate of formation of NO in the rat. Male Wistar rats were kept in a closed-cage system allowing controlled breathing of a mixture of 18O2 and 16O2 in N2 for up to 5h. Blood samples for mass spectrometric analysis of nitrate residues with varying numbers of 18O atoms incorporated were drawn before and during the exposure to 18O2. By comparing the relative incorporation of 18O into nitrate residues to the 16O2/18O2 ratio in the breathing gas mixture in the cage system it was possible to calculate the absolute rate of NO formation in the animal. The rate of formation of NO in anaesthetized rats ranged from 0.33 to 0.85 micromol.kg-1.h-1. The rate of formation did not differ significantly in rats which were awake during the experiment (range 0.36-0.72 micromol.kg-1.h-1). The L-arginine analogue Nomega-nitro-L-arginine methyl ester (L-NAME) dose-dependently inhibited the formation of NO, at a dose of 100mg/kg by more than 99%. The technique presented allows estimation of the total rate of formation of NO in vivo in rats. Application of the technique may yield important information about the physiological and pathophysiological roles of NO. It may also be utilized to evaluate the effect of pharmacological treatment on NO formation. PMID:9461552

Measurements of reactive trace gases and variable O 3 formation rates in some South Carolina biomass burning plumes

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

Akagi, S. K.; Yokelson, R. J.; Burling, I. R.

2013-02-01

. It was possible to measure the chemical evolution of the plume on four of the fires and significant ozone (O 3) formation (ΔO 3/ΔCO from 10-90%) occurred in all of these plumes. Slower O 3 production was observed on a cloudy day with low co-emissions of NO x and the fastest O 3 production was observed on a sunny day when the plume almost certainly incorporated significant additional NO x by passing over the Columbia, SC metropolitian area. Due to rapid plume dilution, it was only possible to acquire high quality downwind data for two other species (formaldehyde and methanol) on two of the fires. In all four cases significant increases were observed. Finally, this is likely the first direct observation of post-emission methanol production in biomass burning plumes and the precursors likely included terpenes.« less

Herschel Survey of Galactic OH+, H2O+, and H3O+: Probing the Molecular Hydrogen Fraction and Cosmic-Ray Ionization Rate

NASA Astrophysics Data System (ADS)

Indriolo, Nick; Neufeld, D. A.; Gerin, M.; Schilke, P.; Benz, A. O.; Winkel, B.; Menten, K. M.; Chambers, E. T.; Black, John H.; Bruderer, S.; Falgarone, E.; Godard, B.; Goicoechea, J. R.; Gupta, H.; Lis, D. C.; Ossenkopf, V.; Persson, C. M.; Sonnentrucker, P.; van der Tak, F. F. S.; van Dishoeck, E. F.; Wolfire, Mark G.; Wyrowski, F.

2015-02-01

In diffuse interstellar clouds the chemistry that leads to the formation of the oxygen-bearing ions OH+, H2O+, and H3O+ begins with the ionization of atomic hydrogen by cosmic rays, and continues through subsequent hydrogen abstraction reactions involving H2. Given these reaction pathways, the observed abundances of these molecules are useful in constraining both the total cosmic-ray ionization rate of atomic hydrogen (ζH) and molecular hydrogen fraction (f_H_2). We present observations targeting transitions of OH+, H2O+, and H3O+ made with the Herschel Space Observatory along 20 Galactic sight lines toward bright submillimeter continuum sources. Both OH+ and H2O+ are detected in absorption in multiple velocity components along every sight line, but H3O+ is only detected along 7 sight lines. From the molecular abundances we compute f_H_2 in multiple distinct components along each line of sight, and find a Gaussian distribution with mean and standard deviation 0.042 ± 0.018. This confirms previous findings that OH+ and H2O+ primarily reside in gas with low H2 fractions. We also infer ζH throughout our sample, and find a lognormal distribution with mean log (ζH) = -15.75 (ζH = 1.78 × 10-16 s-1) and standard deviation 0.29 for gas within the Galactic disk, but outside of the Galactic center. This is in good agreement with the mean and distribution of cosmic-ray ionization rates previously inferred from H_3^+ observations. Ionization rates in the Galactic center tend to be 10-100 times larger than found in the Galactic disk, also in accord with prior studies. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

High rate dry etching of InGaZnO by BCl3/O2 plasma

NASA Astrophysics Data System (ADS)

Park, Wanjae; Whang, Ki-Woong; Gwang Yoon, Young; Hwan Kim, Jeong; Rha, Sang-Ho; Seong Hwang, Cheol

2011-08-01

This paper reports the results of the high-rate dry etching of indium gallium zinc oxide (IGZO) at room temperature using BCl3/O2 plasma. We achieved an etch rate of 250 nm/min. We inferred from the x-ray photoelectron spectroscopy analysis that BOx or BOClx radicals generated from BCl3/O2 plasma cause the etching of the IGZO material. O2 initiates the etching of IGZO, and Ar removes nonvolatile byproducts from the surface during the etching process. Consequently, a smooth etched surface results when these gases are added to the etch gas.

The Vaporization of B2O3(l) to B2O3(g) and B2O2(g)

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Myers, Dwight L.

2011-01-01

The vaporization of B2O3 in a reducing environment leads to formation of both B2O3(g) and B2O2(g). While formation of B2O3(g) is well understood, many questions about the formation of B2O2(g) remain. Previous studies using B(s) + B2O3(l) have led to inconsistent thermodynamic data. In this study, it was found that after heating, B(s) and B2O3(l) appear to separate and variations in contact area likely led to the inconsistent vapor pressures of B2O2(g). To circumvent this problem, an activity of boron is fixed with a two-phase mixture of FeB and Fe2B. Both second and third law enthalpies of formation were measured for B2O2(g) and B2O3(g). From these the enthalpies of formation at 298.15 K are calculated to be -479.9 +/- 41.5 kJ/mol for B2O2(g) and -833.4 +/- 13.1 kJ/mol for B2O3(g). Ab initio calculations to determine the enthalpies of formation of B2O2(g) and B2O3(g) were conducted using the W1BD composite method and show good agreement with the experimental values.

Effect of Er3+ ions on the phase formation and properties of In2O3nanostructures crystallized upon microwave heating

NASA Astrophysics Data System (ADS)

Lemos, Samantha C. S.; Romeiro, Fernanda C.; de Paula, Leonardo F.; Gonçalves, Rosana F.; de Moura, Ana P.; Ferrer, Mateus M.; Longo, Elson; Patrocinio, Antonio Otavio T.; Lima, Renata C.

2017-05-01

Regular sized nanostructures of indium oxide (In2O3) were homogeneously grown using a facile route, i.e. a microwave-hydrothermal method combined with rapid thermal treatment in a microwave oven. The presence of Er3+ doping plays an important role in controlling the formation of cubic (bcc) and rhombohedral (rh) In2O3 phases. The samples presented broad photoluminescent emission bands in the green-orange region, which were attributed to the recombination of electrons at oxygen vacancies. The photocatalytic activities of pure bcc-In2O3 and a bcc-rh-In2O3 mixture towards the UVA degradation of methylene blue (MB) were also evaluated. The results showed that Er+3 doped In2O3 exhibited the highest photocatalytic activity with a photonic efficiency three times higher than the pure oxide. The improved performance was attributed to the higher surface area, the greater concentration of electron traps due the presence of the dopant and the possible formation of heterojunctions between the cubic and rhombohedral phases.

Secondary organic aerosol formation from in situ OH, O3, and NO3 oxidation of ambient forest air in an oxidation flow reactor

NASA Astrophysics Data System (ADS)

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; Ortega, Amber M.; Fry, Juliane L.; Brown, Steven S.; Zarzana, Kyle J.; Dube, William; Wagner, Nicholas L.; Draper, Danielle C.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

2017-04-01

Ambient pine forest air was oxidized by OH, O3, or NO3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O3 and NO3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20-30 min, in order to determine how the availability of SOA precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O3 or NO3 oxidation. This is likely because O3 and NO3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O3 and NO3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O3 and NO3 oxidation produced SOA with elemental O : C and H : C

Secondary organic aerosol formation from in situ OH, O 3, and NO 3 oxidation of ambient forest air in an oxidation flow reactor

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

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.

Ambient pine forest air was oxidized by OH, O 3, or NO 3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics and Nitrogen – Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O 3 and NO 3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20–30 min, in order to determine how the availability of SOAmore » precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O 3 or NO 3 oxidation. This is likely because O 3 and NO 3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O 3 and NO 3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O 3 and NO 3 oxidation produced SOA with

Secondary organic aerosol formation from in situ OH, O 3, and NO 3 oxidation of ambient forest air in an oxidation flow reactor

DOE PAGES

Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; ...

2017-04-25

Ambient pine forest air was oxidized by OH, O 3, or NO 3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H 2O, Organics and Nitrogen – Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O 3 and NO 3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20–30 min, in order to determine how the availability of SOAmore » precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O 3 or NO 3 oxidation. This is likely because O 3 and NO 3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O 3 and NO 3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O 3 and NO 3 oxidation produced SOA with

Effect of Cr2O3 Pickup on Dissolution of Lime in Converter Slag

NASA Astrophysics Data System (ADS)

Yan, Wei; Chen, Weiqing; Zhao, Xiaobo; Yang, Yindong; McLean, Alex

2017-09-01

Application of low-nickel laterite ore containing chromium as charging material for ironmaking can reduce raw material costs, but result in an increase of chromium content in the hot metal and hence, Cr2O3 content in the steelmaking slag, which subsequently causes many problems related to lime dissolution for the steelmaking operation. In this work, a rotating cylinder method was employed to study the effect of Cr2O3 on lime dissolution in steelmaking slag. The lime dissolution mechanism, rate control step and affecting factors, including slag basicity, FeOx and B2O3 content, and the formation of phases at reacted layer, were discussed. It was found that mass transfer was the rate control step in slag phase, increase of Cr2O3 and slag basicity delayed lime dissolution due to the formation of high-melting temperature phases of FeO · Cr2O3 spinel and 2CaO · SiO2 at the slag/lime reacted interface. Addition of B2O3 promoted lime dissolution and suppressed formation of FeO · Cr2O3 spinel.

Crystallization of 21.25Gd 2O 3-63.75MoO 3-15B 2O 3 glass induced by femtosecond laser at the repetition rate of 250 kHz

NASA Astrophysics Data System (ADS)

Zhong, M. J.; Han, Y. M.; Liu, L. P.; Zhou, P.; Du, Y. Y.; Guo, Q. T.; Ma, H. L.; Dai, Y.

2010-12-01

We report the formation of β'-Gd 2(MoO 4) 3 (GMO) crystal on the surface of the 21.25Gd 2O 3-63.75MoO 3-15B 2O 3 glass, induced by 250 kHz, 800 nm femtosecond laser irradiation. The morphology of the modified region in the glass was clearly examined by scanning electron microscopy (SEM). By micro-Raman spectra, the laser-induced crystals were confirmed to be GMO phases and it is found that these crystals have a strong dependence on the number and power of the femtosecond laser pulses. When the irradiation laser power was 900 mW, not only the Raman peaks of GMO crystals but also some new peaks at 214 cm -1, 240 cm -1, 466 cm -1, 664 cm -1 and 994 cm -1which belong to the MoO 3 crystals were observed. The possible mechanisms are proposed to explain these phenomena.

Formation mechanism of self-assembled polarization-dependent periodic nanostructures in β-Ga2O3

NASA Astrophysics Data System (ADS)

Nakanishi, Y.; Shimotsuma, Y.; Sakakura, M.; Shimizu, M.; Miura, K.

2018-02-01

We have successfully observed self-assembled periodic nanostructures inside Si single crystal and GaP crystal, by the femtosecond double-pulse irradiation. These results experimentally indicate that the self-assembly of the periodic nanostructures inside semiconductors triggered by ultrashort pulses irradiation are possibly associated with a direct or an indirect band gap. More recently we have also empirically classified the photoinduced bulk nanogratings into the following three types: (1) structural deficiency, (2) compressed structure, (3) partial crystallization. We have still a big question about what material properties are involved in the bulk nanograting structure formation. In this study, to expand the selectivity of the material for bulk nanograting formation, we have employed β-Ga2O3 crystals (indirect bandgap Eg 4.8 eV) as a sample for femtosecond laser irradiation. The nanograting structure inside β-Ga2O3 crystal was aligned perpendicular to the laser polarization direction. Such phenomenon is similar to the nanograting in SiO2 glass (Eg 9 eV). Moreover, to clarify the band structure, we have also investigate the photoinduced structure in Sn doped β-Ga2O3 crystals, which exhibit direct bandgap according to the first principle calculation.

AGN contamination in total infrared determined star formation rates in dusty galaxies at z~2-3

NASA Astrophysics Data System (ADS)

Mazzei, Renato; Sharon, Chelsea E.; Riechers, Dominik

2017-01-01

Along with theoretical work that suggests feedback from active galactic nuclei (AGN) may quench star formation in massive galaxies, the temporal coincidence between the peak of cosmic star formation rates and black hole accretion rates suggests that AGN are common in star forming galaxies at z~2-3. Since star forming galaxies at these epochs are also very dusty, it is important that we correct galaxies’ long-wavelength properties for the presence of dust-obscured AGN in order to accurately capture their star formation rates and gas characteristics. We present a spectral energy distribution (SED) analysis of several un-lensed z~2-3 dusty star-forming galaxies from Pope et al. (2008) and Coppin et al. (2010), which we compare to several other high-z starbursts with well sampled SEDs. We constructed dust SEDs from existing Spitzer, Herschel, and SCUBA-2 photometry catalogues with data between 3.6 and 850 μm. For the SED fits, we used the Code Investigating GALaxy Emission (CIGALE), since it self-consistently determines the dust attenuation of stars and dust emission in the infrared in addition to determining the dust emission from obscured AGN (Noll et al. 2009; Serra et al. 2011). Our best-fit SEDs have typical reduced χ2 values between 0.2 and ~3. We use the output from CIGALE to determine the fraction of the total infrared luminosity (LTIR 8-1000 um) from star formation and from any potential obscured AGN. In order to examine the effects of buried AGN on the integrated Schmidt-Kennicutt relation (log(LTIR) vs. log(L'CO)), we compare our new LTIR to recently obtained CO(1-0) line luminosities from the Karl G. Jansky Very Large Array. Unaccounted for dust emission from AGN can artificially inflate the star formation rate inferred from LTIR, and may therefore offset starburst galaxies from the local Schmidt-Kennicutt relation and increase the slope of the relation, which can affect the inferred drivers of star formation.

Ferrite Formation Dynamics and Microstructure Due to Inclusion Engineering in Low-Alloy Steels by Ti2O3 and TiN Addition

NASA Astrophysics Data System (ADS)

Mu, Wangzhong; Shibata, Hiroyuki; Hedström, Peter; Jönsson, Pär Göran; Nakajima, Keiji

2016-08-01

The dynamics of intragranular ferrite (IGF) formation in inclusion engineered steels with either Ti2O3 or TiN addition were investigated using in situ high temperature confocal laser scanning microscopy. Furthermore, the chemical composition of the inclusions and the final microstructure after continuous cooling transformation was investigated using electron probe microanalysis and electron backscatter diffraction, respectively. It was found that there is a significant effect of the chemical composition of the inclusions, the cooling rate, and the prior austenite grain size on the phase fractions and the starting temperatures of IGF and grain boundary ferrite (GBF). The fraction of IGF is larger in the steel with Ti2O3 addition compared to the steel with TiN addition after the same thermal cycle has been imposed. The reason for this difference is the higher potency of the TiO x phase as nucleation sites for IGF formation compared to the TiN phase, which was supported by calculations using classical nucleation theory. The IGF fraction increases with increasing prior austenite grain size, while the fraction of IGF in both steels was the highest for the intermediate cooling rate of 70 °C/min, since competing phase transformations were avoided, the structure of the IGF was though refined with increasing cooling rate. Finally, regarding the starting temperatures of IGF and GBF, they decrease with increasing cooling rate and the starting temperature of GBF decreases with increasing grain size, while the starting temperature of IGF remains constant irrespective of grain size.

The processes of formation and epitaxial alignment of SrTiO3 thin films prepared by metallo-organic decomposition

NASA Astrophysics Data System (ADS)

Braunstein, G.; Paz-Pujalt, G. R.; Mason, M. G.; Blanton, T.; Barnes, C. L.; Margevich, D.

1993-01-01

The processes of formation and crystallization of thin films of SrTiO3 prepared by the method of metallo-organic decomposition have been studied with particular emphasis on the relationship between the thermal decomposition of the metallo-organic precursors and the eventual epitaxial alignment of the crystallized films. The films are deposited by spin coating onto single-crystalline silicon and SrTiO3 substrates, pyrolyzed on a hot plate at temperatures ranging from 200 to 450 °C, and subsequently heat treated in a quartz tube furnace at temperatures ranging from 300 to 1200 °C. Heat treatment at temperatures up to 450-500 °C results in the evaporation of solvents and other organic addenda, thermal decomposition of the metallo-organic (primarily metal-carboxylates) precursors, and formation of a carbonate species. This carbonate appears to be an intermediate phase in the reaction of SrCO3 and TiO2 to form SrTiO3. Relevant to this work is the fact that the carbonate species exhibits diffraction lines, indicating the formation of grains that can serve as seeds for the nucleation and growth of randomly oriented SrTiO3 crystallites, thereby leading to a polycrystalline film. Deposition on silicon substrates indeed results in the formation of polycrystalline SrTiO3. However, when the precursor solution is deposited on single-crystalline SrTiO3 substrates, the crystallization process involves a competition between two mechanisms: the random nucleation and growth of crystallites just described, and layer-by-layer solid phase epitaxy. Epitaxial alignment on SrTiO3 substrates can be achieved when the samples are heat treated at temperatures of 1100-1200 °C or at temperatures as low as 600-650 °C when the substrate is heated to about 1100 °C before spin coating.

Operando identification of the point of [Mn- 2]O- 4 spinel formation during gamma-MnO 2 discharge within batteries

DOE PAGES

Gallaway, Joshua W.; Hertzberg, Benjamin J.; Zhong, Zhong; ...

2016-05-07

The rechargeability of γ-MnO 2 cathodes in alkaline batteries is limited by the formation of the [Mn 2]O 4 spinels ZnMn 2O 4 (hetaerolite) and Mn 3O 4 (hausmannite). However, the time and formation mechanisms of these spinels are not well understood. Here we directly observe γ-MnO 2 discharge at a range of reaction extents distributed across a thick porous electrode. Coupled with a battery model, this reveals that spinel formation occurs at a precise and predictable point in the reaction, regardless of reaction rate. Observation is accomplished by energy dispersive X-ray diffraction (EDXRD) using photons of high energy andmore » high flux, which penetrate the cell and provide diffraction data as a function of location and time. After insertion of 0.79 protons per γ-MnO 2 the α-MnOOH phase forms rapidly. α-MnOOH is the precursor to spinel, which closely follows. ZnMn 2O 4 and Mn 3O 4 form at the same discharge depth, by the same mechanism. The results show the final discharge product, Mn 3O 4 or Mn(OH) 2, is not an intrinsic property of γ-MnO 2. While several studies have identified Mn(OH) 2 as the final γ-MnO 2 discharge product, we observe direct conversion to Mn 3O 4 with no Mn(OH) 2.« less

Rate Coefficient for Collisional Removal of O2(X3Σ ^-g, v = 1) with O Atoms at 240 K

NASA Astrophysics Data System (ADS)

Pejaković, D. A.; Campbell, Z.; Kalogerakis, K. S.; Copeland, R. A.; Slanger, T. G.

2004-12-01

Knowledge of the water concentration profile is key to understanding of the chemistry and energy flow in the stratosphere and mesosphere. One of the tasks of the SABER instrument in NASA's TIMED mission is to measure water vapor concentration by detecting H2O(ν 2) emission in the 6.8 μ m region. An important source of the H2O(ν 2) emission is the collisional deactivation of vibrationally excited O2: O2(X3Σ ^-g, v = 1) + H2O <-> O2(X3Σ ^-g, v = 0) + H2O(ν 2). For reliable interpretation of the SABER data it is crucial to determine rate coefficient for the competing process: O2(X3Σ ^-g, v = 1) + O(3P) -> O2(X3Σ ^-g, v = 0) + O(3P) [1]. Laboratory measurements are reported of the rate coefficient for collisional removal of O2(X3Σ ^-g, v = 1) by O(3P) at a temperature of 240 K, relevant to the upper mesosphere. Instead of directly detecting the O2(X3Σ ^-g, v = 1) population, a novel, technically simpler, approach is used in which the v = 1 level of the O2(a1Δ g) state is monitored. With ground-state O2 present, owing to the rapid equilibration of the O2(X3Σ ^-g, v = 1) and O2(a1Δ g, v = 1) populations via the processes O2(a1Δ g, v = 1) + O2(X3Σ ^-g, v = 0) <-> O2(a1Δ g, v = 0) + O2(X3Σ ^-g, v = 1), the information on the O2(X3Σ ^-g, v = 1) kinetics is extracted from the O2(a1Δ g, v = 1) temporal evolution. A two-laser method is employed, in which the pulsed output of the first laser near 285 nm photodissociates ozone to produce atomic oxygen and O2(a1Δ g, v = 1), and the pulsed output of the second laser detects O2(a1Δ g, v = 1) via the resonance-enhanced multiphoton ionization. In the same experiment, rate coefficients for removal of O2(a1Δ g, v = 1) with the atmospherically relevant colliders O2, CO2, and O also were measured at room temperature and 240 K. The measured rate coefficient for O2(X3Σ ^-g, v = 1) removal by O(3P) is in the range 2--3 × 10-12 cm3s-1 at 240 K, compared to the recently measured room temperature value of about 3 × 10

Kinetics of the benzyl + O(3P) reaction: a quantum chemical/statistical reaction rate theory study.

PubMed

da Silva, Gabriel; Bozzelli, Joseph W

2012-12-14

The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O(2). In this study the reaction of benzyl with ground-state atomic oxygen, O((3)P), is examined using quantum chemistry and statistical reaction rate theory. C(7)H(7)O energy surfaces are generated at the G3SX level, and include several novel pathways. Transition state theory is used to describe elementary reaction kinetics, with canonical variational transition state theory applied for barrierless O atom association with benzyl. Apparent rate constants and branching ratios to different product sets are obtained as a function of temperature and pressure from solving the time-dependent master equation, with RRKM theory for microcanonical k(E). These simulations indicate that the benzyl + O reaction predominantly forms the phenyl radical (C(6)H(5)) plus formaldehyde (HCHO), with lesser quantities of the C(7)H(6)O products benzaldehyde, ortho-quinone methide, and para-quinone methide (+H), along with minor amounts of the formyl radical (HCO) + benzene. Addition of O((3)P) to the methylene site in benzyl produces a highly vibrationally excited C(7)H(7)O* adduct, the benzoxyl radical, which can β-scission to benzaldehyde + H and phenyl + HCHO. In order to account for the experimental observation of benzene as the major reaction product, a roaming radical mechanism is proposed that converts the nascent products phenyl and HCHO to benzene + HCO. Oxygen atom addition at the ortho and para ring sites in benzyl, which has not been previously considered, is shown to lead to the quinone methides + H; these species are less-stable isomers of benzaldehyde that are proposed as important combustion intermediates, but

Bimetallic Pt-Au Nanocatalysts on ZnO/Al2O3/Monolith for Air Pollution Control.

PubMed

Kim, Ki-Joong; Ahn, Ho-Geun

2015-08-01

The catalytic activity of a monolithic catalyst with nanosized Pt and Au particles on ZnO/Al2O3 (Pt-Au/ZnO/Al2O3/M) prepared by a wash-coat method was examined, specifically for toluene oxidation. Scanning electron microscopy image showed clearly the formation of a ZnO/Al2O3 layer on the monolith. Nanosized Pt-Au particles on ZnO/Al2O3/M with different sizes could be found in the Pt-Au/ZnO/Al2O3/M catalyst. The conversion of toluene decreased with increasing toluene concentration and was also largely affected by the feed flow rate. The Pt-Au/ZnO/Al2O3/M catalysts prepared in this work have almost the same activity (molecules of toluene per second) compared with a powder Pt-Au/ZnO/Al2O3 catalyst with the same loadings of Pt and Au components; thus this catalyst could be used in controlling air pollution with very low concentrations and high flow rate.

Effects of Al2O3, B2O3, Li2O, Na2O, and SiO2 on Nepheline Crystallization in Hanford High Level Waste Glasses

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

Kroll, Jared O.; Vienna, John D.; Schweiger, Michael J.

2016-09-15

Nepheline (nominally NaAlSiO4) formation during slow cooling of high-alumina (25.4 - 34.5 mass% Al2O3) Hanford high level waste glasses may significantly reduce product durability. To investigate the effects of composition on nepheline crystallization, 29 compositions were formulated by adjusting Al2O3, B2O3, Li2O, Na2O, and SiO2 around a baseline glass that precipitated 12 mass% nepheline. Thirteen of these compositions were generated by adjusting one-component-at-a-time, while two or three components were adjusted to produce the other 16 (with all remaining components staying in the same relative proportions). Quantitative X-ray diffraction was used to determine nepheline concentration in each sample. Twenty two glassesmore » precipitated nepheline, two of which also precipitated eucryptite (nominally LiAlSiO4), and one glass formed only eucryptite upon slow cooling. Increasing Na2O and Li2O had the strongest effect in promoting nepheline formation. Increasing B2O3 inhibited nepheline formation. SiO2 and Al2O3 showed non-linear behavior related to nepheline formation. The composition effects on nepheline formation in these glasses are reported.« less

Improvement of β-phase crystal formation in a BaTiO3-modified PVDF membrane

NASA Astrophysics Data System (ADS)

Lin, SHEN; Lei, GONG; Shuhua, CHEN; Shiping, ZHAN; Cheng, ZHANG; Tao, SHAO

2018-04-01

In this paper, low temperature plasma is used to modify the surface of barium titanate (BaTiO3) nanoparticles in order to enhance the interfacial compatibility between ferroelectric poly(vinylidene fluoride) (PVDF) and BaTiO3 nanoparticles. The results demonstrate that oxygenic groups are successfully attached to the BaTiO3 surface, and the quantity of the functional groups increases with the treatment voltage. Furthermore, the effect of modified BaTiO3 nanoparticles on the morphology and crystal structure of the PVDF/BaTiO3 membrane is investigated. The results reveal that the dispersion of BaTiO3 nanoparticles in the PVDF matrix was greatly improved due to the modification of the BaTiO3 nanoparticles by air plasma. It is worth noting that the formation of a β-phase in a PVDF/modified BaTiO3 membrane is observably promoted, which results from the strong interaction between PVDF chains and oxygenic groups fixed on the BaTiO3 surface and the better dispersion of BaTiO3 nanoparticles in the PVDF matrix. Besides, the PVDF/modified BaTiO3 membrane at the treatment voltage of 24 kV exhibits a lower water contact angle (≈68.4°) compared with the unmodified one (≈86.7°). Meanwhile, the dielectric constant of PVDF/BaTiO3 nanocomposites increases with the increase of working voltage.

An eco-friendly route of γ-Fe2O3 nanoparticles formation and investigation of the mechanical properties of the HPMC-γ-Fe2O3 nanocomposites.

PubMed

Sarkar, Joy; Mollick, Md Masud Rahaman; Chattopadhyay, Dipankar; Acharya, Krishnendu

2017-03-01

In recent times, biosynthetic approaches toward the synthesis of nanoparticles have been shown to have several advantages over physical and chemical methods. Here, we report the extracellular mycosynthesis of γ-Fe 2 O 3 nanoparticles by Alternaria alternata. The fungal biomass when exposed to aqueous iron(III) chloride solution led to the formation of highly stable γ-Fe 2 O 3 nanoparticles extracellularly. The influence of these biosynthesized γ-Fe 2 O 3 nanoparticles on the properties of hydroxyl propyl methyl cellulose was also investigated. Characterization of the biosynthesized γ-Fe 2 O 3 nanoparticles and HPMC-γ-Fe 2 O 3 nanocomposite films were done by the different types of spectral and electron microscopic analysis. The size of the γ-Fe 2 O 3 nanoparticles ranges from 75 to 650 nm. The mechanical effect of the agglomerated γ-Fe 2 O 3 nanoparticles into the HPMC polymer matrix was also investigated.

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

PubMed Central

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

2015-01-01

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

Direct spectroscopic evidence for isolated silanols in SiO x/Al 2O 3 and their formation mechanism

DOE PAGES

Mouat, Aidan R.; Kobayashi, Takeshi; Pruski, Marek; ...

2017-02-27

Here, the preparation and unambiguous characterization of isolated Brønsted-acidic silanol species on silica–alumina catalysts presents a key challenge in the rational design of solid acid catalysts. In this report, atomic layer deposition (ALD) and liquid-phase preparation (chemical liquid deposition, CLD) are used to install the SiO x sites on Al 2O 3 catalysts using the same Si source (tetraethylorthosilicate, TEOS). The ALD-derived and CLD-derived SiO x sites are probed with dynamic nuclear polarization (DNP)-enhanced 29Si– 29Si double-quantum/single-quantum (DQ/SQ) correlation NMR spectroscopy. The investigation reveals conclusively that the SiO x/Al 2O 3 material prepared by ALD and CLD, followed by calcinationmore » under an O 2 stream, contains fully spatially isolated Si species, in contrast with those resulting from the calcination under static air, which is widely accepted as a postgrafting treatment for CLD. Insight into the formation mechanism of these sites is obtained via in situ monitoring of the TEOS + γ-Al 2O 3 reaction in an environmental diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) cell. Upon calcination, the DRIFTS spectra of SiO x/Al 2O 3 reveal a signature unambiguously assignable to isolated Brønsted-acidic silanol species. Surprisingly, the results of this study indicate that the method of preparing SiO x/Al 2O 3 catalysts is less important to the final structure of the silanol sites than the post-treatment conditions. This finding should greatly simplify the methods for synthesizing site-isolated, Brønsted-acidic SiO x/Al 2O 3 catalysts.« less

The Peculiarities of Structure Formation and Properties of Zirconia-Based Nanocomposites with Addition of Al2O3 and NiO

NASA Astrophysics Data System (ADS)

Danilenko, I.; Lasko, G.; Brykhanova, I.; Burkhovetski, V.; Ahkhozov, L.

2017-02-01

The present study is devoted to the problem of enhancing fracture toughness of ZrO2 ceramic materials through the formation of composite structure by addition of Al2O3 and NiO particles. In this paper, we analyzed the general and distinguished features of microstructure of both composite materials and its effect on fracture toughness of materials. In this paper, we used the XRD, SEM, and EDS methods for determination of granulometric, phase, and chemical composition of sintered materials. The peculiarities of dependence of fracture toughness values from dopant concentration and changing the Y3+ amount in zirconia grains allow us to assume that at least two mechanisms can affect the fracture toughness of ZrO2 ceramics. Crack bridging/deflection processes with the "transformation toughening" affect the K1C values depending on the dopant concentration. Crack deflection mechanism affects the K1C values when the dopant concentrations are low, and transformation toughening affects the K1C values when the dopant concentrations begin to have an impact on microstructure reorganization-redistribution of Y3+ ions and formation of Y3+-depleted grains with high ability to phase transformation.

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

γ-Fe2O3 and Fe3O4 magnetic hierarchically nanostructured hollow microspheres: preparation, formation mechanism, magnetic property, and application in water treatment.

PubMed

Xu, Jing-San; Zhu, Ying-Jie

2012-11-01

In this paper, we report the preparation of γ-Fe(2)O(3) and Fe(3)O(4) magnetic hierarchically nanostructured hollow microspheres by a solvothermal combined with precursor thermal conversion method. These γ-Fe(2)O(3) and Fe(3)O(4) magnetic hierarchically nanostructured hollow microspheres were constructed by three-dimensional self-assembly of nanosheets, forming porous nanostructures. The effects of experimental parameters including molar ratio of reactants and reaction temperature on the precursors were studied. The time-dependent experiments indicated that the Ostwald ripening was responsible for the formation of the hierarchically nanostructured hollow microspheres of the precursors. γ-Fe(2)O(3) and Fe(3)O(4) magnetic hierarchically nanostructured hollow microspheres were obtained by the thermal transformation of the precursor hollow microspheres. Both γ-Fe(2)O(3) and Fe(3)O(4) hierarchically nanostructured hollow microspheres exhibited a superparamagnetic property at room temperature and had the saturation magnetization of 44.2 and 55.4 emu/g, respectively, in the applied magnetic field of 20 KOe. Several kinds of organic pollutants including salicylic acid (SA), methylene blue (MB), and basic fuchsin (BF) were chosen as the model water pollutants to evaluate the removal abilities of γ-Fe(2)O(3) and Fe(3)O(4) magnetic hierarchically nanostructured hollow microspheres. It was found that γ-Fe(2)O(3) hierarchically nanostructured hollow microspheres showed a better adsorption ability over SA than MB and BF. However, Fe(3)O(4) hierarchically nanostructured hollow microspheres had the best performance for adsorbing MB. Copyright © 2012 Elsevier Inc. All rights reserved.

Actinometric measurements and theoretical calculations of j/O3/, the rate of photolysis of ozone to O/1D/

NASA Technical Reports Server (NTRS)

Dickerson, R. R.; Stedman, D. H.; Chameides, W. L.; Crutzen, P. J.; Fishman, J.

1979-01-01

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2).

PubMed

Lee, Minju; Merle, Tony; Rentsch, Daniel; Canonica, Silvio; von Gunten, Urs

2017-01-03

The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O 3 /H 2 O 2 and UV/H 2 O 2 ) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k O 3 ) (<0.1-7.9 × 10 3 M -1 s -1 ) or with hydroxyl radicals (k • OH ) (0.9 × 10 9 - 6.5 × 10 9 M -1 s -1 ), photon fluence-based rate constants (k') (210-2730 m 2 einstein -1 ), and quantum yields (Φ) (0.03-0.95 mol einstein -1 ). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO 3 /gDOC to ∼100% at ≥1.0 gO 3 /gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k O 3 and k • OH . The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H 2 O 2 . For a typical UV disinfection dose (400 J/m 2 ), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of H 2 O 2 addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

'Nose method' of calculating critical cooling rates for glass formation

NASA Technical Reports Server (NTRS)

Weinberg, Michael C.; Uhlmann, Donald R.; Zanotto, Edgar D.

1989-01-01

The use of the so-called 'nose method' for computing critical cooling rates for glass formation is examined and compared with other methods, presenting data for the glass-forming systems SiO2, GeO2, and P2O5. It is shown that, for homogeneous crystallization, the nose-method will give an overestimate of Rc, a conclusion which was drawn after assessing the enfluence of a range of values for the parameters which control crystal growth and nucleation. The paper also proposes an alternative simple procedure (termed the 'cutoff method') for computing critical cooling rates from T-T-T diagrams, which was shown in the SiO2 and GeO2 systems to be superior to the nose method.

Atomic Layer Deposition of Al2O3-Ga2O3 Alloy Coatings for Li[Ni0.5Mn0.3Co0.2]O2 Cathode to Improve Rate Performance in Li-Ion Battery.

