A simple one-step method to fabricate hierarchically porous TiO2/Pd composite hollow spheres without any template was developed by using solvothermal treatment. Pd nanoparticles (2-5 nm) were well dispersed in the mesopores of the TiO2 hollow spheres via in-situ reduction. In our experiment, polyvinylpyrrolidone played an important role in the synthetic process as the reducing agent and the connective material between TiO2 and Pd nanoparticles. HF species generated from solvothermal reaction leaded to the formation of TiO2 hollow spheres and Ostwald ripening was another main factor that affected the size and structure of the hollow spheres. The as-prepared TiO2/Pd composite hollow spheres exhibited high electrocatalytic activity towards ...
The influence of selenium dioxide (SeO2) on the microstructure and electrodeposition of manganese coatings obtained from a sulfate based neutral solution was investigated by material characterization methods and electrochemical techniques. The crystal structure and surface morphology of these coatings were studied by scanning electron microscopy (SEM) and powder X-ray diffraction spectroscopy (XRD), respectively. The SEM and XRD data showed that SeO2 could effectively accelerate phase transformation, and facilitate leveled and fine grain growth. The electrochemical results indicated that SeO2 could inhibit hydrogen evolution reaction and promote manganese deposition. The action of selenium dioxide in manganese deposition was found to be a reduction and adsorption mechanism. The process cou...
Chemical looping combustion (CLC) of simulated coal-derived synthesis gas was conducted with NiO oxygen carriers supported on SiO2, ZrO2, TiO2, and sepiolite. The effect of H2S on the performance of these samples for the CLC process was also evaluated. Five-cycle thermogravimetric analysis (TGA) tests at 800 C indicated that all oxygen carriers had a stable performance at 800 C, except NiO/SiO2. Full reduction/oxidation reactions of the oxygen carrier were obtained during the five-cycle test. It was found that support had a significant effect on reaction performance of NiO both in reduction and oxidation rates. The reductionreaction was significantly faster than the oxidation ...
N-doped TiO2 has been prepared by use of sol?gel systems containing titanium alkoxide, with nitric acid as the nitrogen source. The time needed for gelation of the systems was drastically reduced by ultrasonic irradiation. The peaks assigned to the nitrate and nitrous ions were observed by FT-IR measurement during the sol?gel reaction. The N-doping was confirmed by the observation of N?O peaks in the XPS spectrum of the sample heated at 400??C. The nitrate ion acted as an oxidizer of the ethanol solvent and titanium species. The TiO2 became doped with nitrogen oxide species as a result of reduction of nitrate ion incorporated into the dried gel samples. These results indicated that the added nitric acid was reduced during the sol?gel transition and heating process, and the resulting NO spe...
The method of programmed thermodesorption has been used to study the forms of hydrogen adsorption in ZrNiHsub(x) hydride. It is shown that high concentration of the hydrogen, which extracted from hydride in the temperature range of 240-260 deg C results in appearance of ''reverse'' peak. Charge of hydride adsorption properties during its oxidation-reduction treatment is studied. Comparison with spectra of hydrogen thermodesorption from the surface of Ni/ZrO_2 deposited catalyst and zirconium oxide is carried out.
With the assistance of mechanical activation, yttrium-stabilized #alpha#-SiAlON was prepared by combustion synthesis in air, instead of high-pressure N_2 atmosphere for the first time. The reaction activity of metallic particles was remarkably enhanced by mechanical activation, which conduced the reduction of grain size, increased the total surface area and formation of fresh surface. The formation of #alpha#-SiAlON by combustion synthesis in air was explained by a kinetically induced reaction mechanism, in which both initial formation of #alpha#-SiAlON and following avoidance of oxidation were fulfilled by the retardation of O_2 infiltration owing to the short reaction period and fast cooling rate.
Upon addition of permanganate to a solution of tryptophan (Trp), yellow-brown color species appears within the time of mixing of tryptophan in absence and presence of cetyltrimethylammonium bromide (CTAB), which was stable for some days. Spectroscopic and kinetic evidences suggest the formation of water-soluble colloidal MnO2 as the most stable reduction product of MnO4-. Carbon dioxide and ammonia are not formed as the oxidation products. Carbon-carbon double bond of indole moiety of Trp is responsible for the fast reduction of permanganate. Cetyltrimethylammonium bromide catalyses the permanganate oxidation of Trp with a rate enhancement of ca. 200-fold. Sub- and postmicellar catalytic effect of CTAB ascribed to the association/incorporation/solubilization of both reactants (MnO4- and Tr...
Carbothermal reduction-nitridation (CRN) of SiO_2 is an attractive method for manufacturing Si_3N_4 powders with controlled grain morphology. Moreover, #beta#-sialon powders could also be synthesized from either pure powder mixtures or some inexpensive raw minerals by CRN. The resultant powders have shown some advantages, especially in manufacturing sialon products at low cost. However, there have been only a few works on preparing #alpha#-sialon powders. In this work, Ca-#alpha# sialon powder was synthesized by CRN of a SiO_2-Al_2O_3 and CaCO_3 powder mixture An unusual morphology of hollow balls of 200 to 500nm with many nano size #alpha#-sialon particles of 10 to 30nm was identified from the resultant Ca-#alpha# sialon powders. This has never been previously reported for sialon ceramics. It was consequently confirmed that the morphologies of the products were clearly related to ...
Rapid nitridation was used to fabricate reaction-bonded and postsintered -Si6-ZAlZOZN8-Z (Z=1) ceramics with monoclinic ZrO2 added to the starting powder. Thermo-gravimetric analysis revealed that the addition of ZrO2 reduced the starting temperature of the main nitridation reaction. Using a reaction-bonding route with heating rates of 5, 10, and 20C/min, to fabricate -SiAlON ceramics without ZrO2 resulted in unreacted silicon that bled out of the specimens and the Z=1 composition samples did not maintain the original green compact morphology. On the other hand, no such bleeding of melted silicon was observed for samples with ZrO2 additions and the samples following nitridation maintained the original green morphology. The microstructure and mechanical ...
Abstract High-crystallinity hierarchical anatase TiO2 hollow spheres were prepared by a high-temperature (350 C) and non-aqueous solvothermal method in the absence of water, templates, or additives. The hollow structures were assembled from highly crystallized TiO2 nanoparticles and exhibit superior photocatalytic properties relative to those of Degussa P25 TiO2 under irradiation with UV light. The influence of reaction temperature on the crystallinity, morphology, crystallite shape and size, band gap, specific surface area, and pore size distribution of TiO2 has been studied in detail. It is evident that reaction temperature is the most important factor to increase the crystallinity of TiO2 in order to improve its charge transfer and ...
Abstract in english Ru(1%)/SiO2 and Cu(1%)Ru(1%)/SiO2 catalysts were prepared by cogelation. The effect of pH and the amount of water on the physical-chemical properties and the catalytic properties of them were analyzed. The acid medium increased the formation of microporosity and the formation of small size of metallic ruthenium particle. The variation of the water quantity used in the gelation not modify considerably the texture neither the dispersion of the noble metal. The reduction lev (more) el of all prepared catalyst was similar, showing displacement in some of reduction peaks. The toluene hydrogenation indicated that the conversion and the quantity of hydrogenate product varied with the pH and the quantity of water used in the gelation. The addition of copper to Ru/SiO2 catalysts diminished the reactive ...
A series of experimental measurements of ozone concentration produced by irradiation of noble gas (He, Ne, and Ar)-O_2 and noble gas-O_2- SF_6 mixtures with energetic (MeV) helium and lithium ions are reported. Continuous irradiations at dose rates of 10"1"5-10"1"7 eV cm"-"3 S"-"1 for a few hundred milliseconds were used. The resulting ozone concentration was found to be nonlinear with dose rate for a given irradiation time. This nonlinearity was effectively reduced by an increase in noble gas pressure. Few mole percent addition of SF_6 generally resulted in an increase in the ozone concentration. This increase was highest for lower noble gas pressures and longer irradiation times. Further SF_6 addition, however, caused a reduction in the ozone concentration. Results are explained by considering the relevant reactions responsible for ozone production and loss.
Effective work function (m,eff) values of Ru gate electrode on SiO2 and HfO2 MOS capacitors were carefully examined and discussed from the viewpoint of an effect of oxygen incorporation in Ru gate electrode on m,eff. Annealing at 400degreeC in the reduction (3%H2) and the oxidation (1%O2) ambient resulted in similar changes in the m,eff of Ru/HfO2/SiO2 and Ru/SiO2 MOS capacitors. Furthermore, the Ru gate MOS capacitor after annealing in the oxidation condition have shown almost the same m,eff value to that of RuO2 gate MOS capacitors. The oxygen concentration in the Ru/HfO2 interface after annealing in oxidizing atmosphere is ...
Gas phase oxidation and catalytic oxidation of element mercury (Hg(0)) to bivalent mercury (Hg(2+)) were proposed to improve the mercury removal efficiency in the wet flue gas desulfurization (WFGD) system. However, the re-emission of Hg(0), generated by the reduction of absorbed Hg(2+), would lead to a damping of the total mercury removal efficiency. In this paper, the absorption and reduction behaviors of bivalent mercury in the Ca-based WFGD slurry were evaluated in our purpose-built device. According to our experimental results, the slurry chemistry (such as CaSO(3) content, SO(4)(2-), Cl(-) and pH value) had a strong influence on the reduction of absorbed bivalent mercury. And the inlet concentrations of SO(2) and O(2) contribute little to the mercury absorption. Within the typical pH value range of 4.5-5.5, about 70% of inlet bivalent mercury was converted to Hg(0). The ...
Cobalt supported on Beta zeolite catalysts were prepared by impregnation of metal salts in aqueous solution and were tested for the Fischer Tropsch reaction. The support consisted of a Beta zeolite composed by crystallites of nanometric dimensions and a SiO2/Al2O3 molar ratio of about 50. This support was impregnated with Co(NO3)2 aqueous solution using different metal loads of 7.5, 10, 15 and 20wt% Co. These materials were characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), N2 adsorption (BET), thermal programmed reduction (TPR) and FTIR of adsorbed pyridine (i.e., surface acid sites distribution). All the catalysts showed a significant catalytic activity for the F-T reaction from synthesis gas (CO+2H2), in a continuous fixed bed reactor sys...
Levels in "7"2Se were observed via in-beam gamma spectroscopy following the "5"8Ni("1"6O,2p) reaction. Spectra and partial energy level schemes are shown. (3 figures) (U.S.).
The electrode kinetics for oxygen reduction on conducting metal oxides, including lithiated NiO (formed in situ) and Sb-doped SnO/sub 2/, have been investigated. Kinetic measurements were carried out by using ac impedance and coulostatic relaxation methods. The ac behavior on the oxide electrodes was analyzed on the basis of a modified Randles-Ershler type equivalent circuit which takes into account the effect of non-faradaic components due to the semiconducting oxide films. The kinetic parameters (the charge transfer resistance and Warburg coefficient) and the interfacial parameters (the double layer capacity, film capacity and film resistance) were obtained by a least squares curve fitting method under P/sub O2//P/sub CO2/=0.9/0.1 atmosphere. The exchange current density was found to be 10 to 20 mA cm/sup -2/ at the oxide electrodes, assuming n=2. The coulostatic relaxation experiments supported the magnitude of the i/sub ...
At atmospheric pressure and room temperature, dielectric barrier discharge induced plasma oxidation for achieving supported TiO2 photocatalysts derived from TiCl4 adsorbed onto ?-Al2O3 pellets was studied. The supported TiO2/?-Al2O3photocatalysts prepared by a cyclic 'adsorption-discharge' approach, without requirement of heat treatment, exhibit high activity in the photocatalytic degradation reaction of formaldehyde. The mass spectra and optical emission spectra during O2/Ar discharge for oxidizing the adsorbed-state TiCl4 were measured. The mechanism for the TiO2 formation from adsorbed-state TiCl4 by plasma oxidation was discussed.
A novel single-step synthetic method for the preparation of anatase N-doped TiO"2 nanocrystalline at low temperature has been devoleped. The N-doped anatase TiO"2 nanoparticles were synthesized by sonication of the solution of tetraisopropyl titanium and urea in water and isopropyl alcohol at 80^oC for 150min. The as-prepared sample was characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis absorption spectrum. The product structure depends on the reaction temperature and reaction time. The photocatalytic activity of the as-prepared photocatalyst was evaluated via the photodegradation of an azo dye direct sky blue 5B. The results show that the N-doped TiO"2 nanocrystalline prepared via sonication exhibit an excellent photocatalytic...
Abstract The characteristics of desulfurization and denitrification with composite absorbent were researched through aqueous absorption experiments. The removal efficiencies of SO2 and NO were up to 100 and 95%, respectively. The composite absorbent included NaClO2 and component M. Existence of component M in the solution could reduce the absorbent cost compared with using sodium chlorite alone. Chlorine dioxide, as main reaction intermediate product, participated in oxidation reaction. The optimal experimental conditions involved NaClO2 concentration of1.13 mmol/L, solution pH of 5.5, molar ratio (M/NaClO2) of 4.1, reaction temperature of 323 K. The optimal solution pH and reaction temperature were both in the required ranges of limestone-gypsum wet flue gas desulfurization ...
Formation of oxidizing and reducing radicals was studied by pulse radiolysis of [Fe(CN)_6]"4"- - BrO_3"- - CN"- system in ethylene glycol - water solvent mixture. Oxidizing #centre dot#BrO_2 and BrO radicals formed by electron scavenging with #centre dot#BrO_2"- were identified and their reactions were investigated. The reaction of hydroxyl radicals with ethylene glycol leads to formation of reactive radicals with reducing properties and of compounds which reduce slowly in dark the ferricyanide formed in the reaction of #centre dot#BrO_2 radical with ferrocyanide. (author) 21 refs.; 7 figs.
The sunlight-induced photocatalytic oxidation of aqueous benzene on TiO(2)-supported gold nanoparticles was considerably improved when the reaction was conducted under a CO(2) atmosphere. 13% yield and 89% selectivity of phenol was obtained on P25-supported gold nanoparticles under 230 kPa of CO(2). PMID:21952312
A simple model is described to simulate kinetic processes in dielectric barrier discharges for O_2/NO_x mixtures. A threshold of ozone production found experimentally is confirmed by the calculations of this modeling, and the underlying chemical reaction mechanisms are discussed. It is also found that the effects of diffusion processes in the period of the lifetime of O atoms are not important to micro-discharge channels with a large radius, i.e. larger than 150 #mu#m
A sensitive hydrogen peroxide (H2O2) sensor was fabricated based on graphene-Pt (GN-Pt) nanocomposite. The GN-Pt was synthesized by photochemical reduction of K2PtCl4 on GNs, and characterized by atomic force microscope (AFM), transmission electron microscope (TEM), and energy-dispersive X-ray spectroscopy (EDS). Electrochemical investigations indicated that the GN-Pt exhibited a high peak current and low overpotential towards the reduction of H2O2. The GN-Pt modified glass carbon electrode displayed a wide linear range (2-710mM), low limit of detection (0.5mM) and good selectivity for detection of H2O2 with a much higher sensitivity than that of Pt nanoparticles or graphene modified electrode.
TiO2 addition into boiling water reactor (BWR) primary system is being developed as a method to mitigate stress corrosion cracking (SCC) of the BWR structural materials. This technique aims for electrochemical corrosion potential (ECP) decrease of reactor materials by photo-excitation reaction under Cherenkov irradiation. ECP measurement tests have been conducted in the test loop in BWR to investigate the feasibility of the SCC mitigation method with TiO2. The test results showed that the ECP of TiO2 deposited materials was decreased to 2 technique was confirmed to be feasible as a SCC mitigation method for BWR structural materials without hydrogen injection. (author)
Zirconia has demonstrated a very moderate toughening effect in nitrogen-based ceramic composites because the reaction between tetragonal zirconia (t-ZrO_2) and nitrogen results in additional zirconia stabilization to a nontransformable t' or cubic structure. In O'-SiAlON matrices, the oxygen concentration increases and the oxygen-rich intergranular glassy phase prevents zirconia from nitridation. As a result, tetragonal ZrO_2 is maintained and is transformable in the O'-SiAlON materials. The present study has provided transmission electron microscopy (TEM) evidence of the zirconia transformation and the associated toughening effect in a ZrO_2/O'-SiAlON composite. The implications and limitations of the transformation on toughening of the material are discussed.
A series of measurements of O_3 yield in nuclear induced O_2 and O_2-SF_6 discharges created by bombardment with energetic particles from the "1"0B(n,#alpha#)"7Li reaction are reported. Continuous irradiation at dose ratios of 10"1"5-10"1"7 eV.cm"-"3.s"-"1 and pulsed irradiation (approx.10 ms FWHM) at a peak dose rate of approx.10"2"0 eV.cm"-"3.s"-"1 were conducted. At the lower dose rates, SF_6 addition generally increased the ozone yield, which at the high dose rates, SF_6 addition decreased the observed ozone concentration. A numerical model was developed and applied to experimental conditions. The steady-state ozone concentration was found to be limited by the reaction O_3"- + O_3 #-># 2O_2 + O_2"-. A simplified analytical model of steady-state conditions was used to ...
New lithium ion composite electrolyte, LiI?Li2S?La2O2Sm (m=1, 2) was synthesized from the binary Li2S?LaOI system through solid state reaction. The lithium ion conductive property was investigated by AC impedance spectroscopy. And the highest conductivity of the obtained electrolyte at room temperature was found to be 3.0?10?6?S cm?1. The notable ionic conduction was attributed to the in situ formed amorphous LiI.
A series of cation exchange membranes was produced by impregnating and coating both sides of a quartz web with a Nafion solution (1100 EW, 10%wt in water). Inert filler particles (SiO_2, ZrO_2 or TiO_2; 5-20%wt) were incorporated into the aqueous Nafion solution to produce robust, composite membranes. Ion-exchange capacity/equivalent weight, water take-up, thickness change on hydration and ionic and electrical conductivity were measured in 1 mol dm"-"3 sulfuric acid at 298 K. The TiO_2 filler significantly impacted on these properties, producing higher water take-up and increased conductivity. Such membranes may be beneficial for proton exchange membrane (PEM) fuel cell operation at low humidification. The PEM fuel cell performance of the composite membranes containing SiO_2 ...
l-Carnitine is a critical metabolite indispensable for the metabolism of lipids as it facilitates fatty acid transport into the mitochondrion where b-oxidation occurs. Human astrocytes (CCF-STTG1 cells) and hepatocytes (HepG2 cells) exposed to aluminum (Al) and hydrogen peroxide (H2O2), were characterized with lower levels of l-carnitine, diminished b-oxidation, and increased lipid accumulation compared to the controls. g-Butyrobetainealdehyde dehydrogenase (BADH) and butyrobetaine dioxygenase (BBDOX), two key enzymes mediating the biogenesis of l-carnitine, were sharply reduced during Al and H2O2 challenge. Exposure of the Al and H2O2-treated cells to a-ketoglutarate (KG), led to the recovery of l-carnitine production with the concomitant reduction in ROS levels. It appears that the chann...
A series of experimental measurements of the yield of O_3 in nuclear-induced O_2 and O_2-SF_6 discharges are reported. The discharges were created by bombardment with energetic particles from the "1"0B(n,#alpha#)"7Li reaction. Continuous irradiation at dose rates of 10"1"5--10"1"7 eV cm"-"3 s"-"1 and pulsed irradiation (--10 ms FWHM) at a peak dose rate of --10"2"0 eV cm"-"3 s"-"1 were conducted. At the lower dose rates, the addition of SF_6 generally increased the ozone yield due to the slowing of ozone destruction by negative oxygen and ozone ions. In contrast, at the high dose rates, the ozone concentration decreased due to SF_6 suppression of atomic oxygen formation by ion--ion recombination. A numerical model was developed and tested against experimental conditions. This model indicates that the steady-state ozone concentration was limited by the reaction ...