PubMed

Laskar, Masihhur R; Jackson, David H K; Guan, Yingxin; Xu, Shenzhen; Fang, Shuyu; Dreibelbis, Mark; Mahanthappa, Mahesh K; Morgan, Dane; Hamers, Robert J; Kuech, Thomas F

2016-04-27

Metal oxide coatings can improve the electrochemical stability of cathodes and hence, their cycle-life in rechargeable batteries. However, such coatings often impose an additional electrical and ionic transport resistance to cathode surfaces leading to poor charge-discharge capacity at high C-rates. Here, a mixed oxide (Al2O3)1-x(Ga2O3)x alloy coating, prepared via atomic layer deposition (ALD), on Li[Ni0.5Mn0.3Co0.2]O2 (NMC) cathodes is developed that has increased electron conductivity and demonstrated an improved rate performance in comparison to uncoated NMC. A "co-pulsing" ALD technique was used which allows intimate and controlled ternary mixing of deposited film to obtain nanometer-thick mixed oxide coatings. Co-pulsing allows for independent control over film composition and thickness in contrast to separate sequential pulsing of the metal sources. (Al2O3)1-x(Ga2O3)x alloy coatings were demonstrated to improve the cycle life of the battery. Cycle tests show that increasing Al-content in alloy coatings increases capacity retention; whereas a mixture of compositions near (Al2O3)0.5(Ga2O3)0.5 was found to produce the optimal rate performance.

Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios.

PubMed

Lakshmanan, Sandhiya; Pratihar, Subha; Machado, Francisco B C; Hase, William L

2018-05-31

The reaction of 3 CH 2 with 3 O 2 is of fundamental importance in combustion, and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K, and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CH 2 OO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, H 2 CO + O( 3 P), while the singlet surface leads to eight product channels with their relative importance as CO + H 2 O > CO + OH + H ∼ H 2 CO + O( 1 D) > HCO + OH ∼ CO 2 + H 2 ∼ CO + H 2 + O( 1 D) > CO 2 + H + H > HCO + O( 1 D) + H. The reaction on the singlet PES is barrierless, consistent with experiment, and the total rate constant on the singlet surface is (0.93 ± 0.22) × 10 -12 cm 3 molecule -1 s -1 in comparison to the recommended experimental rate constant of 3.3 × 10 -12 cm 3 molecule -1 s -1 . The simulation product yields for the singlet PES are compared with experiment, and the most significant differences are for H, CO 2 , and H 2 O. The reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address (1) the barrier on the triplet PES for 3 CH 2 + 3 O 2 → 3 CH 2 OO, (2) the temperature dependence of the 3 CH 2 + 3 O 2 reaction rate constant and product branching ratios, and (3) the possible non-RRKM dynamics of the 1 CH 2 OO Criegee intermediate.

Formation of multiferroic PbTiO3/PbFe12O19 composite by exceeding the solubility limit of Fe in PbTiO3

NASA Astrophysics Data System (ADS)

Jaffari, G. Hassnain; Bilal, M.; Ur Rahman, Jamil; Lee, Soonil

2017-09-01

PbTiO3/PbFe12O19 composites have been synthesized by keeping the Fe concentration (x) in PbFexTi1-xO3 beyond solubility limit, i.e., x > 0.1% and 5% Pb excess. Both these factors have been successfully utilized to extract Fe doped PbTiO3 tetragonal phase which is composited with Magnetoplumbite (PbFe12O19) phase. A systematic evolution of the tetragonality of the former and improved stoichiometry of the later constituent has been observed. As x increases, emergence of additional Raman mode around 650 cm-1 with Fe addition was observed. Systematic increase in the relative intensity of this mode with x, showed that this mode corresponds to the magnetoplumbite phase. In addition to that resultant composite exhibited noticeable systematic decrease in the value of the energy gap as a function of x. Increasing Fe concentration in PbTiO3 constituent, led to monotonic decrease in c/a and increase in strain experienced by PbTiO3. Increase in the value of the saturation polarization was observed up to x = 0.4, which is identified to be associated with the strain induced by the dopant. A comprehensive magnetic characterization revealed monotonic decrease in magnetization with temperature for all compositions. Finally, we found an anomalous temperature dependent trend in the magnetic coercivity which is explained in terms of low temperature decrease in effective magnetic anisotropy by including magneto-electric coupling. Both constituent phases in the composite being ferroelectric and ferromagnetic at room temperature led to formation of better multiferroic properties and exhibited tunable physical properties with x.

Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

PubMed

Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

2016-04-05

UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

Volatile products from the interaction of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Miller, R. A.; Stearns, C. A.; Fryburg, G. C.; Dillard, J. G.

1977-01-01

Cooled target collection techniques and high pressure mass spectrometric sampling were used to measure the relative rates of oxidative vaporization and to identify the volatile products emanating from samples of chromia and Mg-doped lanthanum chromite. The materials were exposed to partial pressures of KCl with and without H2O in one atmosphere of slowly flowing oxygen at elevated temperatures. Chromia and fresh samples of lanthanum chromite exhibited enhanced rates of oxidative vaporization upon exposure to these reactants. Mass spectrometric identification showed that the enhancements resulted from the heterogeneous formation of complex molecules of the type KCl sub 1,2,3 CrO3 and KOH sub l,2 CrO3. Lanthanum chromite that had undergone prolonged oxidative vaporization exhibited no enhanced oxidation upon exposure to the reactants.

Formation mechanism of Ruddlesden-Popper-type antiphase boundaries during the kinetically limited growth of Sr rich SrTiO3 thin films

PubMed Central

Xu, Chencheng; Du, Hongchu; van der Torren, Alexander J. H.; Aarts, Jan; Jia, Chun-Lin; Dittmann, Regina

2016-01-01

We elucidated the formation process for Ruddlesden-Popper-type defects during pulsed laser deposition of Sr rich SrTiO3 thin films by a combined analysis of in-situ atomic force microscopy, low energy electron diffraction and high resolution scanning transmission electron microscopy. At the early growth stage of 1.5 unit cells, the excess Sr results in the formation of SrO on the surface, resulting in a local termination change from TiO2 to SrO, thereby forming a Sr rich (2 × 2) surface reconstruction. With progressive SrTiO3 growth, islands with thermodynamically stable SrO rock-salt structure are formed, coexisting with TiO2 terminated islands. During the overgrowth of these thermodynamically stable islands, both lateral as well as vertical Ruddlesden-Popper-type anti-phase boundaries are formed, accommodating the Sr excess of the SrTiO3 film. We suggest the formation of thermodynamically stable SrO rock-salt structures as origin for the formation of Ruddlesden-Popper-type antiphase boundaries, which are as a result of kinetic limitations confined to certain regions on the surface. PMID:27922069

Formation mechanism of Ruddlesden-Popper-type antiphase boundaries during the kinetically limited growth of Sr rich SrTiO3 thin films

NASA Astrophysics Data System (ADS)

Xu, Chencheng; Du, Hongchu; van der Torren, Alexander J. H.; Aarts, Jan; Jia, Chun-Lin; Dittmann, Regina

2016-12-01

We elucidated the formation process for Ruddlesden-Popper-type defects during pulsed laser deposition of Sr rich SrTiO3 thin films by a combined analysis of in-situ atomic force microscopy, low energy electron diffraction and high resolution scanning transmission electron microscopy. At the early growth stage of 1.5 unit cells, the excess Sr results in the formation of SrO on the surface, resulting in a local termination change from TiO2 to SrO, thereby forming a Sr rich (2 × 2) surface reconstruction. With progressive SrTiO3 growth, islands with thermodynamically stable SrO rock-salt structure are formed, coexisting with TiO2 terminated islands. During the overgrowth of these thermodynamically stable islands, both lateral as well as vertical Ruddlesden-Popper-type anti-phase boundaries are formed, accommodating the Sr excess of the SrTiO3 film. We suggest the formation of thermodynamically stable SrO rock-salt structures as origin for the formation of Ruddlesden-Popper-type antiphase boundaries, which are as a result of kinetic limitations confined to certain regions on the surface.

Study of the formation of the apatite-type phases La9.33+x(SiO4)6O2+3x/2 synthesized from a lanthanum oxycarbonate La2O2CO3

NASA Astrophysics Data System (ADS)

Pons, A.; Jouin, J.; Béchade, E.; Julien, I.; Masson, O.; Geffroy, P. M.; Mayet, R.; Thomas, P.; Fukuda, K.; Kagomiya, I.

2014-12-01

Lanthanum silicated apatites with nominal composition La9.33+x(SiO4)6O2+3x/2 (-0.2 < x < 0.27) have been successfully synthesized by solid state reaction using a new reagent La2O2CO3 and amorphous SiO2 precursors. The formation mechanism of La2O2CO3 reagent, which cannot be purchased, has been followed by in-situ temperature depend XRD of La2O3 under CO2 atmosphere. The stability of this reagent during the synthesis step allowed to limit the formation of secondary phase La2Si2O7 and made the weighting of the reagent easier. High purity powders could be synthesized at the temperature of 1400 °C. Dense pellets (more than 98.5%) were obtained by isostatic pressing of powders calcined at 1200 °C and then sintered at 1550 °C. Traces of La2SiO5 secondary phase present in synthesized powder disappeared after densification and pure oxyapatite materials were obtained for all the compositions. Electrical measurements confirmed that conductivity behaviors of the sintered pellets were dependent to the oxygen over-stoichiometry. Indeed, a relatively high conductivity of 1 × 10-2 S cm-1 was exhibited at 800 °C for the nominal composition La9.60(SiO4)6O2.405 with low activation energy around 0.79 eV. The ionic conductivity properties were comparable with that of the earlier obtained materials.

Investigation of gamma ray shielding, structural and dissolution rate properties of Bi2O3-BaO-B2O3-Na2O glass system

NASA Astrophysics Data System (ADS)

Dogra, Mridula; Singh, K. J.; Kaur, Kulwinder; Anand, Vikas; Kaur, Parminder; Singh, Prabhjot; Bajwa, B. S.

2018-03-01

In the present study, quaternary system of the composition (0.45 + x) Bi2O3-(0.25 - x) BaO-0.15 B2O3-0.15 Na2O (where 0 ≤ x ≤ 0.2 mol fraction) has been prepared by using melt-quenching technique for investigation of gamma ray shielding properties. Mass attenuation coefficients and half value layer parameters have been determined experimentally at 662 keV by using 137Cs source. It has been found that experimental results of these parameters hold good agreement with theoretical values. The density, molar volume, XRD, FTIR, Raman and UV-visible studies have been used to determine structural properties of the prepared glass samples. Dissolution rate of the samples has also been measured to check their utility as long term durable glasses.

In-situ measurement of texture development rate in CaIrO 3 post-perovskite

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

Hunt, Simon A.; Walker, Andrew M.; Mariani, Elisabetta

The rate of crystallographic preferred orientation (CPO) development during deformation of post-perovskite is crucial in interpreting seismic anisotropy in the lowermost mantle but the stability field of MgSiO 3 post-perovskite prevents high-strain deformation experiments being performed on it. Therefore, to constrain the rate of CPO development in post-perovskite, we deformed CaIrO 3, a low-pressure analogue of MgSiO 3 post-perovskite, in simple shear at 3.2 GPa and 400 °C to a shear strain (γ) of 0.81. From X-ray diffraction patterns acquired during deformation, we invert for CPO as a function of strain. By comparing the CPO that develops with visco-plastic self-consistentmore » (VPSC) models we constrain the critical resolved shear stresses (CRSS) of the non-primary slip-systems in CaIrO 3 to be of order 6 times stronger than the primary [100] (010) slip system. This value is significantly less than has been assumed by previous studies and if applicable to MgSiO 3 implies that seismic anisotropy in the D" layer develops slower than has previously been assumed.« less

A Comparative Study of N2O Formation during the Selective Catalytic Reduction of NOx with NH3 on Zeolite Supported Cu Catalysts

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

Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton

A comparative study was carried out on a small-pore CHA.Cu and a large-pore BEA.Cu zeolite catalyst to understand the lower N2O formation on small-pore zeolite supported Cu catalysts in the selective catalytic reduction (SCR) of NOx with NH3. On both catalysts, the N2O yield increases with an increase in the NO2/NOx ratios of the feed gas, suggesting N2O formation via the decomposition of NH4NO3. Temperature-programmed desorption experiments reveal that NH4NO3 is more stable on CHA.Cu than on BEA.Cu. In situ FTIR spectra following stepwise (NO2 + O2) and (15NO + NH3 + O2) adsorption and reaction, and product distribution analysismore » using isotope-labelled reactants, unambiguously prove that surface nitrate groups are essential for the formation of NH4NO3. Furthermore, CHA.Cu is shown to be considerably less active than BEA.Cu in catalyzing NO oxidation and the subsequent formation of surface nitrate groups. Both factors, i.e., (1) the higher thermal stability of NH4NO3 on CHA.Cu, and (2) the lower activity for this catalyst to catalyze NO oxidation and the subsequent formation of surface nitrates, likely contribute to the higher SCR selectivity with less N2O formation on this catalyst as compared to BEA.Cu. The latter is determined as the primary reason since surface nitrates are the source that leads to the formation of NH4NO3 on the catalysts.« less

Thermal formation of hydroxynitriles, precursors of hydroxyacids in astrophysical ice analogs: Acetone ((CH3)2Cdbnd O) and hydrogen cyanide (HCN) reactivity

NASA Astrophysics Data System (ADS)

Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Duvernay, Fabrice; Theulé, Patrice; Chiavassa, Thierry

2015-11-01

Reactivity in astrophysical environments is still poorly understood. In this contribution, we investigate the thermal reactivity of interstellar ice analogs containing acetone ((CH3)2CO), ammonia (NH3), hydrogen cyanide (HCN) and water (H2O) by means of infrared spectroscopy and mass spectrometry techniques, complemented by quantum chemical calculations. We show that no reaction occurs in H2O:HCN:(CH3)2CO ices. Nevertheless, HCN does indeed react with acetone once activated by NH3 into CN- to form 2-hydroxy-2-methylpropanenitrile (HOsbnd C(CH3)2sbnd CN), with a calculated activation energy associated with the rate determining step of about 51 kJ mol-1. This reaction inhibits the formation of 2-aminopropan-2-ol (HOsbnd C(CH3)2sbnd NH2) from acetone and NH3, even in the presence of water, which is the first step of the Strecker synthesis to form 2-aminoisobutyric acid (NH2C(CH3)2COOH). However, HOsbnd C(CH3)2sbnd CN formation could be part of an alternative chemical pathway leading to 2-hydroxy-2-methyl-propanoic acid (HOC(CH3)2COOH), which could explain the presence of hydroxy acids in some meteorites.

Diffusion quantum Monte Carlo calculations of SrFeO 3 and LaFeO 3

DOE PAGES

Santana, Juan A.; Krogel, Jaron T.; Kent, Paul R. C.; ...

2017-07-18

The equations of state, formation energy, and migration energy barrier of the oxygen vacancy in SrFeO 3 and LaFeO 3 were calculated in this paper with the diffusion quantum Monte Carlo (DMC) method. Calculations were also performed with various Density Functional Theory (DFT) approximations for comparison. DMC reproduces the measured cohesive energies of these materials with errors below 0.23(5) eV and the structural properties within 1% of the experimental values. The DMC formation energies of the oxygen vacancy in SrFeO 3 and LaFeO 3 under oxygen-rich conditions are 1.3(1) and 6.24(7) eV, respectively. Similar calculations with semi-local DFT approximations formore » LaFeO 3 yielded vacancy formation energies 1.5 eV lower. Comparison of charge density evaluated with DMC and DFT approximations shows that DFT tends to overdelocalize the electrons in defected SrFeO 3 and LaFeO 3. Finally, calculations with DMC and local density approximation yield similar vacancy migration energy barriers, indicating that steric/electrostatic effects mainly determine migration barriers in these materials.« less

The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )3 ⋅2 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-12-14

A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )3 ⋅2 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic structure and vacancy formation in La(1 - x) B(x) CoO3 (B=Mg,Ca,Ba and x=0.125)

NASA Astrophysics Data System (ADS)

Salawu, Omotayo; Gan, Liyong; Schwingenschlogl, Udo

2015-03-01

The LaCoO3 class of materials is of interest for cathodes of solid oxide fuel cells. Spin-polarized density functional theory is applied to cubic La0.75(Mg/Ca/Ba)0.125CoO3. The effect of this cation doping on the electronic and magnetic properties as well as oxygen vacancy formation energy is studied. Oxygen vacancies with proximity to the dopant are energetically favourable in most cases. We discuss the effect of distortions of the CoO6 octahedron on the electronic structure and the formation energy of oxygen vacancies. The order of formation oxygen is found to be Mg > Ca > Ba. Cation doping incorporates holes to the Co-O network which enhances the oxygen vacancy formation.

Elucidation of reaction mechanism involved in the formation of LaNiO3 from XRD and TG analysis

NASA Astrophysics Data System (ADS)

Dharmadhikari, Dipti V.; Athawale, Anjali A.

2013-06-01

The present work is focused on the synthesis and elucidation of reaction mechanism involved in the formation of LaNiO3 with the help of X-ray diffraction (XRD) and thermogravimetric (TG) analysis. LaNiO3 was synthesized by hydrothermal method by heating at 160°C under autogenous pressure for 6h. Pure phase product was obtained after calcining the hydrothermally activated product for 6h at 700°C. The various phases of the product obtained after hydrothermal treatment and calcination followed by the formation of pure phase nanocrystalline lanthanum nickel oxide could be determined from XRD analysis of the samples. The reaction mechanism and phase formation temperature has been interpreted by thermogravimetric analysis of the hydrothermally synthesized product and XRD analysis.

Formation of a conducting LaAlO3/SrTiO3 interface studied by low-energy electron reflection during growth

NASA Astrophysics Data System (ADS)

van der Torren, A. J. H.; Liao, Z.; Xu, C.; Gauquelin, N.; Yin, C.; Aarts, J.; van der Molen, S. J.

2017-12-01

The two-dimensional electron gas occurring between the band insulators SrTiO3 and LaAlO3 continues to attract considerable interest, due to the possibility of dynamic control over the carrier density and due to ensuing phenomena such as magnetism and superconductivity. The formation of this conducting interface is sensitive to the growth conditions, but despite numerous investigations there are still questions about the details of the physics involved. In particular, not much is known about the electronic structure of the growing LaAlO3 layer at the growth temperature (around 800°C) in oxygen (pressure around 5 ×10-5 mbar), since analysis techniques at these conditions are not readily available. We developed a pulsed laser deposition system inside a low-energy electron microscope in order to study this issue. The setup allows for layer-by-layer growth control and in situ measurements of the angle-dependent electron reflection intensity, which can be used as a fingerprint of the electronic structure of the surface layers during growth. By using different substrate terminations and growth conditions we observe two families of reflectivity maps, which we can connect either to samples with an AlO2-rich surface and a conducting interface or to samples with a LaO-rich surface and an insulating interface. Our observations emphasize that substrate termination and stoichiometry determine the electronic structure of the growing layer, and thereby the conductance of the interface.

Adsorption of O2, SO2, and SO3 on nickel oxide. Mechanism for sulfate formation

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1985-01-01

Calculations based on the atom superposition and electron delocalization molecular orbital (ASED-MO) technique suggest that O2 will adsorb perferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom is a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the perferred orientation in which the SO3 plane is parallel to the surface. On activation, SO3 adsorbed to an O2(-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Possibilities for alternative mechanisms which require the formation of Ni3(+) or O2(-) are discussed. NiSO4 thus formed leads to the corrosion of Ni at high temperatures in the SO2+O2/SO3 The SO2+O2/SO3 atmosphere, as discussed in the experimental literature.

Nanocrystallized SrHA/SrHA SrTiO3/SrTiO3 TiO2 multilayer coatings formed by micro-arc oxidation for photocatalytic application

NASA Astrophysics Data System (ADS)

Han, Y.; Chen, D. H.; Zhang, L.

2008-08-01

Novel photocatalytic coatings containing strontium hydroxyapatite (SrHA), strontium titanate (SrTiO3), and TiO2 were formed by micro-arc oxidation (MAO) in an aqueous electrolyte containing strontium acetate and β-glycerophosphate disodium at 530 V for 0.1-5 min. The structure evolution of the coatings was investigated as a function of processing time, and the photocatalytic activity of the coatings was evaluated by measuring the decomposition rate of methyl orange under ultraviolet irradiation. During the MAO processing of the coatings, it was observed that some granules appeared in the electrolyte adjacent to the anode and they increased in amount as the processing time was prolonged. The obtained results show that the granules are amorphous and poorly crystallized SrHA with negative charges. The coating prepared for 5 min presents a microporous structure of SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayers, in which the SrHA outermost layer and the SrHA-SrTiO3 intermediate layer are nanocrystallized. It is suggested that formation of the granules, electro-migration of the granules onto the pre-formed layer, and crystallization of the adhered granules are possible mechanisms for the formation of a SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayer coating. This coating shows much higher photocatalytic decomposition efficiency relative to the MAO-formed TiO2 coating, and is expected to have an important photocatalytic application.

Formation of hydroxyapatite onto glasses of the CaO-MgO-SiO2 system with B2O3, Na2O, CaF2 and P2O5 additives.

PubMed

Agathopoulos, S; Tulyaganov, D U; Ventura, J M G; Kannan, S; Karakassides, M A; Ferreira, J M F

2006-03-01

New bioactive glasses with compositions based on the CaO-MgO-SiO(2) system and additives of B(2)O(3), P(2)O(5), Na(2)O, and CaF(2) were prepared. The in vitro mineralization behaviour was tested by immersion of powders or bulk glasses in simulated body fluid (SBF). Monitoring of ionic concentrations in SBF and scanning electron microscopy (SEM) observations at the surface of the glasses were conducted over immersion time. Raman and infrared (IR) spectroscopy shed light on the structural evolution occurring at the surface of the glasses that leads to formation of hydroxyapatite.

Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe 2O 3–FeF 3 Conversion Compounds by Direct Fluorination

DOE PAGES

Zhou, Hui; Ruther, Rose E.; Adcock, Jamie; ...

2015-02-22

In this paper, we report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe 2O 3) to an electrochemically stable and higher energy density iron oxyfluoride/fluoride phase. Interestingly, no noticeable bulk iron oxyfluoride phase (FeOF) phase was observed even at fluorination temperature close to 300 °C. Instead, at fluorination temperatures below 250 °C, scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) and X-ray photoelectron spectroscopy (XPS) analysis showed surface fluorination with nominal composition, Fe 2O 3-xF 2x (x < 1). At fluorination temperatures of 275 °C, STEM-EELSmore » results showed porous interconnected nanodomains of FeF 3 and Fe 2O 3 coexisting within the same particle, and overall the particles become less dense after fluorination. We performed potentiometric intermittent titration and electrochemical impedance spectroscopy studies to understand the lithium diffusion (or apparent diffusion) in both the oxyfluoride and mixed phase FeF 3 + Fe 2O 3 composition, and correlate the results to their electrochemical performance. Finally and further, we analyze from a thermodynamical perspective, the observed formation of the majority fluoride phase (77% FeF 3) and the absence of the expected oxyfluoride phase based on the relative formation energies of oxide, fluoride, and oxyfluorides.« less

Ab initio studies of ClOx reactions. VII. Isomers of Cl2O3 and their roles in the ClO+OClO reaction

NASA Astrophysics Data System (ADS)

Zhu, R. S.; Lin, M. C.

2003-05-01

The mechanism for the reaction ClO+OClO has been investigated by ab initio molecular orbital and transition state theory calculations. Nine stable isomers of Cl2O3 (including optical isomers) are located at the B3LYP/6-311+G(3df ) level. The transition states between pairs of isomers are explored and the stability of the isomers and their dissociation mechanisms are discussed. The relative stability predicted by the modified Gaussian-2 (G2M) method at the G2M//B3LYP/6-311+G(3df ) level is ClOCl(O)O>ClOOOCl(C2)>ClOOOCl(Cs)>ClClO3(C3v)>cyc-ClOOCl(O)>ClOOClO. The formation of ClOCl(O)O is dominant at low temperatures, taking place barrierlessly with the second and third order rate constant, k1∞=3.0×10-10 cm3molecule-1 s-1 and k10=1.1×10-17 T-5.5 exp(-398/T) cm6 molecule-2 s-1 in the temperature range of 200-400 K for N2 as the third-body. Over 500 K, formation of ClOO+ClO becomes dominant and ClOCl+1O2 is also competitive. Their overall rate constants can be given by kClOO=1.0×10-22 T2.8 exp(-78/T) and kClOCl=9.6×10-22 T2.4 exp(-1670/T)cm3 molecule-1 s-1, respectively, in the temperature range of 500-2500 K.

Three-dimensionally scaffolded Co3O4 nanosheet anodes with high rate performance

NASA Astrophysics Data System (ADS)

Liu, Jinyun; Kelly, Sean J.; Epstein, Eric S.; Pan, Zeng; Huang, Xingjiu; Liu, Jinhuai; Braun, Paul V.

2015-12-01

Advances in secondary batteries are required for realization of many technologies. In particular, there remains a need for stable higher energy batteries. Here we suggest a new anode concept consisting of an ultrathin Co3O4 nanosheet-coated Ni inverse opal which provides high charge-discharge rate performance using a material system with potential for high energy densities. Via a hydrothermal process, about 4 nm thick Co3O4 nanosheets were grown throughout a three-dimensional Ni scaffold. This architecture provides efficient pathways for both lithium and electron transfer, enabling high charge-discharge rate performance. The scaffold also accommodates volume changes during cycling, which serves to reduce capacity fade. Because the scaffold has a low electrical resistance, and is three-dimensionally porous, it enables most of the electrochemically active nanomaterials to take part in lithiation-delithiation reactions, resulting in a near-theoretical capacity. On a Co3O4 basis, the Ni@Co3O4 electrode possesses a capacity of about 726 mAh g-1 at a current density of 500 mA g-1 after 50 cycles, which is about twice the theoretical capacity of graphite. The capacity is 487 mAh g-1, even at a current density of 1786 mA g-1.

Bi12TiO20 crystallization in a Bi2O3-TiO2-SiO2-Nd2O3 system

NASA Astrophysics Data System (ADS)

Slavov, S.; Jiao, Z.

2018-03-01

Polycrystalline mono-phase bismuth titanate was produced by free cooling from melts heated to 1170 °C. The control over the initial amounts in the starting compositions in the system Bi2O3/TiO2/SiO2/Nd2O3 and over the thermal gradient of the heat process resulted in the formation of specific structures and microstructures of monophase sillenite ceramics. The main phase Bi12TiO20 belongs to the amorphous network groups based on oxides of silicon, bismuth and titanium. In this work, we demonstrated a way to control the crystalline and amorphous phase formation in bulk poly-crystalline materials in the selected system.

Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag 7Fe 3(P 2O 7) 4)

DOE PAGES

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.; ...

2017-05-11

The formation of conductive metallic silver upon electrochemical reduction and lithiation of Ag 7Fe 3(P 2O 7) 4 is investigated. Alternating current impedance spectroscopy measurements show a 34% decrease in charge transfer resistance upon one electron equivalent (ee) of reduction, which is coincident with the formation of a Ag metal conductive network evidenced by both ex situ and operando X-ray diffraction. Quantitative assessment of Ag metal formation derived from operando XRD shows that only Ag + ions are reduced during the first 3ee, followed by simultaneous reduction of Ag + and Fe 3+ reduction for the next 5ee (3ee tomore » 8ee), culminating in reduction of the remaining Ag +. Scanning electron microscopy images show smaller Ag metal crystallite size and shorter nearest neighbor distance between and among Ag particles with higher depth of discharge. A high rate intermittent pulsatile discharge test is conducted where the cell delivers 12 total pulses during full discharge to probe the effect of Ag metal formation on the Li/Ag 7Fe 3(P 2O 7) 4 cell electrochemistry. The Ohmic resistance is derived from the voltage drop of each pulse. The resistance is 65 Ω initially, reaches its minimum of 26 Ω at 4.5 ee discharge, and levels off at 35 Ω after 7.0 ee reduction. In conclusion, the initial Ag reduction is more significant for the conductive network formation indicated by the decrease of both R ct and Ohmic resistance, which facilitates the high power output of the cell.« less

Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag 7Fe 3(P 2O 7) 4)

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

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.

The formation of conductive metallic silver upon electrochemical reduction and lithiation of Ag 7Fe 3(P 2O 7) 4 is investigated. Alternating current impedance spectroscopy measurements show a 34% decrease in charge transfer resistance upon one electron equivalent (ee) of reduction, which is coincident with the formation of a Ag metal conductive network evidenced by both ex situ and operando X-ray diffraction. Quantitative assessment of Ag metal formation derived from operando XRD shows that only Ag + ions are reduced during the first 3ee, followed by simultaneous reduction of Ag + and Fe 3+ reduction for the next 5ee (3ee tomore » 8ee), culminating in reduction of the remaining Ag +. Scanning electron microscopy images show smaller Ag metal crystallite size and shorter nearest neighbor distance between and among Ag particles with higher depth of discharge. A high rate intermittent pulsatile discharge test is conducted where the cell delivers 12 total pulses during full discharge to probe the effect of Ag metal formation on the Li/Ag 7Fe 3(P 2O 7) 4 cell electrochemistry. The Ohmic resistance is derived from the voltage drop of each pulse. The resistance is 65 Ω initially, reaches its minimum of 26 Ω at 4.5 ee discharge, and levels off at 35 Ω after 7.0 ee reduction. In conclusion, the initial Ag reduction is more significant for the conductive network formation indicated by the decrease of both R ct and Ohmic resistance, which facilitates the high power output of the cell.« less

Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

PubMed

Xu, Z F; Raghunath, P; Lin, M C

2015-07-16

The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

Network topology for the formation of solvated electrons in binary CaO-Al2O3 composition glasses.

PubMed

Akola, Jaakko; Kohara, Shinji; Ohara, Koji; Fujiwara, Akihiko; Watanabe, Yasuhiro; Masuno, Atsunobu; Usuki, Takeshi; Kubo, Takashi; Nakahira, Atsushi; Nitta, Kiyofumi; Uruga, Tomoya; Weber, J K Richard; Benmore, Chris J

2013-06-18

Glass formation in the CaO-Al2O3 system represents an important phenomenon because it does not contain typical network-forming cations. We have produced structural models of CaO-Al2O3 glasses using combined density functional theory-reverse Monte Carlo simulations and obtained structures that reproduce experiments (X-ray and neutron diffraction, extended X-ray absorption fine structure) and result in cohesive energies close to the crystalline ground states. The O-Ca and O-Al coordination numbers are similar in the eutectic 64 mol % CaO (64CaO) glass [comparable to 12CaO·7Al2O3 (C12A7)], and the glass structure comprises a topologically disordered cage network with large-sized rings. This topologically disordered network is the signature of the high glass-forming ability of 64CaO glass and high viscosity in the melt. Analysis of the electronic structure reveals that the atomic charges for Al are comparable to those for Ca, and the bond strength of Al-O is stronger than that of Ca-O, indicating that oxygen is more weakly bound by cations in CaO-rich glass. The analysis shows that the lowest unoccupied molecular orbitals occurs in cavity sites, suggesting that the C12A7 electride glass [Kim SW, Shimoyama T, Hosono H (2011) Science 333(6038):71-74] synthesized from a strongly reduced high-temperature melt can host solvated electrons and bipolarons. Calculations of 64CaO glass structures with few subtracted oxygen atoms (additional electrons) confirm this observation. The comparable atomic charges and coordination of the cations promote more efficient elemental mixing, and this is the origin of the extended cage structure and hosted solvated (trapped) electrons in the C12A7 glass.

Adsorption of O2, SO2, and SO3, on nickel oxide - Mechanism for sulfate formation

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1986-01-01

Calculations based on the atom superposition and electron delocalization molecular orbital technique suggest that O2 will adsorb preferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom in a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the preferred orientation in which the SO3 plane is parallel to the surface. The calculations suggest that the strength of adsorption varies as O2 greater than SO2 greater than SO3. On activation, SO3 adsorbed to an O(2-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Alternative mechanisms which require the formation of Ni(3+) or O(-) are discussed. NiSO4 thus formed may play a passivating role for the corrosion of Ni at low temperatures in the SO2 + O2 + SO3 atmospheres and an active role at high temperatures, as discussed in the experimental literature.

Magnetism and Mössbauer study of formation of multi-core γ -Fe2O3 nanoparticles

NASA Astrophysics Data System (ADS)

Kamali, Saeed; Bringas, Eugenio; Hah, Hien-Yoong; Bates, Brian; Johnson, Jacqueline A.; Johnson, Charles E.; Stroeve, Pieter

2018-04-01

A systematic investigation of magnetic nanoparticles and the formation of a core-shell structure, consisting of multiple maghemite (γ -Fe2O3) nanoparticles as the core and silica as the shell, has been performed using various techniques. High-resolution transmission electron microscopy clearly shows isolated maghemite nanoparticles with an average diameter of 13 nm and the formation of a core-shell structure. Low temperature Mössbauer spectroscopy reveals the presence of pure maghemite nanoparticles with all vacancies at the B-sites. Isothermal magnetization and zero-field-cooled and field-cooled measurements are used for investigating the magnetic properties of the nanoparticles. The magnetization results are in good accordance with the contents of the magnetic core and the non-magnetic shell. The multiple-core γ -Fe2O3 nanoparticles show similar behavior to isolated particles of the same size.

Fast growth rate of epitaxial β-Ga2O3 by close coupled showerhead MOCVD

NASA Astrophysics Data System (ADS)

Alema, Fikadu; Hertog, Brian; Osinsky, Andrei; Mukhopadhyay, Partha; Toporkov, Mykyta; Schoenfeld, Winston V.

2017-10-01

We report on the growth of epitaxial β-Ga2O3 thin films on c-plane sapphire substrates using a close coupled showerhead MOCVD reactor. Ga(DPM)3 (DPM = dipivaloylmethanate), triethylgallium (TEGa) and trimethylgallium (TMGa) metal organic (MO) precursors were used as Ga sources and molecular oxygen was used for oxidation. Films grown from each of the Ga sources had high growth rates, with up to 10 μm/hr achieved using a TMGa precursor at a substrate temperature of 900 °C. As confirmed by X-ray diffraction, the films grown from each of the Ga sources were the monoclinic (2 bar 0 1) oriented β-Ga2O3 phase. The optical bandgap of the films was also estimated to be ∼4.9 eV. The fast growth rate of β-Ga2O3 thin films obtained using various Ga-precursors has been achieved due to the close couple showerhead design of the MOCVD reactor as well as the separate injection of oxygen and MO precursors, preventing the premature oxidation of the MO sources. These results suggest a pathway to overcoming the long-standing challenge of realizing fast growth rates for Ga2O3 using the MOCVD method.

The Relation between [O III]/Hβ and Specific Star Formation Rate in Galaxies at z ˜ 2

NASA Astrophysics Data System (ADS)

Dickey, Claire Mackay; van Dokkum, Pieter G.; Oesch, Pascal A.; Whitaker, Katherine E.; Momcheva, Ivelina G.; Nelson, Erica J.; Leja, Joel; Brammer, Gabriel B.; Franx, Marijn; Skelton, Rosalind E.

2016-09-01

Recent surveys have identified a seemingly ubiquitous population of galaxies with elevated [O III]/Hβ emission line ratios at z > 1, although the nature of this phenomenon continues to be debated. The [O III]/Hβ line ratio is of interest because it is a main component of the standard diagnostic tools used to differentiate between active galactic nuclei and star-forming galaxies as well as the gas-phase metallicity indicators O 23 and R 23. Here, we investigate the primary driver of increased [O III]/Hβ ratios by median-stacking rest-frame optical spectra for a sample of star-forming galaxies in the 3D-HST survey in the redshift range z ˜ 1.4-2.2. Using N = 4220 star-forming galaxies, we stack the data in bins of mass and specific star formation rates (sSFRs), respectively. After accounting for stellar Balmer absorption, we measure [O III]λ5007 Å/Hβ down to M ˜ 109.2 M ⊙ and sSFR ˜ 10-9.6 yr-1, greater than an order of magnitude lower than previous work at similar redshifts. We find an offset of 0.59 ± 0.05 dex between the median ratios at z ˜ 2 and z ˜ 0 at fixed stellar mass, in agreement with existing studies. However, with respect to sSFR, the z ˜ 2 stacks all lie within 1σ of the median SDSS ratios, with an average offset of only -0.06 ± 0.05. We find that the excitation properties of galaxies are tightly correlated with their sSFR at both z ˜ 2 and z ˜ 0, with a relation that appears to be roughly constant over the last 10 Gyr of cosmic time.

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

Investigation of the dipole formation and growth behavior at In2O3|TiO2 heterojunctions using photoemission spectroscopy and atomic force microscopy

NASA Astrophysics Data System (ADS)

Schaefer, Michael; Halpegamage, Sandamali; Batzill, Matthias; Schlaf, Rudy

2016-02-01

This paper discusses the investigation of the dipole formation at In2O3|TiO2 heterojunctions depending on preparation conditions, i.e., cleaning methods. In2O3 films were deposited using atomic layer deposition (ALD) onto solvent and in situ cleaned anatase and rutile film substrates. The interface dipole strength and film thickness were evaluated by photoemission spectroscopy. Our results indicate the formation of a large intrinsic and film thickness dependent interface dipole that reaches its maximum strength at monolayer thick ALD films. In addition, it was observed that UV photoelectron spectroscopy measurements introduced UV induced surface hydroxylation, which resulted in dipole potentials of -0.70 eV and -0.50 eV on solvent cleaned anatase and rutile, respectively. The overlayers also introduced small amounts of band bending (˜0.10 eV) at the interfaces. Taking these effects into account, the total dipole strength at monolayer thick In2O3 films was determined to be -0.96 eV for solvent cleaned anatase and rutile and -0.81 eV for in situ cleaned rutile. The deposition of single ALD cycles on differently cleaned rutile substrates resulted in similar work function values, suggesting little influence of the sample preparation method prior to ALD deposition on the dipole formation. This was assigned to the fact that ALD oxides benefit from ambient water related contamination by integrating the molecules into the growing ALD layer. Highest initial growth was observed on solvent cleaned rutile, followed by in-situ cleaned rutile and solvent cleaned anatase. The In2O3 growth converged at 0.3 Å/c past the nucleation regime.

The quenching rate of O(1D) by O(3P). [with data from Visible Airglow experiment on AE satellites

NASA Technical Reports Server (NTRS)

Abreu, V. J.; Yee, J. H.; Solomon, S. C.; Dalgarno, A.

1986-01-01

The rate coefficient for the quenching of O(1D) by O(3P) has recently been calculated by Yee et al. (1985). Their results indicate that quenching by atomic oxygen should not be ignored in the analysis of the 6300 A emission airglow. Data obtained by the Visible Airglow Experiment on board the AE satellites have been reanalyzed to determine the quenching rate of O(1D) by atomic oxygen. The results of this analysis are presented.

Water adsorption on the Fe3O4(111) surface: dissociation and network formation.

PubMed

Zaki, Eman; Mirabella, Francesca; Ivars-Barceló, Francisco; Seifert, Jan; Carey, Spencer; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Li, Xiaoke; Paier, Joachim; Sauer, Joachim

2018-06-13

We monitored adsorption of water on a well-defined Fe3O4(111) film surface at different temperatures as a function of coverage using infrared reflection-absorption spectroscopy, temperature programmed desorption, and single crystal adsorption calorimetry. Additionally, density functional theory was employed using a Fe3O4(111)-(2 × 2) slab model to generate 15 energy minimum structures for various coverages. Corresponding vibrational properties of the adsorbed water species were also computed. The results show that water molecules readily dissociate on regular surface Fetet1-O ion pairs to form "monomers", i.e., terminal Fe-OH and surface OH groups. Further water molecules adsorb on the hydroxyl covered surface non-dissociatively and form "dimers" and larger oligomers, which ultimately assemble into an ordered (2 × 2) hydrogen-bonded network structure with increasing coverage prior to the formation of a solid water film.

The interaction of NO2 with BaO: from cooperative adsorption to Ba(NO3)2 formation

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

Yi, Cheol-Woo W.; Kwak, Ja Hun; Szanyi, Janos

2007-10-25

The effect of water on the morphology of BaO/Al2O3-based NOx storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multi-spectroscopy study reveal that, in the presence of water, surface Ba-nitrates convert to bulk nitrates, and water facilitates the formation of large Ba(NO3)2 particles. The conversion of surface to bulk Ba-nitrates is completely reversible, i.e. after the removal of water from the storage material a significant fraction of the bulk nitrates re-convert to surface nitrates. NO2 exposure of a H2O-containing (wet) BaO/Al2O3 sample results in the formation ofmore » nitrites and bulk nitrates exclusively, i.e. no surface nitrates form. After further exposure to NO2, the nitrites completely convert to bulk nitrates. The amount of NOx taken up by the storage material is, however, essentially unaffected by the presence of water, regardless of whether the water was dosed prior to or after NO2 exposure. Based on the results of this study we are now able to explain most of the observations reported in the literature on the effect of water on NOx uptake on similar storage materials.« less

[Control on products of NDMA degradation by UV/O3].

PubMed

Xu, Bing-bing; Chen, Zhong-lin; Qi, Fei; Yang, Lei; Huang, Lu-xi

2008-12-01

Comparison experiments of two advanced oxidation processes, UV/O3 and UV/H2O2, were carried out to evaluate their degradation effect of N-nitrosodimethylamine (NDMA) and controlling effect of dimethylamine (DMA) formation. The results showed that UV/H2O2 could enhance NDMA degradation, but could not control on the formation of DMA. UV/O3 was not only effective for NDMA degradation, but also was good at controlling on DMA formation. Furthermore, factors affecting the formation of DMA during degradation of NDMA by UV/O3 were studied. The formation of DMA decreased with O3 dosage increasing and DMA was 0.98 mg x L(-1) with 7.7 mg x L(-1) NDMA and 6.64 mg x L(-1) O3 dose. Solution pH had obvious effect on controlling of DMA formation during degradation of NDMA by UV/O3 . The formation of DMA lightly increased with pH increasing from acid to neutral but dramatically decreased in basic aqueous solution. The formation of DMA was only 0.3 mg x L(-1) when the initial concentration of NDMA was 7.7 mg x L(-1) under pH = 11.0 condition. UV/O3 had better controlling of DMA formation with lesser initial concentration of NDMA.

Heat of formation of petalite, LiAlSi4O10

NASA Astrophysics Data System (ADS)

Faßhauer, D. W.; Cemič, L.

The enthalpy of formation of petalite, LiAlSi4O10, has been measured using high-temperature solution calorimetry. The measurements were carried out in a Calvet-type twin micro calorimeter at 728°C. A 2PbO.B2O3 melt was used as a solvent. Tabulated heats of formation of the components and tabulated heat capacities of the reactants and the product (Robie and Hemingway 1995) were used to calculate the standard heat of formation of petalite from the measured heats of solution. The calculations yielded a mean value of ΔfHpet298.15=-4872+/-5.4 kJ mol-1. This value may be compared to the heat of formation of ΔfHpet298.15= -4886.5+/-6.3 kJ mol-1 determined by the HF solution calorimetry by Bennington etal. (1980). Faßhauer etal. (1998) combined thermodynamic data with phase-equilibrium results to obtain best-fit thermodynamic results using the Bayes method, in order to derive an internally consistent dataset for phases in the NaAlSiO4- LiAlSiO4-Al2O3-SiO2-H2O system. They determined -4865.6+/-0.8kJmol-1 as the enthalpy of formation of petalite, a value that is appreciably closer to the enthalpy found in this work.

Formation of nitro-PAHs from the heterogeneous reaction of ambient particle-bound PAHs with N2O5/NO3/NO2

PubMed Central

Zimmermann, Kathryn; Jariyasopit, Narumol; Massey Simonich, Staci L.; Tao, Shu; Atkinson, Roger; Arey, Janet

2014-01-01

Reactions of ambient particles collected from four sites within the Los Angeles, CA air basin and Beijing, China with a mixture of N2O5, NO2, and NO3 radicals were studied in an environmental chamber at ambient pressure and temperature. Exposures in the chamber system resulted in the degradation of particle-bound PAHs and formation of molecular weight (mw) 247 nitropyrenes (NPYs) and nitrofluoranthenes (NFLs), mw 273 nitrotriphenylenes (NTPs), nitrobenz[a]anthracenes (NBaAs), and nitrochrysene (NCHR), and mw 297 nitrobenzo[a]pyrene (NBaP). The distinct isomer distributions resulting from exposure of filter-adsorbed deuterated fluoranthene to N2O5/NO3/NO2 and that collected from the chamber gas-phase suggest that formation of NFLs in ambient particles did not occur by NO3 radical-initiated reaction, but from reaction of N2O5, presumably subsequent to its surface adsorption. Accordingly, isomers known to result from gas-phase radical-initiated reactions of parent PAHs, such as 2-NFL and 2- and 4-NPY, were not enhanced from the exposure of ambient particulate matter to N2O5/NO3/NO2. The reactivity of ambient particles toward nitration by N2O5/NO3/NO2, defined by relative 1-NPY formation, varied significantly, with the relative amounts of freshly emitted particles versus aged particles (particles that had undergone atmospheric chemical processing) affecting the reactivity of particle-bound PAHs toward heterogeneous nitration. Analyses of unexposed ambient samples suggested that, in nighttime samples where NO3 radical-initiated chemistry had occurred, heterogeneous formation of 1-NPY on ambient particles may have contributed to the ambient 1-NPY concentrations at downwind receptor sites. These results, together with observations that 2-NFL is consistently the dominant particle-bound nitro-PAH measured in ambient atmospheres, suggest that for PAHs that exist in both the gas- and particle-phase, the heterogeneous formation of particle-bound nitro-PAHs is a minor formation

Hole localization, migration, and the formation of peroxide anion in perovskite SrTiO3

NASA Astrophysics Data System (ADS)

Chen, Hungru; Umezawa, Naoto

2014-07-01

Hybrid density functional calculations are carried out to investigate the behavior of holes in SrTiO3. As in many other oxides, it is shown that a hole tend to localize on one oxygen forming an O- anion with a concomitant lattice distortion; therefore a hole polaron. The calculated emission energy from the recombination of the localized hole and a conduction-band electron is about 2.5 eV, in good agreement with experiments. Therefore the localization of the hole or self-trapping is likely to be responsible for the green photoluminescence at low temperature, which was previously attributed to an unknown defect state. Compared to an electron, the calculated hole polaron mobility is three orders of magnitude lower at room temperature. In addition, two O- anions can bind strongly to form an O22- peroxide anion. No electronic states associated with the O22- peroxide anion are located inside the band gap or close to the band edges, indicating that it is electronically inactive. We suggest that in addition to the oxygen vacancy, the formation of the O22- peroxide anion can be an alternative to compensate acceptor doping in SrTiO3.

Ab initio thermal rate calculations of HO + HO = O(3P) + H2O reaction and isotopologues.

PubMed

Nguyen, Thanh Lam; Stanton, John F

2013-04-04

The forward and reverse reactions, HO + HO ⇌ O((3)P) + H2O, which play roles in both combustion and laboratory studies, were theoretically characterized with a master equation approach to compute thermal reaction rate constants at both the low and high pressure limits. Our ab initio k(T) results for the title reaction and two isotopic variants agree very well with experiments (within 15%) over a wide temperature range. The calculated reaction rate shows a distinctly non-Arrhenius behavior and a strong curvature consistent with the experiment. This characteristic behavior is due to effects of positive barrier height and quantum mechanical tunneling. Tunneling is very important and contributes more than 70% of total reaction rate at room temperature. A prereactive complex is also important in the overall reaction scheme.

Effects of alloy composition and Si-doping on vacancy defect formation in (InxGa1-x)2O3 thin films

NASA Astrophysics Data System (ADS)

Prozheeva, V.; Hölldobler, R.; von Wenckstern, H.; Grundmann, M.; Tuomisto, F.

2018-03-01

Various nominally undoped and Si-doped (InxGa1-x)2O3 thin films were grown by pulsed laser deposition in a continuous composition spread mode on c-plane α-sapphire and (100)-oriented MgO substrates. Positron annihilation spectroscopy in the Doppler broadening mode was used as the primary characterisation technique in order to investigate the effect of alloy composition and dopant atoms on the formation of vacancy-type defects. In the undoped samples, we observe a Ga2O3-like trend for low indium concentrations changing to In2O3-like behaviour along with the increase in the indium fraction. Increasing indium concentration is found to suppress defect formation in the undoped samples at [In] > 70 at. %. Si doping leads to positron saturation trapping in VIn-like defects, suggesting a vacancy concentration of at least mid-1018 cm-3 independent of the indium content.

Enhancing the electrochemical performance of Li-rich layered oxide Li1.13Ni0.3Mn0.57O2 via WO3 doping and accompanying spontaneous surface phase formation

NASA Astrophysics Data System (ADS)

Huang, Jiajia; Liu, Haodong; Hu, Tao; Meng, Ying Shirley; Luo, Jian

2018-01-01

WO3 doping and accompanying spontaneous formation of a surface phase can substantially improve the discharge capacity, rate capability, and cycling stability of Co-free Li-rich layered oxide Li1.13Ni0.3Mn0.57O2 cathode material. X-ray photoelectron spectroscopy, in conjunction with ion sputtering, shows that W segregates to the particle surfaces, decreases the surface Ni/Mn ratio, and changes the surface valence state. High-resolution transmission electron microscopy further suggests that W segregation increases surface structural disorder. The spontaneous and simultaneous changes in the surface structure, composition, and valence state represent the formation of a surface phase (complexion) as the preferred surface thermodynamic state. Consequently, the averaged discharge capacity is increased by ∼13% from 251 to 284 mAh g-1 at a low rate of C/20 and by ∼200% from 30 to 90 mAh g-1 at a high rate of 40C, in comparison with an undoped specimen processed under identical conditions. Moreover, after 100 cycles at a charge/discharge rate of 1C, the WO3 doped specimen retained a discharge capacity of 188 mAh g-1, being 27% higher than that of the undoped specimen. In a broader context, this work exemplifies an opportunity of utilizing spontaneously-formed surface phases as a scalable and cost-effective method to improve materials properties.

Stibiconite (Sb3O6OH), senarmontite (Sb2O3) and valentinite (Sb2O3): Dissolution rates at pH 2-11 and isoelectric points

NASA Astrophysics Data System (ADS)

Biver, M.; Shotyk, W.

2013-05-01

Batch reactor experiments were carried out in order to derive rate laws for the proton promoted dissolution of the main natural antimony oxide phases, namely stibiconite (idealized composition SbSb2O6OH), senarmontite (cubic Sb2O3) and (metastable) valentinite (orthorhombic Sb2O3) over the range 2 ⩽ pH ⩽ 11, under standard conditions and ionic strength I = 0.01 mol l-1. The rates of antimony release by stibiconite were r = (2.2 ± 0.2) × 10-9 a(H+)0.11±0.01 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 4.74 and r = (4.3 ± 0.2) × 10-10 a(H+)-0.030±0.003 mol m-2 s-1 for 4.74 ⩽ pH ⩽ 10.54. The rates of dissolution of senarmontite were r = (5.3 ± 2.2) × 10-7 a(H+)0.54±0.05 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 6.93 and r = (1.4 ± 0.3) × 10-14 a(H+)-0.53±0.07 mol m-2 s-1 for 6.93 ⩽ pH ⩽ 10.83. The rates of dissolution of valentinite were r = (6.3 ± 0.2) × 10-8 a(H+)0.052±0.003 mol m-2 s-1 for 1.97 ⩽ pH ⩽ 6.85. Above pH = 6.85, valentinite was found to dissolve at a constant rate of r = (2.79 ± 0.05) × 10-8 mol m-2 s-1. Activation energies were determined at selected pH values in the acidic and basic domain, over the temperature range 25-50 °C. The values for stibiconite are -10.6 ± 1.9 kJ mol-1 (pH = 2.00) and 53 ± 14 kJ mol-1 (pH = 8.7). For senarmontite, we found 46.6 ± 4.7 kJ mol-1 (pH = 3.0) and 68.1 ± 6.1 kJ mol-1 (pH = 9.9) and for valentinite 41.9 ± 1.1 kJ mol-1 (pH = 3.0) and 39.0 ± 4.6 kJ mol-1 (pH = 9.9). These activation energies are interpreted in the text. The solubility of stibiconite at 25 °C in the pH domain from 2 to 10 was determined; solubilities decrease from 452.0 μg l-1 (as Sb) at pH = 2.00 to 153.2 μg l-1 at pH = 7.55 and increase again in the basic region, up to 176.6 μg l-1 at pH = 9.92. A graphical synopsis of all the kinetic results, including those of stibnite (Sb2S3) from earlier work, is presented. This allows an easy comparison between the dissolution rates of stibnite and the minerals examined in the present work

Hierarchical La0.7Ce0.3FeO3/halloysite nanocomposite for photocatalytic degradation of antibiotics

NASA Astrophysics Data System (ADS)

Li, Xiazhang; Zhu, Wei; Yan, Xiangyu; Lu, Xiaowang; Yao, Chao; Ni, Chaoying

2016-08-01

The hierarchical La0.7Ce0.3FeO3/halloysite nanotubes (HNTs) composites have been successfully prepared via sol-gel method. XRD and TEM characterizations indicated that the sheet-like La0.7Ce0.3FeO3 coupled with the co-precipitated CeO2 were evenly deposited onto the surface of halloysite. The photocatalytic degradation of chlortetracycline under visible light irradiation using La0.7Ce0.3FeO3/HNTs as catalyst was evaluated by high-performance liquid chromatography, which exhibited remarkable photocatalytic activity with the removal rate up to 99 % in 90 min, due to the formation of "solid solution/co-precipitation" heterostructure as well as the excellent adsorptive capability of halloysite for antibiotics.

What Determines Star Formation Rates?

NASA Astrophysics Data System (ADS)

Evans, Neal John

2017-06-01

The relations between star formation and gas have received renewed attention. We combine studies on scales ranging from local (within 0.5 kpc) to distant galaxies to assess what factors contribute to star formation. These include studies of star forming regions in the Milky Way, the LMC, nearby galaxies with spatially resolved star formation, and integrated galaxy studies. We test whether total molecular gas or dense gas provides the best predictor of star formation rate. The star formation ``efficiency," defined as star formation rate divided by mass, spreads over a large range when the mass refers to molecular gas; the standard deviation of the log of the efficiency decreases by a factor of three when the mass of relatively dense molecular gas is used rather than the mass of all the molecular gas. We suggest ways to further develop the concept of "dense gas" to incorporate other factors, such as turbulence.

The contribution of hydroxylamine content to spatial variability of N2O formation in soil of a Norway spruce forest

NASA Astrophysics Data System (ADS)

Liu, Shurong; Herbst, Michael; Bol, Roland; Gottselig, Nina; Pütz, Thomas; Weymann, Daniel; Wiekenkamp, Inge; Vereecken, Harry; Brüggemann, Nicolas

2016-04-01

Hydroxylamine (NH2OH), a reactive intermediate of several microbial nitrogen turnover processes, is a potential precursor of nitrous oxide (N2O) formation in the soil. However, the contribution of soil NH2OH to soil N2O emission rates in natural ecosystems is unclear. Here, we determined the spatial variability of NH2OH content and potential N2O emission rates of organic (Oh) and mineral (Ah) soil layers of a Norway spruce forest, using a recently developed analytical method for the determination of soil NH2OH content, combined with a geostatistical Kriging approach. Potential soil N2O emission rates were determined by laboratory incubations under oxic conditions, followed by gas chromatographic analysis and complemented by ancillary measurements of soil characteristics. Stepwise multiple regressions demonstrated that the potential N2O emission rates, NH2OH and nitrate (NO3-) content were spatially highly correlated, with hotspots for all three parameters observed in the headwater of a small creek flowing through the sampling area. In contrast, soil ammonium (NH4+) was only weakly correlated with potential N2O emission rates, and was excluded from the multiple regression models. While soil NH2OH content explained the potential soil N2O emission rates best for both layers, also NO3- and Mn content turned out to be significant parameters explaining N2O formation in both soil layers. The Kriging approach was improved markedly by the addition of the co-variable information of soil NH2OH and NO3- content. The results indicate that determination of soil NH2OH content could provide crucial information for the prediction of the spatial variability of soil N2O emissions.

Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation

NASA Astrophysics Data System (ADS)

Yao, Guisheng; Li, Yong; Jiang, Peng; Jin, Xiuming; Long, Menglong; Qin, Haixia; Kumar, R. Vasant

2017-04-01

Commercial silicon powders are nitrided at constant temperatures (1453 K; 1513 K; 1633 K; 1693 K). The X-ray diffraction results show that small amounts of Si3N4 and Si2N2O are formed as the nitridation products in the samples. Fibroid and short columnar Si3N4 are detected in the samples. The formation mechanisms of Si3N4 and Si2N2O are analyzed. During the initial stage of silicon powder nitridation, Si on the outside of sample captures slight amount of O2 in N2 atmosphere, forming a thin film of SiO2 on the surface which seals the residual silicon inside. And the oxygen partial pressure between the SiO2 film and free silicon is decreasing gradually, so passive oxidation transforms to active oxidation and metastable SiO(g) is produced. When the SiO(g) partial pressure is high enough, the SiO2 film will crack, and N2 is infiltrated into the central section of the sample through cracks, generating Si2N2O and short columnar Si3N4 in situ. At the same time, metastable SiO(g) reacts with N2 and form fibroid Si3N4. In the regions where the oxygen partial pressure is high, Si3N4 is oxidized into Si2N2O.

Connecting the Cosmic Star Formation Rate with the Local Star Formation

NASA Astrophysics Data System (ADS)

Gribel, Carolina; Miranda, Oswaldo D.; Williams Vilas-Boas, José

2017-11-01

We present a model that unifies the cosmic star formation rate (CSFR), obtained through the hierarchical structure formation scenario, with the (Galactic) local star formation rate (SFR). It is possible to use the SFR to generate a CSFR mapping through the density probability distribution functions commonly used to study the role of turbulence in the star-forming regions of the Galaxy. We obtain a consistent mapping from redshift z˜ 20 up to the present (z = 0). Our results show that the turbulence exhibits a dual character, providing high values for the star formation efficiency (< \\varepsilon > ˜ 0.32) in the redshift interval z˜ 3.5{--}20 and reducing its value to < \\varepsilon > =0.021 at z = 0. The value of the Mach number ({{ M }}{crit}), from which < \\varepsilon > rapidly decreases, is dependent on both the polytropic index (Γ) and the minimum density contrast of the gas. We also derive Larson’s first law associated with the velocity dispersion (< {V}{rms}> ) in the local star formation regions. Our model shows good agreement with Larson’s law in the ˜ 10{--}50 {pc} range, providing typical temperatures {T}0˜ 10{--}80 {{K}} for the gas associated with star formation. As a consequence, dark matter halos of great mass could contain a number of halos of much smaller mass, and be able to form structures similar to globular clusters. Thus, Larson’s law emerges as a result of the very formation of large-scale structures, which in turn would allow the formation of galactic systems, including our Galaxy.

Reactivity of Hydrogen and Methanol on (001) Surfaces of WO3, ReO3, WO3/ReO3 and ReO3/WO3

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

Ling, Sanliang; Mei, Donghai; Gutowski, Maciej S.

2011-05-16

Bulk tungsten trioxide (WO3) and rhenium trioxide (ReO3) share very similar structures but display different electronic properties. WO3 is a wide bandgap semiconductor while ReO3 is an electronic conductor. With the advanced molecular beam epitaxy techniques, it is possible to make heterostructures comprised of layers of WO3 and ReO3. These heterostructures might display reactivity different than pure WO3 and ReO3. The interactions of two probe molecules (hydrogen and methanol) with the (001) surfaces of WO3, ReO3, and two heterostructures ReO3/WO3 and WO3/ReO3 were investigated at the density functional theory level. Atomic hydrogen prefers to adsorb at the terminal O1C sitesmore » forming a surface hydroxyl on four surfaces. Dissociative adsorption of a hydrogen molecule at the O1C site leads to formation of a water molecule adsorbed at the surface M5C site. This is thermodynamically the most stable state. A thermodynamically less stable dissociative state involves two surface hydroxyl groups O1CH and O2CH. The interaction of molecular hydrogen and methanol with pure ReO3 is stronger than with pure WO3 and the strength of the interaction substantially changes on the WO3/ReO3 and ReO3/WO3 heterostructures. The reaction barriers for decomposition and recombination reactions are sensitive to the nature of heterostructure. The calculated adsorption energy of methanol on WO3(001) of -65.6 kJ/mol is consistent with the previous experimental estimation of -67 kJ/mol. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Ultrasound assisted synthesis of WO3-ZnO nanocomposites for brilliant blue dye degradation.

PubMed

Hunge, Y M; Yadav, A A; Mathe, V L

2018-07-01

The present work deals with the preparation of WO 3 and WO 3 -ZnO nanocomposites in presence of ultrasonic irradiation, and its use in the sonocatalytic degradation of brilliant blue dye. WO 3 -ZnO nanocomposite is prepared using one step in-situ ultrasound assisted method. The successfully prepared WO 3 and WO 3 -ZnO nanocomposites were characterized using different characterization techniques such as XRD, Raman, BET, FE-SEM and EDS. The XRD pattern reveals that the formation of monoclinic and hexagonal crystal structures of WO 3 and ZnO respectively. BET study shows that WO 3 -ZnO nanocomposite have maximum surface area than that of the WO 3 . EDS study confirms the formation of WO 3 -ZnO nanocomposites. Further the use of the prepared WO 3 and WO 3 -ZnO nanocomposites as a sonocatalyst for the degradation of brilliant blue dye. The rate constant (k) was evaluated as a function of the initial concentration of brilliant blue dye. It is found that WO 3 -ZnO nanocomposites exhibits maximum sonocatalytic activity as compared to WO 3 photocatalyst. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of Er{sup 3+} ions on the phase formation and properties of In{sub 2}O{sub 3}nanostructures crystallized upon microwave heating

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

Lemos, Samantha C.S.; Romeiro, Fernanda C.; Paula, Leonardo F. de

Regular sized nanostructures of indium oxide (In{sub 2}O{sub 3}) were homogeneously grown using a facile route, i.e. a microwave-hydrothermal method combined with rapid thermal treatment in a microwave oven. The presence of Er{sup 3+} doping plays an important role in controlling the formation of cubic (bcc) and rhombohedral (rh) In{sub 2}O{sub 3} phases. The samples presented broad photoluminescent emission bands in the green-orange region, which were attributed to the recombination of electrons at oxygen vacancies. The photocatalytic activities of pure bcc-In{sub 2}O{sub 3} and a bcc-rh-In{sub 2}O{sub 3} mixture towards the UVA degradation of methylene blue (MB) were also evaluated.more » The results showed that Er{sup +3} doped In{sub 2}O{sub 3} exhibited the highest photocatalytic activity with a photonic efficiency three times higher than the pure oxide. The improved performance was attributed to the higher surface area, the greater concentration of electron traps due the presence of the dopant and the possible formation of heterojunctions between the cubic and rhombohedral phases. - Graphical abstract: Photodegradation curves as a function of irradiation time of the samples obtained upon rapid microwave heating. - Highlights: • Efficient and rapid microwave heating to obtain Er{sup 3+} doped In{sub 2}O{sub 3} nanostructures. • Er{sup 3+} ions doping is fundamental to stabilizing the crystalline rhombohedral phase. • Symmetry breaking induced by vacancies in the lattice leads to photoluminescence. • Surface area of doped sample was two times higher than the surface of pure oxide. • The presence of defects in the lattice structure favors photocatalytic activity.« less

Formation of orbital-selective electron states in LaTiO3/SrTiO3 superlattices

NASA Astrophysics Data System (ADS)

Lechermann, Frank; Boehnke, Lewin; Grieger, Daniel

2013-06-01

The interface electronic structure of correlated LaTiO3/SrTiO3 superlattices is investigated by means of the charge self-consistent combination of the local density approximation (LDA) to density functional theory with dynamical mean-field theory. Utilizing a pseudopotential technique together with a continuous-time quantum Monte Carlo approach, the resulting complex multiorbital electronic states are addressed in a coherent fashion beyond static mean field. General structural relaxations are taken into account on the LDA level and cooperate with the driving forces from strong electronic correlations. This alliance leads to a Ti(3dxy) dominated low-energy quasiparticle peak and a lower Hubbard band in line with photoemission studies. Furthermore correlation effects close to the band-insulating bulk SrTiO3 limit as well as the Mott-insulating bulk LaTiO3 limit are studied via realistic single-layer embeddings.

Surface tiny grain-dependent enhanced rate performance of MoO3 nanobelts with pseudocapacitance contribution for lithium-ion battery anode

NASA Astrophysics Data System (ADS)

Cao, Liyun; He, Juju; Li, Jiayin; Yan, Jingwen; Huang, Jianfeng; Qi, Ying; Feng, Liangliang

2018-07-01

In order to improve the rate performance of MoO3, a novel MoO3 nanobelt with tiny grains on surface (named as d-MoO3) is fabricated via one-step facile hydrothermal method with citric acid adding, in which citric acid (CA) serves as a weak reductant as well as surface modification agent. When tested as an anode in LIBs, d-MoO3 displays an improved discharge capacity of 787 mAh·g-1 at 0.1 A g-1 over 100 cycles with capacity retention of ∼91% while MoO3 decays to 50 mAh·g-1 in the 100th cycle. Notably, d-MoO3 delivers enhanced rate capability (536 and 370 mAh·g-1 at high rates of 5 and 10 A g-1 respectively). We consider these excellent electrochemical properties of d-MoO3 electrode are associated with the tiny grains on MoO3 surface, which effectively maintains the electrode's structural integrity. Even though d-MoO3 nanobelt suffers from a degree of in-situ pulverization after several cycles, these pulverized active particles can still maintain stable electrochemical contact and are highly exposed to electrolyte, realizing ultrahigh e-/Li+ diffusion kinetics. In addition, part extrinsic pseudocapacitance contribution to the Li+ storage also explains the high-rate performance. Combining all these merits, d-MoO3 is potentially a high-energy, high-power and well-stable anode material for Li ion batteries (LIBs).

Degradation mechanism of alachlor during direct ozonation and O(3)/H(2)O(2) advanced oxidation process.

PubMed

Qiang, Zhimin; Liu, Chao; Dong, Bingzhi; Zhang, Yalei

2010-01-01

The degradation of alachlor by direct ozonation and advanced oxidation process O(3)/H(2)O(2) was investigated in this study with focus on identification of degradation byproducts. The second-order reaction rate constant between ozone and alachlor was determined to be 2.5+/-0.1M(-1)s(-1) at pH 7.0 and 20 degrees C. Twelve and eight high-molecular-weight byproducts (with the benzene ring intact) from alachlor degradation were identified during direct ozonation and O(3)/H(2)O(2), respectively. The common degradation byproducts included N-(2,6-diethylphenyl)-methyleneamine, 8-ethyl-3,4-dihydro-quinoline, 8-ethyl-quinoline, 1-chloroacetyl-2-hydro-3-ketone-7-acetyl-indole, 2-chloro-2',6'-diacetyl-N-(methoxymethyl)acetanilide, 2-chloro-2'-acetyl-6'-ethyl-N-(methoxymethyl)-acetanilide, and two hydroxylated alachlor isomers. In direct ozonation, four more byproducts were also identified including 1-chloroacetyl-2,3-dihydro-7-ethyl-indole, 2-chloro-2',6'-ethyl-acetanilide, 2-chloro-2',6'-acetyl-acetanilide and 2-chloro-2'-ethyl-6'-acetyl-N-(methoxymethyl)-acetanilide. Degradation of alachlor by O(3) and O(3)/H(2)O(2) also led to the formation of low-molecular-weight byproducts including formic, acetic, propionic, monochloroacetic and oxalic acids as well as chloride ion (only detected in O(3)/H(2)O(2)). Nitrite and nitrate formation was negligible. Alachlor degradation occurred via oxidation of the arylethyl group, N-dealkylation, cyclization and cleavage of benzene ring. After O(3) or O(3)/H(2)O(2) treatment, the toxicity of alachlor solution examined by the Daphnia magna bioassay was slightly reduced. 2009 Elsevier Ltd. All rights reserved.

Effects of calcining temperature on formation of hierarchical TiO2/g-C3N4 hybrids as an effective Z-scheme heterojunction photocatalyst

NASA Astrophysics Data System (ADS)

Lu, Lianying; Wang, Guohong; Zou, Min; Wang, Juan; Li, Jun

2018-05-01

Hierarchical TiO2/g-C3N4 heterojunction photocatalysts with well-defined multiscale porous TiO2 framework are synthesized by simply calcinating tetrabutyl titanate and melamine precursors. The samples have been characterized by XRD, XPS, SEM, TEM, FTIR, nitrogen absorption-desorption equipment and TGA. The photocatalytic activity of these samples has been investigated in photo-degradation of Rhodamine B (RhB). The results show that calcining temperature critically affects the microstructure, surface area, interface structure and catalytic properties of the prepared samples. At the optimal calcining temperature of 550 °C, the apparent reaction rate constant of the catalyst is 55.0 × 10-3 min-1, which is 16.2 fold of pure TiO2 (3.4 × 10-3 min-1) and 3.4 fold of pure g-C3N4 (16.4 × 10-3 min-1), respectively. The strengthened visible-light-driven photocatalytic activity is attributed to the formation of a unique Z-scheme TiO2/g-C3N4 heterojunction due to C- or N-doping at the surface of the porous TiO2 framework. This mechanism explains the observation in a series of radical trapping experiments that superoxide ions and photo-generated holes play major roles in the photo-decolorizing process while hydroxyl radicals are also involved with a minor role.

Enthalpy of formation of Fe 3Al 2Si 3O 12 (almandine) by high temperature alkali borate solution calorimetry

NASA Astrophysics Data System (ADS)

Chatillon-Colinet, C.; Kleppa, O. J.; Newton, R. C.; Perkins, D., III

1983-03-01

A high-temperature solution calorimetric method suitable for thermochemical studies of anhydrous minerals containing Fe 2+ ions has been developed. The method is based on an oxide melt solvent with 52 wt% LiBO 2 and 48 wt% NaBO 2 maintained at a temperature of 750°C. In a first application of this method the enthalpies of solution of synthetic almandine, fayalite, a mixture of fayalite plus quartz on FeSiO 3 composition, and natural quartz were measured. For the reaction: ? the enthalpy change at 1023 K is -3.82 ± 0.87 kcal, based on fayalite, quartz, corundum and almandine, and -5.96 ± 0.90 kcal based on the fayalite plus quartz mixture, corundum, and almandine. These values lead to standard molar enthalpies of formation of almandine from the oxides at 1023 K of -14.10 ± 1.22 kcal and -16.24 ± 1.74 kcal, respectively. The measured enthalpy of formation of almandine is less negative by several kilocalories than values derived from analysis of the phase equilibrium work of HSU (1968), but in closer agreement with the phase equilibrium study of O'NEILL and WOOD (1979) and similar to the phase equilibrium deduction of FROESE (1973). The agreement of the present almandine enthalpy of formation with O'NEILL and WOOD (1979) and FROESE (1973) suggests that almandine entropies at 298 K to be obtained from their studies, in the range 79-81 cal/K, are more nearly correct than the several estimates based on oxide sum and volume-entropy systematics, most of which are much lower.