Ceramic matrix composites in the TiC-Ti, Y-TZP system can be synthesized by the reaction between carbon and the TiO_2-Y_2O_3-ZrO_2 solid solution nanopowder. This method results in the more homogeneous powders than those prepared by the physical mixing of TiC and zirconia s.s. powders. Twelve TiO_2-Y_2O_3-ZrO_2 solid solution nanopowders differing in the proportions of the constituent oxides were prepared by the coprecipitation- calcination route. They were reacted with the pyrolytic carbon evenly distributed within the system. Carbon was introduced by the thermal decomposition of the phenol-formaldehyde resin dissolved in ethyl alcohol and mixed with the zirconia s.s. nanopowder. Reaction was performed in vacuum. Compacts of the composite powders sintered in vacuum give dense ...
In the first part of this paper, IrO_2 electrodes produced by thermal decomposition of H_2IrCl_6 precursor were manufactured using the spin coating deposition technique, where centrifugal forces spread the precursor solution with simultaneous evaporation of the solvent on the rotating Ti substrate. It was found using this technique, that it is possible to obtain thin and uniform IrO_2 coatings with controlled loadings. The influence of the concentration of iridium salt in the precursor solution (c_0) as well as the influence of the rotation speed at which the substrate spins (#omega#) on the IrO_2 loading have been studied using voltammetric charge measurements. From these results, a simple relation has been proposed for the estimation of the IrO_2 loading for a given c_0 and #omega#. In the second part of this paper and ...
The catalytic properties of molybdena-alumina catalysts reduced in hydrogen were studied in the function of the reduction temperature, i.e. in the function of the extent of reduction. The deuterium exchange reaction of benzene was used as model catalytic reaction. It was concluded that the reaction rate constant and the multiplicity factor decreased with the extent of reduction parallel with the change in the extent of dehydroxylation of the catalysts. (orig.)
The synthesis and structural characterization of a novel In(III) complex is described. The reaction between InCl3 with sodium mercapto-acetic acid, (NaSCH2(CO)OH) in 4-methylpyridine, (CH3(C5H5N), (4-Mepy)) at 25 C affords (ClIn(SCH2(CO)O)2)2- ((4-MepyH)2...
In situ optical absorption spectroscopy was used to study the generation of E' centres in amorphous SiO_2 occurring by photo-induced breaking of Si-H groups under 4.7eV pulsed laser radiation. The dependence from laser intensity of the defect generation rate is consistent with a two-photon mechanism for Si-H rupture, while the growth and the saturation of the defects are conditioned by their concurrent annealing due to reaction with mobile hydrogen arising from the same precursor. A rate equation is proposed to model the kinetics of the defects and tested on experimental data.
A problem of the catalytic activity definition for metals, binary metallic alloys, and semiconductor materials is considered within new quantum mechanical and electrodynamics approach in the electron theory of catalysis. The quantitative link between the electron structure parameters of the materials and their catalytic activity on example of simple model reactions of the following type are found: H = H+ + e, O2 + e- = O2-. Copyright 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009
The computational analysis of the model system consisting of the processes of CO2 assimilation and photorespiration shows the appearance of sustained oscillations in the system which might reflect their presence in photosynthesizing cells. Concentrations of CO2 and O2 oscillate in opposite phases causing Rubisco switching continuously between the carboxylase (CO2 assimilation) and the oxygenase (photorespiration) reactions. The results of modeling are consistent with carbon isotopic and other observed data. They show that the oscillation period varies from about 1 s to 3 s depending on the values of parameters taken. Too high concentrations of O2 suppress the oscillations.
Projectilelike fragments following the 80 MeV "1"6O+"2"7Al reaction have been detected using a Bragg-curve spectroscopy ionization chamber (BCS-IC). The atomic number is deduced from the Bragg-peak amplitude. Nitrogen isotopes are clearly resolved using either range or energy loss data. This is the first application of the BCS method for complete ion identification in a heavy-ion-induced reaction.
In this paper, steady-state isotopic transient kinetic analysis (SSITKA) is used to study two model reactions, CO oxidation and CO-NO reactions, on a typical formulation of a three-way auto-catalyst. Under steady-state conditions, abrupt switches in the isotopic composition of CO ("1"2C"1"6O/"1"3C"1"8O) were carried out to produce isotopic transients in both labeled reactants and products. Along with the determination of the average surface lifetimes and concentrations of reaction intermediates, an analysis of the transient responses along the carbon reaction pathway indicated that the distribution of active sites for the formation of CO_2 was bimodal for both reactions. Furthermore, relatively few surface sites contributed to the overall reaction rate.
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO2, PrO2), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two sha...
A novel heteropolyanion-based ionic hybrid was prepared by combining the divalent ionic liquid (IL) cation of 1,1'-(butane-1,4-diyl)-bis(3-methylimidazolium) with the Keggin-structured V-containing heteropolyanion, and characterized by ^1H NMR, FT-IR, ESI-MS, XRD, SEM, TG, BET surface area, melting point, and elemental analysis. Its catalytic activity was evaluated in the hydroxylation of benzene with aqueous H2O2, including the testing of the influence of organic cations, catalytic reusability and optimization of reaction conditions. This hybrid is characterized to be semi-amorphous nanoparticles with a IL-like composition. The hybrid catalyst leads to the liquid-solid biphasic reaction system for hydroxylation of benzene with H2O2, presenting such advantages as high catalytic activity, c...
Reaction between [V^I^VO(acac)2] and the ONN donor Schiff base Hpydx-aepy (I) (Hpydx-aepy=Schiff base obtained by the condensation of pyridoxal and 2-aminoethylpyridine) resulted in the formation of a complex [V^I^VO(acac)(pydx-aepy)] (1). Addition of aqueous 30% H2O2 to 1 yields the poor stable oxidoperoxidovanadium(V) complex [V^VO(O2)(pydx-aepy)] (2). Its formation has also been demonstrated in solution by treating 1 with H2O2 in methanol. Reaction of vanadium exchanged zeolite-Y with I in methanol followed by aerial oxidation gave zeolite-Y encapsulated dioxidovanadium(V) complex, abbreviated as [V^VO2(pydx-aepy)]-Y (4). The crystal and molecular structure of 1 has been determined, confirming the ONN binding mode of the ligand. The encapsulated complex [V^VO2(pydx-aepy)]-Y (4) catalyse...
Atomic oxygen is measured in a pulsed dielectric barrier discharge (DBD) using two-photon absorption laser-induced fluorescence (TALIF). The ground-level atomic oxygen is excited to the 3p "3P state by two-photon absorption at 226 nm. Negative (-40 kV) or positive (+30 kV) pulsed DBD occurs in an O_2-N_2 mixture at atmospheric pressure. The pulse width of the DBD current is approximately 50 ns. The TALIF experiment shows that the decay rate of atomic oxygen increases linearly with O_2 concentration. This result proves that atomic oxygen decays mainly by the third-body reaction, O + O_2 + M #-># O_3 + M. The rate coefficient of the third-body reaction is estimated to be 2.2 x 10"-"3"4 cm"6 s"-"1 in the negative DBD and 0.89 x 10"-"3"4 cm"6 s"-"1 in the positive DBD. It is shown that the decay rate of atomic oxygen ...
A high-voltage cathode initiates an electron emission, resulting in a reduction in the carbon dioxide concentration in exhaust gas from the burning of hydrocarbon fuel. Assuming that the observed carbon dioxide reduction is originated from the molecular decomposition, the energy needed for the endothermic reaction of this carbon dioxide reduction may stem primarily from the internal energy reduction in the exhaust gas in accordance of the first law of the thermodynamics. An oxygen increase due to the reduction in carbon dioxide in a discharge gas was observed in real time.
Full text: The surface properties of poly (tetrafluoroethylene) (PTFE) are changed by the exposure to synchrotron radiation (SR). We succeeded in controlling the wettability of the PTFE surface from hydrophobic to hydrophilic by varying the substrate temperature during the SR irradiation and found that the wettability was ascribable to microstructure and chemical composition of surface.In these previous works, oxygen atoms were found to inhabit on the hydrophobic surface of PTFE. In this study, we investigated the surface modification of PTFE from the SR exposure experiment under the O_2 gas atmosphere. The SR exposure to the PTFE sheet was carried out at beamline 6 (BL6) of the New- SUBARU. The PTFE sheet was irradiated to the white beam, ranging 50-1000 eV at BL6 at room temperature. The gas cell was mounted at the irradiation chamber. The O_2 gas pressure in the gas cell can be maintained at about ...
Monte Carlo calculations performed to validate observed capture reaction rates of "1"2"9I and "2"3"7Np were in a reasonable agreement with experimental data obtained by the Joint Institute for Nuclear Research. The most significant discrepancy between the measurements and calculations (within a factor of 3) was observed for the NpO_2 sample and Pb target at 3.7 GeV proton energy
The paper contains a numerical evaluation of the expressions for the absorptive potential in heavy ion reactions given earlier. With a standard folding expression for the real part of the ion-ion potential general good agreement is found with experimental data for the angular distributions of elastic and inelastic scattering. Special interest is attached to the case of "1"6O + "2"8Si where the calculated imaginary potential is very small at low bombarding energies. (orig.).
Charge reduction electrospray mass spectrometry (CREMS) reduces the charge states of electrospray-generated ions, which concentrates the ions from a protein into fewer peaks spread over a larger...Full Text Available
During solvent extraction of At"-, [At(H_2O)_2]"+, AtCl, AtCl_2"- as well as of astatine compounds with higher oxidation states like AtO_n"-, the astatine species are changed into astatine of the oxidation state zero at the phase boundary independent on the organic solvent used. At(O) probably reacts with components of the organic phase or with decomposition products formed by chemical reactions or by radiolysis. The extraction coefficients of the astatine species depend on the experimental conditions applied, the redox potential, and on complex forming reactions or associations, resp., occuring in the aqueous phase. (author).
The core-shell luminol-doped SiO2 nanoparticles were synthesized and immobilized on the surface of chitosan film coating graphite electrode by the self-assembled technique. Then, a novel electrogenerated chemiluminescence (ECL) sensor for pyrogallol was developed based on its ECL enhancing effect for the core-shell luminol-doped silica nanoparticles. The ECL analytical performances and the sensing mechanism of this ECL sensor for pyrogallol were investigated in detail. The corresponding results showed that: compared with the conventional ECL reaction procedures by luminol ECL reaction system, the electrochemical (EC) reaction of pyrogallol and its subsequent chemiluminescence (CL) reaction occurred in the different spatial region whilst offering a high efficiency to couple the EC with the ...
Abstract Salmonella Typhimurium and Listeria monocytogenes are major bacterial pathogens associated with poultry products. A controlled released ClO2 sachet applied with modified atmosphere packaging (MAP) was evaluated for its ability to control the growth of S. Typhimurium and L. monocytogenes on raw chicken breast during refrigerated storage. The fresh chicken samples were inoculated with one or the other of the pathogens at 104-cfu/g, and the packages (with and without ClO2 sachet) were flushed with ambient air or 30% CO2/70% N2 before sealing, and then stored at 4C for up to 21 days. The maximum reduction in MAP plus ClO2 (compared with MAP alone) was 0.68-log-cfu/g for S. Typhimurium and 1.87-log-cfu/g for L. monocytogenes. Color and pH changes of the chicken breast were observed at ...
Fluoroalkyl end-capped vinyltrimethoxysilane oligomer suffered the sol-gel reaction under alkaline conditions in the presence of titanium oxide nanoparticles in tetrahydrofuran to afford the corresponding fluorinated oligomer/titanium oxide nanocomposites[RF-(VM-SiO2)n-RF/TiO2] in excellent to moderate isolated yields. These fluorinated composites thus obtained were nanometer size-controlled fine particles, and exhibited good dispersibility and stability in traditional organic solvents except for water. These fluorinated nanocomposites were applied to the surface modification of glass to exhibit not only a completely superhydrophobic characteristic (a water contact angle: 180degree) with a non-wetting property against water droplets but also a good oleophobicity imparted by fluoroalkyl seg...
Ozone production in a negative corona discharge has been studied experimentally at atmospheric pressure in mixtures of N_2O+O_2 at ambient temperature. Ozone formation was found to be dramatically reduced with increase in the content of N_2O in the mixture. The reaction of O("1D) with nitrous oxide is the most likely process reducing the rate of ozone generation. A considerable decrease in the mean discharge current at a constant voltage was also observed with increasing content of nitrous oxide in the mixture and is attributed to the formation of anions in the discharge. The low values of the calculated mobility of negative charge carriers in the drift region of the discharge is caused by the formation of O"- #centre dot# (N_2O)_n and NO"-#centre dot#(N_2O)_n cluster anions in the drift region of the negative corona discharge.
Spectrophotometric methods were used to investigate the properties of neptunium(VII), (VI), and (V) in silicate solution. The transition of cationic neptunium(VII) to anionic species in non-complexing environments proceeds in the range of ?? 5.5 to 7.5. In the presence of carbonate, this transition occurs at ?? 10.0 to 11.5 and in silicate solutions at ?? 10.5-12.0. These findings show that cationic neptunium(VII) forms complexes with both carbonate and silicate and that the silicate complex is stronger than that of the carbonate. The competition of complex formation reactions for neptunium(VI) with carbonate and silicate and on the known complex stability constant of NpO2(CO3)34- allowed the NpO2SiO3 complex stability constant, log ? = 16.5, to be estimated. Determination of the formation constant of Np(V) complexes with SiO32- was not possible using similar methods.
Methylation of the DNA bases in the Watson-Crick GC and AT base pairs by the methyldiazonium ion was investigated employing density functional and second order Moller-Plesset (MP2) perturbation theories. Methylation at the N3, N7 and O6 sites of guanine, N1, N3 and N7 sites of adenine, O2 and N3 sites of cytosine and the O2 and O4 sites of thymine were considered. The computed reactivities for methylation follow the order N7(guanine)>N3(adenine)>O6(guanine) which is in agreement with experiment. The base pairing in DNA is found to play a significant role with regard to reactivities of the different sites.
In this study, the degrees of destruction of hemoglobin irradiated in atmospheres of air and argon were compared. Hemoglobin preparations were irradiated in the forms: oxyhemoglobin (HbO_2) deoxyhemoglobin (Hb"2"+) and methemoglobin (MetHb) applying doses of 0.5 to 5 Mrad. The degree of hemoglobin destruction was estimate on the basis of changes in the values of the absorption coefficient at the Soret band, the absorption ratio A_5_0_5/A_5_6_3 determined after conversion of irradiated preparations into MetHb, absorption coefficinets for pyridine hemochromogen obtained from irradiated preparations, and changes in parameters characterizing the hemoglobin oxygenation reaction (log p/sub 1/2/O_2 and the Hill n coefficient). The calculated oxygen enhancement ratios S were generally higher than 1 for the parameters estimated. This indicates that the presence of oxygen during irradiation ...
Sulfated zirconia (SO4-ZrO2) catalysts, prepared with three different sulfur loading contents (0.75%, 1.8% and 2.5%) at two calcination temperatures (500degreeC and 700degreeC), were tested for use in the transesterification of purified palm oil (PPO) and the esterification of palm fatty acid (PFA) in near-critical and super-critical methanol. Techniques including BET, XRD, NH3- and CO2-TPD revealed that the sulfur content and calcination temperature strongly affects the catalyst base-acid site, specific surface area, average pore size, phase structure, and thus the catalytic reactivity. The most suitable sulfur loading content was found to be 1.8% and the optimum calcination temperature 500degreeC. The results show that the use of SO4-ZrO2 reduces esterification reaction times, the amount...
A novel visible light sensitive photocatalyst, AgSbO3 was prepared by a conventional solid-state reaction method. This oxide belonging to a cubic-pyrochlore structure can absorb visible light with wavelength up to about 480nm. From the band structure calculation, we found that the top of the valence band consists of the hybridized Ag 4d and O2p orbitals and the bottom of the conduction band mainly consists of the Ag 5s and the Sb 5s orbitals. Photocatalytic activities were evaluated using O2 evolution from an aqueous silver nitrate solution and decomposition of gaseous 2-propanol under visible light irradiation. We found that AgSbO3 shows a higher O2 evolution activity than WO3 and 2-propanol can be mineralized by the AgSbO3 photocatalysis under visible light irradiation.
Cathodic reduction of non-terminal vinylaxides on Hg cathodes in the presence of electrophiles gives reasonable yields of N-acylated enamines in an electrochemically totally irreversible reaction. In the presence of added H-donors rather high selectivity for formation of saturated amides is achieveable. The influence of reaction conditions on product distribution is discussed.
We report on the single-particle properties of lanthanide-ion doped oxide nanoparticles. We have demonstrated that their size can be accurately determined from their luminosity. The optically determined size distribution is in very good agreement with the distribution obtained from transmission electron microscopy (TEM). We also showed that the photobleaching of these nanoparticles is related to a reduction process and that we can use it to sense in a concentration-dependent manner the presence of an oxidant like H2O2. Finally, we propose a way to perform nanoparticle-protein coupling and to determine the protein-nanoparticle ratio at the single-particle level.
This is the final report of a one-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). In an effort to address the problems of long term storage and nuclear waste minimization, zircon has been proposed as a host medium for plutonium and other actinides recovered from dismantled nuclear weapons. The objective of this work is to investigate the feasibility of large scale fabrication of Pu-bearing zircon. Since PuO_2 is thermodynamically less stable than ZrO_2, it is expected that the process parameters determined for synthesizing ZrSiO_4 (zircon) would be applicable to those for PuSiO_4 (Pu-zircon). Furthermore, since the foremost concern in plutonium processing is the potential for contamination release, this work emphasizes the development of process parameters, using zircon first, to anticipate potential material problems in the containment ...
The degradation of chlorinated solvents by reduction at the surface of zero-valent metals and bimetallic systems has emerged as an important approach to the in-situ remediation of ground water. Reduction by iron metal was studied in batch and column systems to develop a mechanistic understanding of the reaction chemistry and to determine the factors that affect dechlorination rate and long term performance in field applications.
Spectral-luminescent characteristics of Sr2Y8(SiO4)6O2: Eu powder crystal phosphor with the apatite structure and high-intensity luminescence of Eu3+ ions have been studied. The charge state of europium in the samples has been characterized by means of X-ray L3-adsorption spectroscopy. It was established that Eu3+ forms two types of optical centers. Besides, luminescence of Eu2+ions was found. Reduction Eu3+#->#Eu2+ was considered, which may be due to VSr|| vacancy formation in the 4f crystal lattice position and to negative charge transfer by this vacancy to two EuY3+ ions. Thus, in the silicate lattice there exist inhomogeneously distributed oxygen-deficient centers, which are responsible for nonradiative transfer of excitation energy to Eu3+ and Eu2+ ions. To study electron-vibrational interactions in the crystal phosphor samples, their IR and Raman spectra were examined. In the luminescence spectrum of Eu2+, a series ...
In this thesis the rate constants for a number of radical reactions in aqueous solution have been studied in a wide temperature range. The reactions of H with H_2O_2, OH and HO_2 and the reactions of HO_2 with OH, Fe"2"+ and Cu"2"+ have been studied. For each reaction rate constants have been determined as a function of temperature using the technique of high temperature, high pressure (HTP) pulse radiolysis. The rate constants were obtained by fitting a kinetic computer model to the experimental data. From an Arrhenius plot the activation energy of each reaction was determined. The data determined in this way are important for modeling of radiolysis in nuclear light water reactors. A previously developed model for calculation of the effect of water radiolysis products on oxidation and dissolution of spent nuclear fuel has been improved. In ...