The formation and structure of mechano-synthesized nanocrystalline Sr{sub 3}Fe{sub 2}O{sub 6.4}: XRD Rietveld, Mössabuer and XPS analyses

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

Al-Rawas, A.D., E-mail: arawas@squ.edu.om; Widatallah, H.M.; Al-Harthi, S.H.

2015-05-15

Highlights: • The formation of mechano-synthesized nanocrystalline Sr{sub 3}Fe{sub 2}O{sub 7−δ} is investigated. • Pre-milling the reactants substantially lowers the formation temperature. • The core and surface structures were studied. • XRD and {sup 57}Fe Mössbauer spectroscopic analyses indicate the δ-value to be 0.60. • XPS shows a complex surface structure for the mechanosynthesized Sr{sub 3}Fe{sub 2}O{sub 7−δ} nanoparticles. - Abstract: The influence of ball milling and subsequent sintering of a 3:1 molar mixture of SrCO{sub 3} and α-Fe{sub 2}O{sub 3} on the formation of Sr{sub 3}Fe{sub 2}O{sub 7−δ} double perovskite is investigated with different analytical techniques. Milling the mixturemore » for 110 h leads to the formation of SrCO{sub 3}-α-Fe{sub 2}O{sub 3} nanocomposites and the structural deformation of α-Fe{sub 2}O{sub 3} via the incorporation of Sr{sup 2+} ions. Subsequent sintering of the pre-milled reactants’ mixture has led to the partial formation of an SrFeO{sub 3} perovskite-related phase in the temperature range 400–600 °C. This was followed by the progressive development of an Sr{sub 3}Fe{sub 2}O{sub 7−δ} phase that continued to increase with increasing sintering temperature until a single-phased nanocrystalline Sr{sub 3}Fe{sub 2}O{sub 7−δ} phase was attained at 950 °C (12 h). This temperature is ∼350 °C lower than the temperature at which the material is prepared conventionally using the ceramic method. The evolution of different structural phases during the reaction process is discussed. Rietveld refinement of the X-ray diffraction data shows a value of 0.60 for the oxygen deficiency δ, in consistency with the Fe{sup 3+}/Fe{sup 4+} ratio derived from the {sup 57}Fe Mössbauer data recorded at both 300 K and 78 K. The Mössbauer data suggests that the Sr{sub 3}Fe{sub 2}O{sub 6.4} nanoparticles are superparamagnetic with blocking temperatures below 78 K. The surfaces of the Sr{sub 3}Fe{sub 2}O{sub 6

Influence of nanogold additives on phase formation, microstructure and dielectric properties of perovskite BaTiO3 ceramics

NASA Astrophysics Data System (ADS)

Nonkumwong, Jeeranan; Ananta, Supon; Srisombat, Laongnuan

2015-06-01

The formation of perovskite phase, microstructure and dielectric properties of nanogold-modified barium titanate (BaTiO3) ceramics was examined as a function of gold nanoparticle contents by employing a combination of X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray, Archimedes principle and dielectric measurement techniques. These ceramics were fabricated from a simple mixed-oxide method. The amount of gold nanoparticles was found to be one of the key factors controlling densification, grain growth and dielectric response in BaTiO3 ceramics. It was found that under suitable amount of nanogold addition (4 mol%), highly dense perovskite BaTiO3 ceramics with homogeneous microstructures of refined grains (~0.5-3.1 μm) and excellence dielectric properties can be produced.

The Tick-Over Theory Revisited: Formation and Regulation of the Soluble Alternative Complement C3 Convertase (C3(H2O)Bb)

PubMed Central

Bexborn, Fredrik; Andersson, Per Ola; Chen, Hui; Nilsson, Bo; Ekdahl, Kristina N.

2009-01-01

The molecular interactions between the components of the C3 convertase of the alternative pathway (AP) of complement and its regulators, in both surface-bound and fluid-phase form, are still incompletely understood. The fact that the AP convertase is labile makes studies difficult to perform. According to the so called tick-over theory, hydrolyzed C3, called C3(H2O), forms the initial convertase in fluid phase together with factor B. In the present study, we have applied western blot analysis and ELISA together with fluorescence resonance energy transfer (FRET) to study the formation of the fluid-phase AP convertases C3(H2O)Bb and C3bBb and their regulation by factor H and factor I at specific time points and, with FRET, in real time. In our hands, factor B showed a higher affinity for C3(H2O) than for C3b, although in both cases it was readily activated to Bb. However, the convertase activity of C3bBb was approximately twice that of C3(H2O)Bb, as monitored by the generation of C3a. But in contrast, the C3(H2O)Bb convertase was more resistant to inactivation by factor H and factor I than was the C3bBb convertase. Under conditions that totally inactivated C3bBb, C3(H2O)Bb still retained approximately 25% of its initial activity. PMID:18096230

The tick-over theory revisited: formation and regulation of the soluble alternative complement C3 convertase (C3(H2O)Bb).

PubMed

Bexborn, Fredrik; Andersson, Per Ola; Chen, Hui; Nilsson, Bo; Ekdahl, Kristina N

2008-04-01

The molecular interactions between the components of the C3 convertase of the alternative pathway (AP) of complement and its regulators, in both surface-bound and fluid-phase form, are still incompletely understood. The fact that the AP convertase is labile makes studies difficult to perform. According to the so called tick-over theory, hydrolyzed C3, called C3(H(2)O), forms the initial convertase in fluid phase together with factor B. In the present study, we have applied western blot analysis and ELISA together with fluorescence resonance energy transfer (FRET) to study the formation of the fluid-phase AP convertases C3(H(2)O)Bb and C3bBb and their regulation by factor H and factor I at specific time points and, with FRET, in real time. In our hands, factor B showed a higher affinity for C3(H(2)O) than for C3b, although in both cases it was readily activated to Bb. However, the convertase activity of C3bBb was approximately twice that of C3(H(2)O)Bb, as monitored by the generation of C3a. But in contrast, the C3(H(2)O)Bb convertase was more resistant to inactivation by factor H and factor I than was the C3bBb convertase. Under conditions that totally inactivated C3bBb, C3(H(2)O)Bb still retained approximately 25% of its initial activity.

Photoemission from buried interfaces in SrTiO3/LaTiO3 superlattices.

PubMed

Takizawa, M; Wadati, H; Tanaka, K; Hashimoto, M; Yoshida, T; Fujimori, A; Chikamatsu, A; Kumigashira, H; Oshima, M; Shibuya, K; Mihara, T; Ohnishi, T; Lippmaa, M; Kawasaki, M; Koinuma, H; Okamoto, S; Millis, A J

2006-08-04

We have measured photoemission spectra of SrTiO3/LaTiO3 superlattices with a topmost SrTiO3 layer of variable thickness. A finite coherent spectral weight with a clear Fermi cutoff was observed at chemically abrupt SrTiO3/LaTiO3 interfaces, indicating that an "electronic reconstruction" occurs at the interface between the Mott insulator LaTiO3 and the band insulator SrTiO3. For SrTiO3/LaTiO3 interfaces annealed at high temperatures (approximately 1000 degrees C), which leads to Sr/La atomic interdiffusion and hence to the formation of La(1-x)Sr(x)TiO3-like material, the intensity of the incoherent part was found to be dramatically reduced whereas the coherent part with a sharp Fermi cutoff was enhanced due to the spread of charge. These important experimental features are well reproduced by layer dynamical-mean-field-theory calculation.

The effect of clouds on photolysis rates and ozone formation in the unpolluted troposphere

NASA Technical Reports Server (NTRS)

Thompson, A. M.

1984-01-01

The photochemistry of the lower atmosphere is sensitive to short- and long-term meteorological effects; accurate modeling therefore requires photolysis rates for trace gases which reflect this variability. As an example, the influence of clouds on the production of tropospheric ozone has been investigated, using a modification of Luther's two-stream radiation scheme to calculate cloud-perturbed photolysis rates in a one-dimensional photochemical transport model. In the unpolluted troposphere, where stratospheric inputs of odd nitrogen appear to represent the photochemical source of O3, strong cloud reflectance increases the concentration of NO in the upper troposphere, leading to greatly enhanced rates of ozone formation. Although the rate of these processes is too slow to verify by observation, the calculation is useful in distinguishing some features of the chemistry of regions of differing mean cloudiness.

Kinetics of dissolution of sapphire in melts in the CaO-Al2O3-SiO2 system

NASA Astrophysics Data System (ADS)

Shaw, Cliff S. J.; Klausen, Kim B.; Mao, Huahai

2018-05-01

The dissolution rate of sapphire in melts in the CAS system of varying silica activity, viscosity and degree of alumina saturation has been determined at 1600 °C and 1.5 GPa. After an initiation period of up to 1800 s, dissolution is controlled by diffusion of cations through the boundary layer adjacent to the dissolving sapphire. The dissolution rate decreases with increasing silica activity, viscosity and molar Al2O3/CaO. The calculated diffusion matrix for each solvent melt shows that CAS 1 and 9 which have molar Al2O3/CaO of 0.33 and 0.6 and dissolution rate constants of 0.65 × 10-6 and 0.59 × 10-6 m/s0.5 have similar directions and magnitudes of diffusive coupling: DCaO-Al2O3 and DAl2O3-CaO are both negative are approximately equal. The solvent with the fastest dissolution rate: CAS 4, which has a rate constant of 1.5 × 10-6 m/s0.5 and Al2O3/CaO of 0.31 has positive DCaO-Al2O3 and negative DAl2O3-CaO and the absolute values vary by a factor of 4. Although many studies show that aluminium is added to the melts via the reaction: Si4+ =Al3+ + 0.5Ca2+ the compositional profiles show that this reaction is not the only one involved in accommodating the aluminium added during sapphire dissolution. Rather, aluminium is incorporated as both tetrahedrally coordinated Al charge balanced by Ca and as aluminium not charge balanced by Ca (termed Alxs). This reaction: AlIV -Ca =Alxs +CaNBO where CaNBO is a non-bridging oxygen associated with calcium, may involve the formation of aluminium triclusters. The shape of the compositional profiles and oxide-oxide composition paths is controlled by the aluminium addition reaction. When Alxs exceeds 2%, CaO diffusion becomes increasingly anomalous and since the bond strength of Alxs correlates with CaO/CaO + Al2O3, the presence of more than 2% Alxs leads to significantly slower dissolution than when Alxs is absent or at low concentration. Thus, dissolution is controlled by diffusion of cations through the boundary layer, but this

Kinetics of nitrous oxide (N2O) formation and reduction by Paracoccus pantotrophus.

PubMed

Read-Daily, B L; Sabba, F; Pavissich, J P; Nerenberg, R

2016-12-01

Nitrous oxide (N 2 O) is a powerful greenhouse gas emitted from wastewater treatment, as well as natural systems, as a result of biological nitrification and denitrification. While denitrifying bacteria can be a significant source of N 2 O, they can also reduce N 2 O to N 2 . More information on the kinetics of N 2 O formation and reduction by denitrifying bacteria is needed to predict and quantify their impact on N 2 O emissions. In this study, kinetic parameters were determined for Paracoccus pantotrophus, a common denitrifying bacterium. Parameters included the maximum specific reduction rates, [Formula: see text], growth rates, [Formula: see text], and yields, Y, for reduction of NO 3 - (nitrate) to nitrite (NO 2 - ), NO 2 - to N 2 O, and N 2 O to N 2 , with acetate as the electron donor. The [Formula: see text] values were 2.9 gN gCOD -1 d -1 for NO 3 - to NO 2 - , 1.4 gN gCOD -1  d -1 for NO 2 - to N 2 O, and 5.3 gN gCOD -1  d -1 for N 2 O to N 2 . The [Formula: see text] values were 2.7, 0.93, and 1.5 d -1 , respectively. When N 2 O and NO 3 - were added concurrently, the apparent (extant) kinetics, [Formula: see text], assuming reduction to N 2 , were 6.3 gCOD gCOD -1  d -1 , compared to 5.4 gCOD gCOD -1  d -1 for NO 3 - as the sole added acceptor. The [Formula: see text] was 1.6 d -1 , compared to 2.5 d -1 for NO 3 - alone. These results suggest that NO 3 - and N 2 O were reduced concurrently. Based on this research, denitrifying bacteria like P. pantotrophus may serve as a significant sink for N 2 O. With careful design and operation, treatment plants can use denitrifying bacteria to minimize N 2 O emissions.

Volatile molecule PuO 3 observed from subliming plutonium dioxide

NASA Astrophysics Data System (ADS)

Ronchi, C.; Capone, F.; Colle, J. Y.; Hiernaut, J. P.

2000-06-01

Mass spectrometric measurements of effusing vapours over PuO 2 and (U, Pu)O 2 indicate the presence of volatile PuO 3 (g) molecules. The formation of plutonium trioxide vapour is due to a chemical process involving oxygen adsorbed during oxidation of the sample. Although in the examined samples, the fraction of trioxide effusing in vacuo was of the order of 0.02 ppm of the plutonium content, under steady-state oxidation conditions it has been shown that the process can have a relevant effect on the sublimation rate of the dioxide.

Enhanced magnetization in morphologically and magnetically distinct BiFeO3 and La0.7Sr0.3MnO3 composites

NASA Astrophysics Data System (ADS)

Pillai, Shreeja; Reshi, Hilal Ahmad; Bagwaiya, Toshi; Banerjee, Alok; Shelke, Vilas

2017-09-01

Nanomaterials exhibit properties different from those of their bulk counterparts. The modified magnetic characteristics of manganite nanoparticles were exploited to improve magnetization in multiferroic BiFeO3 compound. We studied the composite of two morphologically and magnetically distinct compounds BiFeO3 (BFO) and La0.7Sr0.3MnO3 (LSMO). The microcrystalline BiFeO3 sample was prepared by solid state reaction method and the nanocrystalline La0.7Sr0.3MnO3 by sol-gel method. Composites with nominal compositions (1-x)BiFeO3-(x)La0.7Sr0.3MnO3 were prepared by modified solid state reaction method. The phase purity and crystal structures were checked by using X-ray diffraction. The formation of composites with phase separated BFO and LSMO was confirmed using Raman and Fourier Transform Infrared spectroscopy studies. The composite samples showed relatively high value of magnetization with finite coercivity. This improvement in magnetic behavior is ascribed to the coexistence of multiple magnetic orderings in composite samples. We scrutinized the possibility of oxygen vacancy or Fe mixed valency formation in the samples using X-ray photoelectron spectroscopy technique.

The Origin and Evolution of the Galaxy Star Formation Rate-Stellar Mass Correlation

NASA Astrophysics Data System (ADS)

Gawiser, Eric; Iyer, Kartheik

2018-01-01

The existence of a tight correlation between galaxies’ star formation rates and stellar masses is far more surprising than usually noted. However, a simple analytical calculation illustrates that the evolution of the normalization of this correlation is driven primarily by the inverse age of the universe, and that the underlying correlation is one between galaxies’ instantaneous star formation rates and their average star formation rates since the Big Bang.Our new Dense Basis method of SED fitting (Iyer & Gawiser 2017, ApJ 838, 127) allows star formation histories (SFHs) to be reconstructed, along with uncertainties, for >10,000 galaxies in the CANDELS and 3D-HST catalogs at 0.53. We use these SFHs to measure the normalization, slope, and intrinsic scatter of the underlying correlation between instantaneous and past-average star formation rates, providing new constraints on the level of stochasticity in galaxy formation.

High-throughput and in situ EDXRD investigation on the formation of two new metal aminoethylphosphonates - Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) and Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O

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

Schmidt, Corinna; Feyand, Mark; Rothkirch, Andre

2012-04-15

The system Ca{sup 2+}/2-aminoethylphosphonic acid/H{sub 2}O/NaOH was systematically investigated using high-throughput methods. The experiments led to one new compound Ca(O{sub 3}PC{sub 2} H{sub 4}NH{sub 2}) (1) and the crystal structure was determined using in house X-ray powder diffraction data (monoclinic, P2{sub 1}/c, a=9.7753(3), b=6.4931(2), c=8.4473(2) A, {beta}=106.46(2) Degree-Sign , V=514.20(2) A{sup 3}, Z=4). The formation of 1 was investigated by in situ energy dispersive X-ray diffraction measurements (EDXRD) at beamline F3 at HASYLAB (light source DORIS III), DESY, Hamburg. An intermediate, Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O (2), was observed and could be isolated from the reaction mixture at ambientmore » temperatures by quenching the reaction. The crystal structure of 2 was determined from XRPD data using synchrotron radiation (monoclinic, P2{sub 1}/m, a=11.2193(7), b=7.1488(3), c=5.0635(2) A, {beta}=100.13(4) Degree-Sign , V=399.78(3) A{sup 3}, Z=2). - Graphical abstarct: The detailed in situ energy dispersive X-ray diffraction (EDXRD) investigation on the formation of the new inorganic-organic hybrid compound Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) leads to the discovery of a new crystalline intermediate phase. Both crystal structures were elucidated using X-ray powder diffraction data. Highlights: Black-Right-Pointing-Pointer High-throughput investigation led to new metal aminoethylphosphonate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}). Black-Right-Pointing-Pointer The formation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) was followed by in situ EDXRD measurements. Black-Right-Pointing-Pointer The crystalline intermediate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was discovered. Black-Right-Pointing-Pointer Isolation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was accomplished by quenching experiments. Black-Right-Pointing-Pointer The structures were determined using X

Mechanisms of mercury removal by O 3 and OH in the atmosphere

NASA Astrophysics Data System (ADS)

Calvert, Jack G.; Lindberg, Steve E.

The mechanisms of the reactions of gaseous Hg atoms with O 3 and OH radical are evaluated from current kinetic and enthalpy data. The reaction, O 3+Hg→HgO+O 2, is considered to be an unlikely pathway for atmospheric conditions. Considerations given here suggest that the reaction may occur with initial formation of a metastable HgO 3 molecule that in laboratory experiments is the source of the HgO product observed to accumulate on the walls of the reactor (HgO 3→HgO(s)+O 2). Laboratory studies of the gas phase reaction, Hg+OH→HgOH (2), have been reported using relative rate measurements initiated by photodissociation of an organic nitrite in mixtures of Hg vapor with NO, air and various reference hydrocarbons. Computer simulations of this reaction system suggest that the use of reactive reference gases (e.g., cyclohexane) leads to the generation of significant ozone in these NO x-RH-air mixtures, and the resulting O 3-Hg reaction can result in an over-estimate of the rate of reaction (2). Also the apparent rate coefficients for reaction (2) are highly dependent on the assumed rate coefficients of its competitive reactions of dissociation in HgOH→Hg+OH (3), and association of HgOH molecule with other free radicals present in the system: HgOH+ X→ XHgOH (4); X=OH, HO 2, RO, RO 2, NO, NO 2. Reaction (4) competes successfully with HgOH decomposition for the laboratory conditions employed, and the kinetic measurements relate to the rate determining reaction, Hg+OH→HgOH in this case. However, the use of these laboratory measurements of k2 to determine the extent of Hg removal by OH in the troposphere will greatly over-estimate the importance of Hg removal by this reaction.

Reaction kinetics of O( 3P) with acrylonitrile and crotononitrile

NASA Astrophysics Data System (ADS)

Upadhyaya, Hari P.; Naik, Prakash D.; Pavanaja, Ubaradka B.; Kumar, Awadhesh; Vatsa, Rajesh K.; Sapre, Avinash V.; Mittal, Jai P.

1997-08-01

The reaction of oxygen atoms O( 3P) with unsaturated nitriles (RCN), viz. acrylonitrile (CH 2=CHCN), and crotononitrile (CH 3CH=CHCN), was studied in a flow discharge tube in the pressure range 1.2-1.7 Torr using the O( 3P) chemiluminescence titration method. The rate constants for the reaction O( 3P) + RCN → products was determined at room temperature to be (4.9 ± 1.0) × 10 -13 and (5.4 ± 0.8) × 10 -13 cm 3 molecule -1 s -1 for acrylonitrile and crotononitrile respectively. The activation energies for the above reactions were estimated using the MNDO method. The formation of a biradical involving the addition of an oxygen atom to the double bond is proposed as the major channel for the reaction.

Reaction between NiO and Al2O3 in NiO/γ-Al2O3 catalysts probed by positronium atom

NASA Astrophysics Data System (ADS)

Li, C. Y.; Zhang, H. J.; Chen, Z. Q.

2013-02-01

NiO/γ-Al2O3 catalysts with NiO content of 9 wt% and 24 wt% were prepared by solid state reaction method. They are annealed in air at temperatures from 100 °C to 1000 °C. Positron lifetime spectra were measured to study the microstructure variation during annealing process. Four positron lifetime components were resolved with two long lifetime τ3 and τ4, which can be attributed to the ortho-positronium lifetime in microvoids and large pores, respectively. It was found that the longest lifetime τ4 is rather sensitive to the chemical environment of the large pores. The NiO active centers in the catalysts cause decrease of both τ4 and its intensity I4, which is due to the spin-conversion of positronium induced by NiO. However, after heating the catalysts above 600 °C, abnormal increase of the lifetime τ4 is observed. This is due to the formation of NiAl2O4 spinel from the reaction of NiO and γ-Al2O3. The generated NiAl2O4 weakens the spin-conversion effect of positronium, thus leads to the increase of o-Ps lifetime τ4. Formation of NiAl2O4 is further confirmed by both X-ray diffraction and X-ray photoelectron spectroscopy measurements.

Calcium manganese oxides as oxygen evolution catalysts: O2 formation pathways indicated by 18O-labelling studies.

PubMed

Shevela, Dmitriy; Koroidov, Sergey; Najafpour, M Mahdi; Messinger, Johannes; Kurz, Philipp

2011-05-02

Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in (18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O(2) isotopologues (16)O(2), (16)O(18)O and (18)O(2) in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H(2)O(2)), hydrogen persulfate (HSO(5)(-)) or single-electron oxidants such as Ce(IV) and [Ru(III) (bipy)(3)](3+) . Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar (18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

β-Ga2O3 versus ε-Ga2O3: Control of the crystal phase composition of gallium oxide thin film prepared by metal-organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Zhuo, Yi; Chen, Zimin; Tu, Wenbin; Ma, Xuejin; Pei, Yanli; Wang, Gang

2017-10-01

Gallium oxide thin films of β and ε phase were grown on c-plane sapphire using metal-organic chemical vapor deposition and the phase compositions were analyzed using X-ray diffraction. The epitaxial phase diagram was constructed as a function of the growth temperature and VI/III ratio. A low growth temperature and low VI/III ratio were beneficial for the formation of hexagonal-type ε-Ga2O3. Further structure analysis revealed that the epitaxial relationship between ε-Ga2O3 and c-plane sapphire is ε-Ga2O3 (0001) || Al2O3 (0001) and ε-Ga2O3 || Al2O3 . The structural evolution of the mixed-phase sample during film thickening was investigated. By reducing the growth rate, the film evolved from a mixed phase to the energetically favored ε phase. Based on these results, a Ga2O3 thin film with a phase-pure ε-Ga2O3 upper layer was successfully obtained.

Properties of highly (100) oriented Pb(Mg1/3,Nb2/3)O3-PbTiO3 films on LaNiO3 bottom electrodes

NASA Astrophysics Data System (ADS)

Li, Y. W.; Hu, Z. G.; Yue, F. Y.; Yang, G. Y.; Shi, W. Z.; Meng, X. J.; Sun, J. L.; Chu, J. H.

2007-12-01

The 70%Pb(Mg1/3,Nb2/3)O3-30%PbTiO3 (PMNT) films have been fabricated on LaNiO3 (LNO) coated silicon substrate. The conductive LNO films act as a seed layer for the growth of PMNT films, which depresses the formation of pyrochlore phase and induces the high (100) preferred orientation of perovskite PMNT films. Compared with the PMNT films grown on platinum bottom electrode, the ferroelectric properties of PMNT films grown on LNO are enhanced. The frequency dependence of complex permittivity from PMNT films on LNO is the conjunct result of polarization relaxation and movement of oxygen vacancy, which can be fitted by the function containing Debye and universal dielectric response models, respectively.

Formation of amino acids from NH3 /NO2, CO2 and H2O: implications for the prebiotic origin of biomolecules.

PubMed

Singh, Amrinder; Nisha; Singh, Palwinder

2015-11-15

The search for the conditions which must have prevailed in the long-distant past during the conversion of inanimate matter into animate matter is a fascinating area of research and it continues to draw the attention of the scientific community. The initiation of life on this planet must have been preceded by the development of biomolecules, amongst which amino acids have unique importance. Formation of amino acids under a certain set of conditions is shown in the present experiments. Solutions of ammonium carboxylates or the mixture of two such salts were prepared in 3:6.9:0.1 (v/v/v) acetonitrile/water/formic acid at a concentration of 50 μM. The studies were performed using a quadrupole time-of-flight (QqTOF) mass spectrometer. The formation of different amino acids was detected with high-resolution mass spectrometry. Here, we show the formation of amino acids when a solution of ammonium salts was injected into an electrospray ionization (ESI)-QqTOF-MS instrument. The ammonium salts were the source of NH3 and CO2 and H2 O was available in the medium. It seems that the combination of NH3 , CO2 , and H2 O leads to the formation of amino acids. Further to the literature reports of formation of amino acids under the reduced atmosphere represented by gases such as NH3 , CH4 , H2 and H2 O, here we demonstrate the formation of amino acids by the combination of NH3 /NO2 , CO2 and water vapours in the ESI source of the mass spectrometer. Copyright © 2015 John Wiley & Sons, Ltd.

Twin-induced phase transition from β-Ga2O3 to α-Ga2O3 in Ga2O3 thin films

NASA Astrophysics Data System (ADS)

Choi, Byeongdae; Allabergenov, Bunyod; Lyu, Hong-Kun; Lee, Seong Eui

2018-06-01

We deposited a 300-nm-thick Ga2O3 thin film on an amorphous SiO2/Si substrate via pulsed laser deposition. X-ray diffraction patterns revealed the formation of β-Ga2O3 phase at a substrate temperature of 700 °C. X-ray photoelectron spectra indicated that the degree of oxidation increased after annealing at 700 °C. Further annealings at higher temperatures led to a transition of the β-Ga2O3 phase to the α-Ga2O3 phase; this transition was caused by the twin structure formed during the crystallinity improvement process. In addition, we discuss the mechanism of the transition from the β phase to the α phase in the β-Ga2O3 thin films.

Room-temperature aqueous plasma electrolyzing Al2O3 nano-coating on carbon fiber

NASA Astrophysics Data System (ADS)

Zhang, Yuping; Meng, Yang; Shen, Yonghua; Chen, Weiwei; Cheng, Huanwu; Wang, Lu

2017-10-01

A novel room-temperature aqueous plasma electrolysis technique has been developed in order to prepared Al2O3 nano-coating on each fiber within a carbon fiber bundle. The microstructure and formation mechanism of the Al2O3 nano-coating were systematically investigated. The oxidation resistance and tensile strength of the Al2O3-coated carbon fiber was measured at elevated temperatures. It showed that the dense Al2O3 nano-coating was relatively uniformly deposited with 80-120 nm in thickness. The Al2O3 nano-coating effectively protected the carbon fiber, evidenced by the slower oxidation rate and significant increase of the burn-out temperature from 800 °C to 950 °C. Although the bare carbon fiber remained ∼25 wt.% after oxidation at 700 °C for 20 min, a full destruction was observed, evidenced by the ∼0 GPa of the tensile strength, compared to ∼1.3 GPa of the Al2O3-coated carbon fiber due to the effective protection from the Al2O3 nano-coating. The formation mechanism of the Al2O3 nano-coating on carbon fiber was schematically established mainly based on the physic-chemical effect in the cathodic plasma arc zone.

Temperature dependence of the NO + O3 reaction rate from 195 to 369 K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Allen, J. E., Jr.; Brobst, W. D.

1981-01-01

The temperature dependence of the NO + O3 reaction rate was examined by means of the fast flow technique. Several different experimental conditions and detection schemes were employed. With excess NO or excess O3, NO2 chemiluminescence was monitored. In addition, with excess O3, NO was followed by fluorescence induced by an NO microwave discharge lamp. The results of the three independent sets of data are compared and found to agree within experimental error, indicating the absence of secondary chemistry which might complicate the kinetics. The data exhibit curvature on an Arrhenius plot; however, the simple Arrhenius expression k = (2.6 + or - 0.8) x 10 to the -12th exp(-1435 + or - 64/T) cu cm/molecule s is an adequate description for T between 195 and 369 K. This result is compared to earlier determinations.

Expansion during the formation of the magnesium aluminate spinel (MgAl(2)O(4)) from its basic oxide (MgO and Al(2)O(3)) powders

NASA Astrophysics Data System (ADS)

Duncan, Flavia Cunha

The extraordinary expansion during the reaction sintering of the magnesium aluminate spinel (MgAl2O4) from its basic oxide (MgO and Al2O3) powders was studied. Experimental series of different size fractions of the reacting materials were formulated to produce the Mg-Al spinel. After batches were prepared, specimens were compacted and fired in air from 1200° to 1700°C for a fixed firing time. A separate set of specimens was fired as a function of time to determine the reaction kinetic parameters. Dimensional changes confirmed that extraordinary expansions of three to four times greater than the prediction from the reaction of solids occur. The solid-state reactions were monitored by X-ray diffraction. The activation energy of the spinel reaction formation was determined to be 280 +/- 20 kJ/mol. It is believed to be associated with the diffusivity of Mg 2+ in either magnesia or spinel during the development of the final spinel structure. New porosity developed in the compacts during the reaction formation of spinel. Scanning electron microscopy confirmed that the magnesia evaporated leaving behind porous magnesia grains, condensed on the alumina particles and reacted to form a shell of spinel. Hollow spinel particles resulted from the original particles of alumina. These porosities generated within the reacting materials influenced the expansions. Final volumetric expansion could potentially reach 56% as a result of the reaction of solids and the porosity generation within MgO and Al2O3. Models of a single alumina particle with and without development of internal porosity were developed. 3-D arrangements of particles showed additional porosity, influencing on the expansions. The decrease in porosity of some specimens fired at higher temperatures indicated that sintering and densification occur simultaneously with the reaction formation of spinel. The decrease in the interparticle porosity limits the full expansion of the particulates to levels lower than the

THE FORMATION OF IRIS DIAGNOSTICS. VII. THE FORMATION OF THE O i 135.56 NM LINE IN THE SOLAR ATMOSPHERE

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

Lin, Hsiao-Hsuan; Carlsson, Mats, E-mail: h.h.lin@astro.uio.no, E-mail: mats.carlsson@astro.uio.no

The O i 135.56 nm line is covered by NASA's Interface Region Imaging Spectrograph (IRIS) small explorer mission which studies how the solar atmosphere is energized. We study here the formation and diagnostic potential of this line by means of non-local thermodynamic equilibrium modeling employing both 1D semi-empirical and 3D radiation magnetohydrodynamic models. We study the basic formation mechanisms and derive a quintessential model atom that incorporates essential atomic physics for the formation of the O i 135.56 nm line. This atomic model has 16 levels and describes recombination cascades through highly excited levels by effective recombination rates. The ionizationmore » balance O i/O ii is set by the hydrogen ionization balance through charge exchange reactions. The emission in the O i 135.56 nm line is dominated by a recombination cascade and the line is optically thin. The Doppler shift of the maximum emission correlates strongly with the vertical velocity in its line forming region, which is typically located at 1.0–1.5 Mm height. The total intensity of the line emission is correlated with the square of the electron density. Since the O i 135.56 nm line is optically thin, the width of the emission line is a very good diagnostic of non-thermal velocities. We conclude that the O i 135.56 nm line is an excellent probe of the middle chromosphere, and compliments other powerful chromospheric diagnostics of IRIS such as the Mg ii h and k lines and the C ii lines around 133.5 nm.« less

Diamond formation in the deep lower mantle: a high-pressure reaction of MgCO3 and SiO2

PubMed Central

Maeda, Fumiya; Ohtani, Eiji; Kamada, Seiji; Sakamaki, Tatsuya; Hirao, Naohisa; Ohishi, Yasuo

2017-01-01

Diamond is an evidence for carbon existing in the deep Earth. Some diamonds are considered to have originated at various depth ranges from the mantle transition zone to the lower mantle. These diamonds are expected to carry significant information about the deep Earth. Here, we determined the phase relations in the MgCO3-SiO2 system up to 152 GPa and 3,100 K using a double sided laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. MgCO3 transforms from magnesite to the high-pressure polymorph of MgCO3, phase II, above 80 GPa. A reaction between MgCO3 phase II and SiO2 (CaCl2-type SiO2 or seifertite) to form diamond and MgSiO3 (bridgmanite or post-perovsktite) was identified in the deep lower mantle conditions. These observations suggested that the reaction of the MgCO3 phase II with SiO2 causes formation of super-deep diamond in cold slabs descending into the deep lower mantle. PMID:28084421

Charge transfer mechanism for the formation of metallic states at the KTaO3/SrTiO3 interface

NASA Astrophysics Data System (ADS)

Nazir, S.; Singh, N.; Schwingenschlögl, U.

2011-03-01

The electronic and optical properties of the KTaO3/SrTiO3 heterointerface are analyzed by the full-potential linearized augmented plane-wave approach of density functional theory. Optimization of the atomic positions points at subordinate changes in the crystal structure and chemical bonding near the interface, which is due to a minimal lattice mismatch. The creation of metallic interface states thus is not affected by structural relaxation but can be explained by charge transfer between transition metal and oxygen atoms. It is to be expected that a charge transfer is likewise important for related interfaces such as LaAlO3/SrTiO3. The KTaO3/SrTiO3 system is ideal for disentangling the complex behavior of metallic interface states, since almost no structural relaxation takes place.

Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

NASA Technical Reports Server (NTRS)

Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

1995-01-01

Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

Enhanced magnetoelectric response in 2-2 bilayer 0.50Pb(Ni1/3Nb2/3)O3-0.35PbTiO3-0.15PbZrO3/NiFe2O4 thin films

NASA Astrophysics Data System (ADS)

Ade, Ramesh; Sambasiva, V.; Kolte, Jayant; Karthik, T.; Kulkarni, Ajit R.; Venkataramani, N.

2018-03-01

In this work, room temperature magnetoelectric (ME) properties of 0.50Pb(Ni1/3Nb2/3)O3-0.35PbTiO3-0.15PbZrO3 (PNNZT)/NiFe2O4 (NFO) 2-2 bilayer thin films grown on Pt/Ti/SiO2/Si substrate, using pulsed laser deposition technique, are reported. Structural studies confirm single phase PNNZT/NFO 2-2 bilayer structure formation. PNNZT/NFO 2-2 bilayer thin film shows a maximum ME voltage coefficient (α E ) of ~0.70 V cm-1. Oe-1 at a frequency of 1 kHz. The present study reveals that PNNZT/NFO bilayer thin film can be a potential candidate for technological applications.

Quantum calculations of the rate constant for the O(3P)+HCl reaction on new ab initio 3A″ and 3A' surfaces

NASA Astrophysics Data System (ADS)

Xie, Tiao; Bowman, Joel M.; Peterson, K. A.; Ramachandran, B.