For the reuse of a waste salt from an electrorefining process of a spent oxide fuel, a separation of rare earth elements by an oxidative precipitation in a LiCl-KCl molten salt was tested without using precipitate agents. From the results obtained from the thermochemical calculations by HSC Chemistry software, the most stable rare earth compounds in the oxygen-used rare earth chlorides system were oxychlorides (EuOCl, NdOCl, PrOCl) and oxides (CeO2, PrO2), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides and oxides were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes: small cubic (oxide) and large plate-like (tetragonal) structures. The ...
The oxidation of Cr(III) hydroxides, mixed Fe(III)-Cr(III) hydroxides, and specimens of spinel phases NiCr2O4 and Fe(Cr,Fe)2O4 have been investigated in alkaline suspensions under the action of air and pure oxygen (1-3 atm). The rate of reaction increases with increasing alkali concentration, temperature, and oxygen pressure. Pu(IV) fixed on chromium hydroxides is not oxidized by oxygen under these conditions but is retained in the precipitate.
Inhaled beryllium oxide results in impaired alveolar clearance of inhaled "2"3"9PuO_2 and induces an inflammatory reaction in the lung. However, only one of 184 rats exposed to beryllium developed a lung tumor; none of 128 unexposed rats developed a lung tumor. Fifty-six lung tumors were induced in 181 rats exposed to plutonium. A total of 37 lung tumors were found in 119 rats given combined exposures to beryllium and plutonium. Only in rats given the highest levels of both beryllium and plutonium was there an incidence of lung tumors greater than that seen with exposure to plutonium only.
The principle of operation of shaft furnaces is explained and demonstrated in four practical examples. The conditions and parameters determining coke conversion in the combustion zone and in the Boudouard reaction range are described. The combustion process is treated as a whole while the reduction process is discussed separately for the blast furnace, the cupola furnace, and the shaft furnace. The possibilities describing the Boudouard reaction as a function of the temperature level are discussed and consequences are derived for further experimental and theoretical studies.
In this contribution we compare the electron scattering processes observed in pure O_2 clusters and mixed clusters like O_2/Ne, O_2/Ar and O_2/N_2. The overlap and positions of the potential curves of O_2 states show the different possible electron attachment processes and also explain the formation of O_2 in clusters. (author).
CuO/bentonite and CuO-BHA nanocomposites were studied as oxygen carriers in chemical-looping combustion (CLC) of simulated synthesis gas. Global reaction rates of reduction and oxidation, as the function of reaction conversion, were calculated from 10-cycle oxidation/reduction tests utilizing thermogravimetric analysis at atmospheric pressure between 700 and 900{degree}C. It was found that the reductionreactions are always faster than oxidation reactions; reaction temperature and particle size do not significantly affect the reaction performance of CuO/bentonite. Multicycle CLC tests conducted in a high-pressure flow reactor showed stable reactivity for production of CO{sub 2} from fuel gas at 800 and 900{degree}C and full consumption of hydrogen during the reaction. Results of ...
A dense Pd-Ag membrane reactor (MR) with 100% hydrogen selectivity packed with either Rh/La2O3 or Rh/La2O3-SiO2 as catalysts was used to carry out the dry reforming of methane. The membrane reactor simulation was performed using a well-known reactor model. For this purpose, we employed the equations derived from complete kinetic studies of the dry reforming of methane reaction in connection with both catalysts. In addition, we developed the kinetic equation for the reverse water gas shift reaction (RWGS). The combination of detailed kinetic studies with the measured permeation flux for the Pd-Ag membrane allowed a complete comparison between experimental and simulated operation variables. The variables studied for both catalysts were methane conversion and hydrogen permeation as a function...
Synthesis of O'/#beta#' SiAlON composites was studied. As starting materials, Si_3N_4, Al_2O_3 and SiO_2 powders were used. Pressureless sintering was applied as consolidation technique and was performed at 1400-1700 C. Densification and reaction taking place during sintering were followed. Microstructure of O'/#beta#' composites is discussed. It was found that without additives liquid phase amount formed within the samples was below critically needed for full densification, but promoted reaction of O' and #beta#' formation. Using yttria as additive densification was enhanced. O'/#beta#' ratio decreased while H_V and K_I_c increased with increasing amount of additive. (orig.).
Simple hydroxamic acids have been shown to have useful applications in an Advanced Purex process for the reprocessing of irradiated nuclear fuel. They are especially suited to the separation of neptunium (IV) from uranium (VI) by the selective formation of a hydrophilic complex with Np(IV). U(VI) extraction in to 30% tributyl phosphate is unaffected. However, they have also been shown to be very fast reducing agents for Np(VI). The timescales of the reduction have been defined under a range of typical Purex Process conditions although the accurate determination of the reaction kinetics was not possible due to the rapidity of the reaction. U(VI) was shown not to be reduced. Therefore, Np(VI) can be efficiently reductively stripped when solvent phase (30% tributyl phosphate in odourless kerosene) solutions of Np(VI) and U(VI) are contacted with aqueous phase hydroxamic acid solutions. The slow ...
A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe{sub 2}O{sub 3} powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe{sub 2}O{sub 3} powder was used to oxidize a high carbon ...
Phenylpropenes, a large group of plant volatile compounds that serve in multiple roles in defense and pollinator attraction, contain a propenyl side chain. Eugenol synthase (EGS) catalyzes the reductive...Full Text Available
The mechanism by which mechanical force regulates the kinetics of a chemical reaction is unknown. Here, we use single-molecule force–clamp spectroscopy and protein engineering to study the effect...Full Text Available
Artifacts in two-dimensional electrophoresis (2-DE) caused by the presence of salts in isoelectric focusing (IEF) have been previously described as a result of increasing conductivity and inducing electroosmosis....Full Text Available
The effect is reported of seven inorganic oxide additives on both the formation mechanism and the densification of X-Sialon prepared by a silicothermal process. The oxides were added to the starting mixture of halloysite clay, alumina and elemental silicon at a level of 1 wt% of the calculated final product, and fired in nitrogen at 1200-1500 deg C. The formation of X-Sialon was monitored by thermal analysis, powder XRD and 2"7"Al and "2"9Si solid state MAS NMR The effects of the additives are temperature dependent and influence the various stages of the reaction by differing degrees. The oxides which best promote the formation of crystalline X-Sialon (Y_2O_3, CaO and MgO) are also those which facilitate the conversion of initially-formed Si_3N_4 to SiO_2N_2 and SiO_3N units. Densification is most enhanced by Y_2O_3 CaO and CeO_2; MgO exerts its maximum effect on sintering at lower ...
In this study nanocrystalline powders of yttria-stabilized zirconia (ZrO_2-8Y_2O_3) have been synthesized through 'polymerized complex method'. Zirconium chloride, yttrium nitrate, citric acid and ethylene glycol were polymerized at 80 "oC to produce a gel-like mass in which metallic ions were uniformly distributed. During the thermal treatment of dried gel, nanocrystalline powder was formed at 450 "oC and 650 "oC for 2 h. Thermal reactions and crystalline phase formation of the dried gel were investigated through thermal analysis and X-ray diffraction analysis, respectively. The results of thermal analysis and XRD showed the formation of nanocrystalline powder at less than 600 "oC. Chemical bonding of the dried gel was investigated by Fourier transform infrared spectroscopy analysis. Morphology of powder calcined at 650 "oC was analyzed by scanning electron microscope. Yttria-stabilized zirconia powders with the mean ...
ZrO_2/O'-sialon composites were obtained via reaction sintering of ZrSiO_4 and Si_3N_4 powders at about 1700 deg C. Y_2O_3 was effective in both stabilizing of zirconia and densifying the composites. However, it is not easy to select an optimum value of the single additive to balance these two requirements simultaneously. With low Y_2O_3 addition, some tetragonal zirconia grains in the sintered samples are transformable during mechanical grinding but the full densification of the material is then sacrificed. On the other hand, addition more Y_2O_3 to achieve complete densification results in the zirconia being stabilized into undesirable t' or cubic forms. Therefore no improved toughening effects have been achieved in the composites. Heat-treatment of the materials at 1400 deg C. results in the diffusion of yttria from the grain boundary phase to zirconia and the formation of the O'-cubic zirconia composite may still ...
The CaWO_4:Ln"3"+ SiO_2 (Ln=Tb, Dy and Ho) nanoparticles were synthesized via a combustion process at 800 "oC, using citric acid as chelating agent and fuel, ammonium nitrate as fuel, boric acid as flux material and silica as supports. The persistent phosphor nanoparticles were characterized by X-ray diffraction (XRD), reflectance UV-vis and fluorescence spectroscopy (PL) and transmission electron microscopy (TEM) techniques. XRD patterns indicated that crystalline calcium tungstate with scheelite structure was produced. The reflectance UV-vis spectra showed the broad absorption band of WO_4"2"- groups and the PL spectra showed the WO_4"2"- wide excitation band, broad emission band of WO_4"2"- and characteristic emissions of Ln"3"+ ions. The average particle sizes were determined by TEM, which are about 50 nm.
Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm"-"3 sodium formate and 2 mmol dm"-"3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O_2"."-"b"a"r decay as monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O_2"."-"b"a"r. A red shift of 0_2"."-"b"a"r absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and ...
Here we report a new method for measuring the heterogeneous chemistry of submicron organic aerosol particles using a continuous flow stirred tank reactor. This approach is designed to quantify the real time heterogeneous kinetics, using a relative rate method, under conditions of low oxidant concentration and long reaction times that more closely mimic the real atmosphere. A general analytical expression, which couples the aerosol chemistry with the flow dynamics in the chamber is developed and applied to the heterogeneous oxidation of squalane particles by hydroxyl radicals (OH) in the presence of O2. The particle phase reaction is monitored via photoionization aerosol mass spectrometry and yields a reactive uptake coefficient of 0.51+-0.10, using OH concentrations of 1-7x108 molec cdot cm-3 and reaction times of 1.5+-3 hours. This uptake coefficient is larger than that found for ...
The effect of a series of complexing and reducing agents on the extraction-chemical behavior of technetium as applied to extraction splitting of uranium and plutonium in the Purex process was examined. Kinetic parameters of the catalytic decomposition of N2H5NO3 under the action of Tc in the presence of these agents were evaluated. Variation of the ratio of the oxidized and reduced Tc species in the course of the process and in the hydrazine-free systems was determined. Reagents preventing oxidation of the reduced technetium and decomposition of N2H5NO3 in nitric acid solutions (acetohydroxamic acid, hydroxylamine, ascorbic acid, etc.), inhibiting the reduction of Tc with hydrazine nitrate (H2O2, HN3, etc.), and known as complexing agents toward quadrivalent actinides but indifferent to Tc...
Summary Exposures to natural and simulated altitudes are combined with a reduction of the available oxygen (hypoxia) and may provoke health problems or even emergencies. Although millions of people are living at high altitudes, are regularly or occasionally performing mountain sport activities, are transported by airplanes, and are increasingly frequently exposed to hypoxia at their workplace, e.g. with fire control systems, there is no consensus about the level of hypoxia which is well tolerated by most of human beings. Thus, the present mini review tries to define such a level. This review indicates that although humans show adaptive responses even to altitudes below 2000 m or corresponding normobaric hypoxia (FiO2: >16%) most of these subjects without severe pre-existing diseases well t...
Solar syngas production from CO"2 and H"2O is considered in a two-step thermochemical cycle via Zn/ZnO redox reactions, encompassing: 1) the ZnO thermolysis to Zn and O"2 using concentrated solar radiation as the source of process heat, and 2) Zn reacting with mixtures of H"2O and CO"2 yielding high-quality syngas (mainly H"2 and CO) and ZnO; the ZnO is recycled to the first, solar step, resulting in net reaction @bCO"2 + (1 - @b)H"2O -> @bCO + (1 - @b)H"2. Syngas is further processed to liquid hydrocarbon fuels via Fischer-Tropsch or other catalytic processes. Second-law thermodynamic analysis is applied to determine the cycle efficiencies attainable with and without heat recuperation for varying molar fractions of CO"2:H"2O and solar reactor temperatures in the range 1900-2300 K. Conside...
The effect of combustion conditions on conversion of char nitrogen to N2 was studied in the combustion experiment of char obtained by pyrolysis of coal. Char specimen was prepared by holding ZN coal of Chinese lignite in Ar atmosphere at 1123K for one hour. A batch scale quartz-made fluidized bed reactor was used for combustion experiment. After the specimen was fluidized in reaction gas, it was rapidly heated to start combustion reaction. CO, CO2 and N2 in produced gases were online measured by gas chromatography (GC). As the experimental result, under the incomplete combustion condition where a large amount of CO was produced by consuming almost all of O2, no NOx and N2O produced from char were found, and almost all of N-containing gas was N2. At the final stage of combustion, pyridinic-N disappeared completely, and pyrrolic-N decreased, while O-containing nitrogen complexes became a main component. ...
The reduction of oxygen was studied in 0.1 M KCl at 70 deg. C using the rotating disk electrode (RDE) technique on platinum and electrodeposited ZnO thin film electrodes deposited on platinum substrates. In the absence of Zn{sup 2+} ions in solution, a Tafel slope of 139 mV dec{sup -1} was obtained, a value close to that measured on bare platinum electrode (133 mV dec{sup -1}) and ascribed to the limitation of the reaction rate by the first electron transfer. The main difference between the noble metal and the oxide electrode was a shift of the curves towards more negative potentials. In the presence of Zn{sup 2+} ions, the current density decreased significantly and the Tafel slope was measured at 282 mV dec{sup -1} showing that the electrode was partially blocked by zinc oxide formation reaction intermediates.
Chemical-looping combustion is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO{sub 2}. Chemical-looping combustion of methane with calcium sulfate as a novel oxygen carrier was conducted in a laboratory scale fixed bed reactor. The effects of reaction temperature, gas flow rate, sample mass, and particle size on reductionreactions were investigated and an optimum operating condition was determined. The results show that this novel oxygen carrier has a high reduction reactivity and stability in a long-time reduction/oxidation test. The conversions of CH{sub 4} increased with a higher temperature, smaller gas flow rate, larger sample mass and smaller particle size. The suitable reaction temperature seems to be around 950 deg. C. Low temperatures lead to a low CH{sub 4} conversion, but a ...
Chemical-looping combustion is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO{sub 2}. Chemical-looping combustion of methane with calcium sulfate as a novel oxygen carrier was conducted in a laboratory scale fixed bed reactor. The effects of reaction temperature, gas flow rate, sample mass, and particle size on reductionreactions were investigated and an optimum operating condition was determined. The results show that this novel oxygen carrier has a high reduction reactivity and stability in a long-time reduction/oxidation test. The conversions of CH{sub 4} increased with a higher temperature, smaller gas flow rate, larger sample mass and smaller particle size. The suitable reaction temperature seems to be around 950 C. Low temperatures lead to a low CH{sub 4} conversion, but a ...
Fully fluorinated compounds (perfluoro compounds) represent a class of chemicals which include many extremely inert species-inert to both chemical reaction and photodissociation. Well known examples include SF6 and the perfluorocarbons (PFCs) CF_4 and Teflon. SF_6 is used industrially in electrical switch gear and as an atmospheric tracer. CF_4 and C_2F_6 are released into the atmosphere as a by-product of aluminum manufacture. Several perfluoro compounds have been proposed as substitutes for the ozone-destroying Freons and halons; proposed substitutes include SF_6, c-C_4F_8, C_5F_1_2, and C_6F_1_4. These chemicals were chosen in part because they do not harm the stratospheric ozone layer and were therefore considered environmentally friendly. Recently, Ravishankara et al. reported that perfluoro compounds have significant global warming potential (GWP), contributing to the greenhouse effect due to strong infrared absorption. The perfluoro compounds have ...
The microstructure of a pressureless sintered (1,605 C, 90 min) O' + #beta#' SiAlON ceramic with CeO_2 doping has been investigated. It is duplex in nature, consisting of very large, slablike elongated O' grains (20--30 #mu#m long), and a continuous matrix of small rodlike #beta#' grains (< 1.0 #mu#m in length). Many #alpha#-Si_3N_4 inclusions (0.1--0.5 #mu#m in size) were found in the large O' grains. CeO_2-doping and its high doping level as well as the high Al_2O_3 concentration were thought to be the main reasons for accelerating the reaction between the #alpha#-Si_3N_4 and the Si-Al-O-N liquid to precipitate O'-SiAlON. This caused the supergrowth of O' grains. The rapid growth of O' crystals isolated the remnant #alpha#-Si_3N_4 from the reacting liquid, resulting in a delay in the #alpha# #-># #beta#-Si_3N_4 transformation. The large O' grains and the #alpha#-Si_3N_4 ...
To improve the photocatalytic application performances of TiO2, in this work, firstly CdS modified Degussa P25 TiO2 (CdS/TiO2) composites were prepared by two methods, sol-gel method and precipitation method. Next they, sol-gel-CdS/TiO2 (sg-CdS/TiO2) and precipitation-CdS/TiO2 (pp-CdS/TiO2), were loaded on activated carbon fibers (ACFs) by dip-coating method using the sodium carboxymethyl cellulose as adhesives. The composites were characterized by XRD, UV-vis absorbance spectra, SEM, EDS and BET. The photocatalytic activities under sunlight were investigated by the degradation of methylene blue. The results showed that CdS/TiO2 composites were mainly ...
Most plans for the disposition of surplus nuclear materials involve storage in sealed containers where the evolution of gases from reactions of adsorbed water could present both pressure and flammability hazards[l] . Despite efforts such as calcining the material to minimize the water content prior to packaging, both residual moisture and readsorbed water may be present in the final containers . Given the anticipated temperature excursions during transportation and storage, this water may thermally desorb, increasing the pressure, and/or thermally dissociate to produce H2 gas, increasing flammability hazards . In addition, the radiation from the nuclear material may induce radiolysis of the water with the likely products being water vapor, H2, 02 and H2O2. In order to better understand the relative importance of the thermal- and radiationinduced chemistry, we have studied the interactions of water on single crystals of ...
The ozone production process in a pulsed positive dielectric barrier discharge (DBD) is studied by measuring the spatial distribution of ozone density using a two-dimensional laser absorption method. DBD occurs in a 6 mm point-to-plane gap with a 1 mm-thick glass plate placed on the plane electrode. First, the propagation of DBD is observed using a short-gated ICCD camera. It is shown that DBD develops in three phases: primary streamer, secondary streamer and surface discharge phases. Next, the spatial distribution of ozone density is measured. It is shown that ozone is mostly produced in the secondary streamer and surface discharge, while only a small amount of ozone is produced in the primary streamer. The rate coefficient of the ozone production reaction, O + O_2 + M #-># O_3 + M, is estimated to be 2.5 x 10"-"3"4 cm"6 s"-"1.