2003-11-01

We report the thermal rate constant of the O(3P)+HCl→OH+Cl reaction calculated from 200 to 3200 K, using new fits to extensive ab initio calculations [B. Ramachandran and K. A. Peterson, J. Chem. Phys. 119, 9590 (2003), preceding paper]. The rate constants are obtained for both the 3A″ and 3A' surfaces using exact quantum reactive scattering calculations for selected values of the total angular momentum and the J-shifting approximation for both the 3A″ and 3A' surfaces. The results are compared with the ICVT/μOMT rate constants calculated by the POLYRATE program and all available experimental data. Other related high-energy reaction channels are also studied qualitatively for their contribution to the total thermal rate constant at high temperature.

A molecular beam mass spectrometric study of the formation and photolysis of C(lc)lO dimer

NASA Technical Reports Server (NTRS)

Greene, Frank T.; Robaugh, David A.

1992-01-01

A study of the chlorine oxides present at temperatures and pressures typical of the Antarctic stratosphere was carried out. A series of low temperature flow reactors was constructed and used in conjunction with molecular beam mass spectrometric techniques to identify species and characterize their kinetic behavior at temperatures of -20 to -70 C and pressures of from 30 to 130 Torr. It was found that the gas phase chlorine-oxygen system was quite complex at low temperatures. ClO dimer was identified and found to be thermodynamically very stable under stratospheric conditions. It was also found that any system which contained ClO also contained a larger oxide. The oxide was identified as Cl2O3. A survey of possible higher oxides, which have been postulated as possible chlorine sinks in the stratosphere, was also carried out. The rate of formation of ClO dimer was measured as a function of temperature and pressure. Measurements were made of both the decay of ClO and the formation of the dimer. By comparing these rates it was determined that virtually all of the ClO was converted to the dimer under stratospheric conditions, and that the other ClO reactions were not important under these conditions.

Spacelab uplink/downlink data flow and formats

NASA Technical Reports Server (NTRS)

Kandefer, F.

1978-01-01

The results of an analysis of the Spacelab (SL) data uplink/downlink structure and those data system elements associated with the support of this data flow are presented. Specific objectives of this report are to present the results of the following analyses: (1) operations of the SL high rate multiplexer, including format structure, data rates, format combinations, format switching, etc.; (2) operations of SL data recorders to include the definition of modes, data rates and forms; (3) operations of the high rate demultiplexer as described above; (4) potential experiment data formats defining formatting parameters to be considered in decommutation analysis; (5) SL computer input/output (I/O) decommutation channels, including the definition of structure, quantity and use of this I/O data; (6) detailed requirements of the data quality monitoring philosophy for this function.

O({sup 3}P{sub J}) formation and desorption by 157-nm photoirradiation of amorphous solid water

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

DeSimone, Alice J.; Orlando, Thomas M., E-mail: thomas.orlando@chemistry.gatech.edu; School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332–0400

2014-03-07

Photodissociation of amorphous solid water (ASW) deposited on a thinly oxidized copper substrate at 82 K was studied by measuring O({sup 3}P{sub J=2,1,0}) photoproducts detected with resonance-enhanced multiphoton ionization. For each spin-orbit state, the oxygen atom time-of-flight spectrum was measured as a function of H{sub 2}O exposure, which is related to ice thickness, and 157-nm irradiation time. Four Maxwell-Boltzmann distributions with translational temperatures of 10 000 K, 1800 K, 400 K, and 82 K were found to fit the data. The most likely formation mechanisms are molecular elimination following ionization of water and ion-electron recombination, secondary recombination of hydroxyl radicals, andmore » photodissociation of adsorbed hydroxyl radicals. Evidence for O-atom diffusion through bulk ASW was found for H{sub 2}O exposures of at least 5 Langmuir (1 L = 10{sup −6} Torr s). The cross sections for O({sup 3}P{sub 2}) depletion were 1.3 × 10{sup −19} and 6.5 × 10{sup −20} cm{sup 2} for 1 and 5 L, respectively.« less

Study of formation of deep trapping mechanism by UV, beta and gamma irradiated Eu(3+) activated SrY2O4 and Y4Al2O9 phosphors.

PubMed

Dubey, Vikas; Kaur, Jagjeet; Parganiha, Yogita; Suryanarayana, N S; Murthy, K V R

2016-04-01

This paper reports the thermoluminescence properties of Eu(3+) doped different host matrix phosphors (SrY2O4 and Y4Al2O9). The phosphor is prepared by high temperature solid state reaction method. The method is suitable for large scale production and fixed concentration of boric acid using as a flux. The prepared samples were characterized by X-ray diffraction technique and the crystallite size calculated by Scherer's formula. The prepared phosphor characterized by Scanning Electron Microscopic (SEM), Fourier Transform Infrared (FTIR), Energy Dispersive X-ray analysis (EDX), thermoluminescence (TL) and Transmission Electron Microscopic (TEM) techniques. The prepared phosphors for different concentration of Eu(3+) ions were examined by TL glow curve for UV, beta and gamma irradiation. The UV 254nm source used for UV irradiation, Sr(90) source was used for beta irradiation and Co(60) source used for gamma irradiation. SrY2O4:Eu(3+)and Y4Al2O9:Eu(3+) phosphors which shows both higher temperature peaks and lower temperature peaks for UV, beta and gamma irradiation. Here UV irradiated sample shows the formation of shallow trap (surface trapping) and the gamma irradiated sample shows the formation of deep trapping. The estimation of trap formation was evaluated by knowledge of trapping parameters. The trapping parameters such as activation energy, order of kinetics and frequency factor were calculated by peak shape method. Here most of the peak shows second order of kinetics. The effect of gamma, beta and UV exposure on TL studies was also examined and it shows linear response with dose which indicate that the samples may be useful for TL dosimetry. Formation of deep trapping mechanism by UV, beta and gamma irradiated Eu(3+) activated SrY2O4 and Y4Al2O9 phosphors is discussed in this paper. Copyright © 2015 Elsevier Ltd. All rights reserved.

Preparation of U.sub.3 O.sub.8

DOEpatents

Johnson, David R.

1980-01-01

A method is described for the preparation of U.sub.3 O.sub.8 nuclear fuel material by direct precipitation of uranyl formate monohydrate from uranyl nitrate solution. The uranyl formate monohydrate precipitate is removed, dried and calcined to produce U.sub.3 O.sub.8 having a controlled particle size distribution.

Kinetic modeling and transient DRIFTS–MS studies of CO 2 methanation over Ru/Al 2O 3 catalysts

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

Wang, Xiang; Hong, Yongchun; Shi, Hui

CO 2 methanation was investigated on 5% and 0.5% Ru/Al 2O 3 catalysts (Ru dispersions: ~18% and ~40%, respectively) by steady-state kinetic measurements and transient DRIFTS–MS. Methanation rates were higher over 5% Ru/Al 2O 3 than over 0.5% Ru/Al 2O 3. The measured activation energies, however, were lower on 0.5% Ru/Al 2O 3 than on 5% Ru/Al 2O 3. Transient DRIFTS–MS results demonstrated that direct CO 2 dissociation was negligible over Ru. CO 2 has to first react with surface hydroxyls on Al 2O 3 to form bicarbonates, which, in turn, react with adsorbed H on Ru to produce adsorbed formate species. Formates, most likely at the metal/oxide interface, can react rapidly with adsorbed H forming adsorbed CO, only a portion of which is reactive toward adsorbed H, ultimately leading to CH4 formation. The measured kinetics are fully consistent with a Langmuir–Hinshelwood type mechanism in which the H-assisted dissociation of the reactive CO* is the rate-determining step (RDS). The similar empirical rate expressions (r CH4 = kPmore » $$0.1\\atop{CO2}$$P$$0.3-0.5\\atop{H2}$$) and DRIFTS–MS results on the two catalysts under both transient and steady-state conditions suggest that the mechanism for CO 2 methanation does not change with Ru particle size under the studied experimental conditions. Kinetic modeling results further indicate that the intrinsic activation barrier for the RDS is slightly lower on 0.5% Ru/Al 2O 3 than on 5% Ru/Al 2O 3. Due to the presence of unreactive adsorbed CO under reaction conditions, the larger fraction of such surface sites that bind CO too strongly on 0.5% Ru/Al 2O 3 than on 5% Ru/Al 2O 3, as revealed by FTIR measurements, is regarded as the main reason for the lower rates for CO 2 methanation on 0.5% Ru/Al 2O 3. The catalyst preparation and catalytic measurements were supported by a Laboratory Directed Research and Development (LDRD) project. The authors gratefully acknowledge the financial support of this work by the US Department

CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.

PubMed

Papadimitriou, Vassileios C; Karafas, Emmanuel S; Gierczak, Tomasz; Burkholder, James B

2015-07-16

The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k∞(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The

The formation of tungsten doped Al2O3/ZnO coatings on aluminum by plasma electrolytic oxidation and their application in photocatalysis

NASA Astrophysics Data System (ADS)

Stojadinović, Stevan; Vasilić, Rastko; Radić, Nenad; Tadić, Nenad; Stefanov, Plamen; Grbić, Boško

2016-07-01

Tungsten doped Al2O3/ZnO coatings are formed by plasma electrolytic oxidation of aluminum substrate in supporting electrolyte (0.1 M boric acid + 0.05 M borax + 2 g/L ZnO) with addition of different concentrations of Na2WO4·2H2O. The morphology, crystal structure, chemical composition, and light absorption characteristics of formed surface coatings are investigated. The X-ray diffraction and X-ray photoelectron spectroscopy results indicate that formed surface coatings consist of alpha and gamma phase of Al2O3, ZnO, metallic tungsten and WO3. Obtained results showed that incorporated tungsten does not have any influence on the absorption spectra of Al2O3/ZnO coatings, which showed invariable band edge at about 385 nm. The photocatalytic activity of undoped and tungsten doped Al2O3/ZnO coatings is estimated by the photodegradation of methyl orange. The photocatalytic activity of tungsten doped Al2O3/ZnO coatings is higher thanof undoped Al2O3/ZnO coatings; the best photocatalytic activity is ascribed to coatings formed in supporting electrolyte with addition of 0.3 g/L Na2WO4·2H2O. Tungsten in Al2O3/ZnO coatings acts as a charge trap, thus reducing the recombination rate of photogenerated electron-hole pairs. The results of PL measurements are in agreement with photocatalytic activity. Declining PL intensity corresponds to increasing photocatalytic activity of the coatings, indicating slower recombination of electron-hole pairs.

Effect of LiF as Sintering Agent on the Densification and Phase Formation in Al2O3-4 Wt Pct Nb2O5 Ceramic Compound

NASA Astrophysics Data System (ADS)

Santos, J. L.; Marçal, R. L. S. B.; Jesus, P. R. R.; Gomes, A. V.; Lima, E. P.; Monteiro, S. N.; de Campos, J. B.; Louro, L. H. L.

2017-10-01

Different amounts of LiF were added to an Al2O3-4 pct Nb2O5 basic ceramic, as sintering agent. Improved new ceramics were obtained with LiF concentrations varying from 0.25 to 1.50 wt pct and three sintering temperatures of 1573 K, 1623 K, and 1673 K (1300 °C, 1350 °C, and 1400 °C). The addition of 0.5 wt pct LiF yielded the highest densification, 94 pct of the theoretical density, in association with a sintering temperature of 1673 K (1400 °C). Based on X-ray diffraction (XRD), this improvement was due not only to the presence of transformed phases, more precisely Nb3O7F, but also to the absence of LiAl5O8. The preferential interaction of LiF with Nb2O5, instead of Al2O3, contributed to increase the alumina sintering ability by liquid phase formation. Scanning electron microscopy (SEM) results revealed well-connected grains and isolated pores, whereas the chemical composition analysis by energy dispersive energy (EDX) indicated a preferential interaction of fluorine with niobium, in agreement with the results of XRD. It was also observed from thermal analysis that the polyethylene glycol binder burnout temperature increased for all LiF concentrations. This may be related to the formation of hydrogen bridge bonds.

Comparison of fusion rate and clinical results between CaO-SiO2-P2O5-B2O3 bioactive glass ceramics spacer with titanium cages in posterior lumbar interbody fusion.

PubMed

Lee, Jae Hyup; Kong, Chang-Bae; Yang, Jae Jun; Shim, Hee-Jong; Koo, Ki-Hyoung; Kim, Jeehyoung; Lee, Choon-Ki; Chang, Bong-Soon

2016-11-01

The CaO-SiO 2 -P 2 O 5 -B 2 O 3 glass ceramics spacer generates chemical bonding to adjacent bones with high mechanical stability to produce a union with the end plate, and ultimately stability. The authors aimed to compare the clinical efficacy and safety of CaO-SiO 2 -P 2 O 5 -B 2 O 3 glass ceramics with a titanium cage that is widely used for posterior lumbar interbody fusion (PLIF) surgery in the clinical field. This is a prospective, stratified randomized, multicenter, single-blinded, comparator-controlled non-inferiority trial. The present study was conducted in four hospitals and enrolled a total of 86 patients between 30 and 80 years of age who required one-level PLIF due to severe spinal stenosis, spondylolisthesis, or huge disc herniation. The Oswestry Disability Index (ODI), Short Form-36 Health Survey (SF-36), and pain visual analog scale (VAS) were assessed before surgery and at 3, 6, and 12 months after surgery. The spinal fusion rate was assessed at 6 and 12 months after surgery. The spinal fusion rate and the area of fusion, subsidence of each CaO-SiO 2 -P 2 O 5 -B 2 O 3 glass ceramics and titanium cage, and the extent of osteolysis were evaluated using a dynamic plain radiography and a three-dimensional computed tomography at 12 months after surgery. The present study was supported by BioAlpha, and some authors (JHL, C-KL, and B-SC) have stock ownership (<10,000 US dollars). From the plain radiography results, the 6-month fusion rates for the bioactive glass ceramics group and the titanium group were 89.7% and 91.4%, respectively. In addition, the 12-month fusion rates based on CT scan were 89.7% and 91.2%, respectively, showing no significant difference. However, the bone fusion area directly attached to the end plate of either bioactive glass ceramics or the titanium cage was significantly higher in the bioactive glass ceramics group than in the titanium group. The ODI, SF-36, back pain, and lower limb pain in both groups significantly improved

An evaluation of the rate of absorption of solar radiation in the O2(X3Sigma-g - b1Sigma-g) transition

NASA Technical Reports Server (NTRS)

Mlynczak, Martin G.

1993-01-01

The rate at which molecular oxygen absorbs radiation in the O2(X3Sigma-g - b1Sigma-g) transition is calculated using a line-by-line radiative transfer model. This rate is critical to the determination of the population of the O2(b1Sigma-g) state required for studies of the O2(b1Sigma-g - X3Sigma-g) dayglow, the O2(a1Delta-g - X3Sigma-g) dayglow, and possibly the rates of oxidation of H2 and N2O. Previous evaluations of this rate (which is sometimes called the g-factor) have significantly overestimated its value. The rate is tabulated as a function of altitude, pressure, and solar zenith angle.

Surface reactivity and hydroxyapatite formation on Ca5MgSi3O12 ceramics in simulated body fluid

NASA Astrophysics Data System (ADS)

Xu, Jian; Wang, Yaorong; Huang, Yanlin; Cheng, Han; Seo, Hyo Jin

2017-11-01

In this work, the new calcium-magnesium-silicate Ca5MgSi3O12 ceramic was made via traditional solid-state reaction. The bioactivities were investigated by immerging the as-made ceramics in simulated body fluid (SBF) for different time at body temperature (37 °C). Then the samples were taken to measure X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), X-ray energy-dispersive spectra (EDS), and Fourier transform infrared spectroscopy (FT-IR) measurements. The bone-like hydroxyapatite nanoparticles formation was observed on the ceramic surfaces after the immersion in SBF solutions. Ca5MgSi3O12 ceramics possess the Young's modulus and the bending strength and of 96.3 ± 1.2 GPa and 98.7 ± 2.3 MPa, respectively. The data suggest that Ca5MgSi3O12 ceramics can quickly induce HA new layers after soaking in SBF. Ca5MgSi3O12 ceramics are potential to be used as biomaterials for bone-tissue repair. The cell adherence and proliferation experiments are conducted confirming the reliability of the ceramics as a potential candidate.

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Multiphase nanodomains in a strained BaTiO3 film on a GdScO3 substrate

NASA Astrophysics Data System (ADS)

Kobayashi, Shunsuke; Inoue, Kazutoshi; Kato, Takeharu; Ikuhara, Yuichi; Yamamoto, Takahisa

2018-02-01

Controlling the crystal structure of ferroelectric materials via epitaxial strain, which is a well-known technique in strain engineering, can lead to the formation of unique domain structures generating non-intrinsic phenomena such as electronic conductivity, photovoltages, and enhanced piezoelectric characteristics. Strained BaTiO3 films are promising ferroelectric materials as theoretical modeling predicts that different domain morphologies can introduce additional properties not observed in conventional BaTiO3 ceramics. To rationally design materials for practical application, a thorough understanding of the formation mechanisms and stabilities of different domain structures in strained BaTiO3 films is required. However, there have been very few experimental reports on this topic, and details about the domain structures in strained BaTiO3 films are currently lacking. In this paper, we report multiphase nanodomains in a strained BaTiO3 film deposited on an orthorhombic GdScO3 substrate. The phase-transition behavior of the strained BaTiO3 film reveals that it contains multiple phases at room temperature; the film first undergoes a phase-transition upon heating at around 550 K, and then a paraelectric phase forms at temperatures above 690 K. A picometer-scale analysis of the Ti ion displacements, using an advanced scanning transmission electron microscopy technique, is used to characterize the complex multiphase nanodomains, providing useful insights into the control of domain structures in BaTiO3 films by applying epitaxial strain.

Phase-pure eutectic CoFe2O4-Ba1-xSrxTiO3 composites prepared by floating zone melting

NASA Astrophysics Data System (ADS)

Breitenbach, Martin; Ebbinghaus, Stefan G.

2018-02-01

Composites consisting of ferrimagnetic CoFe2O4 and ferroelectric Ba1-xSrxTiO3 were grown by the floating zone technique. The influence of Sr substitution, growth rate and atmosphere during the floating zone process were investigated. The formation of the non-ferroelectric, hexagonal modification of BaTiO3 was avoided by a slight Sr substitution of 3 mol% and the formation of BaFe12O19 was suppressed using pure nitrogen as atmosphere during the floating zone melting. These synthesis parameters led to phase-pure, but electrically conductive CoFe2O4-Ba1-xSrxTiO3 composites. A thermal treatment at 973 K in air resulted in a strong increase of the electric resistivity accompanied by a decrease of the unit-cell parameters of both components indicating the healing of oxygen defects. SEM investigations revealed a variety of different geometric structures and crack-free interfaces between both phases. The low porosities observed in the micrographs correspond with densities above 90%. Magnetoelectric (ME) measurements confirmed a coupling between the ferroic orders of both phases with a hysteresis and maximum αME of 1.3 mV Oe-1 cm-1.

The spatial extent and distribution of star formation in 3D-HST mergers at z ˜ 1.5

NASA Astrophysics Data System (ADS)

Schmidt, Kasper B.; Rix, Hans-Walter; da Cunha, Elisabete; Brammer, Gabriel B.; Cox, Thomas J.; van Dokkum, Pieter; Förster Schreiber, Natascha M.; Franx, Marijn; Fumagalli, Mattia; Jonsson, Patrik; Lundgren, Britt; Maseda, Michael V.; Momcheva, Ivelina; Nelson, Erica J.; Skelton, Rosalind E.; van der Wel, Arjen; Whitaker, Katherine E.

2013-06-01

We present an analysis of the spatial distribution of star formation in a sample of 60 visually identified galaxy merger candidates at z > 1. Our sample, drawn from the 3D-HST survey, is flux limited and was selected to have high star formation rates based on fits of their broad-band, low spatial resolution spectral energy distributions. It includes plausible pre-merger (close pairs) and post-merger (single objects with tidal features) systems, with total stellar masses and star formation rates derived from multiwavelength photometry. Here we use near-infrared slitless spectra from 3D-HST which produce Hα or [O III] emission line maps as proxies for star formation maps. This provides a first comprehensive high-resolution, empirical picture of where star formation occurred in galaxy mergers at the epoch of peak cosmic star formation rate. We find that detectable star formation can occur in one or both galaxy centres, or in tidal tails. The most common case (58 per cent) is that star formation is largely concentrated in a single, compact region, coincident with the centre of (one of) the merger components. No correlations between star formation morphology and redshift, total stellar mass or star formation rate are found. A restricted set of hydrodynamical merger simulations between similarly massive and gas-rich objects implies that star formation should be detectable in both merger components, when the gas fractions of the individual components are the same. This suggests that z ˜ 1.5 mergers typically occur between galaxies whose gas fractions, masses and/or star formation rates are distinctly different from one another.

Formation of unusual Cr5+ charge state in CaCr0.5Fe0.5O3 perovskite

NASA Astrophysics Data System (ADS)

Dai, Jian-Hong; Zhao, Qing; Sun, Qian; Zhang, Shuo; Wang, Xiao; Shen, Xu-Dong; Liu, Zhe-Hong; Shen, Xi; Yu, Ri-Cheng; Chan, Ting-Shan; Li, Lun-Xiong; Zhou, Guang-Hui; Yang, Yi-feng; Jin, Chang-Qing; Long, You-Wen

2018-03-01

A new oxide CaCr0.5Fe0.5O3 was prepared under high pressure and temperature conditions. It crystallizes in a B-site disordered Pbnm perovskite structure. The charge combination is determined to be Cr5+/Fe3+ with the presence of unusual Cr5+ state in octahedral coordination, although Cr4+ and Fe4+ occur in the related perovskites CaCrO3 and CaFeO3. The randomly distributed Cr5+ and Fe3+ spins lead to short-range ferromagnetic coupling, whereas an antiferromagnetic phase transition takes place near 50 K due to the Fe3+–O–Fe3+ interaction. In spite of the B-site Cr5+/Fe3+ disorder, the compound exhibits electrical insulating behavior. First-principles calculations further demonstrate the formation of {CaCr}}0.55+{Fe}}0.53+{{{O}}}3 charge combination, and the electron correlation effect of Fe3+ plays an important role for the insulting ground state. CaCr0.5Fe0.5O3 provides the first Cr5+ perovskite system with octahedral coordination, opening a new avenue to explore novel transition-metal oxides with exotic charge states. Project supported by the National Natural Science Foundation of China (Grant Nos. 11574378, 51772324, and 61404052),the National Basic Research Program of China (Grant No. 2014CB921500), and the Chinese Academy of Sciences (Grant Nos. YZ201555, QYZDB-SSW-SLH013, GJHZ1773, and XDB07030300).

Indirect synthesis of Al{sub 2}O{sub 3}via radiation- or photochemical formation of its hydrated precursors

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

Barta, Jan, E-mail: jan.barta@fjfi.cvut.cz; Pospisil, Milan; Cuba, Vaclav

Graphical abstract: - Highlights: • Al{sub 2}O{sub 3} precursors were produced by UV/e-beam irradiation of aqueous solutions. • Depending on the aluminium salt (Cl{sup −} or NO{sub 3}{sup −}), either γ-AlOOH or Al(OH){sub 3} is formed. • The mechanism involved strongly depends on the presence of formate anion. • Prepared mesoporous solid phase has high specific surface area (<190 m{sup 2} g{sup −1}). • Calcination of the precursor leads to the formation of γ-/η-, θ- and α-Al{sub 2}O{sub 3}. - Abstract: γ-, θ- and α-modifications of aluminium oxide (alumina) were successfully prepared by calcination of precursor solid phase obtained bymore » irradiation of clear aqueous solutions by UV light or electron beam. For the precipitate to form, formate anion must be present in the solution in sufficient concentration. According to X-ray diffraction, the precipitate was found to consist of γ-AlOOH or a mixture of γ- and α-Al(OH){sub 3}, when aluminium chloride or aluminium nitrate was used, respectively. The addition of hydrogen peroxide as a ·OH radical source and sensitizer markedly improved the efficiency of the preparation. Some hints for the apparently very complex mechanism involved were listed and discussed. Calcination of the dried precipitate at 500–800 °C produced highly porous γ-alumina with high specific surface area (ca. 150 m{sup 2} g{sup −1}). Mixture of γ- and θ-transition aluminas was obtained at 1000 °C and pure, stable corundum α-Al{sub 2}O{sub 3} formed at 1200 °C. Samples were further investigated by means of scanning electron microscopy and specific surface area or porosity measurement. According to N{sub 2} adsorption isotherm, the precipitate contains mostly mesopores with average pore size 7 nm with specific surface area of ca. 100 m{sup 2} g{sup −1}. Possible applications of the material as sorbent or catalyst as well as a pure matrix for thermoluminescence dosimetry were briefly contemplated. Strong light

Comparison of the growth kinetics of In{sub 2}O{sub 3} and Ga{sub 2}O{sub 3} and their suboxide desorption during plasma-assisted molecular beam epitaxy

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

Vogt, Patrick, E-mail: vogt@pdi-berlin.de; Bierwagen, Oliver, E-mail: bierwagen@pdi-berlin.de

2016-08-08

We present a comprehensive study of the In{sub 2}O{sub 3} growth kinetics during plasma-assisted molecular beam epitaxy and compare it to that of the related oxide Ga{sub 2}O{sub 3} [P. Vogt and O. Bierwagen, Appl. Phys. Lett. 108, 072101 (2016)]. The growth rate and desorbing fluxes were measured during growth in-situ by a laser reflectometry set-up and line-of-sight quadrupole mass spectrometer, respectively. We extracted the In incorporation as a function of the provided In flux, different growth temperatures T{sub G}, and In-to-O flux ratios r. The data are discussed in terms of the competing formation of In{sub 2}O{sub 3} andmore » desorption of the suboxide In{sub 2}O and O. The same three growth regimes as in the case of Ga{sub 2}O{sub 3} can be distinguished: (i) In-transport limited, O-rich (ii) In{sub 2}O-desorption limited, O-rich, and (iii) O-transport limited, In-rich. In regime (iii), In droplets are formed on the growth surface at low T{sub G}. The growth kinetics follows qualitatively that of Ga{sub 2}O{sub 3} in agreement with their common oxide and suboxide stoichiometry. The quantitative differences are mainly rationalized by the difference in In{sub 2}O and Ga{sub 2}O desorption rates and vapor pressures. For the In{sub 2}O, Ga{sub 2}O, and O desorption, we extracted the activation energies and frequency factors by means of Arrhenius-plots.« less

Fabrication of SiO2@ZrO2@Y2O3:Eu3+ core-multi-shell structured phosphor.

PubMed

Gao, Xuan; He, Diping; Jiao, Huan; Chen, Juan; Meng, Xin

2011-08-01

ZrO2 interface was designed to block the reaction between SiO2 and Y2O3 in SiO2@Y2O3:Eu coreshell structure phosphor. SiO2@ZrO2@Y2O3:Eu core-multi-shell phosphors were successfully synthesized by combing an LBL method with a Sol-gel process. Based on electron microscopy, X-ray diffraction, and spectroscopy experiments, compelling evidence for the formation of the Y2O3:Eu outer shell on ZrO2 were presented. The presence of ZrO2 layer on SiO2 core can block the reaction of SiO2 core and Y2O3 shell effectively. By this kind of structure, the reaction temperature of the SiO2 core and Y2O3 shell in the SiO2@Y2O3:Eu core-shell structure phosphor can be increased about 200-300 degrees C and the luminescent intensity of this structure phosphor can be improved obviously. Under the excitation of ultraviolet (254 nm), the Eu3+ ion mainly shows its characteristic red (611 nm, 5D0-7F2) emissions in the core-multi-shell particles from Y2O3:Eu3+ shells. The emission intensity of Eu3+ ions can be tuned by the annealing temperatures, the number of coating times, and the thickness of ZrO2 interface, respectively.

Computational study of C(sp3)-O bond formation at a PdIV centre.

PubMed

Canty, Allan J; Ariafard, Alireza; Camasso, Nicole M; Higgs, Andrew T; Yates, Brian F; Sanford, Melanie S

2017-03-14

This report describes a computational study of C(sp 3 )-OR bond formation from Pd IV complexes of general structure Pd IV (CH 2 CMe 2 -o-C 6 H 4 -C,C')(F)(OR)(bpy-N,N') (bpy = 2,2'-bipyridine). Dissociation of - OR from the different octahedral Pd IV starting materials results in a common square-pyramidal Pd IV cation. An S N 2-type attack by - OR ( - OR = phenoxide, acetate, difluoroacetate, and nitrate) then leads to C(sp 3 )-OR bond formation. In contrast, when - OR = triflate, concerted C(sp 3 )-C(sp 2 ) bond-forming reductive elimination takes place, and the calculations indicate this outcome is the result of thermodynamic rather than kinetic control. The energy requirements for the dissociation and S N 2 steps with different - OR follow opposing trends. The S N 2 transition states exhibit "PdCO" angles in a tight range of 151.5 to 153.0°, resulting from steric interactions between the oxygen atom and the gem-dimethyl group of the ligand. Conformational effects for various OR ligands and isomerisation of the complexes were also examined as components of the solution dynamics in these systems. In all cases, the trends observed computationally agree with those observed experimentally.

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

PubMed

Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

2011-01-20

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF

Bone Formation Rate in Experimental Disuse Osteoporosis in Monkeys

NASA Technical Reports Server (NTRS)

Cann, Christopher; Young, Donald R.

1976-01-01

Specific mechanisms underlying weightless and hypodynamic bone loss are obscure. A principal relationship which must be affected is the balance between bone formation and bone resorption rates. In order to better define the influence of those parameters on bone loss, and also to develop measurements in other species as a useful adjunct to human research, studies were undertaken with experimental monkeys. Tests were conducted with a total of 6 adult male monkeys, weighing 10-13 kg, and approximately 10-12 yrs. of age to evaluate specifically bone formation rate during the development of disuse osteoporosis and osteopenia. Three animals were restrained in a semi-recumbent position for six months; three animals served as normal caged controls. Food intake (Purina) was held relatively constant at 200g/day for each animal. Using a Norland Bone Mineral Analyzer, bone mineral losses of 3.5 to 6% were seen in the mid-shaft of the tibia and in the distal radius. Bone loss was confirmed radiographically, with observation of thinning of the proximal tibial cortex and trabeculae in the calcaneus. Bone formation rate was determined using standard Ca-47 kinetics under metabolic balance conditions. After six months of restraint, accretion was 7.2-13.2 mg Ca/kg/day, compared to 3.2-4.1 mg Ca/kg/day in caged controls and 3-8 mg Ca/kg/day in normal adult humans. Fecal and urine calcium was 25-40% higher in restrained animals than in controls. Dietary calcium absorption decreases during restraint, and calcium turnover increases, implying a rise in bone resorption rate concommitant with the observed rise in bone accretion rate. Further studies dealing specifically with bone resorption are underway to define this more fully.

Modification of Ga2O3 by an Ag-Cr core-shell cocatalyst enhances photocatalytic CO evolution for the conversion of CO2 by H2O.

PubMed

Pang, Rui; Teramura, Kentaro; Tatsumi, Hiroyuki; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2018-01-25

A core-shell structure of Ag-Cr dual cocatalyst loaded-Ga 2 O 3 was found to significantly enhance the formation rate of CO and selectivity toward CO evolution for the photocatalytic conversion of CO 2 where H 2 O is used as an electron donor.

Initial stages of ion beam-induced phase transformations in Gd2O3 and Lu2O3

NASA Astrophysics Data System (ADS)

Chen, Chien-Hung; Tracy, Cameron L.; Wang, Chenxu; Lang, Maik; Ewing, Rodney C.

2018-02-01

The atomic-scale evolution of lanthanide sesquioxides Gd2O3 and Lu2O3 irradiated with 1 MeV Kr ions at room temperature and 120 K, up to fluences of 1 × 1016 ions/cm2 (˜20 dpa), has been characterized by in situ transmission electron microscopy. At room temperature, both oxides exhibited high radiation tolerance. Irradiation did not cause any observable structural change in either material, likely due to the mobility of irradiation-induced point defects, causing efficient defect annihilation. For Gd2O3, having the larger cation ionic radius of the two materials, an irradiation-induced stacking fault structure appeared at low fluences in the low temperature irradiation. As compared with the cubic-to-monoclinic phase transformations known to result from higher energy (˜GeV) ion irradiation, Kr ions of lower energies (˜MeV) yield much lower rates of damage accumulation and thus less extensive structural modification. At a fluence of 2.5 × 1015 ions/cm2, only the initial stages of the cubic-to-monoclinic (C to B) phase transformation process, consisting of the formation and aggregation of defects, have been observed.

Formation and growth rates of atmospheric nanoparticles: four years of observations at two West Siberian stations

NASA Astrophysics Data System (ADS)

Arshinov, Mikhail Yu.; Belan, Boris D.; Davydov, Denis K.; Kozlov, Artem V.; Arshinova, Victoria

2015-04-01

In spite of fact that the first report on the new particle formation (NPF) itself was done by John Aitken more than one century ago (Aitken, 1898), a phenomenon of NPF bursts taken place in the atmosphere was discovered not very long ago. Nevertheless, to date it is known that they may occur quite often in a variety of environments (Kulmala et al., 2004; Hirsikko et al., 2011). Siberia occupies a vast area covered by forests, but the comprehensive data on burst frequency, as well as on formation and growth rates of freshly nucleated particles in this key region are still lacking. Continuous measurements of aerosol size distribution carried out in recent years at two West Siberian stations (TOR-station - 56o28'41"N, 85o03'15"E; Fonovaya Observatory - 56o25'07"N, 84o04'27"E) allowed this gap in data to be filled up. Analysis of the size spectra classified in accordance with criteria proposed by Dal Maso et al. (2005) and Hammed et al. (2007) enabled a conclusion to be drawn that NPF events in Wets Siberia are more often observed during spring (from March to May) and early autumn (secondary frequency peak in September). On average, particle formation bursts took place on 23-28 % of all days. Such a seasonal pattern of the NPF occurrence is very similar to one observed at SMEAR II Station (Hyytiälä, Finland; Dal Maso et al. 2005, 2007). Formation rates (FR) of particles with diameters below 25 nm varied in a wide range from 0.1 to 10 cm-3 s-1. Mean values of FR for the entire period of observations were 1.7 cm-3s-1 (median = 1.13 cm-3 s-1) at TOR-station and 0.88 cm-3 s-1 (median = 0.69 cm-3 s-1) at Fonovaya Observatory. Enhanced values of FR are usually observed from spring to autumn. Mean growth rates of observed at TOR-station and Fonovaya Observatory were 6.5 nm h-1 (median = 5.0 nm h-1) and 8.3 nm h-1 (median = 6.4 nm h-1), respectively. This work was supported by the Branch of Geology, Geophysics and Mining Sciences of RAS (Program No. 5); State contracts of

Role of strained nano-regions in the formation of subgrains in CaCu3Ti4O12

NASA Astrophysics Data System (ADS)

Fang, Tsang-Tse; Wang, Yong-Huei; Kuo, Jui-Chao

2011-07-01

Single-phase CaCu3Ti4O12 (CCTO) was synthesized by solid-state reaction. Electron backscatter diffraction, scanning electron microscopy, and atomic force microscopy were adopted to characterize the grain orientation, microstructure, and surface morphology of the CCTO samples with or without thermal etching. Bump strained nano-regions induced by the local compositional disorder at a nano-scale have been discovered, being the origin of the formation of subgrains in CCTO. The proposed mechanism for the formation of subgrains involves the formation of etched pits and subboundaries pertaining to the strained nano-regions rather than dislocation displacement. The dielectric response inside the grains of CCTO relevant to the strained nano-regions is also discussed.

Bimetallic cooperative effect on O-O bond formation: copper polypyridyl complexes as water oxidation catalyst.