Low fluorescence in the field of the Eu3+ photoluminescence spectrum is registered against a bach ground of the continuum of solvent emanation when multi-bubble sonolysis of EuCl3 (0.1 mol l-1) solutions saturated by the air and argon in heavy water. Distinctive sonoluminescence of europium ion is not found earlier in aqueous solutions. Possible reasons of low values of Eu3+ sonoluminescence as compared with other lanthanide ions (Ln3+), and effect of europium on the spectrum of solvent continuum connected, in particular, with the quenching of electron-excited products of the H2O* (O2O*) and Eu3+* sonolysis in the reactions of electron transfer are discussed
The response regulator protein is a core element of two-component signaling pathway. In this study, we investigated functions of BRRG-1 of Botrytis cinerea, a gene that encodes a putative response regulator protein, which is homologous to Rrg-1 in Neurospora crassa. The BRRG-1 gene deletion mutant ?Brrg1-62 was unable to produce conidia. The mutant showed increased sensitivity to osmotic stress mediated by NaCl and KCl, and to oxidative stress generated by H2O2. Additionally, the mutant was more sensitive to the fungicides iprodione, fludioxonil, and triadimefon than the parental strain. Western-blot analysis showed that the Bos-2 protein, the putative downstream component of Brrg-1, was not phosphorylated in the ?Brrg1-62. Real-time polymerase chain reaction assays showed that expression ...
In the present contribution, the innovative in situ Raman micro-spectroscopy was applied to investigate the in vitro reactivity of various bioactive glasses. All the investigated glasses belonged to the Na2O\\K2O-CaO-P2O5-SiO2 system, but contained sensibly different percentages of network modifiers. The glasses were immersed for increasing times, up to 96h, in simulated body fluid (SBF) and in tris-buffered (TRIS) solution. In this way, two fundamental items were addressed, i.e. the effect of the glass composition and the nature of the soaking fluid on the overall reactivity. As regards the SBF, all the glasses were able to promote the formation of a hydroxyl-carbonate apatite (HCA) surface layer in very short times. The reaction rate was particularly quick for the 45S5 Bioglass and for it...
To investigate the characteristics of a reactor and a neutron generator, a small scintillation detector with an optical fiber with ThO_2 has been developed to measure fast neutrons. However, experimental facilities where "2"3"2Th can be used are limited by regulations, and S/N ratio is low because the background counts of this detector are increase by alpha decay of "2"3"2Th. The purpose of this study is to develop a new optical fiber detector for measuring fast neutrons that does not use nuclear material such as "2"3"2Th. From the measured and calculated results, the new optical fiber detector which uses ZnS(Ag) as a converter material together with a scintillator have the highest detection efficiency among several developed detectors. It is applied for the measurement of reaction rates generated from fast neutrons; furthermore, the absolute detection efficiency of this detector was obtained experimentally.
Oxidative degradation of methylene blue (MB) by Co^2^+-HCO3^- system with H2O2 in aqueous solution was studied. Nearly complete decolorization of the dye was obtained in less than 50min in diluted NaHCO3 solution (25mM) in the presence of only 20mM Co^2^+ ions. Meanwhile, the conjugated structure and phenyl rings of the MB molecule were destroyed or even broken down into small organic acids and inorganic ions, as indicated by FT-IR spectra and ion-chromatography. Photoluminescence probing and radical scavenging technologies suggested that the reaction of MB degradation in this system mainly involved the generation and participation of hydroxyl radicals. Furthermore, by cyclovoltammetric measurements, the in situ formed different complexes between Co^2^+ and HCO3^- were observed at differen...
4-Methylcoumarins that possess two hydroxyl groups ortho to each other in the benzenoid ring have shown to have excellent antioxidant and radical-scavenging properties in different experimental models. Furthermore, they cannot be metabolized by the liver P450 monoxygenases and thus cannot form 3,4-coumarin epoxides, which are believed to be mutagenic. Herein, we present a study on the structure activity relationship of eight synthetic 4-methylcoumarins, carried out by employing a series of different chemical cell-free tests. These compounds were tested by means of three assays involving one redox reaction with the oxidant (DPPH assay, ABTS+ assay and FRAP). Other assays were employed to evaluate the antioxidant properties of the coumarins under investigation against NO, O2- and HClO, which...
We demonstrate that the excess vacancies induced by a 1 MeV Si implant reduce the excess interstitials generated by a 40 keV Si implant during thermal annealing when these two implants are superimposed in silicon. It is shown that this previously observed reduction is dominated by vacancy annihilation and not by gettering to deeper interstitial-type extended defects. Interstitial supersaturations were measured using B doping superlattices (DSL) grown on a silicon-on-insulator (SOI) substrate. Implanting MeV and keV Si ions into the B DSL/SOI structure eliminated the B transient enhanced diffusion normally associated with the keV implant. The buried SiO_2 layer in the SOI substrate isolates the deep interstitials-type extended defects of the MeV implant, thereby eliminating the possibility that these defects getter the interstitial excess induced by the keV Si implant. copyright 1999 American Institute of Physics.
Previous studies have documented dissimilatory growth of bacteria on solid Mn{sup 4+} oxide, but Mn{sup 3+} oxides have not been previously studied; here the authors have demonstrated for the first time the bacterial reduction of manganite. Strain MR-4 of Shewanella putrefaciens was able to grow on and rapidly reduce insoluble needle-shaped crystals of synthetic manganite (MnOOH), converting them to soluble Mn{sup 2+} in the process. The rate of Mn{sup 3+} reduction was optimal at pH of 7.0 and 26 C consistent with an enzymatic reaction. In addition the rates of reduction were in proportion to the amount of manganite added, but nearly independent of the cell concentration present (e.g., cell number had only a small effect on the rate of Mn{sup 3+} reduction at early stages of growth) suggesting that surface properties were dictating the rates of metal reduction. ...
The effect of hydrogen sulfide (H2S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxidesssuch as iron oxide, nickel oxide, manganese oxide, and copper oxideswas investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H2S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H2S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence of H2S, but both manganese oxide and copper oxide showed decreased ...
With an objective to learn reactivity of coal at its surface, surfaces of oxidized coal samples were investigated. Miike coal was oxidized by using {sup 18}O2 in a closed loop system. As the reaction progresses, proportion of CO2 including isotopes increased rapidly as a result of oxidation of CO sites existing in the coal and the newly generated C{sup 18}O sites. The oxidizing reaction progressed via oxygen adsorbing sites generated near the surface, and oxygen containing groups. An FT-IR analysis estimated the depth of the oxidized layer to be 10{mu}m or less from particle surface. The oxidized coal was pulverized to see its surface condition. Functional groups introduced by the oxidation enter into the vicinity of the surface in a form to desorb as CO. CO2 is trapped in inner pores. The coal surface was observed by using an atomic force microscope. No observable openings in the pore structure were ...
Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate.
Partial oxidation of 2-propanol was carried out on AB{sub 1-x}B`{sub x}O{sub 3} (A=Ba, B=Pb, Ce, Ti; B`=Bi, Sb and Cu) type perovskite oxides. Acetone was the major product observed on all the catalysts. All the catalysts underwent partial reduction during the reaction depending on the composition of the reactant, nature of the B site cation and the extent of substitution at B site. The catalytic activity has been correlated with the reducibility of the perovskite oxides determined from Temperature Programmed Reduction (TPR) studies. (orig.)
A new series of anatase TiO2 hollow structures were prepared by a facile hydrothermal process. When the hydrothermal time was increased from 20min to 72h, the resulting TiO2 solid spheres gradually transformed into TiO2 hollow spheres with higher surface crystallinity and exposed {001} facets. The as-prepared TiO2-72h sample exhibited the highest activity comparing to other TiO2-based samples and commercial product Degussa P-25 towards the selective photocatalytic oxidation of toluene to benzaldehyde. Such great photocatalytic performance was mainly attributed to enhanced UV-adsorption and better charge separation efficiency due to higher surface crystallinity of TiO2-72h.
In energy industries, it is always of difficulty to produce high heat value(HHV) gas continuously using pulverized coal. In this paper, a new type furnace for partitioned alternative gasification using pulverized coal is developed, in which the oxidation and reductionreaction occur alternatively with the dropping of pulverized coal and finally HHV gas could be continuously obtained at the reduction zone exit and low heat value(LHV) gas at the oxidation zone exit. Furthermore, the gasification characteristics and their factors in furnace are numerically simulated under two dimensional model with a self-coded program, based on heat, mass and energy transfer as well as reaction principles. It is found that the producing rate of HHV gas is 1.10Nm3/kg with heat value of 11.72MJ/Nm3, however, t...
In closed systems, the O2 compensation point (?O) was previously defined as the upper limit of O2 level, at a given CO2 level, above which plants cannot have positive carbon balance and survive. Studies with 18O2 measure the actual O2 uptake by photorespiration due to the dual function of Rubisco, the enzyme that fixes CO2 and takes O2 as an alternative substrate. One-step modelling of CO2 and O2 uptakes allows calculating a plant specificity factor (Sp) as the sum of the biochemical specificity of Rubisco and a biophysical specificity, function of the resistance to CO2 transfer from the atmosphere to Rubisco. The crossing points (Cx, Ox) are defined as CO2 and O2 concentrations for which ...
Alkaline fuel cells (AFCs) provide a less corrosive environment and can provide higher electrode reaction kinetics than proton exchange membrane fuel cells (PEMFCs). The alkaline media also allows for the replacement of platinum (Pt) based electrocatalysts with non-Pt electrocatalysts. Studies have shown that palladium (Pd) and silver (Ag) form a homogenous solid solution with a face-centred cubic structure within a large range of temperatures. This study described the results of an oxygen reductionreaction (ORR) on lead-silver (Pd-Ag) alloy electrodes in alkaline media. The reaction was compared with Pd and Ag electrodes. The alloys were synthesized as thin films using a sequential electroless deposition of Pd and Ag on stainless steel discs followed by an annealing procedure in an Ar stream. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used ...
AFFF has fabricated the (U, Pu)O_2 mixed oxide fuels for PHWRs, BWRs, PFBRs and FBTRs. The quantitative dissolution of the fuel samples are required within time for accurate determination of uranium-plutonium in chemical quality control laboratory. This paper describes the use of microwave heating technique in quantitative dissolution of (U, Pu)O_2 MOX (from 0.4% to 44% PuO_2). (author)
Palladium silicide was formed on the sol-gel derived SiO2 supported Pd catalysts prepared by ion-exchange method (Pd/SiO2-SG-ion). However, the catalysts exhibited superior performances than commercial SiO2 supported ones in liquid-phase semihydrogenation of phenylacetylene. It was probably due to an inhibition of a product of styrene, which is adsorbed on the surface of Pd, more strongly on Pd/SiO2-SG in which Pd is electron-deficient as shown by larger binding energy from XPS results.
Hardened CMOS/SOI 29101 microprocessor, elementary cells and transistor shave been irradiated at levels between 10 Mrad(SiO_2) and 1 Grad(SiO_2) ("6"0Co and 10 keV x-rays). SIMOX buried oxide behavior in the range of 100 Mrad(SiO_2) and a channel-stopped MOS/SOI structure avoiding lateral leakage current are presented. These two items indicate the feasibility of a CMOS/SOI technology operating in the hundred Mrad(SiO_2) range.
Consideration is given to the process of the formation of a titanium sponge alloyed with niobium or tantalum, in the joint metallic reduction of titanium, niobium and tantanum chlorides. A percentage composition of the phases observed and the structure of the alloyed sponge have been studied. It is shown that after one remelting operation of the alloyed sponge the alloys of titanium with niobium and tantalum have a uniform component distribution. At the stage of chloride reduction there appear solid solutions based on titanium and an alloying component. The stage of vacuum separation of the reaction mass is associated with a mutual dissolution of the primary phases and the formation of the solid solutions of the alloyed titanium sponge, which, by their composition, are close to the desired alloy composition. The principal features of the formation of a titanium sponge alloyed with niobium and tantalum are in a perfect ...
This illustrated final report for the Swiss Federal Office of Energy (SFOE) presents the results of a project concerning a new, highly active oxygen reduction electrode for PEM fuel cell and zinc/air battery applications. The goal of this project was, according to the authors, to increase the efficiency of the oxygen reductionreaction by lowering the activation polarisation through the right choice of catalyst and by lowering the concentration polarisation. In this work, carbon nanotubes are used as support material. The use of these nanotubes grown on perovskites is discussed. Theoretical considerations regarding activation polarisation are discussed and alternatives to the use of platinum are examined. The results of experiments carried out are presented in graphical and tabular form. The paper is completed with a comprehensive list of references.
Using the method of statistic planning of an experiment, the SrSO_4 desulfurization process has been studied in the case of reductive roasting of celestine with the use blast-furnace coke. The main factors that determine the rate of the SrSO_4 desulfurization are the roasting temperature and charge components dispersity. The desulfurization rate increases proportionally to the increase in the roasting temperature and dispersity of the reaction mixture components. To decrease the SrSO_4 desulfurization and the concentration of sulfur-containing components in gases released at rather a high celestine reduction rate, the roasting is recommended to proceed at the temperature of 1100 to 1150 deg, in this case it is necessary to limit the content of small (less than 3.2 mm) fractions of reagents.
The development of an electrolytic reduction technology for spent fuels in the form of oxide is of essence to introduce LWR SFs to a pyroprocessing. In this research, the technology was investigated to scale a reactor up, the electrochemical behaviors of FPs were studied to understand the process and a reaction rate data by using U{sub 3}O{sub 8} was obtained with a bench scale reactor. In a scale of 20 kgHM/batch reactor, U{sub 3}O{sub 8} and Simfuel were successfully reduced into metals. Electrochemical characteristics of LiBr, LiI and Li{sub 2}Se were measured in a bench scale reactor and an electrolytic reduction cell was modeled by a computational tool.
In this, the last of a series of three papers, we discuss a method of forming iron phosphate ceramics by a reduction process. We report the formation of iron oxide ceramics by reducing hematite with iron in a phosphoric acid solution. The reaction results in a rapid-setting ceramic (at room temperature) with a compressive strength of 3700 psi and a density of 1.7 g/cm{sup 3}. Although the exact mineral form of the binder is difficult to determine because it is mostly amorphous and hence is not amenable to X-ray diffraction analyses, this material is expected to consist of iron hydrophosphates. The reduction process is very useful in recycling several industrial wastes that are rich in hematite, including iron mine tailings, red mud (a caustic waste from the alumina industry), and machining swarfs. Formation of ceramics with red mud and swarfs is also discussed.
HgTe rod-shape composed of crystalline particles has been prepared by a hydrothermal method, and characterized by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transition electron microscopy (TEM). The effects of capping agents, reductants, reaction temperatures, and reaction times on crystal structures and shapes of HgTe have been investigated. The results showed that the CTAB as capping agent plays a crucial role in the hydrothermal process. The synthesis procedure is simple and uses less toxic reagents than the previously reported methods.
As part of our effort to develop a semicontinuous PuO/sub 2/ reduction process, we are investigating promising materials for containing a 900/sup 0/C molten CaCl/sub 2/ . CaO chlorination reaction. We want the material to contain this reaction and to be reusable. We tested candidate materials in a simulated salt (no plutonium) using anhydrous HCl as the chlorinating agent. Data are presented on the performance of 36 metals and alloys, 9 ceramics, and 3 coatings.
An improved method for the synthesis of (/sup 15/N) 16-Doxyl stearate, a fatty-acid spin label, is reported. The method requires only one mole of (/sup 15/N) 2-amino-2-methyl propanol per mole of methyl keto stearate with an overall yield of about 50%. In contrast, the previous method produced only 1-3% yield. The great improvement in yield was achieved mainly through the reduction of reaction volume which increases the reaction rate by the law of mass action.
Reaction of At(I) with triphenylphosphine, triethylphosphite and tri-n-octylphosphine oxide was investigated in ethanolic solution by means of electromigration. A cationic complex with triphenylphosphine was identified being stable at pH = 1,9 in the concentration range of the ligand between c = 10{sup -5} to 10{sup -3} M. At a higher ligand concentration and at pH>2, the reduction effect of phosphine is superimposed on the complex formation. Complex formation is confirmed by ligand exchange reactions with Br{sup -} and I{sup -}. A comparatively weak complex is formed by triethylphosphite and At(I). No compound is formed by tri-n-octylphosphine oxide and At(I). (orig.).
Reaction of At(I) with triphenylphosphine, triethylphosphite and tri-n-octylphosphine oxide was investigated in ethanolic solution by means of electromigration. A cationic complex with triphenylphosphine was identified being stable at pH = 1,9 in the concentration range of the ligand between c = 10"-"5 to 10"-"3 M. At a higher ligand concentration and at pH>2, the reduction effect of phosphine is superimposed on the complex formation. Complex formation is confirmed by ligand exchange reactions with Br"- and I"-. A comparatively weak complex is formed by triethylphosphite and At(I). No compound is formed by tri-n-octylphosphine oxide and At(I). (orig.).
In this study, considering that Hg(2+) in wet flue gas desulfurization (FGD) systems can easily be reduced and then released into atmosphere, causing secondary pollution, the researches about Hg(2+) reduction and Hg(0) re-emission mechanism were carried out. The effects of several experimental parameters on the reduction were studied, including initial pH, temperature, and concentrations of Cl(-) and S(IV). Our experimental results indicated that Cl(-) had a restraining effect on the Hg(2+) reduction and Hg(0) re-emission, after 24h reaction, only 20.5% of Hg(2+) was reduced with 100mM Cl(-) in simulated desulfurization solution. Cl(-) can slow Hg(2+) reduction and Hg(0) re-emissions dramatically through changing reaction mechanism, with formation of new intermediate: ClHgSO(3)(-), which can decompose to Hg(0), but much more slowly than Hg(SO(3))(2)(2-) or ...
The aim of this work is to be able to describe transformations, occurring when solids and gases are in non isothermal and non isobaric conditions, with kinetic models. A methodology has been used. Two essential processes have to be taken into account: the germination and the growth. The germs are supposed to be formed (at constant temperature and pressure) in the grains surface with a constant velocity by surface unit, (gamma), called germination surface frequency (number of germs.m{sup -2}.s{sup -1}. The growth velocity is characterized by a growth surface reactivity, (phi) (in mol.m{sup -2}.s{sup -1}). With an appropriate transformation model, it is possible to obtain the variations of (gamma) and (phi) in terms of the temperature and pressure which are then used in the calculation of the velocity in non isothermal and non isobaric conditions. In order to validate the developed method, two reactions have been studied. For the first one, the kaolinite ...
Present and potential future changes to the global environment have important implications for marine pollution and for the air-sea exchange of both anthropogenic and natural substances. This report addresses three issues related to the potential impact of global change on the air-sea exchange of chemicals: Global change and the air-sea transfer of the nutrients nitrogen and iron. Global change and the air-sea exchange of gases. Oceanic responses to radiative and oxidative changes in the atmosphere. The deposition of atmospheric anthropogenic nitrogen has probably increased biological productivity in coastal regions along many continental margins. Atmospheric deposition of new nitrogen may also have increased productivity somewhat in mid-ocean regions. The projected future increases of nitrogen oxide emissions from Asia, Africa and South America will provide significant increases in the rate of deposition of oxidized nitrogen to the central North Pacific, the equatorial Atlantic, and ...
The electrochemical behavior of Sb(III) ions was investigated in LiCl-KCl molten salt at 673K. The reaction mechanism and transport parameters of electroactive species were determined by transient electrochemical techniques (such as cyclic voltammetry, square wave voltammetry, chronopotentiometry and chronoamperometry) at a molybdenum electrode. The results showed that electrochemical reduction of Sb(III) in LiCl-KCl melts occurred in a reaction step with an exchange of three electrons. A voltammogram with a different scan rate in LiCl-KCl containing 1.45x10^-^4molcm^-^3 SbCl3 showed that the deposition/dissolution reaction of Sb(III) ions was not completely reversible. The diffusion coefficient of Sb(III) ions was 1.65(+/-0.01)x10^-^5cm^-^2s^-^1 at 673K. The electroreduction of Sb(III) io...
High resolution Monte-Carlo simulations show that the neutron spectrum, fuel burnup and fuel temperature feedback effect of a PWR core loaded with Thoria-based fuel (Th/Pu-O_2) do not significantly differ from the MOX fuelled one due to the similar neutronic characteristics of both fertile materials (Th-232, U-238). The core physics of this fuel variant is characterized by an enhanced moderator/void temperature coefficient (by factor 2.4) and high incineration rate for Pu (approx. 60 %). A PWR core loaded with the Molybdenum-based inert matrix fuel (IMF) - in contrast to MOX-, shows a harder spectrum, resulting in small temperature coefficients of reactivity and particularly in a higher fuel depletion rate as well as an enhanced TRU reduction performance. The incineration of Pu amounts to 46 % resulting, in turn, in generation of minor actinides of about 10 % of the total Pu consumption. The higher excess reactivity ...
Highly conductive biaxially textured RuO_2 thin films were deposited on technically important SiO_2/Si substrates by pulsed laser deposition, where yttria-stabilized zirconia (YSZ) produced by ion-beam-assisted-deposition (IBAD) was used as a template to enhance the biaxial texture of RuO_2 on SiO_2/Si. The biaxially oriented RuO_2 had a room-temperature resistivity of 37 #mu##OMEGA#-cm and residual resistivity ratio above 2. We then deposited Ba_0_._5Sr_0_._5TiO_3 thin films on RuO_2/IBAD-YSZ/SiO_2/Si. The Ba_0_._5Sr_0_._5TiO_3 had a pure (111) orientation normal to the substrate surface and a dielectric constant above 360 at 100 kHz. copyright 1998 Materials Research Society.
4.82 wt% AIN and 2.98 wt% Y_2O_3 were added to Si_3N_4 as sintering agents in order to have #alpha#_Sialon composition of x=0.15 and monoclinic ZrO_2 between 0 to 10 wt% was admixed with Si_3N_4 based ceramics were fabricated by hot-pressing at 1,750 deg C for 90 min under 30 MPa in argon and nitrogen atmospheres effects of sintering atmospheres and addition of ZrO_2 on mechanical properties of Si_3N_4 based ceramics were investigated. As ZrO_2 content increased, the fraction of #alpha#-Sialon tended to decrease and the amount of cubic ZrO_2 increased because Y_2O_3 acted as the stabilizer of ZrO_2. The sintering atmospheres didn't affect on the sintering behavior and the product phases in hot-pressing of Si_3N_4. Bending strength increased when ...
The purpose of work is systematical studying of benzo (B) of thiophene-1,1-dioxides and their 2,3-di-hydro derivatives behaviour in the reactions of electrophflic, radical, nucleophilic nitration, reduction of nitro group, embodiment of synthesis of N-amino derivatives, investigation of sulfur containing hetero-cyclic compounds, including of residues of some steroids
Abstract A diacrylate polysulfone oligomer is synthesized and used as the acrylic oligomer for the in situ synthesis of noble metal/PSU nanocomposites through UV-induced simultaneous radical polymerization of acrylic functionalities and NP formation by reduction of their precursors. Thus, silver or gold NPs are formed in situ during polymer network formation. FESEM analysis of the morphology of the cured systems demonstrates that the nanoparticles of the noble metals are homogeneously distributed in the network without macroscopic agglomeration.
The selective catalytic reduction of nitric oxide by methane over copper ion-exchanged natural zeolites was investigated in a packed-bed tubular reactor. The catalytic activity of Cu-N and Cu-H-N catalysts was confirmed as NO, CH{sub 4}, and O{sub 2} displayed very little reaction in the absence of any catalyst and zeolite without ion exchange was totally inactive. A maximum NO conversion of 33% at 650 C for Cu-N-66 was achieved with 2% NO and 1% CH{sub 4} and a contact time of 0.9 g s/cm{sup 3}, but the introduction of 2% O{sub 2} reduced the NO conversion to only 12%. Ion exchange for the H-form prior to copper ion exchange was essential for oxygen to promote catalytic activity over the temperature range 250--650 C, with a maximum conversion of 30% at 450 C with O{sub 2} present. The direct reduction of NO by methane was ruled out as a possible reaction pathway.
The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reductionreaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The ...
The electrochemical treatment of solutions containing C.I. Basic Yellow 2 (BY2) in aqueous solutions with carbon-PTFE (polytetrafluoroethylene) and carbon nanotube (CNT)-PTFE electrodes as cathode has been studied. The fabricated electrodes were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The amount of electrogenerated H2O2 on the surface of these electrodes was investigated, too. The results showed that the amount of H2O2 obtained with the CNT-PTFE electrode was nearly three times higher than that of carbon-PTFE electrode. The decolorization efficiency of BY2 in peroxi-coagulation process reached 62% and 96% in the first 10 min by carbon-PTFE and CNT-PTFE electrodes at 100 mA, respectively. The effect of operational parameters such as applied current, initial pH and initial dye concentration was studied in an attempt to reach higher decolorization efficiency. ...
Recent work has indicated that the suppression of boron transient enhanced diffusion (TED) in carbon-rich Si is caused by nonequilibrium Si point defect concentrations, specifically the undersaturation of Si self-interstitials, that result from the coupled out-diffusion of carbon interstitials via the kick-out and Frank--Turnbull reactions. This study of boron TED reduction in Si{sub 1-x-y}Ge{sub x}C{sub y} during 750{sup o}C inert anneals has revealed that the use of an additional reaction that further reduces the Si self-interstitial concentration is necessary to describe accurately the time evolved diffusion behavior of boron. In this article, we present a comprehensive model which includes {l_brace}311{r_brace} defects, boron-interstitial clusters, a carbon kick-out reaction, a carbon Frank--Turnbull reaction, and a carbon interstitial-carbon substitutional (C{sub i}C{sub s}) ...
Recent work has indicated that the suppression of boron transient enhanced diffusion (TED) in carbon-rich Si is caused by nonequilibrium Si point defect concentrations, specifically the undersaturation of Si self-interstitials, that result from the coupled out-diffusion of carbon interstitials via the kick-out and Frank--Turnbull reactions. This study of boron TED reduction in Si_1_-_x_-_yGe_xC_y during 750"oC inert anneals has revealed that the use of an additional reaction that further reduces the Si self-interstitial concentration is necessary to describe accurately the time evolved diffusion behavior of boron. In this article, we present a comprehensive model which includes #left brace#311#right brace# defects, boron-interstitial clusters, a carbon kick-out reaction, a carbon Frank--Turnbull reaction, and a carbon interstitial-carbon substitutional (C_iC_s) pairing ...
TiO2 hollow microspheres with sea urchin-like hierarchical architectures were synthesized by a simple hydrothermal method. The as-synthesized hollow microspheres with hierarchical architectures consisting of many rhombic building units exhibit high specific surface area. Electrorheological (ER) properties of hierarchical hollow TiO2-based suspension were investigated under steady and oscillatory shear. The hollow TiO2-based suspensions show much higher yield stress and elasticity than pure TiO2 suspension at the same electric field strength. This phenomenon was elucidated well in view of their dielectric spectra analysis. The sea urchin-like architectures result in stronger interfacial polarization of hollow TiO2 suspension upon an electric field, showing higher ER activity. ...
SnO2/graphene nanocomposites have been fabricated by a simple chemical method. In the fabrication process, the control of surface charge causes echinoid-like SnO2 nanoparticles to be formed and uniformly decorated on the graphene. The electrostatic attraction between a graphene nanosheet (GNS) and the echinoid-like SnO2 particles under controlled pH creates a unique nanostructure in which extremely small SnO2 particles are uniformly dispersed on the GNS. The SnO2/graphene nanocomposite has been shown to perform as a high capacity anode with good cycling behavior in lithium rechargeable batteries. The anode retained a reversible capacity of 634 mA?h?g?1 with a coulombic efficiency of 98% after 50 cycles. The high reversibility can be attributed to the mechanical buffering by the ...
The transients involved in the reaction of tetracycline (TC) with reducing radicals such as e{sub aq}{sup -}, (CH{sub 3}){sub 2}COH and CO{sub 2}{sup .-}have been characterized by the pulse radiolysis technique. The semi-reduced species formed ({lambda}{sub max} = 630 nm, {epsilon} 3.4 x 10{sup 3} dm{sup 3} mol{sup -1} cm{sup -1}) has been found to be a strong reductant with reduction potential lying in the range -0.450 to -1.40 V vs NHE. TC reacts with e{sub aq}{sup -} at diffusion-controlled rates and the rate constant, depending upon the ionic form of TC existing at a particular pH, varies from 1.2 x 10{sup 10} to 2.8 x 10{sup 10} dm{sup 3} mol{sup -1} s{sup -1}. Based on these results a plausible site of electron addition has been suggested. Reaction of H atoms with TC gives rise to a transient which exhibits spectral and kinetic features different from that of semi-reduced species. (author).
Three abiotic systems are described that catalyze the reductive dehalogenation of heavily halogenated environmental pollutants, including carbon tetrachloride, trichloroethene, and perchloroethene. These systems include (a) an electrolytic reactor in which the potential on the working electrode (cathode) is fixed by using a potentiostat, (b) a light-driven system consisting of a semiconductor and (covalently attached) macrocycle that can accept light transmitted via an optical fiber, and a light-driven, two-solvent (isopropanol/acetone) system that promotes dehalogenation reactions via an unknown mechanism. Each is capable of accelerating reductive dehalogenation reactions to very high rates under laboratory conditions. Typically, millimolar concentrations of aqueous-phase targets can be dehalogenated in minutes to hours. The description of each system includes the elements of ...
The effects of the structure of a carboxylic acid on the processes of oxidation and reduction of iron ions in irradiated aqueous solutions were directly observed during irradiation. The solutions contained the mono- or dicarboxylic acid, H/sub 2/SO/sub 4/, Fe(NH/sub 4/)/sub 2/(SO/sub 4/)/sub 2/ and O/sub 2/. Th e ferrous oxidation was rather independent of the acid and its concentration, but the reduction of ferric was possible in the presence of formic, oxalic, or valeric acid only. The radical formed from the valeric acid acts similar to those formed from hydrocarbons. The G-values of oxidation and reduction of the iron ions were established. The molar extinction coefficients for oxalic and malonic complexes of ferric ions were determined. (auth)
Schiff-base condensation of a equimolar proportion of diacetyl-monoxime monohydrazone and 1-methylimidazole-2-carboxaldehyde in methanol gives rise to the imidazole azine, 3-(1-methylimidazol-2-yl)methylenehydrazonobutan-2-one oxime(HL). Reaction of 1:1 stoichiometric proportion of HL with copper(II)perchlorate hexahydrate in methanol yields a dimeric oximato bridged copper compound, [Cu2L2(H2O)2](ClO4)2 (1). The compound is characterized by C, H and N analyses, FT-IR, ESI?MS, conductivity measurement, UV?Vis spectra and X-ray single crystal diffraction. The title compound (1) crystallizes in the monoclinic space group P21/c with a?=?6.8533 (8), b?=?18.413 (2), c?=?11.7399 (14) ?, ??=?93.685 (2)?, V?=?1478.4 (3) ?3 and Z?=?2. The geometry around each copper center is distorted square pyram...
Propylene polymerizations were carried out with #phi#_2C(Flu)(Cp)ZrCl_2 and SiMe_2(Ind)2ZrCl_2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f_2C(Flu)(Cp)ZrCl_2, SiO_2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)
The formation kinetics of Pd_2Si for fully silicided (FUSI) gate formation and the work function tuning of a Pd_2Si FUSI gate by impurity predoping were investigated. It has been found that the morphology and phase of a formed FUSI layer depend not only on the silicidation annealing temperature but also on the heating ramp-up rate and the presence of impurities. Fast ramp-up annealing was necessary to avoid defect formation, such as voids in the silicide film at the oxide interface, and to obtain a homogeneous silicide film containing only Pd_2Si phase. The most severe effect on the silicidation reaction, that is the increase in defect formation, was brought about by As predoping. The work function of the Pd_2Si FUSI gate was modulated by impurity pileup at the Pd_2Si/SiO_2 interface, as in the case of the NiSi FUSI gate. However, the work function shifted in the opposite direction to that of the NiSi FUSI gate for As, P, ...
The nature of the electrolyte strongly influences the electrode kinetics of the oxygen evolution reaction (OER) and electrochemical ozone production (EOP) mainly by affecting the degree of coverage by the intermediates of both processes. The anomalous behaviour of the Tafel coefficient, b, as a function of temperature was attributed to surface adsorption of the electrolyte species, and the competition between them, as well as gas bubble adherence. Comparison of the current efficiencies of the EOP, PHI_E_O_P, determined for different temperatures and supporting electrolyte compositions, showed the presence of fluorinated anions increases PHI_E_O_P. The influence of the anion nature on PHI_E_O_P, when analysed in the light of the proposed electrode mechanism, reveals introduction into the electrolyte of anions having a high electronegativity changes the double layer structure resulting in an increase of surface concentration of the active centres leading to EOP. The ...
To reduce the volume of radioactive wastes after evaporation, activity carriers can be separated from the inactive salt load. Boric acid separation from PWR concentrates was considered a preliminary stage for nuclide precipitation. In connection with the precipitation process, the reaction conditions for boric acid separation were determined by bench-scale experiments. After evaluating the known purification processes, crystallization was suggested as a practicable method. After inactive bench-scale experiments, mixed crystal formation with iron hexacyanoferrate for Cs removal was chosen. The disturbing effect of the complexing agents was neutralized by a pre-dose of iron-III-salts. By specifying the precipitation conditions, for Cs-134 an activity separation from 3,0 E + 06 Bg/l to 1,9 E + 02 Bg/l, and for Cs-137 from 5,9 E + 06 Bg/l to 1,2 E + 02 Bg/l was achieved. Accordingly, the decontamination factor for Cs-134 was 16000, and for Cs-137 48000. For the ...
In this paper, we prepared by the sol-gel method alkaline titania catalysts, doped by gelling titanium alkoxide with aqueous solutions containing potassium, rubidium or cesium chlorides. XRD patterns showed that samples annealed at 400 and 600degreeC contained a single crystalline phase, anastase. Specific surface areas were higher in samples annealed at 400degreeC (>100m2/g) than in those annealed at 600degreeC (25m2/g). The weight density of basic sites determined by CO2-TPD drastically diminished in samples treated at 600degreeC. Catalysts were tested for the self-condensation of acetone at 300degreeC; main reaction products were isomesityl oxide, mesityl oxide and mesitylene. Samples annealed at 600degreeC showed lower acetone conversion rate and low formation of mesitylene than that o...
Information is presented concerning solute concentration in a porous layer; solute concentration in a packed crevice; corrosion of a packed carbon steel crevice in NaCl-O"2 solutions; and effect of copper on corrosion in NaCl-O"2 solutions.
24 isotopes of astatine element 85, are known today, three of which occur naturally as decay products of "2"1"5U and "2"5"8U, respectively. Because these isotopes being very short-lived, all experiments dealing with this heaviest element of the halogen group need be done with "2"0"9"-"2"1"1At, having half-lifes in the several hours region. Mixtures of them may be obtained either by #alpha#-bombardment (E#alpha# approximately 30-50 MeV) of "2"0"9Bi or as spallation products by the reaction of high-energy protons with thorium and uranium targets. - In its chemical reactions astatine shows a behaviour which is between an halogen and a metal. The following oxidation states have been shown to exist: -1, 0, +1, +5 and +7. At"-, AtO_2"- and AtO_4"- are the ionic species for At(-I), At(+V) and At(+VII) whereas no definite species have been established for the other oxidation states. Furthermore, At_2 could not ...
Host matrices for actinide immobilisation will undergo the formation of large helium quantities due to alpha decay. Helium diffusion rate has to be known in order to predict the long-term behaviour of the material, and particularly, the influence of helium accumulation on mechanical properties. A nuclear reaction analysis method, namely the "3He(d, p)"4He reaction, has been used to analyse the evolution of "3He profiles after ion implantations at 1 and 3 MeV in two materials, monoclinic ZrO_2 (as a test material) and Ca_9Nd(PO_4)_5(SiO_4)F_1_._5(OH)_0_._5 britholite (envisaged for Am and Pu long-term storage). Two data processing methods are used: the classical excitation curve (proton yields versus deuteron energy) and second, the proton energy spectrum for a given deuteron energy. The characteristics of the "3He profiles (depth, width) obtained by both methods are compared to SRIM estimations. Their ...
Nuclear Reaction Analysis (NRA) with deuteron ion beams has been used to probe for ion implanted nitrogen and carbon with high sensitivity in zinc oxide and silicon single crystals. The ion implanted N was measured using 1.4 MeV deuteron ion beams and was found to be in agreement with calculated values. The limit of detection for N in ZnO is 8x1014 ions cm-2. Raman measurements of the ion implanted samples showed three additional modes at 275, 504, and 644 cm-1 compared to the un-implanted ZnO crystals. The NRA and Raman results provided information on the N concentration, depth distribution, and structural changes that occur in dependence on the nitrogen ion fluences. The deuterium induced 12C(d,p)13C reaction was used to measure the carbon impurity/dose in ion implanted silicon. It was found that the use of a large cold shield (liquid nitrogen trap) in the ion implanter chamber greatly reduces the amount of carbon impurity on the surface of ...
With the help of self-assembly, thermal sintering, selective etching techniques and sol-gel process, the non-close packed (ncp) face-centered cubic (fcc) photonic crystals of titanium dioxide (TiO2) hollow spheres connected by TiO2 cylindrical tubes have been fabricated using silica template. The photonic bandgap calculations indicate that the ncp structure of TiO2 hollow spheres was easier to open the pseudogaps than close packed system at the lowest energy. PMID:17097102
Selective catalytic reduction (SCR) of nitrogen oxides(NO{sub x}) in flue gas or engine exhaust gas with hydrocarbons as the reductant has great potential for less expense, less pollution, and easier operation than SCR with ammonia. Methane is the preferred reducing gas because of its low cost and low toxicity. Stable, low-cost catalysts for SCR with methane are required to demonstrate this technology for controlling NO{sub x} emissions. Several cobalt and nickel catalysts on synthetic clay and uranium oxide supports were investigated for their activities in reducing NO{sub x} with methane in the presence of air. The efficiency of the synthetic clay-supported nickel and cobalt catalysts for nitric oxide (NO) reduction with methane as the reducing gas was poor. The nickel oxide-uranium oxide catalyst, which was chosen for its high stability, was also ineffective. Results from the two-step experiments conducted at ...
Studies were initiated to examine in rats the effects of a protracted exposure to inhaled "2"3"9PuO_2. Graphs are presented to show effect of multiple exposures to "2"3"9PuO_2 on the deposition and clearance of "2"3"9Pu in the alveoli.
PuO_2 particles behaved similarly in the lungs of rat and hamster. The relative concentrations of PuO_2 up to 1-yr postexposure were 1.0 for lung parenchyma, 1.3 for subpleural areas, 0.5 for peribronchiolar regions and 0.2 for perivascular regions in the lungs.
Lithium (Li) plating-stripping reaction properties at the lithium phosphorus oxynitride glass electrolyte (LiPON)/copper thin film (Cu) interface is improved by the insertion of nano-thickness platinum (Pt) layer at the interface. The LiPON films are formed on mirror-polished lithium-ion conductive solid electrolyte sheets, and current collector thin films of Li, Cu-Pt multi layer, and Cu are formed on the LiPON films. The plating-stripping reactions at the LiPON/current collector films interface are carried out by galvanostatic and potential sweep measurements. Galvanostatic measurements reveal that Pt layer insertion reduces the overvoltage of the reaction and improves its coulomb efficiency. Also, cyclic voltammetry measurement suggests formation of Li-Pt alloys at higher voltages than 0 V (vs. Li/Li{sup +}) during the lithium plating process. Scanning electron microscopy observation clarifies that platinum insertion ...