PubMed

Su, Xiao-Jun; Zheng, Chu; Hu, Qin-Qin; Du, Hao-Yi; Liao, Rong-Zhen; Zhang, Ming-Tian

2018-06-13

The performance of water oxidation catalysis by a Cu-based polypyridyl complex, [CuII(TPA)(OH2)]2+ (1H; TPA = tris-(pyridylmethyl)amine), has been investigated in neutral aqueous solution by electrochemical methods. Compared with our previously reported binuclear catalyst, [(BPMAN)(CuII)2(μ-OH)]3+ (2; BPMAN = 2,7-[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine), mononuclear catalyst 1 has a higher overpotential and lower catalytic activity toward water oxidation under the same conditions. Experimental results revealed that the O-O bond formation occurred via a water nucleophilic attack mechanism in which formal CuIV(O) is proposed as a key intermediate for the mononuclear catalyst 1H. In contrast, for the binuclear catalyst, O-O bond formation was facilitated by bimetallic cooperation between the two CuIII centers.

Ozone and alkyl nitrate formation from the Deepwater Horizon oil spill atmospheric emissions

NASA Astrophysics Data System (ADS)

Neuman, J. A.; Aikin, K. C.; Atlas, E. L.; Blake, D. R.; Holloway, J. S.; Meinardi, S.; Nowak, J. B.; Parrish, D. D.; Peischl, J.; Perring, A. E.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Trainer, M.

2012-05-01

Ozone (O3), alkyl nitrates (RONO2), and other photochemical products were formed in the atmosphere downwind from the Deepwater Horizon (DWH) oil spill by photochemical reactions of evaporating hydrocarbons with NOx (=NO + NO2) emissions from spill response activities. Reactive nitrogen species and volatile organic compounds (VOCs) were measured from an instrumented aircraft during daytime flights in the marine boundary layer downwind from the area of surfacing oil. A unique VOC mixture, where alkanes dominated the hydroxyl radical (OH) loss rate, was emitted into a clean marine environment, enabling a focused examination of O3 and RONO2 formation processes. In the atmospheric plume from DWH, the OH loss rate, an indicator of potential O3 formation, was large and dominated by alkanes with between 5 and 10 carbons per molecule (C5-C10). Observations showed that NOx was oxidized very rapidly with a 0.8 h lifetime, producing primarily C6-C10 RONO2 that accounted for 78% of the reactive nitrogen enhancements in the atmospheric plume 2.5 h downwind from DWH. Both observations and calculations of RONO2 and O3 production rates show that alkane oxidation dominated O3 formation chemistry in the plume. Rapid and nearly complete oxidation of NOx to RONO2 effectively terminated O3 production, with O3 formation yields of 6.0 ± 0.5 ppbv O3 per ppbv of NOx oxidized. VOC mixing ratios were in large excess of NOx, and additional NOx would have formed additional O3 in this plume. Analysis of measurements of VOCs, O3, and reactive nitrogen species and calculations of O3 and RONO2 production rates demonstrate that NOx-VOC chemistry in the DWH plume is explained by known mechanisms.

Thermodynamic characterization of Ni3TeO6, Ni2Te3O8 and NiTe2O5

NASA Astrophysics Data System (ADS)

Dawar, Rimpi; Babu, R.; Ananthasivan, K.; Anthonysamy, S.

2017-09-01

Measurement of vapour pressure of TeO2(g) over the biphasic mixture Ni3TeO6 (s) + NiO(s) in the temperature range 1143-1272 K was carried out using transpiration-thermogravimetric technique (TTG). Gibbs energy of formation of Ni3TeO6 was obtained from the temperature dependence of vapour pressure of TeO2 (g) generated by the incongruent vapourisation reaction, Ni3TeO6 (s) → NiO(s) + TeO2 (g) + 1/2 O2 in the temperature range 1143-1272 K. An isoperibol type drop calorimeter was used to measure the enthalpy increments of Ni3TeO6, Ni2Te3O8 and NiTe2O5. Thermodynamic functions viz., heat capacity, entropy and Gibbs energy functions of these compounds were derived from the experimentally measured enthalpy increment values. Third-law analysis was carried out to ascertain absence of temperature dependent systematic errors in the measurement of vapour pressure of TeO2 (g). A value of -1265.1 ± 1.5 kJ mol-1 was obtained for Δ Hf,298K o (Ni3TeO6) using third-law analysis.

Crystal orientation of monoclinic β-Ga2O3 thin films formed on cubic MgO substrates with a γ-Ga2O3 interfacial layer

NASA Astrophysics Data System (ADS)

Nakagomi, Shinji; Kokubun, Yoshihiro

2017-12-01

The crystal orientation relationship between β-Ga2O3 and MgO in β-Ga2O3 thin films prepared on (1 0 0), (1 1 1), and (1 1 0) MgO substrates was investigated by X-ray diffraction measurements and cross-sectional transmission electron microscopy images. The γ-Ga2O3 interfacial layer was present between β-Ga2O3 and MgO acted as a buffer to connect β-Ga2O3 on MgO. The following conditions were satisfied under each case: β-Ga2O3 (1 0 0)||MgO (1 0 0) and β-Ga2O3 [0 0 1]||MgO 〈0 1 1〉 for the formation of β-Ga2O3 on (1 0 0) MgO, and β-Ga2O3 (2 bar 0 1)||MgO (1 1 1) for the formation of β-Ga2O3 on (1 1 1) MgO, as well as each condition of β-Ga2O3 [0 1 0] (1 0 0)||MgO [ 1 bar 1 0 ] (0 0 1), β-Ga2O3 [0 1 0] (1 0 0)||MgO [ 0 1 bar 1 ] (1 0 0), and β-Ga2O3 [0 1 0] (1 0 0)||MgO [ 1 0 1 bar ] (0 1 0). β-Ga2O3 (1 bar 0 2)||MgO(1 1 0) and β-Ga2O3 [0 1 0] ⊥ MgO [0 0 1] for β-Ga2O3 formed on (1 1 0) MgO. The β-Ga2O3 formed on (1 1 1) MgO at 800 °C exhibited a threefold structure. The β-Ga2O3 formed on (1 1 0) MgO had a twofold structure but different by 90° from the result reported previously.

Combining active and passive remote sensing from research aircraft with atmospheric models to evaluate NOx emission fluxes and O3 formation in the Los Angeles Megacity

NASA Astrophysics Data System (ADS)

Baidar, Sunil; Oetjen, Hilke; Senff, Christoph; Alvarez, Raul, II; Hardesty, Michael; Langford, Andrew; Kim, Si-Wan; Trainer, Michael; Volkamer, Rainer

2013-04-01

Ozone (O3) and nitrogen dioxide (NO2) are two important components of air pollution. We have measured vertical column amounts of NO2, and vertical profiles of O3 and wind speed by means of measurements of solar stray light by CU Airborne MAX-DOAS, and active remote sensing using the NOAA TOPAZ lidar, and the University of Leeds Doppler lidar aboard the NOAA Twin Otter research aircraft. A total of 52 flights (up to 4 hours each) were carried out between May 19 and July 19 2010 during the CalNex and CARES field campaigns. These flights cover most of California. The boundary layer height was measured by TOPAZ lidar, and trace gas concentrations of NO2 and O3 were integrated over boundary layer height. These column integrated quantities are then combined with direct wind speed measurements to quantify directly the pollutant flux across the boundary, as defined by the flight track. By tracking the pollution fluxes during transects that are flown upwind and in various distances downwind of a NOx emission source, the NOx emission rate, and the ozone formation rate are quantified. These pollutant fluxes are calculated here for the first time exclusively based on measurements (i.e., without need to infer wind speed from a model). These fluxes provide constraints to quantify localized NOx emissions, and are being compared with WRF-Chem model simulations.

Electrocatalytic Oxidation of Formate by [Ni(P R 2 N R' 2 ) 2 (CH 3 CN)] 2+ Complexes

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

Galan, Brandon R.; Schöffel, Julia; Linehan, John C.

2011-08-17

New [Ni(P R 2N R` 2) 2+(CH 3CN)] 2+ complexes with R = Ph, R` = 4-MeOPh; R = Cy, R` = Ph and a mixed ligand [Ni(P R 2N R` 2)(P R`` 2N R` 2)] 2+ with R = Cy, R` = Ph, R`` = Ph have been synthesized and characterized by single crystal X-ray crystallography. These complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO 2, protons, and electrons with rates which are first order in catalyst and in formate at formate concentrations below approximately 0.05 M. For the catalysts studied,more » maximum observed turnover frequencies vary from <1.1 s -1 to 12.5 s -1 at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. A mechanistic scheme is proposed which involves an initial nickel complex bound <1-OC(O)H followed by a rate limiting hydride transfer step. An acetate complex demonstrating the η 1-OC(O)CH 3 binding mode to nickel has also been synthesized and characterized by single crystal X-ray crystallography. The pendant amines have been demonstrated to be essential for this electrocatalytic activity as no activity toward formate was found for the similar [Ni(depe) 2][BF 4] 2+ (depe = diethylphosphinoethane) complex. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Photocatalytic self-cleaning transparent 2Bi2O3-B2O3 glass ceramics

NASA Astrophysics Data System (ADS)

Sharma, Sumeet Kumar; Singh, V. P.; Chauhan, Vishal S.; Kushwaha, H. S.; Vaish, Rahul

2017-09-01

Photocatalytic response of as-quenched and heat-treated 2Bi2O3-B2O3 glasses was studied. X ray diffraction reveals that the controlled heat treatment of glasses at 380 °C for 1 h, 2 h, and 3 h shows the formation of Bi4B2O9 crystals embedded in 2Bi2O3-B2O3 the host glass matrix. Scanning electron microscopic images reveal the presence of nanocrystallization in as-quenched glass. Significant photocatalytic activities were observed in as-quenched transparent glass. Photocatalytic activities were studied using the degradation of Resazurin as well as pharmaceutical 17 β-Estradiol under UV irradiation. Measurement of contact angle shows enhanced hydrophilicity with the increase in crystallization of the samples. Further, for as quenched 2Bi2O3-B2O3 glass ceramic, under UV irradiation, the water contact angle decreased from 92.7° to 39.5° and the sample surface transformed from hydrophobic to hydrophilic. Effective photocatalytic performance along with photoinduced hydrophilicity promotes 2Bi2O3-B2O3 glass ceramics in self-cleaning applications.

Understanding oxidative dehydrogenation of ethane on Co 3O 4 nanorods from density functional theory

DOE PAGES

Fung, Victor; Tao, Franklin; Jiang, De-en

2016-05-20

Co 3O 4 is a metal oxide catalyst with weak, tunable M–O bonds promising for catalysis. Here, density functional theory (DFT) is used to study the oxidative dehydrogenation (ODH) of ethane on Co 3O 4 nanorods based on the preferred surface orientation (111) from the experimental electron-microscopy image. The pathway and energetics of the full catalytic cycle including the first and second C–H bond cleavages, hydroxyl clustering, water formation, and oxygen-site regeneration are determined. We find that both lattice O and Co may participate as active sites in the dehydrogenation, with the lattice-O pathway being favored. Here, we identify themore » best ethane ODH pathway based on the overall energy profiles of several routes. We identify that water formation from the lattice oxygen has the highest energy barrier and is likely a rate-determining step. This work of the complete catalytic cycle of ethane ODH will allow further study into tuning the surface chemistry of Co 3O 4 nanorods for high selectivity of alkane ODH reactions.« less

Synthesis, cytotoxicity, and hydroxyapatite formation in 27-Tris-SBF for sol-gel based CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses

NASA Astrophysics Data System (ADS)

Kaur, Gurbinder; Pickrell, G.; Kimsawatde, G.; Homa, D.; Allbee, H. A.; Sriranganathan, N.

2014-03-01

CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses were prepared via an optimized sol-gel method. The current investigation was focused on producing novel zinc based calcium phosphoborosilicate glasses and to evaluate their mechanical, rheological, and biocompatible properties. The morphology and composition of these glasses were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The particle size, mechanical and flexural strength was also determined. Furthermore, the zeta potential of all the glasses were determined to estimate their flocculation tendency. The thermal analysis and weight loss measurements were carried out using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) respectively. For assessing the in-vitro bioactive character of synthesized glasses, the ability for apatite formation on their surface upon their immersion in simulated body fluid (SBF) was checked using SEM and pH measurements. MTS assay cytotoxicity assay and live-dead cell viability test were conducted on J774A.1 cells murine macrophage cells for different glass concentrations.

Synthesis, cytotoxicity, and hydroxyapatite formation in 27-Tris-SBF for sol-gel based CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses.

PubMed

Kaur, Gurbinder; Pickrell, G; Kimsawatde, G; Homa, D; Allbee, H A; Sriranganathan, N

2014-03-18

CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses were prepared via an optimized sol-gel method. The current investigation was focused on producing novel zinc based calcium phosphoborosilicate glasses and to evaluate their mechanical, rheological, and biocompatible properties. The morphology and composition of these glasses were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The particle size, mechanical and flexural strength was also determined. Furthermore, the zeta potential of all the glasses were determined to estimate their flocculation tendency. The thermal analysis and weight loss measurements were carried out using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) respectively. For assessing the in-vitro bioactive character of synthesized glasses, the ability for apatite formation on their surface upon their immersion in simulated body fluid (SBF) was checked using SEM and pH measurements. MTS assay cytotoxicity assay and live-dead cell viability test were conducted on J774A.1 cells murine macrophage cells for different glass concentrations.

Synthesis, cytotoxicity, and hydroxyapatite formation in 27-Tris-SBF for sol-gel based CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses

PubMed Central

Kaur, Gurbinder; Pickrell, G.; Kimsawatde, G.; Homa, D.; Allbee, H. A.; Sriranganathan, N.

2014-01-01

CaO-P2O5-SiO2-B2O3-ZnO bioactive glasses were prepared via an optimized sol–gel method. The current investigation was focused on producing novel zinc based calcium phosphoborosilicate glasses and to evaluate their mechanical, rheological, and biocompatible properties. The morphology and composition of these glasses were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The particle size, mechanical and flexural strength was also determined. Furthermore, the zeta potential of all the glasses were determined to estimate their flocculation tendency. The thermal analysis and weight loss measurements were carried out using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) respectively. For assessing the in-vitro bioactive character of synthesized glasses, the ability for apatite formation on their surface upon their immersion in simulated body fluid (SBF) was checked using SEM and pH measurements. MTS assay cytotoxicity assay and live-dead cell viability test were conducted on J774A.1 cells murine macrophage cells for different glass concentrations. PMID:24637634

Thermal characteristics, Raman spectra, optical and structural properties of TiO2-Bi2O3-B2O3-TeO2 glasses

NASA Astrophysics Data System (ADS)

Gupta, Nupur; Khanna, Atul; Gonzàlez, Fernando; Iordanova, Reni

2017-05-01

Tellurite and borotellurite glasses containing Bi2O3 and TiO2 were prepared and structure-property correlations were carried out by density measurements, X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Raman and UV-visible spectroscopy. Titanium tellurite glasses require high melt-cooling rates and were fabricated by splat quenching. On adding B2O3, the glass forming ability (GFA) enhances, and glasses could be synthesized at lower quenching rates. The density of glasses shows a direct correlation with molecular mass of the constituents. UV-visible studies were used to determine the optical band gap and refractive index. Raman studies found that the co-ordination number of tellurium ions with oxygen (NTe-O) decreases with the increase in B2O3 as well as Bi2O3 content while, TiO2 produce only a small decrease in NTe-O, which explains the lower GFA of titanium tellurite glasses that do not contain Bi2O3 and B2O3. DSC studies show that the glass transition temperature (Tg) increases with B2O3 and TiO2 concentrations and that Tg correlates well with bond enthalpy of the metal oxides.

Star-formation rate in compact star-forming galaxies

NASA Astrophysics Data System (ADS)

Izotova, I. Y.; Izotov, Y. I.

2018-03-01

We use the data for the Hβ emission-line, far-ultraviolet (FUV) and mid-infrared 22 μm continuum luminosities to estimate star formation rates < SFR > averaged over the galaxy lifetime for a sample of about 14000 bursting compact star-forming galaxies (CSFGs) selected from the Data Release 12 (DR12) of the Sloan Digital Sky Survey (SDSS). The average coefficient linking < SFR > and the star formation rate SFR0 derived from the Hβ luminosity at zero starburst age is found to be 0.04. We compare < SFR > s with some commonly used SFRs which are derived adopting a continuous star formation during a period of {˜} 100 Myr, and find that the latter ones are 2-3 times higher. It is shown that the relations between SFRs derived using a geometric mean of two star-formation indicators in the UV and IR ranges and reduced to zero starburst age have considerably lower dispersion compared to those with single star-formation indicators. We suggest that our relations for < SFR > determination are more appropriate for CSFGs because they take into account a proper temporal evolution of their luminosities. On the other hand, we show that commonly used SFR relations can be applied for approximate estimation within a factor of {˜} 2 of the < SFR > averaged over the lifetime of the bursting compact galaxy.

Positron annihilation studies on the behaviour of vacancies in LaAlO3/SrTiO3 heterostructures

NASA Astrophysics Data System (ADS)

Yuan, Guoliang; Li, Chen; Yin, Jiang; Liu, Zhiguo; Wu, Di; Uedono, Akira

2012-11-01

The formation and diffusion of vacancies are studied in LaAlO3/SrTiO3 heterostructures. Oxygen vacancies (VOS) appear easily in the SrTiO3 substrate during LaAlO3 film growth at 700 °C and 10-4 Pa oxygen pressure rather than at 10-3-10-1 Pa, thus the latter two-dimensional electron gas should come from the polarity discontinuity at the (LaO)+/(TiO2)0 interface. For SrTiO3-δ/LaAlO3/SrTiO3, high-density VOS of the SrTiO3-δ film can pass through the LaAlO3 film and then diffuse to 1.7 µm depth in the SrTiO3 substrate, suggesting that LaAlO3 has VOS at its middle-deep energy levels within the band gap. Moreover, high-density VOS may combine with a strontium/titanium vacancy (VSr/Ti) to form VSr/Ti-O complexes in the SrTiO3 substrate at 700 °C.

Formation of gamma'-Ni3Al via the Peritectoid Reaction: gamma plus beta (+Al2O3) equals gamma'(+Al2O3)

NASA Technical Reports Server (NTRS)

Copland, Evan

2008-01-01

The activities of Al and Ni were measured using multi-cell Knudsen effusion-cell mass spectrometry (multi-cell KEMS), over the composition range 8 - 32 at.%Al and temperature range T = 1400 - 1750 K in the Ni-Al-O system. These measurements establish that equilibrium solidification of gamma'-Ni3Al-containing alloys occurs by the eutectic reaction, L (+ Al2O3) = gamma + beta (+ Al2O3), at 1640 plus or minus 1 K and a liquid composition of 24.8 plus or minus 0.2 at.%Al (at an unknown oxygen content). The {gamma + beta + Al2O3} phase field is stable over the temperature range 1633 - 1640 K, and gamma'-Ni3Al forms via the peritectiod, gamma + beta (+ Al2O3) = gamma'(+ Al2O3), at 1633 plus or minus 1 K. This behavior is inconsistent with the current Ni-Al phase diagram and a new diagram is proposed. This new Ni-Al phase diagram explains a number of unusual steady state solidification structures reported previously and provides a much simpler reaction scheme in the vicinity of the gamma'-Ni3Al phase field.

Evaluation of the photocatalytic activity of Ln3+-TiO2 nanomaterial using fluorescence technique for real wastewater treatment.

PubMed

Saif, M; Aboul-Fotouh, S M K; El-Molla, S A; Ibrahim, M M; Ismail, L F M

2014-07-15

Evaluation the photocatalytic activity of different Ln(3+) modified TiO2 nanomaterials using fluorescence based technique has rarely been reported. In the present work, xmol Ln(3+) modified TiO2 nanomaterials (Ln = Nd(3+), Sm(3+), Eu(3+), Gd(3+), Dy(3+) and Er(3+) ions; x = 0.005, 0.008, 0.01, 0.02 and 0.03) were synthesized by sol-gel method and characterized using different advanced techniques. The photocatalytic efficiency of the modified TiO2 expressed in the charge carrier separation and OH radicals formation were assigned using TiO2 fluorescence quenching and fluorescence probe methods, respectively. The obtained fluorescence measurements confirm that doping treatment significantly decreases the electron-hole recombination probability in the obtained Ln(3+)/TiO2. Moreover, the rate of OH radicals formation is increased by doping. The highly active nanoparticles (0.02Gd(3+)/TiO2 and 0.01Eu(3+)/TiO2) were applied for industrial wastewater treatment using solar radiation as a renewable energy source. Copyright © 2014 Elsevier B.V. All rights reserved.

Facile synthesis of SnO2/α-Fe2O3 nanocomposite for supercapacitor capacitor applications

NASA Astrophysics Data System (ADS)

Rani, B. Jansi; Saravanakumar, B.; Ravi, G.; Yuvakkumar, R.

2018-05-01

Facile and economically viable one step hydrothermal route was adapted to synthesis SnO2/α-Fe2O3 nanocomposite with and without hexamine (HMT) as surfactant successfully. The formation of SnO2/α-Fe2O3 nanocomposite was confirmed through XRD, Raman, PL and FTIR studies. The presence of well defined XRD diffraction peaks of both SnO2 and α-Fe2O3 revealed the formation SnO2/α-Fe2O3 nanocomposite. The obtained characteristic Raman active (Eg+Eg+Eu+A2u) mode of vibrations confirmed the formation of SnO2/α-Fe2O3 nanocomposite. Photoluminescence study revealed the emission behavior of the product. Metal oxygen vibrations of Fe-O in both octahedral, tetrahedral sites and Sn-O were confirmed by the bands located at 466, 580 and 673 cm-1 respectively through FTIR. The spherical morphology of the product synthesized with and without the surfactant HMT has been revealed by SEM images. The electrochemical behavior of the product was investigated through CV and EIS studies in 1M Na2SO4 electrolyte solution and obtained the highest specific capacitance of 211.25 F/g at 5 mV for the surfactant assisted product.

Thermodynamics of formation of coffinite, USiO4

PubMed Central

Guo, Xiaofeng; Szenknect, Stéphanie; Mesbah, Adel; Labs, Sabrina; Clavier, Nicolas; Poinssot, Christophe; Ushakov, Sergey V.; Curtius, Hildegard; Bosbach, Dirk; Ewing, Rodney C.; Burns, Peter C.; Dacheux, Nicolas; Navrotsky, Alexandra

2015-01-01

Coffinite, USiO4, is an important U(IV) mineral, but its thermodynamic properties are not well-constrained. In this work, two different coffinite samples were synthesized under hydrothermal conditions and purified from a mixture of products. The enthalpy of formation was obtained by high-temperature oxide melt solution calorimetry. Coffinite is energetically metastable with respect to a mixture of UO2 (uraninite) and SiO2 (quartz) by 25.6 ± 3.9 kJ/mol. Its standard enthalpy of formation from the elements at 25 °C is −1,970.0 ± 4.2 kJ/mol. Decomposition of the two samples was characterized by X-ray diffraction and by thermogravimetry and differential scanning calorimetry coupled with mass spectrometric analysis of evolved gases. Coffinite slowly decomposes to U3O8 and SiO2 starting around 450 °C in air and thus has poor thermal stability in the ambient environment. The energetic metastability explains why coffinite cannot be synthesized directly from uraninite and quartz but can be made by low-temperature precipitation in aqueous and hydrothermal environments. These thermochemical constraints are in accord with observations of the occurrence of coffinite in nature and are relevant to spent nuclear fuel corrosion. PMID:25964321

Star Formation Rates in Cooling Flow Clusters: A UV Pilot Study with Archival XMM-Newton Optical Monitor Data

NASA Technical Reports Server (NTRS)

Hicks, A. K.; Mushotzky, R.

2006-01-01

We have analyzed XMM-Newton Optical Monitor (OM) UV (180-400 nm) data for a sample of 33 galaxies. 30 are cluster member galaxies, and nine of these are central cluster galaxies (CCGs) in cooling flow clusters having mass deposition rates which span a range of 8 - 525 Solar Mass/yr. By comparing the ratio of UV to 2MASS J band fluxes, we find a significant UV excess in many, but not all, cooling flow CCGs, a finding consistent with the outcome of previous studies based on optical imaging data (McNamara & O'Connell 1989; Cardiel, Gorgas, & Aragon-Salamanca 1998; Crawford et al. 1999). This UV excess is a direct indication of the presence of young massive stars, and therefore recent star formation, in these galaxies. Using the Starburst99 spectral energy distribution (SED) model of continuous star formation over a 900 Myr period, we derive star formation rates of 0.2 - 219 solar Mass/yr for the cooling flow sample. For 2/3 of this sample it is possible to equate Chandra/XMM cooling flow mass deposition rates with UV inferred star formation rates, for a combination of starburst lifetime and IMF slope. This is a pilot study of the well populated XMM UV cluster archive and a more extensive follow up study is currently underway.

Preparation of MgO-SnO2-TiO2 Materials and Their Corrosion in Na3AlF6-AlF3-K3AlF6 Bath

NASA Astrophysics Data System (ADS)

Xu, Yibiao; Li, Yawei; Sang, Shaobai; Ren, Bo; Qin, Qingwei; Yang, Jianhong

2015-01-01

New types of refractory materials need to be developed for designing the so-called ledge-free sidewalls of the Hall-Héroult cell for aluminum extraction, which are currently constructed using Si3N4 bonded SiC refractories. In the present paper, MgO-based materials as potential candidate sidewalls were prepared using fused magnesia, tin dioxide, and anatase powder as starting materials. The reaction sintering process of the MgO-SnO2-TiO2 materials was investigated by means of X-ray diffraction and scanning electron microscope (SEM). All the specimens were corroded in a Na3AlF6-AlF3-K3AlF6 bath to assess the electrolyte corrosion resistance. The results show that reaction sintering occurs in the MgO-SnO2-TiO2 system in the range of 1373 K to 1873 K (1100 °C to 1600 °C). Firstly, MgO reacts separately with TiO2 and SnO2 to produce the Mg2TiO4 and Mg2SnO4 phases at 1373 K (1100 °C), which in turn react to form the Mg2Ti x Sn1-x O4 composite spinel at temperatures above 1373 K (1100 °C). All the specimens prepared are composed of the composite spinel and periclase phases. Increasing the SnO2 addition from 2 to 10 wt pct enhances densification of the specimens, which is accompanied by the formation of homogeneously distributed composite spinels in the MgO matrix, but the density of the specimen decreases when the amount of SnO2 added is higher than 10 wt pct due to larger volume expansion and agglomeration of the composite spinel. The MgO-SnO2-TiO2 refractories prepared exhibit good corrosion resistance to the electrolyte melts owing to their high density and formation of the composite spinel in the specimens. Their corrosion resistance increases progressively with the increase in the SnO2 addition owing to the formation of more chemically stable composite spinel.

Phase formation and UV luminescence of Gd{sup 3+} doped perovskite-type YScO{sub 3}

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

Shimizu, Yuhei; Ueda, Kazushige, E-mail: kueda@che.kyutech.ac.jp

Synthesis of pure and Gd{sup 3+}doped perovskite-type YScO{sub 3} was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd{sup 3+} doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phasemore » at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO{sub 3} formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO{sub 3}. Because Gd{sup 3+} ions were also dissolved into the single C-type phase in Gd{sup 3+} doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase. - Graphical abstract: A pure perovskite-type YScO{sub 3} phase was successfully synthesized by a polymerized complex (PC) method. The perovskite-type YScO{sub 3} was generated through a solid solution of C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} with drastic change of morphology. The PC method enabled a preparation of the single phase of the perovskite-type YScO{sub 3} at lower temperature and in shorter heating time. Gd{sup 3+} doped perovskite-type YScO{sub 3} was found to show a strong sharp UV emission at 314 nm. - Highlights: • Pure YScO{sub 3} phase was successfully synthesized by polymerized complex (PC) method. • Pure perovskite-type YScO{sub 3} phase was generated from pure C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} one. • YScO{sub 3} was obtained at lower

Monolayer dispersion of CoO on Al2O3 probed by positronium atom

NASA Astrophysics Data System (ADS)

Liu, Z. W.; Zhang, H. J.; Chen, Z. Q.

2014-02-01

CoO/Al2O3 catalysts were prepared by wet impregnation method with CoO contents ranging from 0 wt% to 24 wt%. X-ray diffraction and X-ray photoelectron spectroscopy measurements suggest formation of CoO after calcined in N2. Quantitative X-ray diffraction analysis indicates monolayer dispersion capacity of CoO in CoO/Al2O3 catalysts to be about 3 wt%. Positron annihilation lifetime and coincidence Doppler broadening measurements were performed to study the dispersion state of CoO on Al2O3. The positron lifetime measurements reveal two long lifetime components τ3 and τ4, which correspond to ortho-positronium annihilation lifetime in microvoids and large pores, respectively. It was found that the positronium atom is very sensitive to the dispersion state of CoO on Al2O3. The presence of CoO significantly decreases both the lifetime and the intensity of τ4. Detailed analysis of the coincidence Doppler broadening measurements suggests that with the CoO content lower than the monolayer dispersion, spin conversion reaction of positronium is induced by CoO. When the cobalt content is higher than the monolayer dispersion capacity, inhibition of positronium formation becomes the dominate effect.

Spectroscopic properties and energy transfer analysis of Tm3+-doped BaF2-Ga2O3-GeO2-La2O3 glass.

PubMed

Yu, Shenglei; Yang, Zhongmin; Xu, Shanhui

2010-05-01

This paper reports on the spectroscopic properties and energy transfer analysis of Tm(3+)-doped BaF(2)-Ga(2)O(3)-GeO(2)-La(2)O(3) glasses with different Tm(2)O(3) doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm-2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm(3+), cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm(2)O(3) doping concentrations. The maximum fluorescence intensity at around 1.8 mum has been obtained in Tm(2)O(3)-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm(3+) in this sample is about 0.48 x 10(-20) cm(2) at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm(3+)-doped BaF(2)-Ga(2)O(3)-GeO(2)- La(2)O(3) glass for 2.0-microm optical fiber laser.

Electrocatalytic Oxidation of Formate by [Ni(P R 2N R' 2) 2(CH 3CN)] 2+ Complexes

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

Galan, Brandon R.; Schöffel, Julia; Linehan, John C.

2011-08-17

[Ni(P R 2N R' 2) 2(CH 3CN)] 2+ complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P R 2N R' 2)(P R" 2N R' 2)(CH 3CN)] 2+ with R = Cy, R' = Ph, R" = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO 2, protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ~0.04 M (34 equiv). At concentrationsmore » above ~0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s –1 at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η 1-OC(O)CH 3 binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO 2 liberation. Finally, the pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe) 2] 2+ (depe = 1,2-bis(diethylphosphino)ethane) complex.« less

Electrocatalytic oxidation of formate by [Ni(P(R)2N(R')2)2(CH3CN)]2+ complexes.

PubMed

Galan, Brandon R; Schöffel, Julia; Linehan, John C; Seu, Candace; Appel, Aaron M; Roberts, John A S; Helm, Monte L; Kilgore, Uriah J; Yang, Jenny Y; DuBois, Daniel L; Kubiak, Clifford P

2011-08-17

[Ni(P(R)(2)N(R')(2))(2)(CH(3)CN)](2+) complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P(R)(2)N(R')(2))(P(R''(2))N(R'(2)))(CH(3)CN)](2+) with R = Cy, R' = Ph, R'' = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO(2), protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ∼0.04 M (34 equiv). At concentrations above ∼0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s(-1) at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η(1)-OC(O)CH(3) binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO(2) liberation. The pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe)(2)](2+) (depe = 1,2-bis(diethylphosphino)ethane) complex.

Formation and nitrile hydrogenation performance of Ru nanoparticles on a K-doped Al2O3 surface.

PubMed

Muratsugu, Satoshi; Kityakarn, Sutasinee; Wang, Fei; Ishiguro, Nozomu; Kamachi, Takashi; Yoshizawa, Kazunari; Sekizawa, Oki; Uruga, Tomoya; Tada, Mizuki

2015-10-14

Decarbonylation-promoted Ru nanoparticle formation from Ru3(CO)12 on a basic K-doped Al2O3 surface was investigated by in situ FT-IR and in situ XAFS. Supported Ru3(CO)12 clusters on K-doped Al2O3 were converted stepwise to Ru nanoparticles, which catalyzed the selective hydrogenation of nitriles to the corresponding primary amines via initial decarbonylation, the nucleation of the Ru cluster core, and the growth of metallic Ru nanoparticles on the surface. As a result, small Ru nanoparticles, with an average diameter of less than 2 nm, were formed on the support and acted as efficient catalysts for nitrile hydrogenation at 343 K under hydrogen at atmospheric pressure. The structure and catalytic performance of Ru catalysts depended strongly on the type of oxide support, and the K-doped Al2O3 support acted as a good oxide for the selective nitrile hydrogenation without basic additives like ammonia. The activation of nitriles on the modelled Ru catalyst was also investigated by DFT calculations, and the adsorption structure of a nitrene-like intermediate, which was favourable for high primary amine selectivity, was the most stable structure on Ru compared with other intermediate structures.

Effect of the Molar Ratio of B2O3 to Bi2O3 in Al Paste with Bi2O3-B2O3-ZnO Glass on Screen Printed Contact Formation and Si Solar Cell Performance

NASA Astrophysics Data System (ADS)

Kim, Bit-Na; Kim, Hyeong Jun; Chang, Hyo Sik; Hong, Hyun Seon; Ryu, Sung-Soo; Lee, Heon

2013-10-01

In this study, eco-friendly Pb-free Bi2O3-B2O3-ZnO glass frits were chosen as an inorganic additive for the Al paste used in Si solar cells. The effects of the molar ratio of Bi2O3 to B2O3 in the glass composition on the electrical resistance of the Al electrode and on the cell performance were investigated. The results showed that as the molar ratio of Bi2O3 to B2O3 increased, the glass transition temperature and softening temperature decreased because of the reduced glass viscosity. In Al screen-printed Si solar cells, as the molar ratio of Bi2O3 to B2O3 increased, the sheet electrical resistance of the Al electrode decreased and the cell efficiency increased. The uniformity and thickness of the back-surface field was significantly influenced by the glass composition.

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

NASA Astrophysics Data System (ADS)

Glassell, M.; Robles, J.; Das, R.; Phan, M. H.; Srikanth, H.

Iron oxide nanoparticles especially Fe3O4, γ-Fe2O3 have been extensively studied for magnetic hyperthermia because of their tunable magnetic properties and stable suspension in superparamagnetic regime. However, their relatively low heating capacity hindered practical application. Recently, a large improvement in heating efficiency has been reported in exchange-coupled nanoparticles with exchange coupling between soft and hard magnetic phases. Here, we systematically studied the effect of core and shell size on the heating efficiency of the Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) showed formation of spherical shaped Fe3O4 and Fe3O-/CoFe2O4 nanoparticles. Magnetic measurements showed high magnetization (≅70 emu/g) and superparamagnetic behavior for the nanoparticles at room temperature. Magnetic hyperthermia results showed a large increase in specific absorption rate (SAR) for 8nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of the same size. The heating efficiency of the Fe3O4/CoFe2O4 with 1 nm CoFe2O4 (shell) increased from 207 to 220 W/g (for 800 Oe) with increase in core size from 6 to 8 nm. The heating efficiency of the Fe3O4/CoFe2O4 with 2 nm CoFe2O4 (shell) and core size of 8 nm increased from 220 to 460 W/g (for 800 Oe). These exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.