Reactions of reducing species from acetonitrile media with silver iodide particles (#approx#25-angstrom diameter) have been investigated by pulse radiolysis techniques. Injection of electrons into these ultrasmall particles leads to transient bleaching of the adsorption of AgI at wavelengths close to the onset of absorption (#approx#400 nm) with the concomitant reduction of AgI to metallic silver. The reduction of Ag"+ ions and formation of silver atoms and/or dimeric Ag_2 molecules on three different size AgI particles (#approx#100, 35, and #approx#25 angstrom) have also been examined by picosecond laser spectroscopy.
Upon irradiation of aqueous ethylene glycol/water solutions of native chloroperoxidase (CPO) with {sup 60}Co-gamma rays at 77K one observes the one-electron reduction of the enzyme active site by radiolytically generated thermolyzed electrons. In the present study the first absorption spectrum of a low-spin ferrous form of CPO is reported which has peaks at 438, 532 and 563 nm, similar to those observed previously for cytochrome P-450. All previously described ferrous forms of CPO are high spin. In order to observe the final results of the CPO reaction with electrons, the spectral changes of native enzyme after room temperature-gamma-irradiation have also been investigated. Evidence of changes is also presented probably connected with disruption of the tertiary structure of enzyme, correlated with decrease of enzyme activity.
Upon irradiation of aqueous ethylene glycol/water solutions of native chloroperoxidase (CPO) with "6"0Co-gamma rays at 77K one observes the one-electron reduction of the enzyme active site by radiolytically generated thermolyzed electrons. In the present study the first absorption spectrum of a low-spin ferrous form of CPO is reported which has peaks at 438, 532 and 563 nm, similar to those observed previously for cytochrome P-450. All previously described ferrous forms of CPO are high spin. In order to observe the final results of the CPO reaction with electrons, the spectral changes of native enzyme after room temperature-gamma-irradiation have also been investigated. Evidence of changes is also presented probably connected with disruption of the tertiary structure of enzyme, correlated with decrease of enzyme activity.
Abstract Green tea extract showed false-negative results in the determination of glucose via glucose oxidase (GOD) test. This investigation was undertaken to verify and find out the precise mechanism underlying this interference by determining the reaction kinetics of production and reduction of end-point chromophore. The peroxidase step of the GOD test was found to be interfered and phenols of the green tea were the interfering compounds. Green tea interfered and exerted its influence in a dual fashion. A part of the interference was observed as a result of the reduction of the finally formed chromophore, whereas the other form of interference was due to its hydrogen peroxide/free radical-scavenging activity. Reducing potential and the free radical-scavenging activity of the phenols in th...
A liquid column was used for the experiments reported in Part 1. However, it only gives the observation of the effect of fast reaction because the liquid flow was controlled to uniform laminar flow and the contact is limited to short time of around 10 ms. In practical absorbing operation, turbulence is involved in liquid flow, and the residence time for contact is long. Hence, the absorption of trace iodine in the purified air has been experimented by using a constant interface area type stirred absorption tank. Prior to the experiment, the characteristics of the absorption tank was investigated by conducting pure carbon dioxide absorption test with purified water. It gave the conclusion that the tank was sufficiently usable for fundamental researches. In short contact time absorption, the iodine dissolved and absorbed in liquid phase is affected by reaction of hypoiodous acid and poly-iodide ion formation due to hydrolysis by basic catalyst, ...
The interaction of Np(V), Pu(VI) and Tc(VII) with metal reductants Zn, Cr, Sn and their alloys was investigated in 0.5-4 mol l"-"1 NaOH solutions in static and dynamic conditions (by filtration of solutions through the column filled with grains of metal). In this paper, it was found that the reduction and succeeding precipitation hydroxides of these elements, on the surface of metal grains from 0.5 to 4 mol l"-"1 NaOH solutions, gives a decontamination factor (DF) from 1.1 to 67. The best result was achieved for Pu (DF=67) on Cr grains after 2.5 h contact at 60 C with 0.5 mol l"-"1 NaOH solution containing Pu(VI). Increasing the NaOH concentration, and the addition of chromate ions and complex-forming agents to alkaline solution results in a decrease of the decontamination factor (DF). A better result for Np sorption from 1 mol l"-"1 NaOH solutions was achieved after longer contact, than for Pu, with Cr and Zn grains. The maximum DF=8.9 was ...
Eu3+ ions are anchored on TiO2 matrix by coupling with 2,2'-bipyridyl 4,4'-dicarboxylic acid. Five different luminescence centers are observed for TiO2|2,2'-bipyridyl 4,4'-dicarboxylic acid|Eu3+ electrodes due to electron transitions between d and f orbitals. Photo-luminescence of TiO2|2,2'-bipyridyl 4,4'-dicarboxylic acid|Eu3+ electrodes is increased by attaching 2-thenoyltrifluoroacetone to Eu3+ ions. Immersion of TiO2|2,2'-bipyridyl 4,4'-dicarboxylic acid|Eu3+|2-thenoyltrifluoroacetone electrodes in propylsulfide is found to be further increased intensities of luminescence bands by a factor of three.
An electrochemical biosensor for determination of hydrogen peroxide (H2O2) was fabricated, based on the electrostatic immobilization of horseradish peroxidase (HRP) with one-dimensional gold nanowires (Au NWs) and TiO2 nanoparticles (nano-TiO2) on a gold electrode. The nano-TiO2 can give a biocompatible microenvironment and compact film, and the Au NWs can provide fast electron transferring rate and greatly add the amount of HRP molecules immobilized on the electrode surface. Au NWs were characterized by ultraviolet?visible spectra and transmission electron microscope. The electrode modification process was probed by cyclic voltammetry and electrochemical impedance spectroscopy. Chronoamperometry was used to study the electrochemical performance of the resulting biosensor. Under optimal co...
Reduction of silver myristate (AgMy) under mild thermal reaction conditions in a dipolar aprotic solvent i.e. N, N-dimethylformamide (DMF) has been carried out. UV-visible absorption measurements of dried and re-dispersible brown flocculants showed broad features of surface plasmon resonance (SPR) due to silver nanoparticles. The freshly isolated particles showed absorption bands at 414 and 485 nm, respectively, due to inter-particle coupling or clustering of silver ions and silver atoms. X-ray diffraction (XRD) pattern of fcc zero-valent silver resulted in crystallite size of about 10 nm. Scanning electron microscopy (SEM) revealed formation of rod shaped silver with increasing reaction temperature. Thermal analysis (TGA) showed about 10% weight loss due to organic capping.
In the present work, quaternary chitosans as water-soluble compounds were prepared based on three-step process. Schiff bases were firstly synthesized by the reaction between the amino groups of chitosan with aliphatic aldehydes followed by a reduction with sodium borohydride (NaBH4) to form N-(alkyl) chitosans. N,N,N-(dimethyl alkyl) chitosans were then obtained by a reaction of chitosan containing N-butyl, N-pentyl, N-hexyl, N-heptyl, and N-octyl substituents with methyl iodide. The compounds were characterized using IR and NMR spectroscopy. Subsequent experiments were conducted to test their antimicrobial activities against the most economic plant pathogenic bacteria of crown gall disease Agrobacterium tumefaciens, soft mold disease Erwinia carotovora, fungi of grey mold Botrytis cinerea...
Chemical modification of poly(?-caprolactone) PCL by oxidation with potassium permanganate in solution was investigated. According to the data obtained from Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance 1H NMR, after the oxidation reactions the PCL chains exhibited new functional groups (vinyl and hydroxyl) and possible intermolecular recombination, producing an oxidized-polycaprolactone (PCL-OX). Solution viscometry indicated that degradation also occurred during the oxidation reactions (30% drop in viscosity average molecular weight was detected). Differential scanning calorimetry (DSC) also indicated that PCL was chemically modified and degraded. The successive self-nucleation/annealing (SSA) treatment confirmed that a reduction (or interruption) in line...
The ECP of construction materials in the water steam circuits of power plants is influenced by many parameters, including: reactions of oxidants, such as O{sub 2} or dissolved copper species; and reactions of reducing species, namely N{sub 2}H{sub 4}. Electrochemical measurements were performed to clarify the role of hydrazine for the open circuit potential in water/steam circuits. Current density electrode potential curves of the electrochemical oxidation of hydrazine and the reduction of oxygen in aqueous solutions were measured as a function of temperature in the range from room temperature to approximately 260{degrees}C. The electrode materials used were platinum, gold and Alloy 800 mod.. In addition, corrosion potentials were measured in water containing oxygen or hydrazine.
The phase transformations and properties of a precipitation-hardened Ni-Cr-based alloy are investigated as a function of C, B, Nb, and Cr contents. It is found that the primary role of Nb consists in the formation of an independent phase, delta-Ni3Nb, a part of a gamma/gamma-prime-delta eutectoid (for high C and B concentrations) and in stimulating the gamma-sigma reaction consecutively with the gamma double prime-delta reaction (for low C and B concentrations). In both cases, the long-term strength characteristics of the Nb-alloyed system are relatively low. The substitution of boron for carbon contributes to a reduction in the number of nucleation sites for topologically close-packed phases and to the formation of more stable (with respect to excess compounds) M3B2 and MB2 borides. The high-boron material exhibits better properties and phase stability under mechanical and thermal loading. 13 references.
A WO(3)/TiO(2) composite, hollow-sphere photocatalyst with average diameter of 320 nm and shell thickness of 50 nm was successfully prepared using a template method. UV-vis diffuse reflectance spectra illustrated that the main absorption edges of the WO(3)/TiO(2) hollow spheres were red-shifted compared to the TiO(2) hollow spheres, indicating an extension of light absorption into the visible region of the composite photocatalyst. The WO(3) and TiO(2) phases were confirmed by X-ray diffraction analysis. BET isotherms revealed that the specific surface area and average pore diameter of the hollow spheres were 40.95 m(2)/g and 19 nm, respectively. Photocatalytic experiments indicate that 78% MB was degraded by WO(3)/TiO(2) hollow spheres under visible light within 80 min. Under the ...
Mesporous anatase-phase TiO(2) hollow spheres with high photocatalytic activity were prepared by hydrothermal treatment and self-transformation of amorphous TiO(2) solid spheres in an NH(4)F aqueous solution. The prepared samples were characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, N(2) adsorption-desorption isotherms and UV-vis absorption spectroscopy. The photocatalytic activity was evaluated by photocatalytic oxidation decomposition of acetone in air under UV irradiation. It is found that F(-) plays an essential role in the formation of TiO(2) hollow spheres. F(-) not only induces the hollowing of TiO(2) solid spheres, but also promotes the crystallization of anatase TiO(2) nanocrystals. A possible formation ...
Inductively coupled fluorocarbon (CF4/Ar and C4F8/Ar) plasmas were used to etch HfO2, which is a promising high-dielectric-constant material for the gate of complementary metal-oxide-semiconductor devices. The etch rates of HfO2 in CF4/Ar plasmas exceeded those in C4F8/Ar plasmas. The tendency for etch rates to become higher in fluorine-rich (high F/C ratio) conditions indicates that HfO2 can be chemically etched by fluorine-containing species. In C4F8/Ar plasmas with a high Ar dilution ratio, the etch rate of HfO2 increased with increasing bias power. The etch rate of Si, however, decreasd with bias power, suggesting that the deposition of carbon-containing species increased with increasing the power and inhibited the etching of Si. The HfO2/Si selectivity monotonically ...
Color formation in aqueous solutions of the ditetrazolium salt blue tetrazolium (BT{sup 2+}) in the absence or presence of oxygen is a complex radiation chemical reaction. The final stable product is the poorly soluble diformazan violet to blue pigment having a broad spectral absorption band ({lambda}{sub max}=552 nm). The reaction of BT{sup 2+} with the hydrated electron proceeds by rapid reduction of BT{sup 2+} followed by protonation at the nitrogen closest to the unsubstituted phenyl group, via the two intermediate tetrazolinyl radicals shared by the ditetrazole ring nitrogens. The effect of solution pH, N{sub 2}O saturation, and the presence of the reducing agent dextrose are examined. The system serves as a radiochromic sensor and a dosimeter of ionizing radiations. Solutions of 5 mmol l{sup -1} BT{sup 2+} at pH 7.3 serve as dosimeters over an absorbed-dose range of approximately 0.2-6 kGy (dearated, with a range of ...
Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. Oxide catalysis can be a complex process with both metal cation and oxygen anions participating in ...
An isotopic exchange method was used to label lipiodol with [sup 131]I. The labelling efficiency was > 92.5%, and the radiochemical purity of [[sup 131]I]lipiodol was above 98% as determined by ITLC. The influencing factors e.g. the heating temperature, reaction, pH and storage conditions were studied and the optimum conditions were determined. In a pilot study injecting [[sup 131]I]lipiodol for the treatment of hepatoma, about 70% of hepatoma patients had a response to the treatment with a reduction of [alpha]-fetoprotein and decrease of hepatoma sizes. The overall median survival was 9 months (range 2-17 months). (author).
The phenomenon of time resonances (or explosions) can explain the exponential reduction of the energy, which is accompanied for the certain degree by slight fluctuations under some conditions in the range of the energy strongly overlapped compound-resonances. These resonant explosions correspond to formation of several highly-exited non-exponentially decaying nuclear clots (partial compound nuclei consisting of several small groups of projectile nucleons and targets). This paper is a continuation and expansion of theoretical authors' work, which is a more general self-consistent version of the time-evolution approach in comparison with the traditional Izumo-Araseki time compound-nucleus model.
Objective of the project is characterization of electrode reactions in molten salt by using metal oxides and silica-based electrode. The scope of project are characterization of metal oxide properties in molten salt and miniaturization of 3-electrode electrochemical test cell. Electrochemical micro-cell for actinide-LiCl-KCl molten salt was newly designed. Electroless and electrochemical deposition technique was applied to Mo coating on quartz tube. From the design of electrode and 3-electrode electrochemical cell suitable for the tests in molten salt electrolyte, so it is anticipated to get the information on the electrochemical behavior of metallic electrode in molten salt and to secure the information on oxidation/reduction behavior of actinide
Surface oxide films were grown on 99.99% copper and brass (copper-zinc alloy, Cu77Zn21Al2) in 0.1 mol L{sup -1} borax solution at open circuit potential and were characterized using various experimental techniques. The composition of the passive films formed in situ on the different materials was studied using differential reflectance spectroscopy. The thickness of the oxide layers on copper and brass was compared by chronopotentiometric curves and potentiodynamic reductions. The electrical properties of each oxide were analyzed by means of electrochemical impedance spectroscopy. Their influence on the oxygen reductionreaction was also investigated using voltammetry hydrodynamic tools such as the rotating disk electrode. The results show that the incorporation of Zn to Cu in brass changes the composition and the thickness of the surface film. The films grown on brass tend to be thicker but less resistive and Zn compounds ...
The oxidation of boron carbide in steam or air was recently extensively studied especially in Forschungszentrum Karlsruhe, Institut fuer Materialforschung. An important data set is available for the interaction modelling. An oxygen diffusion model through the superficial liquid boron oxide formed on the boron carbide external surface associated to a superficial reaction between the liquid boron oxide and steam is proposed to simulate the experimental kinetics from BOX rig and thermogravimetric tests on the interaction between steam and boron carbide at a temperature range 800 C to 1400 C. The oxygen diffusion model will be also useful to simulate interaction between boron carbide and Ar+O2 (air simulation) atmosphere when the steam pressure becomes zero. From the analysis of BOX rig experimental kinetics of non-condensable (H2, CO2, CO and CH4) gases we propose an oxygen diffusion model through the liquid boron oxide and a ...
In order to discuss effects of lithium iodide (LiI) doping on condensation structure of brown coals during heating, spectral changes were measured by using an in-situ FT-IR. It was found that the LiI doping accelerates weight reduction due to heating, and the doping effect is affected by coal structure. Both of Loy Yang (LY) coal and its LiI doped coal (DLY) had absorption intensity of the FT-IR spectra decreased with rising temperature, and the absorption center belonging to an OH group shows different shifts between the LY and DLY coals. This indicates that the LiI doping has affected the change in hydrogen bonding patterns associated with heating. Both of South Banko (SB) and LY coals had the absorption spectral intensity in the OH group decreased as the weight reduction (conversion) rate increased. Reduction in the OH groups associated with heating is caused by volatilization and condensation ...
It has been reported by the present authors that behavior of tritium release from solid breeder grain is consisted of diffusion in grain, tritium transfer at surface layer and surface reactions on grain surface such as adsorption or isotope exchange reactions. Tritium release curves estimated using the tritium release model gave good agreement with observed tritium release curves from Li_4SiO_4, Li_2ZrO_3 or LiAlO_2. Tritium release behavior from Li_2TiO_3 under humid purge gas, dry purge gas and dry purge gas with hydrogen conditions is discussed in this study, tritium release curves using the release model that we proposed previously give a good agreements with experimental tritium release curves. Tritium effective diffusivity in the crystal grain of Li_2TiO_3 is also estimated in this study using a curve-fitting method applied to the release curves obtained under the humid purge gas condition. It is ...
In this study, silver nanoparticles were formed on a natural macroporous matrix, the stem of rice-paper plant, by reducing Ag{sup +} in aqueous solution through in situ processing without using any other stabilizers. The pores of the matrix, with their size of about 100 {mu}m, were thought to act as reaction compartments for the nucleation and growth of silver nanoparticles, and the control of nucleation of silver crystal during the reductionreaction was found to be important to the successful formation of nanosized silver particles onto the matrix. The diameter and amount of resultant silver particles can be controlled by changing the reaction conditions. Under optimized conditions, the content of silver particles in the matrix can reach as high as 1.8 wt% with the particle diameters being kept below 100 nm. The anti-microbial activities in terms of minimum inhibitory concentration (MIC) for the ...
Nanodimensional powders of cubic copper ferrite are synthesized by two-steps procedure of co-precipitation of copper and iron hydroxide carbonates, followed by mechanochemical treatment. X-ray powder diffraction, Moessbauer spectroscopy and temperature-programmed reduction are used for the characterization of the obtained materials. Their catalytic behavior is tested in methanol decomposition to hydrogen and CO and total oxidation of toluene. Formation of nanosized ferrite material is registered even after one hour of milling time. It is established that the prolonging of treatment procedure decreases the dispersion of the obtained product with the appearance of Fe2O3. It is demonstrated that the catalytic behavior of the samples depends not only on their initial phase composition, but on the concomitant ferrite phase transformations by the influence of the reaction medium. -- Graphical abstract: It is demonstrated that the catalytic behavior ...
Chemical-looping combustion is a two-stage process proposed as an alternative for the combustion of carbonaceous materials, such as natural gas or coal gas, for almost complete CO{sub 2} capture. In the reduction stage, the structural oxygen contained in the lattice of a reducible inorganic oxide, is used for combustion of the carbonaceous material. In the regeneration stage the oxygen carrier, found in a reduced state after the reduction stage, is regenerated with pure air to recover the physical and chemical properties of the carrier, ready to reinitiate a new cycle reduction-regeneration. In a typical multicycle reactor test, the carriers are subjected to accumulative chemical and thermal stresses and the performance will, probably, decay progressively with the number of cycles. The occurrence of some side reactions may limit the efficiency of the overall process in CO{sub 2} capture. In this paper, ...
A WO3/TiO2 composite, hollow-sphere photocatalyst with average diameter of 320nm and shell thickness of 50nm was successfully prepared using a template method. UV-vis diffuse reflectance spectra illustrated that the main absorption edges of the WO3/TiO2 hollow spheres were red-shifted compared to the TiO2 hollow spheres, indicating an extension of light absorption into the visible region of the composite photocatalyst. The WO3 and TiO2 phases were confirmed by X-ray diffraction analysis. BET isotherms revealed that the specific surface area and average pore diameter of the hollow spheres were 40.95m^2/g and 19nm, respectively. Photocatalytic experiments indicate that 78% MB was degraded by WO3/TiO2 hollow spheres under visible light within 80min. Under the same conditions, only ...
The importance of soil heterogeneity for methane emission from a wetland soil is assessed by in situ point measurements of depth-specific O2 and CH4 concentrations and simultaneous soil CH4 fluxes at contrasting water levels. Profile measurements, and associated assumptions in their interpretation, were validated in a controlled mesocosm drainage and saturation experiment applying planar O2 optodes and membrane inlet mass spectrometry. Results show that peat soil is heterogeneous containing dynamic macropore systems created by both macrofauna and flora, which facilitate preferential flow of water, O2 and CH4 and vary temporally with changes in the moisture regime. The O2 content above the water table after drainage varied horizontally from 0 to 100% air saturation within few mm. Oxic zones...
We prepared submicron-scale spherical hollow particles of anatase TiO2 by using a polystyrene-bead template. The obtained particles were very uniform in size, with a diameter of 490 nm and a shell thickness of 30 nm. The Brunauer-Emmett-Teller surface area measurements revealed a large value of 70 m2/g. The photocatalytic property was investigated by the complete decomposition of gaseous isopropyl alcohol under UV irradiation. It was indicated that the activity of the hollow spheres was 1.8 times higher than that of the conventional P25 TiO2 nanoparticles with a diameter of 30 nm. Furthermore, we fabricated a dye-sensitized solar cell (DSC) using an electrode of the TiO2 hollow spheres, and examined the photovoltaic performance under simulated sunlight. Although the per-area efficiency was rather low (1.26%) because of a low area density of ...
Several dioxomolybdenum(VI) complexes of the schiff bases derived from salicylaldehyde, 2-hydroxy-1-naphthaldehyde, o-hydroxyacetophenone or pyridoxal and o-aminobenzylalcohol, o-aminophenol, o-hydroxybenzylamine, o-hydroxy(methylbenzyl)amine or 3-amino-2-naphthoic acid have been synthesized and characterized by elemental analysis, electrical conductance, molecular weight, IR and electronic spectral and magnetic susceptibility measurements. The schiff bases behave as dibasic, tridentate ligands and coordinate through ONO donor system forming complexes of the type MoO_2L.X (where LH_2=schiff base, X=H_2O or Ch_3OH). The compounds MoO_2L.Ch_3OH react with 2,2'-dipyridyl to form heterochelates of the type MoO_2L.dipyridyl. The complexes are non-electrolytes, monomers, diamagnetic and possess a cis-MoO_2 structure. The ...
Ordered mesoporous C-TiO2 nanocomposites with crystalline framework were prepared by the evaporation-induced triconstituent co-assembly method. The products were characterized by XRD, TEM, N2 adsorption-desorption and TG. Their microwave absorption properties were investigated by mixing the product and epoxy resin. It is found that the peak with minimum reflection loss value moves to lower frequencies and the ordered mesoporous C-TiO2 nanocomposite possesses an excellent microwave absorbing property with the maximum reflection loss of -25.4 dB and the bandwidth lower than -10 dB is 6.6 GHz. The attenuation of microwave can be attributed to dielectric loss and their absorption mechanism is discussed in detail. The mesoporous C-TiO2 nanocomposites also exhibit a lower infrared emissivity in the wavelength from 8 to 14 ?m than that of ...
Dye-sensitized solar cells (DSSCs) based on anatase TiO2 hollow spheres (TiO2HS)/multi-walled carbon nanotubes (CNT) nanocomposite films are prepared by a directly mechanical mixing and doctor blade method. The prepared samples are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy and N2 adsorption-desorption isotherms. The photoelectric conversion performances of the DSSCs based on TiO2HS/CNT composite film electrodes are also compared with commercial-grade Degussa P25 TiO2 nanoparticles (P25)/CNT composite solar cells at the same film thickness. The results indicate that the photoelectric conversion efficiencies () of the TiO2HS/CNT composite DSSCs are dependent on CNT loading in the electrodes. A ...
Endurance-trained older men have a higher proportion of lean tissue and greater muscle cell oxidative capacity, reversing age-related trends and suggesting major changes in protein metabolism. In this study, protein turnover was determined in 6 middle-aged (52+/-1 yr) men who were well trained (VO_2 max 55.2+/-5.0 ml O_2/kg.min) and lean (body fat 18.9+/-2.8%, muscle mass 36.6+/-0.6%). The maintained habitual exercise while consuming 0.6, 0.9 or 1.2 g protein/kg.day for 10-day periods. N flux was measured from "1"5N in urea after oral "1"5N-glycine administration. Myofibrillar protein breakdown was estimated from urinary 3-methyl-histidine. Dietary protein had no effect on turnover rates, even when N balance was negative. Whole body protein synthesis was 3.60+/-0.12 g/kg.day and breakdown was 3.40+/-0.14 g/kg.day for all N intakes. Whole body protein flux, synthesis and breakdown were similar to values reported for sedentary young (SY) or ...
The physicochemical forms and partitioning of corrosion products released from stainless steel upon exposure to selected environmental conditions is the subject of this investigation. This report describes the influence of calcareous sediment on the rate of release and fate of corrosion products produced when neutron-activated stainless steel specimens were exposed to a Globigerina ooze taken from the Northeast Pacific Ocean. The calcareous ooze used in this study consists largely of planktonic formanifera tests and was found to be about 90% CaCO_3. The trace metal content of this sediment was typical of average deep-sea carbonate sediments, and the ratios of trace elements to Ti were not remarkably different from a coastal clayey silt or a Northeast Pacific pelagic red clay. Most (>80%) of the trace metals extracted by sequential chemical treatment were associated with reductant-soluble materials, i.e., amorphous Mn and Fe oxides, or were incorporated in the ...
A study was conducted to determine the feasibility and the opportunity of photochemical pretreatment on the biodegradation and detoxification of Methyl Tert Butyl Ether (MTBE), Ethyl Tert Butyl Ether (ETBE) and Tert Amyl Methyl Ether (TAME), the most common oxygenates used as octane enhancers in unleaded gasoline. The production, storage, uses and disposal of oxygenates result in an unknown amount of groundwater pollution. Because of their high solubility, MTBE, ETBE and TAME are detected in large portions in saturated zones of aquifers. The biodegradation of these oxygenates is difficult and slow, and information regarding their biodegradability is scarce. Photo-decomposition of oxidants under appropriate UV radiation has been shown to be very effective because the hydroxyl radicals produced possess high oxidation potential. In this study, the H_2O_2/UV process was used to generate hydroxyl radicals. Maximal oxygenates transformation was ...
The intensity of erbium up-conversion luminescence could be limited by a saturation effect due to increased pump power. We studied the luminescence saturation of the 550 nm emission on erbium-doped, SiO_2-TiO_2 sol-gel powders under pulsed excitation at 979 and 1532 nm. From the latter, the up-converted luminescence intensity decreased with increasing excitation power, whereas no saturation was observed at 979 nm excitation. We proposed that the saturation effect is determined by the pump power, the erbium content and the lifetime of the corresponding first excited states at different pumping schemes.
The TiO2 hollow microspheres were prepared by microwave-assisted solvothermal treatment without template. The morphology and the phase of TiO2 hollow microspheres were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and BET surface areas. The results show that the particles have hollow structures and the shell was covered by nanocrystals and have higher specific surface area. The possible formation mechanism of hollow TiO2 spherical structures has simply been proposed. The activity was evaluated by the photocatalytic degradation of methyl orange (MO). The results show that the particles having specific surface area show higher photocatalytic activity. It can be attribute to the doped ...
The phosphate complexation of Np(V) is investigated in the pH range from 6.4 to 10.0 in 0.1 M NaClO_4 at 22#+-#2 C by absorption spectroscopy. The formation of two phosphate complexes is confirmed by spectroscopic speciation: NpO_2HPO"-_4 at 988.8 nm and NpO_2PO"2"-_4 at 993.6 nm with molar extinction coefficients of 251#+-#8 and 201#+-#11 1/mol cm, respectively. The complexation constants are determined to be log #beta# = 2.54#+-#0.02 for NpO_2HPO"-_4 and log #beta# = 6.33#+-#0.08 for NpO_2PO"2"-_4. The competition of the phosphate complexation with the carbonate complexation is demonstrated by speciation calculation under different geochemical conditions. (orig.).
Selective formation of ZnO nanodots was accomplished by metalorganic chemical vapor deposition on nanopatterned SiO_2/Si substrates. Self-organized ZnO nanodots were selectively formed in nanopatterned lines of Si created by etching of SiO_2 with focused ion beam (FIB), whereas any nanodots were hardly observed on the SiO_2 surface in the vicinity of the FIB-sputtered Si areas. The mechanism of the selective formation of ZnO nanodots on FIB-nanopatterned lines is mainly attributed to the effective migration of Zn adatoms diffusing on the SiO_2 surface into the Si lines followed by the nucleation at surface atomic steps and kinks created by Ga"+ ion sputtering. Cathodoluminescence measurements confirmed that the emission originated from the selectively grown ZnO nanodots.
Fe-doped MnO2 with a hollow sea urchin-like ball chain shape was first synthesized under a high magnetic field of 10 T. The formation mechanism was investigated and discussed in detail. The synthesized samples were characterized by XRD, SEM, TEM, EMPA, and vector network analysis. By doping MnO2 with Fe, the relative complex permittivity of MnO2 and its corresponding loss tangent clearly decreases, but its relative complex permeability and its corresponding loss tangent markedly increases. Moreover, the theoretically calculated values of reflection loss show that with increasing the Fe content, the as-prepared Fe-doped MnO2 exhibits good microwave absorption capability. -- Graphical Abstract: Fe-doped MnO2 with a hollow sea urchin-like ball chain shape was first synthesized in a ...
Zirconia-toughened sialon composites have been fabricated using conventional hot-pressing techniques. The fracture toughness and microstructure were determined for CeO_2- and Y_2O_3-stabilized ZrO_2 additives and also as a function of volume percent ZrO_2. The Yttria system showed a linear increase in fracture toughness with increasing volume fraction zirconia content while the ceria-stabilized system exhibited a peak in fracture toughness at 20 vol% ZrO_2 content. The fracture toughness at 800 C was measured and correlated with the microstructure. High-temperature stability was determined and it was found that the deleterious nitride phases of zirconium could be precluded from the microstructure.
Oxide ionic conductivities of (CeO_2)_x(Sc_2O_3)_(_0_._1_1_-_x_)(ZrO_2)_0_._8_9 (x = 0.01-0.10) electrolytes were optimized for the application in intermediate-temperature solid oxide fuel cell (IT-SOFC). Powders with different contents of CeO_2 and Sc_2O_3 were prepared via a co-precipitation method. The obtained powders and pellets were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and impedance spectroscopy. Among all the compositions, (CeO_2)_0_._0_4(Sc_2O_3)_0_._0_7(ZrO_2)_0_._8_9(4Ce7ScZr) gives the highest ionic conductivity of 0.065 S cm"-"1 at 800 "oC. The effects on densification and electrical properties of different sintering additives, such as SiO_2, MgO, ...
Manganese dioxide (MnO2) was prepared using the ultrasonic method. Its electrochemical performance was evaluated as the cathode material for a high voltage hybrid capacitor. And the specific capacitance of the MnO2 electrode reached 240 F.g-1. The new hybrid capacitor was constructed, combining Al/Al2O3 as the anode and MnO2 as the cathode with electrolyte for the aluminum electrolytic capacitor to solve the problem of low working voltage of a supercapacitor unit. The results showed that the hybrid capacitor had a high energy density and the ability of quick charging and discharging according to the electrochemical performance test. The capacitance was 84.4 mF, and the volume and mass energy densities were greatly improved compared to those of the traditional aluminum electrolytic capacito...
The fuel cell control problem was studied. Attempts were made to control the output current of the fuel cell by starving it of hydrogen and oxygen. The motivation of this work was to increase efficiency by minimizing waste of fuel. The following findings were obtained: H2 starvation works better than O2 starvation; An optimal H2 to O2 ratio exists for combined H2&O2 starvation; The control scheme for H2&O2 starvation works well for 3 different disturbance tests and at 25 degrees C, 60 degrees C, and 80 degrees C; Fuel cell under reactant starvation is stable for at least 72 hrs.
Hierarchical TiO2 hollow spheres had been prepared based on bubble templates by a simple one-step hydrothermal method. The diameter of hollow spheres was about 700nm and the shell thickness of them was 69nm. They were composed of similar spindle- or needle-like building units. Furthermore, hydrothermal time had an important influence on the morphology and crystallinity of hollow spheres. Moreover, the UV-Vis diffuse reflectance spectra of TiO2 hollow spheres heated at 150^oC for 10h showed the strongest absorption in the UV-Vis region and the Raman spectrum demonstrated the anatase sample. Additionally, a possible formation mechanism of TiO2 hollow spheres was proposed. So this novel and simple method would provide a development direction to fabricate all kinds of inorganic hollow spheres ...
Carbothermal reduction-nitridation (CRN) of talc (Mg_3(Si_2O_5)_2(OH)_2) and halloysite (Al_2Si_2O_5(OH)_4) clay provides a useful route for preparing low-cost Mg-#alpha# sialon powder. In this study, the chosen molecular ratios of talc to halloysite were 0.1:1, 0.2:1, 1.5:1.0 and 2.0:1. The CRN reaction was conducted at 1450 to 1520 deg C and 2 to 6h holding time using carbon black as a reducing agent in flowing N_2 (gas). The results showed the synthesized powder was composed of #alpha#-sialon, #beta#-sialon and small amounts of SiC, 15R and AlN phases that greatly depended on the ratio of talc to halloysite, the reaction temperature and holding time. The highest content of Mg-#alpha# sialon, as much as 90wt%, was achieved at 1480 deg C for a holding time of 4h at a talc to halloysite ratio of 1.5:1.0. SiC was considered as an intermediate compound. We also discuss the evaporation loss of Mg caused by talc decomposing ...
Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. Copper ions were exchanged into nanocrystalline NaY to increase the catalytic activity. ...
The sol-gel-immobilized Tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)_3 "2"+] electrogenerated chemiluminescence (ECL) sensor was applied to the reversed-phase high-performance liquid chromatography (HPLC) determination of phenothiazine derivatives (promazine, chlorpromazine, triflupromazine, thioridazine, and trifluoperazine) and erythromycin in human urine samples. In this method, Ru(bpy)_3 "2"+ was immobilized in sol-gel-derived titania (TiO_2)-Nafion nanocomposite films coated on a dual platinum electrode. This method eliminates an extra pump needed for the delivery of Ru(bpy)_3 "2"+ reagent into a reaction/observation zone in front of photomultiplier tube because the immobilized-Ru(bpy)_3 "2"+ is recycled on the electrode surface by an applied potential at +1.3 V versus Ag/AgCl (3 M NaCl) reference electrode. The resulting analytical performances such as detection limit, working range, sensitivity, and measurement ...
Different SiAlON composites based on #alpha#'-SiAlON are investigated, with respect to the phase relationships, densification behavior, and mechanical properties. The compositions are located on a phase-diagram line parallel to the Si_3N_4-Y_2O_3#centre dot#9AlN compound in the Si_3N_4-SiO_2-AlN-Al_2O_3-Y_2O_3-YN system. Analysis of the reaction sequences shows that the formation of the composites is associated with the transient appearance of Y_4Al_2O_9 (YAM), yttrium-aluminum-garnet (YAG), melilite, and a nitrogen-rich liquid phase. The small shift of compositions on the Si_3N_4-Y_2O_3#centre dot#9AlN compound phase-diagram line toward the Al_2O_3-rich side offers the advantage of a higher sinterability and the removal of the melilite phase from a wide range of compositions containing #alpha#'-SiAlON and polytypes. The #alpha#'/#beta#'-SiAlON composites show better mechanical properties in comparison to pure ...
Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial delta13C 3.2-3.8 per thousand), gypsum (initial delta34S 7.6-8.6 per thousand), and aqueous solution. Reducing conditions exist below a boundary that appears to move vertically as a function of changes in pond water level. Under reducing conditions, bacteria partially reduce aqueous sulfate to low-delta34S sulfide, consuming organic carbon and generating low-delta13C bicarbonate. Under oxidizing conditions, sulfide is converted to sulfate, leading to calcite dissolution, gypsum precipitation, and isotopic re-equilibration of remaining calcite with dissolved bicarbonate near the pond surface. The gypsum has delta34S near 6 per thousand, and calcite has delta13C as low as -1.7 per thousand; the changes from initial values correspond to predictions based on isotopic balance and reaction stoichiometry. The pond largely contains the products of ...
Plutonium metal is produced by reducing PuF{sub 4} prepared from PuO{sub 2} by fluorination. Both fluorination and reduction are batch processes at the Los Alamos Plutonium Facility. The conversion of plutonium oxide to fluoride greatly increases the neutron yield, a result of the high cross section for alpha-neutron ({alpha},n) reactions on fluorine targets compared to the (more than 100 times) smaller {alpha},n yield on oxygen targets. Because of the increase, total neutron counting can be used to monitor the conversion process. This monitoring ability can lead to an improved metal product, reduced scrap for recycle, waste reduction, minimized reagent usage, and reduce personnel radiation exposures. A new stirred-bed fluorination process has been developed simultaneously with a recent evaluation of an automated neutron-counting instrument for quantitative process monitoring. Neutrons are counted with ...
Hard surface finishing represents the final manufacturing step for functional areas of machine elements in state-of-the-art production. Raceways of rolling bearing rings are ground and honed to the required low roughness. Plastic deformation is restricted to a narrow edge zone of the hardened steel. Reheating of the machined components below the martensite tempering or bainite transformation temperature results in a marked decrease of the XRD line width on the surface. The investigated samples are made of through-hardened standard bearing steel 100Cr6 (international denotation: SAE 52100). On the basis of a material model that explains the effect as a complex diffusion process of dislocational carbon segregation, i.e. static strain aging, the measured kinetics of the XRD line width reduction is simulated by an Arrhenius-type equation, which describes the rate-controlling reaction step of temper carbide dissolution. The formation of a small ...
In dissipative ordinary differential equation systems different time scales cause anisotropic phase volume contraction along solution trajectories. Model reduction methods exploit this for simplifying chemical kinetics via a time scale separation into fast and slow modes. The aim is to approximate the system dynamics with a dimension-reduced model after eliminating the fast modes by enslaving them to the slow ones via computation of a slow attracting manifold. We present a novel method for computing approximations of such manifolds using trajectory-based optimization. We discuss Riemannian geometry concepts as a basis for suitable optimization criteria characterizing trajectories near slow attracting manifolds and thus provide insight into fundamental geometric properties of multiple time scale chemical kinetics. The optimization criteria correspond to a suitable mathematical formulation of "minimal relaxation" of chemical forces along reaction ...
The objectives of this project were to develop technologies to manufacture self-reducing briquettes out of waste iron oxides and to recycle them in an electric arc furnace or a cupola furnace. CRM has investigated and determined the optimal characteristics (binder, size, grain size, compositions and activator for the reductionreaction) for briquettes containing mixtures of mill scales, mill sludges, electric arc furnace (EAF) dust and coal as reduction agent. The goal of obtaining briquettes, in which iron oxides are totally reduced when these briquettes are loaded with the scrap into an electric arc furnace, was achieved. Trials at ProfilARBED have shown that it is possible to recycle mill and EAF by-products conditioned in self-reducing briquettes in an electric arc furnace without influence on the performance and on the environment. The iron content of the slag does not increase as the iron of the by-product is almost ...