Mechanism of CO 2 Hydrogenation on Pd/Al 2 O 3 Catalysts: Kinetics and Transient DRIFTS-MS Studies

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

Wang, Xiang; Shi, Hui; Kwak, Ja Hun

The hydrogenation of CO 2 was investigated over a wide range of reaction conditions, using two Pd/γ-Al 2O 3 catalysts with different Pd loadings (5% and 0.5%) and dispersions (~11% and ~100%, respectively). Turnover rates for CO and CH 4 formation were both higher over 5% Pd/Al 2O 3 with a larger average Pd particle size than those over 0.5% Pd/Al 2O 3 with a smaller average particle size. The selectivity to methane (22-40%) on 5% Pd/Al 2O 3 was higher by a factor of 2-3 than that on 0.5% Pd/Al 2O 3. The drastically different rate expressions and apparentmore » energies of activation for CO and CH 4 formation lead us to conclude that reverse water gas shift and CO 2 methanation do not share the same rate-limiting step on Pd, and that the two pathways are probably catalyzed at different surface sites. Measured reaction orders in CO 2 and H 2 pressures were similar over the two catalysts, suggesting that the reaction mechanism for each pathway does not change with particle size. In accordance, the DRIFTS results reveal that the prevalent surface species and their evolution patterns are comparable on the two catalysts during transient and steady-state experiments, switching feed gases among CO 2, H 2 and CO 2+H 2. The DRIFTS and MS results also demonstrate that no direct dissociation of CO 2 takes place over the two catalysts, and that CO 2 has to first react with surface hydroxyls on the oxide support. The thus-formed bicarbonates react with dissociatively adsorbed hydrogen on Pd particles to produce adsorbed formate species (bifunctional catalyst: CO 2 activation on the oxide support, and H 2 dissociation on the metal particles). Formates near the Pd particles (most likely at the metal/oxide interface) can react rapidly with adsorbed H to produce CO, which then adsorbs on the metallic Pd particles. Two types of Pd sites are identified: one has a weak interaction with CO, which easily desorbs into gas phase at reaction temperatures, while the other interacts more

Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia

NASA Astrophysics Data System (ADS)

Robles, J.; Das, R.; Glassell, M.; Phan, M. H.; Srikanth, H.

2018-05-01

We report a systematic study of the effects of core and shell size on the magnetic properties and heating efficiency of exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) confirmed the formation of spherical Fe3O4 and Fe3O4/CoFe2O4 nanoparticles. Magnetic measurements showed high saturation magnetization for the nanoparticles at room temperature. Increasing core diameter (6.4±0.7, 7.8±0.1, 9.6±1.2 nm) and/or shell thickness (˜1, 2, 4 nm) increased the coercive field (HC), while an optimal value of saturation magnetization (MS) was achieved for the Fe3O4 (7.8±0.1nm)/CoFe2O4 (2.1±0.1nm) nanoparticles. Magnetic hyperthermia measurements indicated a large increase in specific absorption rate (SAR) for 8.2±1.1 nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of same size. The SAR of the Fe3O4/CoFe2O4 nanoparticles increased from 199 to 461 W/g for 800 Oe as the thickness of the CoFe2O4 shell was increased from 0.9±0.5 to 2.1±0.1 nm. The SAR enhancement is attributed to a combination of the large MS and the large HC. Therefore, these Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.

Synthesis, crystal structure, and physical properties of the Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8} phases

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

Forbes, Scott; Yuan, Fang; Kosuda, Kosuke

The second and third known rare-earth bismuthide oxides, Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8}, have been discovered via high temperature reactions at 1300 °C. Like its Gd–Sb–O counterparts, the Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8} phases crystallize in the monoclinic C2/m space group, with the latter containing disordered Bi atoms along the b direction of the unit cell. Unlike the RE{sub 8}Sb{sub 3}O{sub 8} series, the formation of the Gd{sub 3}BiO{sub 3} phase does not necessarily precede the formation of Gd{sub 8}Bi{sub 3}O{sub 8}, which is likely due to the difficulty of accommodating bismuth in themore » RE–O framework due to its larger size. Physical property measurements performed on a pure Gd{sub 8}Bi{sub 3}O{sub 8} sample reveal semiconducting behavior. Although electronic structure calculations predict metallic behavior due to an unbalanced electron count, the semiconducting behavior originates from the Anderson localization of the Bi p states near the Fermi level as a result of atomic disorder. - Graphical abstract: Reaction of GdBi and Gd{sub 2}O{sub 3} at high temperatures yields Gd–Bi–O phases. - Highlights: • Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8}, the second and third rare-earth bismuthide oxides, have been discovered. • Gd{sub 3}BiO{sub 3} and Gd{sub 8}Bi{sub 3}O{sub 8} are isostructural with RE{sub 3}SbO{sub 3} and RE{sub 8}Sb{sub 3}O{sub 8}. • Gd{sub 8}Bi{sub 3}O{sub 8} displays semiconducting behavior despite an unbalanced electron count. • Anderson localization of Bi p states results in semiconducting behavior in Gd{sub 8}Bi{sub 3}O{sub 8}.« less

On the Star Formation-AGN Connection at zeta (is) approximately greater than 0.3

NASA Technical Reports Server (NTRS)

LaMassa, Stephanie M.; Heckman, T. M.; Ptak, Andrew; Urry, C. Megan

2013-01-01

Using the spectra of a sample of approximately 28,000 nearby obscured active galaxies from Data Release 7 of the Sloan Digital Sky Survey (SDSS), we probe the connection between active galactic nucleus (AGN) activity and star formation over a range of radial scales in the host galaxy. We use the extinction-corrected luminosity of the [O iii] 5007A line as a proxy of intrinsic AGN power and supermassive black hole (SMBH) accretion rate. The star formation rates (SFRs) are taken from the MPA-JHU value-added catalog and are measured through the 3 inch SDSS aperture. We construct matched samples of galaxies covering a range in redshifts. With increasing redshift, the projected aperture size encompasses increasing amounts of the host galaxy. This allows us to trace the radial distribution of star formation as a function of AGN luminosity. We find that the star formation becomes more centrally concentrated with increasing AGN luminosity and Eddington ratio. This implies that such circumnuclear star formation is associated with AGN activity, and that it increasingly dominates over omnipresent disk star formation at higher AGN luminosities, placing critical constraints on theoretical models that link host galaxy star formation and SMBH fueling. We parameterize this relationship and find that the star formation on radial scales (is) less than 1.7 kpc, when including a constant disk component, has a sub-linear dependence on SMBH accretion rate: SFR in proportion to solar mass(sup 0.36), suggesting that angular momentum transfer through the disk limits accretion efficiency rather than the supply from stellar mass loss.

Formation of hydroxyl radicals and Co3+ in the reaction of Co(2+)-EDTA with hydrogen peroxide. Catalytic effect of Fe3+.

PubMed

Eberhardt, M K; Santos, C; Soto, M A

1993-05-07

Co2+ ions (Co(NO3)2.6H2O) react with H2O2 only in presence of EDTA to yield OH radicals and Co3+. This reaction was carried out in unbuffered aqueous solutions (pH = 2.6). The formation of Co3+ was confirmed by spectroscopy. The Co(3+)-EDTA complex shows two typical absorptions at 382 nm and 532 nm. The Co(3+)-EDTA complex can be prepared by a number of oxidizing agents, like Fe3+, Fe(3+)-EDTA, Ag+, Ag2+, Ce4+, and hydroxyl radicals. Since Fe3+ oxidizes Co(2+)-EDTA to Co(3+)-EDTA and Fe2+ we initiate a chain reaction for .OH formation. Our results show that there are two modes for H2O2 decomposition: (1) One electron transfer to give OH radicals and (2) Decomposition of H2O2 to H2O and O2 without intermediate .OH formation. This reaction depends strongly on the pH of the buffer. The H2O2 decomposition increases with increasing pH and increasing Co2+ concentration.

Phase relations in the system Cu-Gd-O and Gibbs energy of formation of CuGd[sub 2]O[sub 4

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

Jacob, K.T.; Mathews, T.; Hajra, J.P.

1993-07-01

The phase relations in the system Cu-Gd-O have been determined at 1,273 K by X-ray diffraction, optical microscopy, and electron microprobe analysis of samples equilibrated in quartz ampules and in pure oxygen. Only one ternary compound, CuGd[sub 2]O[sub 4], was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt, Cu[sub 2]O + CuGd[sub 2]O[sub 4] + Gd[sub 2]O[sub 3]//(Y[sub 2]O[sub 3])ZrO[sub 2]//CuO + Cu[sub 2]O, Pt in the temperature range of 900 to 1,350 K. For the formation of CuGd[sub 2]O[sub 4] from its binary component oxides, CuOmore » (s) + Gd[sub 2]O[sub 3] (s) [r arrow] CuGd[sub 2]O[sub 4] (s) [Delta]G[degree] = 8230 - 11.2T([plus minus]50)J/mol. Since the formation is endothermic, CuGd[sub 2]O[sub 4] becomes thermodynamically unstable with respect to CuO and Gd[sub 2]O[sub 3] below 735 K. When the oxygen partial pressure over CuGd[sub 2]O[sub 4] is lowered, it decomposes according to the reaction 4CuGd[sub 2]O[sub 4] (s) [r arrow] 4Gd[sub 2]O[sub 3] (s) + 2Cu[sub 2]O (s) + O[sub 2] (g) for which the equilibrium oxygen potential is given by [Delta][mu][sub o][sub 2] = [minus]227,970 + 143.2T([plus minus]500)J/mol. An oxygen potential diagram for the system Cu-Gd-O at 1,273 is presented.« less

Electronic Reconstruction at the Isopolar LaTiO3/LaFeO3 Interface: An X-Ray Photoemission and Density-Functional Theory Study

NASA Astrophysics Data System (ADS)

Kleibeuker, J. E.; Zhong, Z.; Nishikawa, H.; Gabel, J.; Müller, A.; Pfaff, F.; Sing, M.; Held, K.; Claessen, R.; Koster, G.; Rijnders, G.

2014-12-01

We report the formation of a nonmagnetic band insulator at the isopolar interface between the antiferromagnetic Mott-Hubbard insulator LaTiO3 and the antiferromagnetic charge transfer insulator LaFeO3. By density-functional theory calculations, we find that the formation of this interface state is driven by the combination of O band alignment and crystal field splitting energy of the t2 g and eg bands. As a result of these two driving forces, the Fe 3 d bands rearrange and electrons are transferred from Ti to Fe. This picture is supported by x-ray photoelectron spectroscopy, which confirms the rearrangement of the Fe 3 d bands and reveals an unprecedented charge transfer up to 1.2 ±0.2 e-/interface unit cell in our LaTiO3/LaFeO3 heterostructures.

Spatial distribution of hydroxylamine and its role in aerobic N2O formation in a Norway spruce forest soil

NASA Astrophysics Data System (ADS)

Liu, S.; Weymann, D.; Gottselig, N.; Wiekenkamp, I.; Vereecken, H.; Brueggemann, N.

2014-12-01

Hydroxylamine (HA) as a crucial intermediate in the microbial oxidation of ammonium to nitrite (nitrification) is a potential precursor of abiotic N2O formation in the soil. However, the determination of HA concentration in natural soil samples has not been reported until now. Here, we determined the HA concentrations in organic (Oh) and mineral (Ah) layers of 135 soil samples collected from a spruce forest (Wüstebach, Eifel National Park, Germany) using a novel approach, based on the fast extraction of HA from the soil at a pH of 1.7, the oxidation of HA to N2O with Fe3+, and the analysis of produced N2O using gas chromatography (GC). Meanwhile, N2O emission rates were determined by means of aerobic laboratory incubations of 3-g soil in 22-mL vials. Subsequently, the spatial distribution of soil HA concentrations and N2O emission rates in the Oh and Ah layers of the whole sampling area were analyzed using a geostatistical approach. The correlations among soil HA, N2O emission rate, pH, soil C, N, Fe, Mn and soil water content (SWC) were further explored. The HA concentrations ranged from 0.3-44.6 μg N kg-1 dry soil and 0.02-16.2 μg N kg-1 dry soil in the Oh and the Ah layer, respectively. The spatial distribution of HA was similar in both layers, with substantial spatial variability dependent on soil type, tree density and distance to a stream. For example, HA concentration was greater at locations with a thick litter layer or at locations close to the stream. The average N2O emission rate in the Oh layer was 0.38 μg N kg-1 dry soil h-1, 10-fold larger than in the Ah layer. Interestingly, N2O emission rate exhibited high correlation with soil HA content in the Oh (R2 = 0.65, p < 0.01) and Ah (R2 = 0.45, p < 0.05) layer. The results demonstrated that HA is a crucial component for aerobic N2O formation and emission in spruce forest soils. Moreover, HA concentration was negatively correlated with pH and positively correlated with SWC in the Oh layer, while

Influence of Y2O3 Addition on Crystallization, Thermal, Mechanical, and Electrical Properties of BaO-Al2O3-B2O3-SiO2 Glass-Ceramic for Ceramic Ball Grid Array Package

NASA Astrophysics Data System (ADS)

Li, Bo; Li, Wei; Zheng, Jingguo

2018-01-01

Y2O3 addition has a significant influence on the crystallization, thermal, mechanical, and electrical properties of BaO -Al2O3 -B2O3 -SiO2 (BABS) glass-ceramics. Semi-quantitative calculation based on x-ray diffraction demonstrated that with increasing Y2O3 content, both the crystallinity and the phase content of cristobalite gradually decreased. It is effective for the additive Y2O3 to inhibit the formation of cristobalite phase with a large coefficient of thermal expansion value. The flexural strength and the Young's modulus, thus, are remarkably increased from 140 MPa to 200 MPa and 56.5 GPa to 63.7 GPa, respectively. Also, the sintering kinetics of BABS glass-ceramics with various Y2O3 were investigated using the isothermal sintering shrinkage curve at different sintering temperatures. The sintering activation energy Q sharply decreased from 99.8 kJ/mol to 81.5 kJ/mol when 0.2% Y2O3 was added, which indicated that a small amount of Y2O3 could effectively promote the sintering procedure of BABS glass-ceramics.

SMA observations of the W3(OH) complex: Dynamical differentiation between W3(H2O) and W3(OH)

NASA Astrophysics Data System (ADS)

Qin, Sheng-Li; Schilke, Peter; Wu, Jingwen; Liu, Tie; Wu, Yuefang; Sánchez-Monge, Álvaro; Liu, Ying

2016-03-01

We present Submillimeter Array observations of the HCN (3-2) and HCO+ (3-2) molecular lines towards the W3(H2O) and W3(OH) star-forming complexes. Infall and outflow motions in the W3(H2O) have been characterized by observing HCN and HCO+ transitions. High-velocity blue/red-shifted emission, tracing the outflow, show multiple knots, which might originate in episodic and precessing outflows. `Blue-peaked' line profiles indicate that gas is infalling on to the W3(H2O) dust core. The measured large mass accretion rate, 2.3 × 10-3 M⊙ yr-1, together with the small free-fall time-scale, 5 × 103 yr, suggest W3(H2O) is in an early evolutionary stage of the process of formation of high-mass stars. For the W3(OH), a two-layer model fit to the HCN and HCO+ spectral lines and Spizter/Infrared Array Camera (IRAC) images support that the W3(OH) H II region is expanding and interacting with the ambient gas, with the shocked neutral gas being expanding with an expansion time-scale of 6.4 × 103 yr. The observations suggest different kinematical time-scales and dynamical states for the W3(H2O) and W3(OH).

About recent star formation rates inferences

NASA Astrophysics Data System (ADS)

Cerviño, M.; Bongiovanni, A.; Hidalgo, S.

2017-03-01

Star Formation Rate (SFR) inferences are based in the so-called constant SFR approximation, where synthesis models are require to provide a calibration; we aims to study the key points of such approximation to produce accurate SFR inferences. We use the intrinsic algebra used in synthesis models, and we explore how SFR can be inferred from the integrated light without any assumption about the underling Star Formation history (SFH). We show that the constant SFR approximation is actually a simplified expression of more deeper characteristics of synthesis models: It is a characterization of the evolution of single stellar populations (SSPs), acting the SSPs as sensitivity curve over different measures of the SFH can be obtained. As results, we find that (1) the best age to calibrate SFR indices is the age of the observed system (i.e. about 13 Gyr for z = 0 systems); (2) constant SFR and steady-state luminosities are not requirements to calibrate the SFR ; (3) it is not possible to define a SFR single time scale over which the recent SFH is averaged, and we suggest to use typical SFR indices (ionizing flux, UV fluxes) together with no typical ones (optical/IR fluxes) to correct the SFR from the contribution of the old component of the SFH, we show how to use galaxy colors to quote age ranges where the recent component of the SFH is stronger/softer than the older component. Particular values of SFR calibrations are (almost) not affect by this work, but the meaning of what is obtained by SFR inferences does. In our framework, results as the correlation of SFR time scales with galaxy colors, or the sensitivity of different SFR indices to sort and long scale variations in the SFH, fit naturally. In addition, the present framework provides a theoretical guideline to optimize the available information from data/numerical experiments to improve the accuracy of SFR inferences. More info en Cerviño, Bongiovanni & Hidalgo A&A 588, 108C (2016)

Importance of ERK activation in As2O3-induced differentiation and promyelocytic leukemia nuclear bodies formation in neuroblastoma cells.

PubMed

Petit, A; Delaune, A; Falluel-Morel, A; Goullé, J-P; Vannier, J-P; Dubus, I; Vasse, M

2013-11-01

Neuroblastoma malignant cell growth is dependent on their undifferentiated status. Arsenic trioxide (As2O3) induces neuroblastoma cell differentiation in vitro, but its mechanisms still remains unknown. We used three human neuroblastoma cell lines (SH-SY5Y, IGR-N-91, LAN-1) that differ from their MYCN and p53 status to explore the intracellular events activated by As2O3 and involved in neurite outgrowth, a morphological marker of differentiation. As2O3 (2μM) induced neurite outgrowth in all cell lines, which was dependent on ERK activation but independent on MYCN status. This process was induced either by a sustained (3 days) or a transient (2h) incubation with As2O3, indicating that very early events trigger the induction of differentiation. In parallel, As2O3 induced a rapid assembly of promyelocytic leukemia nuclear bodies (PML-NB) in an ERK-dependent manner. In conclusion, mechanisms leading to neuroblastoma cell differentiation in response to As2O3 appear to involve the ERK pathway activation and PML-NB formation, which are observed in response to other differentiating molecules such as retinoic acid derivates. This open new perspectives based on the use of treatment combinations to potentiate the differentiating effects of each drug alone and reduce their adverse side effects. Copyright © 2013 Elsevier Ltd. All rights reserved.

Oxygen potentials in Ni + NiO and Ni + Cr2O3 + NiCr2O4 systems

NASA Astrophysics Data System (ADS)

Kale, G. M.; Fray, D. J.

1994-06-01

The chemical potential of O for the coexistence of Ni + NiO and Ni + Cr2O3 + NiCr2O4 equilibria has been measured employing solid-state galvanic cells, (+) Pt, Cu + Cu2O // (Y2O3)ZrO2 // Ni + NiO, Pt (-) and (+) Pt, Ni + NiO // (Y2O3)ZrO2 // Ni + Cr2O3 + NiCr2O4, Pt (-) in the temperature range of 800 to 1300 K and 1100 to 1460 K, respectively. The electromotive force (emf) of both the cells was reversible, reproducible on thermal cycling, and varied linearly with temperature. For the coexistence of the two-phase mixture of Ni + NiO, δΜO 2(Ni + NiO) = -470,768 + 171.77T (±20) J mol-1 (800 ≤ T ≤ 1300 K) and for the coexistence of Ni + Cr2O3 + NiCr2O4, δΜO 2(Ni + Cr2O3 + NiCr2O4) = -523,190 + 191.07T (±100) J mol-1 (1100≤ T≤ 1460 K) The “third-law” analysis of the present results for Ni + NiO gives the value of ‡H{298/o} = -239.8 (±0.05) kJ mol-1, which is independent of temperature, for the formation of one mole of NiO from its elements. This is in excellent agreement with the calorimetric enthalpy of formation of NiO reported in the literature.

Pilot-scale treatment of atrazine production wastewater by UV/O3/ultrasound: Factor effects and system optimization.

PubMed

Jing, Liang; Chen, Bing; Wen, Diya; Zheng, Jisi; Zhang, Baiyu

2017-12-01

This study shed light on removing atrazine from pesticide production wastewater using a pilot-scale UV/O 3 /ultrasound flow-through system. A significant quadratic polynomial prediction model with an adjusted R 2 of 0.90 was obtained from central composite design with response surface methodology. The optimal atrazine removal rate (97.68%) was obtained at the conditions of 75 W UV power, 10.75 g h -1 O 3 flow rate and 142.5 W ultrasound power. A Monte Carlo simulation aided artificial neural networks model was further developed to quantify the importance of O 3 flow rate (40%), UV power (30%) and ultrasound power (30%). Their individual and interaction effects were also discussed in terms of reaction kinetics. UV and ultrasound could both enhance the decomposition of O 3 and promote hydroxyl radical (OH·) formation. Nonetheless, the dose of O 3 was the dominant factor and must be optimized because excess O 3 can react with OH·, thereby reducing the rate of atrazine degradation. The presence of other organic compounds in the background matrix appreciably inhibited the degradation of atrazine, while the effects of Cl - , CO 3 2- and HCO 3 - were comparatively negligible. It was concluded that the optimization of system performance using response surface methodology and neural networks would be beneficial for scaling up the treatment by UV/O 3 /ultrasound at industrial level. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of calcination routes on phase formation of BaTiO3 and their electronic and magnetic properties

NASA Astrophysics Data System (ADS)

Majumder, Supriyo; Choudhary, R. J.; Tripathi, M.; Phase, D. M.

2018-05-01

We have investigated the phase formation and correlation between electronic and magnetic properties of oxygen deficient BaTiO3 ceramics, synthesized by solid state reaction method, following different calcination paths. The phase analysis divulge that a higher calcination temperature above 1000° C is favored for tetragonal phase formation than the cubic phase. The core level X-ray photo electron spectroscopy measurements confirm the presence of oxygen vacancies and oxygen vacancy mediated Ti3+ states. As the calcination temperature and calcination time increases these oxygen vacancies and hence Ti3+ concentrations reduce in the sample. The temperature dependent magnetization curves suggest unexpected magnetic ordering, which may be due to the presence of unpaired electron at the t2g state (d1) of nearest-neighbor Ti atoms. In magnetization vs magnetic field isotherms, the regular decrease of saturation moment value with increasing calcination temperature and calcination time, can be discussed considering the amount of oxygen deficiency induced Ti3+ concentrations, present in the sample.

The Evolution and Physical Parameters of WN3/O3s: A New Type of Wolf–Rayet Star

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

Neugent, Kathryn F.; Massey, Philip; Hillier, D. John

As part of a search for Wolf–Rayet (WR) stars in the Magellanic Clouds, we have discovered a new type of WR star in the Large Magellanic Cloud (LMC). These stars have both strong emission lines, as well as He ii and Balmer absorption lines and spectroscopically resemble a WN3 and O3V binary pair. However, they are visually too faint to be WN3+O3V binary systems. We have found nine of these WN3/O3s, making up ∼6% of the population of LMC WRs. Using cmfgen, we have successfully modeled their spectra as single stars and have compared the physical parameters with those ofmore » more typical LMC WNs. Their temperatures are around 100,000 K, a bit hotter than the majority of WN stars (by around 10,000 K), though a few hotter WNs are known. The abundances are what you would expect for CNO equilibrium. However, most anomalous are their mass-loss rates, which are more like that of an O-type star than a WN star. While their evolutionary status is uncertain, their low mass-loss rates and wind velocities suggest that they are not products of homogeneous evolution. It is possible instead that these stars represent an intermediate stage between O stars and WNs. Since WN3/O3 stars are unknown in the Milky Way, we suspect that their formation depends upon metallicity, and we are investigating this further by a deep survey in M33, which possesses a metallicity gradient.« less

Measuring star formation rates in blue galaxies

NASA Technical Reports Server (NTRS)

Gallagher, John S., III; Hunter, Deidre A.

1987-01-01

The problems associated with measurements of star formation rates in galaxies are briefly reviewed, and specific models are presented for determinations of current star formation rates from H alpha and Far Infrared (FIR) luminosities. The models are applied to a sample of optically blue irregular galaxies, and the results are discussed in terms of star forming histories. It appears likely that typical irregular galaxies are forming stars at nearly constant rates, although a few examples of systems with enhanced star forming activity are found among HII regions and luminous irregular galaxies.

Physical properties and surface/interface analysis of nanocrystalline WO3 films grown under variable oxygen gas flow rates

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

Vemuri, R. S.; Carbjal-Franco, G.; Ferrer, D. A.

2012-10-15

Nanocrystalline WO3 films were grown by reactive magnetron sputter-deposition in a wide range of oxygen gas flow rates while keeping the deposition temperature fixed at 400 oC. The physical characteristics of WO3 films were evaluated using grazing incidence X-ray diffraction (GIXRD), X-ray reflectivity (XRR) and transmission electron microscopy (TEM) measurements. Physical characterization indicates that the thickness, grain size, and density of WO3 films are sensitive to the oxygen gas flow rate during deposition. XRD data indicates the formation of tetragonal WO3 films. The grain size increases from 21 to 25 nm with increasing oxygen gas flow rate to 65%, atmore » which point the grain size exhibits a decreasing trend to attain the lowest value of 15 nm at 100% oxygen. TEM analysis provides a model consisting of isotropic WO3 film (nanocrystalline)-SiO2 interface (amorphous)-Si(100) substrate. XRR simulations, which are based on this model, provide excellent agreement to the experimental data indicating that the normalized thickness of WO3 films decreases with the increasing oxygen gas flow rate. The density of WO3 films increases with increasing oxygen gas flow rate.« less

High rate DC-reactive sputter deposition of Y 2O 3 film on the textured metal substrate for the superconducting coated conductor

NASA Astrophysics Data System (ADS)

Kim, Ho-Sup; Park, Chan; Ko, Rock-Kil; Shi, Dongqui; Chung, Jun-Ki; Ha, Hong-Soo; Park, Yu-Mi; Song, Kyu-Jeong; Youm, Do-Jun

2005-10-01

Y2O3 film was directly deposited on Ni-3at%W substrate by DC reactive sputtering. DC reactive sputtering was carried out using metallic Y target and water vapor for oxidizing the elements of metallic target on the substrate. The detailed conditions of DC reactive sputtering for depositions of Y2O3 films were investigated. The window of water vapor for proper growth of Y2O3 films was determined by sufficient oxidations of the Y2O3 films and the non-oxidation of the target surface, which was required for high rate sputtering. The window turned out to be fairly wide in the chamber used. As the sputtering power was raised, the deposition rate increased without narrowing the window. The fabricated Y2O3 films showed good texture qualities and surface morphologies. The YBCO film deposited directly on the Y2O3 buffered Ni-3at%W substrate showed Tc, Ic (77 K, self field), and Jc (77 K, self field) of 89 K, 64 A/cm and 1.1 MA/cm2, respectively.

Carrier density independent scattering rate in SrTiO3-based electron liquids

PubMed Central

Mikheev, Evgeny; Raghavan, Santosh; Zhang, Jack Y.; Marshall, Patrick B.; Kajdos, Adam P.; Balents, Leon; Stemmer, Susanne

2016-01-01

We examine the carrier density dependence of the scattering rate in two- and three-dimensional electron liquids in SrTiO3 in the regime where it scales with Tn (T is the temperature and n ≤ 2) in the cases when it is varied by electrostatic control and chemical doping, respectively. It is shown that the scattering rate is independent of the carrier density. This is contrary to the expectations from Landau Fermi liquid theory, where the scattering rate scales inversely with the Fermi energy (EF). We discuss that the behavior is very similar to systems traditionally identified as non-Fermi liquids (n < 2). This includes the cuprates and other transition metal oxide perovskites, where strikingly similar density-independent scattering rates have been observed. The results indicate that the applicability of Fermi liquid theory should be questioned for a much broader range of correlated materials and point to the need for a unified theory. PMID:26861764

Influence of reaction conditions on formation of ionic liquid-based nanostructured Bi2O3 as an efficient visible-light-driven photocatalyst

NASA Astrophysics Data System (ADS)

Bagheri, Mozhgan; Heydari, Mojgan; Vaezi, Mohammad Reza

2018-01-01

In this study, nanostructured bismuth oxide was synthesized based on the chemical reaction of bismuth nitrate and NaOH in the ionic liquid 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) under ultrasonic irradiation. The effect of sodium hydroxide with a different molar ratio of NaOH to bismuth in the range of 3-10 was investigated. The results of fourier-transform infrared spectroscopy (FT-IR) and X-ray powder diffraction (XRD) showed that NaOH has a critical role in the formation of pure α-Bi2O3. So, at high concentrations of NaOH (NaOH:Bi ≥ 7.5), the chloride anion from the ionic liquid cannot be entered into the crystalline structure of bismuth oxide, which resulted in the formation of pure bismuth oxide, while at lower concentrations of NaOH (NaOH:Bi ≤ 5), Bi3O4Cl was formed with a layered structure. The XRD results revealed that the synthesized α-Bi2O3 has a monoclinic structure and scanning electron microscopy (SEM) images showed that the sample consists of needle like particles with an average thickness of 50 nm. The ionic liquid has an important role in the prevention of an agglomeration of particles in the Bi2O3 sample. The photocatalytic activity of the synthesized Bi2O3 was investigated to study the degradation of malachite green dye as a model pollutant under visible light. The effects of various parameters such as the pH, concentration of the dye, and the catalyst on the degradation of malachite green were also investigated.

Direct observation of ozone formation on SiO2 surfaces in O2 discharges

NASA Astrophysics Data System (ADS)

Marinov, D.; Guaitella, O.; Booth, J. P.; Rousseau, A.

2013-01-01

Ozone production is studied in a pulsed O2 discharge at pressures in the range 1.3-6.7 mbar. Time-resolved absolute concentrations of O3 and O are measured in the post-discharge using UV absorption spectroscopy and two-photon absorption laser-induced fluorescence. In a bare silica discharge tube ozone is formed mainly by three-body gas-phase recombination. When the tube surface is covered by a high specific surface silica catalyst heterogeneous formation becomes the main source of ozone. The efficiency of this surface process increases with O2 pressure and is favoured by the presence of OH groups and adsorbed H2O on the surface. At p = 6.7 mbar ozone production accounts for up to 25% of the atomic oxygen losses on the surface.

Characterization of bacterial community and iron corrosion in drinking water distribution systems with O3-biological activated carbon treatment.

PubMed

Xing, Xueci; Wang, Haibo; Hu, Chun; Liu, Lizhong

2018-07-01

Bacterial community structure and iron corrosion were investigated for simulated drinking water distribution systems (DWDSs) composed of annular reactors incorporating three different treatments: ozone, biologically activated carbon and chlorination (O 3 -BAC-Cl 2 ); ozone and chlorination (O 3 -Cl 2 ); or chlorination alone (Cl 2 ). The lowest corrosion rate and iron release, along with more Fe 3 O 4 formation, occurred in DWDSs with O 3 -BAC-Cl 2 compared to those without a BAC filter. It was verified that O 3 -BAC influenced the bacterial community greatly to promote the relative advantage of nitrate-reducing bacteria (NRB) in DWDSs. Moreover, the advantaged NRB induced active Fe(III) reduction coupled to Fe(II) oxidation, enhancing Fe 3 O 4 formation and inhibiting corrosion. In addition, O 3 -BAC pretreatment could reduce high-molecular-weight fractions of dissolved organic carbon effectively to promote iron particle aggregation and inhibit further iron release. Our findings indicated that the O 3 -BAC treatment, besides removing organic pollutants in water, was also a good approach for controlling cast iron corrosion and iron release in DWDSs. Copyright © 2017. Published by Elsevier B.V.

Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.

PubMed

Cox, Nicholas; Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A; Boussac, Alain; Lubitz, Wolfgang

2014-08-15

The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S3) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectroscopy reveals that all four manganese ions of the catalyst are structurally and electronically similar immediately before the final oxygen evolution step; they all exhibit a 4+ formal oxidation state and octahedral local geometry. Only one structural model derived from quantum chemical modeling is consistent with all magnetic resonance data; its formation requires the binding of an additional water molecule. O-O bond formation would then proceed by the coupling of two proximal manganese-bound oxygens in the transition state of the cofactor. Copyright © 2014, American Association for the Advancement of Science.

Microstructure, Thermal, Mechanical, and Dielectric Properties of BaO-CaO-Al2O3-B2O3-SiO2 Glass-Ceramics

NASA Astrophysics Data System (ADS)

Li, Bo; Bian, Haibo; Fang, Yi

2017-12-01

BaO-CaO-Al2O3-B2O3-SiO2 (BCABS) glass-ceramics were prepared via the method of controlled crystallization. The effect of CaO modification on the microstructure, phase evolution, as well as thermal, mechanical, and dielectric properties was investigated. XRD identified that quartz is the major crystal phase; cristobalite and bazirite are the minor crystal phases. Moreover, the increase of CaO could inhibit the phase transformation from quartz to cristobalite, but excessive CaO would increase the porosity of the ceramics. Additionally, with increasing the amount of CaO, the thermal expansion curve tends to be linear, and subsequently the CTE value decreases gradually, which is attributed to the decrease of cristobalite with high CTE and the formation of CaSiO3 with low CTE. The results indicated that a moderate amount of CaO helps attaining excellent mechanical, thermal, and dielectric properties, that is, the specimen with 9 wt% CaO sintered at 950 °C has a high CTE value (11.5 × 10-6/°C), a high flexural strength (165.7 MPa), and good dielectric properties (ɛr = 6.2, tanδ = 1.8 × 10-4, ρ = 4.6 × 1011 Ω•cm).

Monodisperse Zn-doped Fe3O4 formation and photo-Fenton activity for degradation of rhodamine B in water

NASA Astrophysics Data System (ADS)

Cen, Huoshi; Nan, Zhaodong

2018-10-01

Zn-doped Fe3O4 can be used as a catalyst in the photo-Fenton process to degrade dye molecules dissolved in water, in which cluster-shaped Zn-doped Fe3O4 (CSZnFe) was synthesized. To enhance the catalytic activity, monodisperse Zn-doped Fe3O4 (MZnFe) was facilely synthesized by a modified solvothermal method through replacement of sodium acetate by urea as a base. The particle size of MZnFe was about 9-16 nm. MZnFe exhibits a larger surface area and higher photo-Fenton catalytic activity for degradation of rhodamine B in water than CSZnFe. Additionally, MZnFe exhibits high saturation magnetization (about 80 emu/g), which is very convenient for separation of MZnFe from solution by a magnet. The growth processes for MZnFe were proposed on the basis of results from in situ calorimetry and other techniques, which indicated different formation mechanisms for MZnFe and CSZnFe.

A comparative study of CeO2-Al2O3 support prepared with different methods and its application on MoO3/CeO2-Al2O3 catalyst for sulfur-resistant methanation

NASA Astrophysics Data System (ADS)

Jiang, Minhong; Wang, Baowei; Yao, Yuqin; Li, Zhenhua; Ma, Xinbin; Qin, Shaodong; Sun, Qi

2013-11-01

The CeO2-Al2O3 supports prepared with impregnation (IM), deposition precipitation (DP), and solution combustion (SC) methods for MoO3/CeO2-Al2O3 catalyst were investigated in the sulfur-resistant methanation. The supports and catalysts were characterized by N2-physisorption, transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy (RS), and temperature-programmed reduction (TPR). The N2-physisorption results indicated that the DP method was favorable for obtaining better textural properties. The TEM and RS results suggested that there is a CeO2 layer on the surface of the support prepared with DP method. This CeO2 layer not only prevented the interaction between MoO3 and γ-Al2O3 to form Al2(MoO4)3 species, but also improved the dispersion of MoO3 in the catalyst. Accordingly, the catalysts whose supports were prepared with DP method exhibited the best catalytic activity. The catalysts whose supports were prepared with SC method had the worst catalytic activity. This was caused by the formation of Al2(MoO4)3 and crystalline MoO3. Additionally, the CeO2 layer resulted in the instability of catalysts in reaction process. The increasing of calcination temperature of supports reduced the catalytic activity of all catalysts. The decrease extent of the catalysts whose supports were prepared with DP method was the lowest as the CeO2 layer prevented the interaction between MoO3 and γ-Al2O3.

Rate constant for the reaction SO + BrO yields SO2 + Br

NASA Technical Reports Server (NTRS)

Brunning, J.; Stief, L.

1986-01-01

The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

Effects of frit addition on the surface morphology and structural properties of ZnO-Bi2O3-Mn2O3 discs

NASA Astrophysics Data System (ADS)

Shahardin, Ahmad Hajidi; Mahmud, Shahrom; Sendi, Rabab Khalid

2015-04-01

ZnO-Bi2O3-Mn2O3 discs were prepared using conventional ceramic processing method and sintered at 1000°C. The different percentages of frit on the ZnO-Bi2O3-Mn2O3 discs were 0.0%, 0.5%, 1.0% and 3.0%. From FESEM observation, the grain structure and grain growth were more uniformly constructed and well distributed. Frit addition was found to cause a big drop in the average grain size from 4.59 µm to 2.76 µm even with an addition of 0.5 mol%. The Si and Al content in the frit recipe might have played a role as inhibiting agents in grain growth during sintering. RAMAN intensity and phase shifting were not affected by frit addition except at 3 mol%. Frit addition did not affect the formation of secondary phases. Frit addition below 3 mol% in ZnO-Bi2O3-Mn2O3 varistor discs can be used as a method in controlling grain size without affecting other properties.

Reactivity of OH and CH3OH Between 22 and 64 K: Modelling the Gas Phase Production of CH3O in Barnard 1B

PubMed Central

Antiñolo, M.; Agúndez, M.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Dib, G. El; Albaladejo, J.; Cernicharo, J.

2016-01-01

In the last years, ultra-low temperature chemical kinetic experiments have demonstrated that some gas-phase reactions are much faster than previously thought. One example is the reaction between OH and CH3OH, which has been recently found to be accelerated at low temperatures yielding CH3O as main product. This finding opened the question of whether the CH3O observed in the dense core Barnard 1b could be formed by the gas-phase reaction of CH3OH and OH. Several chemical models including this reaction and grain-surface processes have been developed to explain the observed abundance of CH3O with little success. Here we report for the first time rate coefficients for the gas-phase reaction of OH and CH3OH down to a temperature of 22 K, very close to those in cold interstellar clouds. Two independent experimental set-ups based on the supersonic gas expansion technique coupled to the pulsed laser photolysis-laser induced fluorescence technique were used to determine rate coefficients in the temperature range 22-64 K. The temperature dependence obtained in this work can be expressed as k(22-64 K) = (3.6 ± 0.1) × 10−12(T/300 K)−(1.0±0.2) cm3 molecule−1 s−1. Implementing this expression in a chemical model of a cold dense cloud results in CH3O/CH3OH abundance ratios similar or slightly lower than the value of ∼ 3 × 10−3 observed in Barnard 1b. This finding confirms that the gas-phase reaction between OH and CH3OH is an important contributor to the formation of interstellar CH3O. The role of grain-surface processes in the formation of CH3O, although it cannot be fully neglected, remains controversial. PMID:27279655

Reactivity of OH and CH3OH Between 22 and 64 K: Modelling the Gas Phase Production of CH3O in Barnard 1B.

PubMed

Antiñolo, M; Agúndez, M; Jiménez, E; Ballesteros, B; Canosa, A; Dib, G El; Albaladejo, J; Cernicharo, J

2016-05-20

In the last years, ultra-low temperature chemical kinetic experiments have demonstrated that some gas-phase reactions are much faster than previously thought. One example is the reaction between OH and CH 3 OH, which has been recently found to be accelerated at low temperatures yielding CH 3 O as main product. This finding opened the question of whether the CH 3 O observed in the dense core Barnard 1b could be formed by the gas-phase reaction of CH 3 OH and OH. Several chemical models including this reaction and grain-surface processes have been developed to explain the observed abundance of CH 3 O with little success. Here we report for the first time rate coefficients for the gas-phase reaction of OH and CH 3 OH down to a temperature of 22 K, very close to those in cold interstellar clouds. Two independent experimental set-ups based on the supersonic gas expansion technique coupled to the pulsed laser photolysis-laser induced fluorescence technique were used to determine rate coefficients in the temperature range 22-64 K. The temperature dependence obtained in this work can be expressed as k (22-64 K) = (3.6 ± 0.1) × 10 -12 ( T/ 300 K) -(1.0±0.2) cm 3 molecule -1 s -1 . Implementing this expression in a chemical model of a cold dense cloud results in CH 3 O/CH 3 OH abundance ratios similar or slightly lower than the value of ∼ 3 × 10 -3 observed in Barnard 1b. This finding confirms that the gas-phase reaction between OH and CH 3 OH is an important contributor to the formation of interstellar CH 3 O. The role of grain-surface processes in the formation of CH 3 O, although it cannot be fully neglected, remains controversial.

Self-Assembled Amphiphilic Water Oxidation Catalysts: Control of O-O Bond Formation Pathways by Different Aggregation Patterns.

PubMed

Yang, Bing; Jiang, Xin; Guo, Qing; Lei, Tao; Zhang, Li-Ping; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

2016-05-17

The oxidation of water to molecular oxygen is the key step to realize water splitting from both biological and chemical perspective. In an effort to understand how water oxidation occurs on a molecular level, a large number of molecular catalysts have been synthesized to find an easy access to higher oxidation states as well as their capacity to make O-O bond. However, most of them function in a mixture of organic solvent and water and the O-O bond formation pathway is still a subject of intense debate. Herein, we design the first amphiphilic Ru-bda (H2 bda=2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts (WOCs) of formula [Ru(II) (bda)(4-OTEG-pyridine)2 ] (1, OTEG=OCH2 CH2 OCH2 CH2 OCH3 ) and [Ru(II) (bda)(PySO3 Na)2 ] (2, PySO3 (-) =pyridine-3-sulfonate), which possess good solubility in water. Dynamic light scattering (DLS), scanning electron microscope (SEM), critical aggregation concentration (CAC) experiments and product analysis demonstrate that they enable to self-assemble in water and form the O-O bond through different routes even though they have the same bda(2-) backbone. This work illustrates for the first time that the O-O bond formation pathway can be regulated by the interaction of ancillary ligands at supramolecular level. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A computational study of the addition of ReO3L (L = Cl(-), CH3, OCH3 and Cp) to ethenone.

PubMed

Aniagyei, Albert; Tia, Richard; Adei, Evans

2016-01-01

The periselectivity and chemoselectivity of the addition of transition metal oxides of the type ReO3L (L = Cl, CH3, OCH3 and Cp) to ethenone have been explored at the MO6 and B3LYP/LACVP* levels of theory. The activation barriers and reaction energies for the stepwise and concerted addition pathways involving multiple spin states have been computed. In the reaction of ReO3L (L = Cl(-), OCH3, CH3 and Cp) with ethenone, the concerted [2 + 2] addition of the metal oxide across the C=C and C=O double bond to form either metalla-2-oxetane-3-one or metalla-2,4-dioxolane is the most kinetically favored over the formation of metalla-2,5-dioxolane-3-one from the direct [3 + 2] addition pathway. The trends in activation and reaction energies for the formation of metalla-2-oxetane-3-one and metalla-2,4-dioxolane are Cp < Cl(-) < OCH3 < CH3 and Cp < OCH3 < CH3 < Cl(-) and for the reaction energies are Cp < OCH3 < Cl(-) < CH3 and Cp < CH3 < OCH3 < Cl CH3. The concerted [3 + 2] addition of the metal oxide across the C=C double of the ethenone to form species metalla-2,5-dioxolane-3-one is thermodynamically the most favored for the ligand L = Cp. The direct [2 + 2] addition pathways leading to the formations of metalla-2-oxetane-3-one and metalla-2,4-dioxolane is thermodynamically the most favored for the ligands L = OCH3 and Cl(-). The difference between the calculated [2 + 2] activation barriers for the addition of the metal oxide LReO3 across the C=C and C=O functionalities of ethenone are small except for the case of L = Cl(-) and OCH3. The rearrangement of the metalla-2-oxetane-3-one-metalla-2,5-dioxolane-3-one even though feasible, are unfavorable due to high activation energies of their rate-determining steps. For the rearrangement of the metalla-2-oxetane-3-one to metalla-2,5-dioxolane-3-one, the trends in activation barriers is found to follow the order OCH3 < Cl(-) < CH3 < Cp. The trends in the activation energies for

Effects of nano-YAG (Y 3Al 5O 12) crystallization on the structure and photoluminescence properties of Nd 3+-doped K 2O-SiO 2-Y 2O 3-Al 2O 3 glasses

NASA Astrophysics Data System (ADS)

Tarafder, Anal; Molla, Atiar Rahaman; Karmakar, Basudeb

2010-10-01

Nd 3+-doped precursor glass in the K 2O-SiO 2-Y 2O 3-Al 2O 3 (KSYA) system was prepared by the melt-quench technique. The transparent Y 3Al 5O 12 (YAG) glass-ceramics were derived from this glass by a controlled crystallization process at 750 °C for 5-100 h. The formation of YAG crystal phase, size and morphology with progress of heat-treatment was examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transformed infrared reflectance spectroscopy (FT-IRRS). The crystallite sizes obtained from XRD are found to increase with heat-treatment time and vary in the range 25-40 nm. The measured photoluminescence spectra have exhibited emission transitions of 4F 3/2 → 4I J ( J = 9/2, 11/2 and 13/2) from Nd 3+ ions upon excitation at 829 nm. It is observed that the photoluminescence intensity and excited state lifetime of Nd 3+ ions decrease with increase in heat-treatment time. The present study indicates that the incorporation of Nd 3+ ions into YAG crystal lattice enhance the fluorescence performance of the glass-ceramic nanocomposites.

Kinetics of O{sub 2}({sup 1{Sigma}}) formation in the reaction O{sub 2}({sup 1{Delta}}) + O{sub 2}({sup 1{Delta}}) {yields} O{sub 2}({sup 1{Sigma}}) + O{sub 2}({sup 3{Sigma}})

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

Zagidullin, M V; Khvatov, N A; Nyagashkin, A Yu

2011-02-28

The dependence of the ratio of specific powers of dimole radiation of singlet oxygen in the 634 nm band and in the b - X band of the O{sub 2}({sup 1{Sigma}}) molecule in the O{sub 2}(X) - O{sub 2}({sup 1{Delta}}) - O{sub 2}({sup 1{Sigma}}) - H{sub 2}O - CO{sub 2} mixture on the CO{sub 2} concentration is measured. As a result, the rate constant of the reaction O{sub 2}({sup 1{Delta}}) + O{sub 2}({sup 1{Delta}}) {yields} O{sub 2}({sup 1{Sigma}}) + O{sub 2}({sup 3{Sigma}}) at the temperature {approx}330 K is found to equal (4.5 {+-} 1.1) 10{sup -17} cm{sup 3} s{sup -1}.more » (active media)« less

Elevated tropospheric CO2 and O3 may not alter initial wood decomposition rate or wood-decaying fungal community composition of Northern hardwoods

Treesearch

Emmanuel Ebanyenle; Andrew J. Burton; Andrew J. Storer; Dana L. Richter; Jessie A. Glaeser

2016-01-01

We examined the effects of elevated CO2 and/or O3 on the wood-decaying basidiomycete fungal community and wood decomposition rates at the Aspen Free-Air CO2 and O3 Enrichment (Aspen FACE) project. Mass loss rates were determined after one year of log decomposition on the soil...

Optical properties of the Al2O3/SiO2 and Al2O3/HfO2/SiO2 antireflective coatings

NASA Astrophysics Data System (ADS)

Marszałek, Konstanty; Winkowski, Paweł; Jaglarz, Janusz

2014-01-01

Investigations of bilayer and trilayer Al2O3/SiO2 and Al2O3/HfO2/SiO2 antireflective coatings are presented in this paper. The oxide films were deposited on a heated quartz glass by e-gun evaporation in a vacuum of 5 × 10-3 [Pa] in the presence of oxygen. Depositions were performed at three different temperatures of the substrates: 100 °C, 200 °C and 300 °C. The coatings were deposited onto optical quartz glass (Corning HPFS). The thickness and deposition rate were controlled with Inficon XTC/2 thickness measuring system. Deposition rate was equal to 0.6 nm/s for Al2O3, 0.6 nm - 0.8 nm/s for HfO2 and 0.6 nm/s for SiO2. Simulations leading to optimization of the thin film thickness and the experimental results of optical measurements, which were carried out during and after the deposition process, have been presented. The optical thickness values, obtained from the measurements performed during the deposition process were as follows: 78 nm/78 nm for Al2O3/SiO2 and 78 nm/156 nm/78 nm for Al2O3/HfO2/SiO2. The results were then checked by ellipsometric technique. Reflectance of the films depended on the substrate temperature during the deposition process. Starting from 240 nm to the beginning of visible region, the average reflectance of the trilayer system was below 1 % and for the bilayer, minima of the reflectance were equal to 1.6 %, 1.15 % and 0.8 % for deposition temperatures of 100 °C, 200 °C and 300 °C, respectively.

Enhanced Photocatalytic Activity of Two-Pot-Synthesized BiFeO3-ZnFe2O4 Heterojunction Nanocomposite

NASA Astrophysics Data System (ADS)

Ghasemi, A.; Hasheminiasari, M.; Masoudpanah, S. M.; Safizade, B.

2018-04-01

BiFeO3-ZnFe2O4 heterojunction nanocomposites have been produced by a chemical synthesis method using one- and two-pot approaches. X-ray diffraction patterns of as-calcined samples indicated formation of pure zinc ferrite (ZnFe2O4) and bismuth ferrite (BiFeO3) phases, each retaining its crystal structure. Diffuse reflectance spectrometry was applied to calculate the optical bandgap of the photocatalysts, revealing values in the range from 2.03 eV to 2.17 eV, respectively. The maximum photodegradation of methylene blue of about 97% was achieved using two-pot-synthesized photocatalyst after 120 min of visible-light irradiation due to the higher probability of charge separation of photogenerated electron-hole pairs in the heterojunction structure. Photoluminescence spectra showed lower emission intensity of two-pot-synthesized photocatalyst, due to its lower recombination rate originating from greater charge separation.

In situ DRIFTS study of O3 adsorption on CaO, γ-Al2O3, CuO, α-Fe2O3 and ZnO at room temperature for the catalytic ozonation of cinnamaldehyde

NASA Astrophysics Data System (ADS)

Wu, Jianfeng; Su, Tongming; Jiang, Yuexiu; Xie, Xinling; Qin, Zuzeng; Ji, Hongbing

2017-08-01

In situ DRIFTS were conducted to identify adsorbed ozone and/or adsorbed oxygen species on CaO, ZnO, γ-Al2O3, CuO and α-Fe2O3 surfaces at room temperature. Samples were characterized by means of TG, XRD, N2 adsorption-desorption, pyridine-IR, nitrobenzene-IR, chloroform-IR, and CO2-TPD. Pyridine-DRIFTS measurements evidence two kinds of acid sites in all the samples. Nitrobenzene, chloroform-DRIFTS, and CO2-TPD reveal that there are large amounts of medium-strength base sites on all the metal oxides, and only CaO, ZnO, and γ-Al2O3 have strong base sites. And the benzaldehyde selectivity was increased in the same order of the alkalinity of the metal oxides. With weaker sites, ozone molecules form coordinative complexes bound via the terminal oxygen atom, observed by vibrational frequencies at 2095-2122 and 1026-1054 cm-1. The formation of ozonide O3- at 790 cm-1, atomic oxygen at 1317 cm-1, and superoxide O2- at 1124 cm-1 was detected; these species are believed to be intermediates of O3 decomposition on strong acid/base sites. The adsorption of ozone on metal oxides is a weak adsorption, and other gases, such as CO2, will compete with O3 adsorption. The mechanism of cinnamaldehyde ozonation at room temperature over CaO shows that cinnamaldehyde can not only be oxidized into cinnamic acid, but also be further oxidized into benzaldehyde, benzoic acid, maleic anhydride, and ultimately mineralized to CO2 in the presence of O3.

High rate performance of LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} cathode material synthesized by a carbon gel–combustion process for lithium ion batteries

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

Chen, Jian, E-mail: chemcj@126.com; Zhao, Na; Li, Guo-Dong, E-mail: lgd@jlu.edu.cn

2016-01-15

Graphical abstract: The cycling stability of the LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} electrode was investigated at different discharge rates from 5 C to 50 C. - Highlights: • The LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} was prepared via a carbon gel–combustion process. • The sample showed high purity and nanosized particles. • The LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} electrode shows excellent rate capability and cyclic performance. - Abstract: The LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} electrode material was prepared via a carbon gel–combustion process using resorcinol–formaldehyde gel as fuel and nitrate as an oxidizer. The carbon gel process ensures the molecular-level homogeneitymore » of the chemical product. The gas derived from carbon gel separates the raw material particles and restrains the growth of the grains to some extent, and well-crystallized nanosized powders are obtained with calcination at 700 °C for 6 h. As the cathode material for lithium-ion batteries, the discharge capacity of LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} was as high as 175.6 mA h g{sup −1} in the first cycle at 0.5 C, and it could remain 163.0 mA h g{sup −1} within the voltage range of 2.5–4.4 V after 50 cycles. The electrode also showed outstanding rate capacities at high discharge rates such as 30 C and 50 C, suggesting the applications of the material in high power lithium-ion batteries.« less

Optical characterization of Tm(3+) doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2.

PubMed

Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

2016-08-10

In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd-Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm(3+) ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH(-) absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10(-21) cm(2)) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm(3+): (4)F3 → (3)H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation ((3)H6 + (3)H4 → (3)F4 + (3)F4) rate. Our results suggest that the Tm(3+) doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system.

Optical characterization of Tm3+ doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2

PubMed Central

Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

2016-01-01

In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd–Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm3+ ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH− absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10−21 cm2) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm3+: 4F3 → 3H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation (3H6 + 3H4 → 3F4 + 3F4) rate. Our results suggest that the Tm3+ doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system. PMID:27506152

Network topology for the formation of solvated electrons in binary CaO–Al2O3 composition glasses

PubMed Central

Akola, Jaakko; Kohara, Shinji; Ohara, Koji; Fujiwara, Akihiko; Watanabe, Yasuhiro; Masuno, Atsunobu; Usuki, Takeshi; Kubo, Takashi; Nakahira, Atsushi; Nitta, Kiyofumi; Uruga, Tomoya; Weber, J. K. Richard; Benmore, Chris J.

2013-01-01

Glass formation in the CaO–Al2O3 system represents an important phenomenon because it does not contain typical network-forming cations. We have produced structural models of CaO–Al2O3 glasses using combined density functional theory–reverse Monte Carlo simulations and obtained structures that reproduce experiments (X-ray and neutron diffraction, extended X-ray absorption fine structure) and result in cohesive energies close to the crystalline ground states. The O–Ca and O–Al coordination numbers are similar in the eutectic 64 mol % CaO (64CaO) glass [comparable to 12CaO·7Al2O3 (C12A7)], and the glass structure comprises a topologically disordered cage network with large-sized rings. This topologically disordered network is the signature of the high glass-forming ability of 64CaO glass and high viscosity in the melt. Analysis of the electronic structure reveals that the atomic charges for Al are comparable to those for Ca, and the bond strength of Al–O is stronger than that of Ca–O, indicating that oxygen is more weakly bound by cations in CaO-rich glass. The analysis shows that the lowest unoccupied molecular orbitals occurs in cavity sites, suggesting that the C12A7 electride glass [Kim SW, Shimoyama T, Hosono H (2011) Science 333(6038):71–74] synthesized from a strongly reduced high-temperature melt can host solvated electrons and bipolarons. Calculations of 64CaO glass structures with few subtracted oxygen atoms (additional electrons) confirm this observation. The comparable atomic charges and coordination of the cations promote more efficient elemental mixing, and this is the origin of the extended cage structure and hosted solvated (trapped) electrons in the C12A7 glass. PMID:23723350

Experimental studies of magnetite formation in the solar nebula

NASA Astrophysics Data System (ADS)

Hong, Y.; Fegley, B., Jr.

1998-09-01

Oxidation of Fe metal and Gibeon meteorite metal to magnetite via the net reaction 3 Fe (metal) + 4 H2O (gas) = Fe3O4 (magnetite) + 4 H2 (gas) was experimentally studied at ambient atmospheric pressure at 91-442oC in H2 and H2-He gas mixtures with H2/H2O molar ratios of ~4-41. The magnetite produced was identified by X-ray diffraction. Electron microprobe analyses showed 3.3 wt% NiO and 0.24 wt% CoO (presumably as NiFe2O4 and CoFe2O4) in magnetite formed from Gibeon metal. The NiO and CoO concentrations are higher than expected from equilibrium between metal and oxide under the experimental conditions. Elevated NiO contents in magnetite were also observed by metallurgists during initial stages of oxidation of Fe-Ni alloys. The rate constants for magnetite formation were calculated from the weight gain data using a constant surface area model and the Jander, Ginstling-Brounshtein, and Valensi-Carter models for powder reactions. Magnetite formation followed parabolic (i.e., diffusion controlled) kinetics. The rate constants and apparent activation energies for Fe metal and Gibeon metal are: cm2 hour-1 Eact = 92=B15(2s) kJ mol-1 cm2 hour-1 Eact = 95=B112(2s) kJ mol-1 These rate constants are significantly smaller than the parabolic rate constants for FeS growth on Fe metal in H2S-H2 gas mixtures containing 1000 or 10,000 ppmv H2S (Lauretta et al. 1996a). The experimental data for Fe and Gibeon metal are used to model the reaction time of Fe alloy grains in the solar nebula as a function of grain size and temperature. The reaction times for 0.1-1 micron radius metal grains are generally within estimated lifetimes of the solar nebula (0.1-10 million years). However, the calculated reaction times are probably lower limits and further study of magnetite formation at larger H2/H2O ratios, at lower temperatures and pressures, and as a function of metal alloy composition is needed for further modeling of nebular magnetite formation.

O2 on ganymede: Spectral characteristics and plasma formation mechanisms

USGS Publications Warehouse

Calvin, W.M.; Johnson, R.E.; Spencer, J.R.

1996-01-01

Weak absorption features in the visible reflectance spectrum of Jupiter's satellite Ganymede have been correlated to those observed in the spectrum of molecular oxygen. We examine the spectral characteristics of these absorption features in all phases of O2 and conclude that the molecular oxygen is most likely present at densities similar to the liquid or solid ??-phase. The contribution of O2 to spectral features observed on Ganymede in the near-infrared wavelength region affects the previous estimates of photon pathlength in ice. The concentration of the visible absorption features on the trailing hemisphere of Ganymede suggests an origin due to bombardment by magneto-spheric ions. We derive an approximate O2 formation rate from this mechanism and consider the state of O2 within the surface.

Thermal formation effect of g-C3N4 structure on the visible light driven photocatalysis of g-C3N4/NiTiO3 Z-scheme composite photocatalysts

NASA Astrophysics Data System (ADS)

Pham, Thanh-Truc; Shin, Eun Woo

2018-07-01

The development of efficient visible-light driven photocatalysts has attracted considerable attention in environmental protection and remediation. In this study, the facile thermal polymerization of dicyandiamide (DCDA) to graphitic carbon nitride (g-C3N4) in the presence of nickel titanium trioxide (NiTiO3) was investigated for fabricating g-C3N4 and NiTiO3 composite (CNT) photocatalysts to understand the influence of the presence of NiTiO3 on the thermal formation of g-C3N4 layers from DCDA and to find an optimal processing temperature for fabricating CNT photocatalysts. To examine the effect of NiTiO3 on the fabrication of CNT photocatalysts, a gas phase environment (flowing air or nitrogen) and different processing temperatures were employed as preparation variables to control the properties of the CNT photocatalysts. In addition, the CNT photocatalysts were applied for the visible light driven photocatalytic degradation of methylene blue to evaluate their photocatalytic performances. The CNT photocatalyst prepared at T = 500 °C showed the highest photocatalytic activity, which was caused by the optimal morphology of g-C3N4 in the composite photocatalysts. The NiTiO3 inorganic phase in the composite photocatalysts acted as a catalyst to accelerate the thermal polymerization to form the g-C3N4 structure and as a promoter to increase the photocatalytic activity during photodegradation.

High-rate deposition of LiNb 1- xTa xO 3 films by thermal plasma spray CVD

NASA Astrophysics Data System (ADS)

Majima, T.; Yamamoto, H.; Kulinich, S. A.; Terashima, K.

2000-12-01

LiNb 1- xTa xO 3 films were prepared by a thermal plasma spray CVD method using liquid source materials. Preferentially (0 0 1)-oriented LiNb 1- xTa xO 3 films with satisfactory in-plane and out-of-plane alignment were fabricated on sapphire (0 0 1) substrates. The full-width at half-maximum (FWHM) of the (0 0 6) rocking curve could achieve 0.12°, which was comparable with those of LiNbO 3 and LiTaO 3 films prepared by other conventional vapor-phase deposition methods. The deposition rate was up to 0.07 μm/min, which was 5-40 times faster than those for most other conventional vapor-phase deposition methods. From inductively coupled plasma atomic emission spectroscopy analysis, x values of these films were estimated to be 0.36-0.49.

Communication: Equilibrium rate coefficients from atomistic simulations: The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction at temperatures relevant to the hypersonic flight regime.

PubMed

Castro-Palacio, Juan Carlos; Bemish, Raymond J; Meuwly, Markus

2015-03-07

The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20,000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions.

Rates of weathering rind formation on Costa Rican basalt

NASA Astrophysics Data System (ADS)

Sak, Peter B.; Fisher, Donald M.; Gardner, Thomas W.; Murphy, Katherine; Brantley, Susan L.

2004-04-01

= 2.9 ± 0.1 cm) is coincident with stage 5e (ca. 125 ka) and that Qt 3 (rr = 0.9 ± 0.1 cm) is consistent with OIS 3 (ca. 37 ka). These assignments yield a value of kapp of 8.6 × 10-13 cm s-1 (R2 = 0.99). Only this value satisfies both the existing age controls and yields ages coincident with sea level maxima. Using this value, elemental weathering release fluxes across a weathering rind from Qt 2 range from 6.0 × 10-9 mol Si m-2 s-1 to 2.5 × 10-11 mol K m-2 s-1. The rate of rind advance for the Costa Rican terraces is 2.8 × 10-7 m yr-1. Basalt rind formation rates in lower temperature settings described in the literature are also consistent with interface-controlled weathering with an apparent activation energy of about 50 kJ mol-1. Rates of rind formation in Costa Rica are an order of magnitude slower than reported for global averages of soil formation rates.

Cu3V2O8 hollow spheres in photocatalysis and primary lithium batteries

NASA Astrophysics Data System (ADS)

Zhang, Shaoyan; Sun, Yan; Li, Chunsheng; Ci, Lijie

2013-11-01

In this paper, Cu3V2O8 hollow spheres have been successfully synthesized via a liquid precipitation method with colloidal carbon spheres as template followed by a subsequent heat treatment process. On the basis of XRD analysis, SEM observation, and TG-DSC analysis of the precursor and products, the formation mechanism of Cu3V2O8 hollow spheres was proposed. UV-vis diffuse reflectance spectra showed that the Cu3V2O8 hollow spheres exhibit strong absorption in a wide wavelength range from UV to visible light. The photocatalytic activity experiment indicated that the as-prepared Cu3V2O8 hollow spheres exhibited good photocatalytic activity in degradation of methyl orange (MO) under 150-W xenon arc lamp light irradiation. Furthermore, electrochemical measurements showed that the Cu3V2O8 hollow spheres exhibited high discharge capacity and excellent high-rate capability, indicating potential cathode candidates for primary lithium batteries used in long-term implantable cardiac defibrillators (ICDs).

Fabrication by Electrophoretic Deposition of Nano-Fe3O4 and Fe3O4@SiO2 3D Structure on Carbon Fibers as Supercapacitor Materials

NASA Astrophysics Data System (ADS)

Hajalilou, Abdollah; Abouzari-Lotf, Ebrahim; Etemadifar, Reza; Abbasi-Chianeh, Vahid; Kianvash, Abbas

2018-05-01

Core-shell nanostructured magnetic Fe3O4@SiO2 with particle size ranging from 3 nm to 40 nm has been synthesized via a facile precipitation method. Tetraethyl orthosilicate was employed as surfactant to prepare core-shell structures from Fe3O4 nanoparticles synthesized from pomegranate peel extract using a green method. X-ray diffraction analysis, Fourier-transform infrared and ultraviolet-visible (UV-Vis) spectroscopies, transmission electron microscopy, and scanning electron microscopy with energy-dispersive spectroscopy were employed to characterize the samples. The prepared Fe3O4 nanoparticles were approximately 12 nm in size, and the thickness of the SiO2 shell was 4 nm. Evaluation of the magnetic properties indicated lower saturation magnetization for Fe3O4@SiO2 powder ( 11.26 emu/g) compared with Fe3O4 powder ( 13.30 emu/g), supporting successful wrapping of the Fe3O4 nanoparticles by SiO2. As-prepared powders were deposited on carbon fibers (CFs) using electrophoretic deposition and their electrochemical behavior investigated. The rectangular-shaped cyclic voltagrams of Fe3O4@CF and Fe3O4@C@CF samples indicated electrochemical double-layer capacitor (EDLC) behavior. The higher specific capacitance of 477 F/g for Fe3O4@C@CF (at scan rate of 0.05 V/s in the potential range of - 1.13 to 0.45 V) compared with 205 F/g for Fe3O4@CF (at the same scan rate in the potential range of - 1.04 to 0.24 V) makes the former a superior candidate for use in energy storage applications.

Al2O3 Passivation Effect in HfO2·Al2O3 Laminate Structures Grown on InP Substrates.

PubMed

Kang, Hang-Kyu; Kang, Yu-Seon; Kim, Dae-Kyoung; Baik, Min; Song, Jin-Dong; An, Youngseo; Kim, Hyoungsub; Cho, Mann-Ho

2017-05-24

The passivation effect of an Al 2 O 3 layer on the electrical properties was investigated in HfO 2 -Al 2 O 3 laminate structures grown on indium phosphide (InP) substrate by atomic-layer deposition. The chemical state obtained using high-resolution X-ray photoelectron spectroscopy showed that interfacial reactions were dependent on the presence of the Al 2 O 3 passivation layer and its sequence in the HfO 2 -Al 2 O 3 laminate structures. Because of the interfacial reaction, the Al 2 O 3 /HfO 2 /Al 2 O 3 structure showed the best electrical characteristics. The top Al 2 O 3 layer suppressed the interdiffusion of oxidizing species into the HfO 2 films, whereas the bottom Al 2 O 3 layer blocked the outdiffusion of In and P atoms. As a result, the formation of In-O bonds was more effectively suppressed in the Al 2 O 3 /HfO 2 /Al 2 O 3 /InP structure than that in the HfO 2 -on-InP system. Moreover, conductance data revealed that the Al 2 O 3 layer on InP reduces the midgap traps to 2.6 × 10 12 eV -1 cm -2 (compared to that of HfO 2 /InP, that is, 5.4 × 10 12 eV -1 cm -2 ). The suppression of gap states caused by the outdiffusion of In atoms significantly controls the degradation of capacitors caused by leakage current through the stacked oxide layers.

Quantum Chemical Study of CH3 + O2 Combustion Reaction System: Catalytic Effects of Additional CO2 Molecule.

PubMed

Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

2017-08-03

The supercritical carbon dioxide diluent is used to control the temperature and to increase the efficiency in oxycombustion fossil fuel energy technology. It may affect the rates of combustion by altering mechanisms of chemical reactions, compared to the ones at low CO 2 concentrations. Here, we investigate potential energy surfaces of the four elementary reactions in the CH 3 + O 2 reactive system in the presence of one CO 2 molecule. In the case of reaction CH 3 + O 2 → CH 2 O + OH (R1 channel), van der Waals (vdW) complex formation stabilizes the transition state and reduces the activation barrier by ∼2.2 kcal/mol. Alternatively, covalently bonded CO 2 may form a six-membered ring transition state and reduce the activation barrier by ∼0.6 kcal/mol. In case of reaction CH 3 + O 2 → CH 3 O + O (R2 channel), covalent participation of CO 2 lowers the barrier for the rate limiting step by 3.9 kcal/mol. This is expected to accelerate the R2 process, important for the branching step of the radical chain reaction mechanism. For the reaction CH 3 + O 2 → CHO + H 2 O (R3 channel) with covalent participation of CO 2 , the activation barrier is lowered by 0.5 kcal/mol. The reaction CH 2 O + OH → CHO + H 2 O (R4 channel) involves hydrogen abstraction from formaldehyde by OH radical. Its barrier is reduced from 7.1 to 0.8 kcal/mol by formation of vdW complex with spectator CO 2 . These new findings are expected to improve the kinetic reaction mechanism describing combustion processes in supercritical CO 2 medium.

Investigation of hybrid plasma-catalytic removal of acetone over CuO/γ-Al2O3 catalysts using response surface method.

PubMed

Zhu, Xinbo; Tu, Xin; Mei, Danhua; Zheng, Chenghang; Zhou, Jinsong; Gao, Xiang; Luo, Zhongyang; Ni, Mingjiang; Cen, Kefa

2016-07-01

In this work, plasma-catalytic removal of low concentrations of acetone over CuO/γ-Al2O3 catalysts was carried out in a cylindrical dielectric barrier discharge (DBD) reactor. The combination of plasma and the CuO/γ-Al2O3 catalysts significantly enhanced the removal efficiency of acetone compared to the plasma process using the pure γ-Al2O3 support, with the 5.0 wt% CuO/γ-Al2O3 catalyst exhibiting the best acetone removal efficiency of 67.9%. Catalyst characterization was carried out to understand the effect the catalyst properties had on the activity of the CuO/γ-Al2O3 catalysts in the plasma-catalytic reaction. The results indicated that the formation of surface oxygen species on the surface of the catalysts was crucial for the oxidation of acetone in the plasma-catalytic reaction. The effects that various operating parameters (discharge power, flow rate and initial concentration of acetone) and the interactions between these parameters had on the performance of the plasma-catalytic removal of acetone over the 5.0 wt% CuO/γ-Al2O3 catalyst were investigated using central composite design (CCD). The significance of the independent variables and their interactions were evaluated by means of the Analysis of Variance (ANOVA). The results showed that the gas flow rate was the most significant factor affecting the removal efficiency of acetone, whilst the initial concentration of acetone played the most important role in determining the energy efficiency of the plasma-catalytic process. Copyright © 2016 Elsevier Ltd. All rights reserved.