To develop oxygen electrodes for rechargeable metal-air batteries, the electrochemical behaviour of gas-diffusion-type carbon electrodes loaded with Pr-Mn-Fe-based perovskite-type oxides was examined for the reduction and evolution of oxygen in 8 M KOH at 60 C. Among the oxides tested, Pr{sub 0.2}Ca{sub 0.8}Mn{sub 0.1}Fe{sub 0.9}O{sub 3} gave the highest electrode performances, e.g., current densities of 275 mA/cm{sup 2} (for oxygen reduction) and 225 mA/cm{sup 2} (for oxygen evolution) at -300 and +650 mV vs. Hg/HgO, respectively. The electrode performances were found to depend on both the catalytic activity of the oxides for H{sub 2}O{sub 2} decomposition reaction and the amounts of oxygen desorbed from the oxides. Furthermore, it was confirmed that the small zinc-air battery including the gas-diffusion-type electrode loaded with Pr{sub 0.2}Ca{sub 0.8}Mn{sub 0.1}Fe{sub 0.9}O{sub 3} showed good discharge and charge ...
Zr-Al metallo-organic compounds were thermally decomposed to prepare ZrO_2-Al_2O_3 composite powders. The specific surface area was dependent on the organofunctional groups of the starting organic compounds. The pore size distribution was dependent on the heating rate when the heating temperature was the same. 4 refs.; 4 figs.
In this Communication, we report the fabrication of well-crystallized rutile-phase TiO2 hollow spheres using potassium titanium oxalate as the precursor. The spheres exhibited unique three-dimensional hierarchical architectures and demonstrated a significantly improved photocatalytic performance. The synthetic strategy used in this process represents a general approach and therefore may contribute to the formation mechanisms of hollow nanostructures. PMID:16634578
In order to investigate the role of amorphous SiO2 particles in corrosion and wear resistance of Ni-based metal matrix composite alloying layer, the amorphous nano-SiO2 particles reinforced Ni-based composite alloying layer has been prepared by double glow plasma alloying on AISI 316L stainless steel surface, where Ni/amorphous nano-SiO2 was firstly predeposited by brush plating. The composition and microstructure of the nano-SiO2 particles reinforced Ni-based composite alloying layer were analyzed by using SEM, TEM and XRD. The results indicated that the composite alloying layer consisted of ?-phase and amorphous nano-SiO2 particles, and under alloying temperature (1000 deg. C) condition, the nano-SiO2 particles were uniformly ...
TEM and HRTEM have been used to characterise the microstructures of materials formed by hot-pressing silicon nitride with an Al_2O_3-SiO_2-TiO_2 densification aid system, to form #beta#'-sialon-TiN composites in which the TiN particles are of 20-100 nm dimension. (orig.).
Epitaxial CeO_2 buffer layers were fabricated by pulsed laser deposition (PLD) on r-cut sapphire substrates. An atomically flat CeO_2 surface with a high density of nanodots was formed by a self-assembly process. Scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy investigation showed that the nanodots were CeO_2 other than impurities. YBa_2Cu_3O_7_-_#delta# (YBCO) thin films were then grown on the annealed and the as-grown CeO_2-buffered sapphires by PLD. The transport measurement results showed that the nanodots enhanced the effective pinning potential and significantly increased critical current density (J _c). Especially, YBCO films with an annealed CeO_2 buffer layer showed a high J _c peak when the applied field was directed along the c-axis ...
The physical, chemical and mechanical properties of magnesium alloys make them attractive materials for automotive and aerospace applications. However, these materials are susceptible to corrosion and wear. This work discusses the potential of using sol-gel based coatings consisting of ZrO_2 and 15 wt.% of CeO_2. The CeO_2 component provides enhanced corrosion protection, while ZrO_2 impart corrosion as well as wear resistance. Coating deposition was performed by the dip coating technique on two magnesium alloy substrates with different surface finishes: AZ91D (as-casted, sand-blasted, and machined) and AZ31 (rolled and machined). All as-deposited coatings (xerogel coatings) were then subjected to 10 h annealing: a temperature of 180 C was applied to the AZ91D alloy and 140 C to the AZ31 alloy. Morphological and ...
This study demonstrates amplified spontaneous emission (ASE) of the ultraviolet (UV) electroluminescence (EL) from ZnO at #lambda##approx#380 nm in the n-ZnO/ZnO nanodots-SiO_2 composite/p- Al_0_._1_2Ga_0_._8_8N heterojunction light-emitting diode. A SiO_2 layer embedded with ZnO nanodots was prepared on the p-type Al_0_._1_2Ga_0_._8_8N using spin-on coating of SiO_2 nanoparticles followed by atomic layer deposition (ALD) of ZnO. An n-type Al-doped ZnO layer was deposited upon the ZnO nanodots-SiO_2 composite layer also by the ALD technique. High-resolution transmission electron microscopy (HRTEM) reveals that the ZnO nanodots embedded in the SiO_2 matrix have diameters of 3-8 nm and the wurtzite crystal structure, which allows the transport of carriers through the thick ZnO ...
Chlorine clearly inhibits the CO{sub 2}-gasification reaction of charcoal at 800{sup o}C. From this and other observations the picture emerges that the reduction in the gasification reactivity of the charcoal is intimately related to the deactivation of the catalytically active alkali metals residing in the wood due to the formation of the chloride salt. It is argued that the heavy metal chlorides will likely transfer the chlorine to the indigenous alkali metals during the pyrolysis stage of the wood. The fate of the thus formed alkali metal chlorides can then be either their removal from the sample (evaporation), or, when present at the gasification stage, re-activation (i.e., de-chlorination) under our gasification conditions. (author) 3 figs., 4 refs.
The introduction of oxygen in the vicinity of a metallic target surface, bombarded with positive argon ions of twenty kiloelectron-volts, increases the number of sputtered atoms in the excited state. This phenomenon of exaltation, very sensitive in the case of nickel and aluminium, is much less marked in the case of molybdenum. Moreover, the emission of excited particles coming from the beam's ions is not modified. A quantum-mechanical model of a kinetic emission process, which permits the interpretation of the clean metallic target's emission phenomena, seems insufficient to explain all of the results obtained in the presence of oxygen. In this last case one can therfore use a thermodynamic model in which excited metallic particles can be formed directly by chemical surface reactions of neutralization or reduction. (orig.).
An enantiocontrolled route to aziridinomitosenes had been developed from l-serine methyl ester hydrochloride. The tetracyclic target ring system was assembled by an internal azomethine ylide cycloaddition reaction based on silver ion-assisted intramolecular oxazole alkylation and cyanide-induced ylide generation via a labile oxazoline intermediate (62 to 66). Other key steps include reductive detritylation of 26, methylation of the N-H aziridine 56, oxidation of the sensitive cyclohexenedione 68 to quinone 70, and carbamoylation using Fmoc-NCO. Although the aziridinomitosene tetracycle is sensitive, a range of protecting group manipulations and redox chemistry can be performed if suitable precautions are taken. A study of DNA alkylation by the first C-6,C-7-unsubstituted aziridinomitosene 11a has been carried out, and evidence for DNA cross-link formation involving nucleophilic addition to the quinone subunit is described. PMID:14677970
Metallic nanoparticles was synthesized in SiO{sub 2} matrices by means of a process of two stages. The first one proceeded via sol-gel, incorporating the metallic precursors to the reaction system before the solidification of the matrix. Later on, the samples underwent a thermal treatment in atmosphere of H{sub 2}, carrying out the reduction of the metals that finally formed to the nanoparticles. Then it was detected the presence of smaller nanoparticles than 20 nm, dispersed and with the property of being liberated easily of the matrix, conserving a free surface, chemically reactive and with response to external electromagnetic radiation. The system SiO{sub 2}-Pd showed an important thermoluminescent response. (Author)
The synthesis of 3-O-sulphamoyl derivatives of 1,2:5,6-di-O-isopropylidene-#alpha#-D-glucofuranose, 1,2-O-isopropylidene-#alpha#-D-glucofuranose, and 5,6-di-O-acetyl-1,2-O-isopropylidene-#alpha#-D-glucofuranose is described. A study of the reactions of carbohydrate chlorosulphates with azide has demonstrated the relative case with which certain chlorosulphonyloxy groups may be converted into azidosulphates. These azidosulphates could have potential synthetic value if a facile method for their conversion into sulphamoyl (aminosulphate) derivatives were available, since some sulphamoyl carbohydrates have been shown to possess antibiotic and antitrypanosomal activity. This report deals with the application of sodium borohydride and platinum oxide-hydrogen to the reduction of some 3-O-azidosulphate glucofuranose derivatives. "1H-n.m.r. spectra and infrared spectra were used.
Presented are the results from a laboratory test program conducted to identify and evaluate materials for converting hazardous geothermal residues to a non-hazardous and potentially usable form. Results indicate that the residues can be effectively incorporated, as a fine aggregate, into portland cement-based composites. Five geothermal residues obtained from sites in the Salton Sea area of California were evaluated. Three of these were classified as hazardous. After mixing with cement, the leach rates were all well below specified levels. Although structural-grade composites were produced, gradual reductions in properties with time up to 1 yr were noted. This indicates ongoing chemical reactions between the cement paste and the constituents of the residues. Further research is necessary before the composites could be considered for use in structural applications. 3 refs., 8 tabs.
Recycling of carbon by the photorespiratory pathway involves enzymatic steps in the chloroplast, mitochondria, and peroxisomes. Most of these reactions are essential for plants growing under ambient CO2 concentrations. However, some disruptions of photorespiratory metabolism cause subtle phenotypes in plants grown in air. For example, Arabidopsis thaliana lacking both of the peroxisomal malate dehydrogenase genes (pmdh1pmdh2) or hydroxypyruvate reductase (hpr1) are viable in air and have rates of photosynthesis only slightly lower than wild-type plants. To investigate how disruption of the peroxisomal reduction of hydroxypyruvate to glycerate influences photorespiratory carbon metabolism we analyzed leaf gas exchange in A. thaliana plants lacking peroxisomal HPR1 expression. In addition, b...
Beta-SiAlON powders have been synthesized using natural clay containing kaolin and quartz by carbothermal reduction and nitridation (CRN), then beta-SiAlON bonded corundum multiphase materials have been sintered using the as prepared powders. The results indicated that both the holding time and sintering temperature are relatively significant in accordance with optimal analysis by orthogonal method. Reaction process can be briefly interpreted by means of X-ray Diffraction and Difference Temperature Analysis as well as phase diagram principle. Bending strength and bulk density were measured in SiAlON in situ bonded corundum materials with doped various sintering agents. Furthermore, the relevant mechanical properties and microstructure were discussed in detail.
In order to apply chemical-looping combustion to a practical power plant, carbon deposition on the solid particle is one of the key problems to be overcome. Six kinds of solid particles were examined to clarify the kinetic behavior of carbon deposition. The effects of the solid composition, feed gas composition, and reaction temperature on carbon deposition were investigated by thermogravimetrical reactor on the basis of NiO/YSZ particle. From the viewpoints of both reactivity and resistance against carbon deposition, the particle of NiO mixed with YSZ (i.e., yttria-stabilized zirconia) was found to be a good candidate for chemical-looping combustion. It has been observed that carbon deposition could be completely avoided with very low concentration of water vapor. By means of a proposed model, the condition that carbon deposition would be avoided was identified. 12 refs., 8 figs., 2 tabs.
This paper explores the through-/in-plane characteristics of water transport in the cathode gas diffusion layer (GDL) of a polymer electrolyte fuel cell (PEFC). Theoretical analysis is performed on the non-isothermal two-phase flow under flow channels. A dimensionless group Da (Damkohler number for PEFC operation), defined as the ratio of water generation rate to water vapor-phase removal rate, is formulated to characterize the flow regimes in a PEFC. This group, lumping geometrical parameters and physical properties, compares the water vapor-phase removal capability (via water diffusion and holding capacity) with the rate of water production by the oxygen reductionreaction. We find that this dimensionless group can be used to characterize the non-isothermal, two-phase phenomena: when Da&...
A new mathematical framework is formulated to derive the effective equations of motion for the constrained quantum system which possesses an internal clock. In the realm close to classical behavior, the quantum evolution is approximated by a finite system of coupled but ordinary differential equations adhered to the weakly imposed Hamiltonian constraint. For the simplified version of loop quantum cosmology in the Bianchi I model with a free massless scalar filed, the resulting effective equations of motion affirm the bouncing scenario predicted by the previous studies: The big bang singularity is resolved and replaced by the big bounces, which take place up to three times, once in each diagonal direction, whenever the directional density approaches the critical value in the regime of Planckian density. It is also revealed that back-reaction arises from the quantum corrections and modifies the precise value of the directional density at the bouncing epoch. ...
The effect of complexing agents DTPA and H2C2O4 on the extraction-chemical behavior of Tc, as applied to extractive splitting of U and Pu in the Purex process, was studied. The kinetic relationships of catalytic decomposition of N2H5NO3 under the action of Tc in the presence of these agents were determined. Variation of the ratio of the oxidized and reduced Tc species in the course of this process at various HNO3 concentrations was examined. In the final step of the reaction of N2H5NO3 with Tc in a nitric acid solution, when the reductant content is stabilized, the oxidation of reduced Tc also stops or continues at a considerably lower rate than before stabilization. The presence of DTPA decreases the rate of Tc(IV) oxidation owing to its binding in a complex and decreases the fraction of ...
The iodinated oil lipiodol is commonly used as a carrier for in situ delivery of drugs or radioactivity to hepatic tumors. Recently, we reported a new kit formulation for high-activity labeling of lipiodol with the {beta}-emitting radionuclide Re-188. Since the whole preparation involves different steps and complex manipulations of high-activity samples, we describe here an automated synthesis module that allows the easy preparation of sterile and pyrogen-free samples of Re-188 lipiodol ready to be administered to the patient. Important advantages include the possibility to incorporate high Re-188 activity into the lipiodol hydrophobic phase and a sharp reduction of radiation exposure of the operator assisting the labelling procedure. Application of this modular reaction system could be also extended to the preparation of other Re-188 radiopharmaceuticals and to compound labelled with different {beta}-emitting therapeutic radionuclides.
A gas core fission reactor that utilizes americium in place of uranium is examined for potential utilization as a nuclear rocket for space propulsion. The isomer [sup 242m]Am with a half life of 141 years is obtained from an (n, [gamma]) capture reaction with [sup 241]Am, and has the highest known thermal fission cross section. We consider a 7500 MW reactor, whose propulsion characteristics with [sup 235]U have already been established, and re-examine it using americium. We find that the same performance can be achieved at a comparable fuel density, and a radial size reduction (of both core and moderator/reflector) of about 70%.
The cyclic voltammetry indicated that the oxygen reductionreaction (ORR) proceeded by the four-electron pathway mechanism on larger Ag particles (174 nm), and that the ORR proceeded by the four-electron pathway and the two-electron pathway mechanisms on finer Ag particles (4.1 nm), simultaneously. The kinetics towards ORR was measured at a rotating disk electrode (RDE) with Ag/C electrode. The number of exchanged electrons for the ORR was found to be close to four on larger Ag particles (174 nm) and close to three on finer Ag particles (4.1 nm). The zinc-air battery with Ag/C catalysts (25.9 nm) was fabricated and examined. (author)
The layered cobaltate La0.30CoO2 was prepared from NaxCoO2 precursor by a solid-state ionic exchange and was characterized by means of X-ray and neutron diffraction, magnetic, thermal and electric transport measurements. The compound consists of hexagonal sheets of edge-sharing CoO6 octahedra interleaved by lanthanum monolayers. Compared to Na+ in the parent system, the La3+ ions occupy only one-third of available sites, forming a 2-dimensional superstructure. The deviation from the ideal stoichiometry La1/3CoO2 introduces extra hole carriers into the diamagnetic LS Co3+ matrix making the sample Pauli paramagnetic. The temperature dependence of the electrical conductivity in La0.30CoO2 follows Mott's T?1/3 law up to about 400K, which is in contrast w...
Secondary ion mass spectrometry (SIMS) has been used to investigate changes that occur in an advanced Ir-0.3W alloy during high temperature aging. This alloy is used to clad "2"3"8PuO_2 heat sources used in thermoelectric generators for deep space reconnaissance satellites. Long-term direct contact with PuO_2 at 1400"0C leads to physical and chemical changes within the cladding alloy that affect its metallurgical properties. SIMS was used to show that Cr, Fe, Ni, and in some cases O, diffuse from the PuO_2 into the alloy. Thorium and aluminum diffuse out of the alloy in these same regions. This SIMS study suggests that inward O diffusion and subsequent formation of ThO_2 on grain boundaries may stabilize the alloy against enhanced grain growth.
This study investigates the applicability of n-type TiO2 and p-type NiO on the FTO-glass (Fluorine doped tin oxide, SnO2:F) substrate of the working electrode in a dye-sensitized solar cell (DSSC). The working electrode was designed and fabricated by depositing a film of TiO2/NiO composite particles, which were prepared by mixing the Ni powder with TiO2 particles using dry mixing method, on a FTO-glass substrate using a spin coating process. The working electrode was then immersed in the solution of N-719 (Ruthenium) dye at a temperature of 70degreeC for 6h. Moreover, a thin film of platinum (Pt) was deposited on the FTO-glass substrate of the counter electrode using an E-beam evaporator. Finally, the DSSC was assembled, and the short-circuit photocurrent, the open-circuit photovoltage and...
First-principles plane-wave pseudopotential and full-potential linearized-augmented plane-wave methods have been used to study the elastic and electronic properties of several potential superhard RuO_2 phases. The structures, relative stabilities, and the elastic constants and bulk moduli of these phases have been calculated within local-density approximation (LDA) and generalized gradient approximation (GGA). In RuO_2, the LDA and GGA approximations yield smaller and larger lattice constants, respectively, for the Pa3-bar-RuO_2 structure. The internal structural parameter for oxygen atoms in the Pa3-bar structure has a volume dependence that differs from the experimental result and therefore implies a significantly different compression mechanism. The calculated bulk moduli are very similar for the fluorite and Pa3-bar structures and therefore apparently ...
Characteristic study for the recycled fuel cycle, MOX fuel and Th-MOX fuel in PWR was performed with the comparison of 4 w/o UO2 fuel. It was assumed that there are no limit in reprocessing and no technical difficulty in recycling of spent fuel. The effect of recycling, plutonium composition, conversion ratio, MTC, FTC was investigated to each cycle. (Th+Pu)O_2 recycle option was advantageous because the loading amount of plutonium could be reduced from 8.3 w/o at once-through cycle to 3.5 w/o. (Th+Pu)O_2 recycled fuel was known to be higher Pu-239 consumption rate and more Pu-240(242) production rate. The (Th+U)O2 and (U+Pu)O2 once-through fuel cycle revealed high conversion ratio. The (U+Pu)O_2 recycled fuel cycle, however, showed low conversion ratio. Safety of each cycle was ...
The carbothermal reduction of clay minerals in a nitrogen atmosphere is a well established method for producing #beta#'-sialon. There has been some debate within the literature concerning the role that Fe plays in the formation of the #beta#'-sialon phase. However, most workers accept that Fe is able to either catalyze or promote the formation of #beta#'-sialon although some workers have indicated that the function of the Fe is controlled by gas flow rate and there is evidence that Fe also promotes formation of additional phases. The aim of the present study was to characterize the behaviour of Fe within the #beta#'-sialon synthesis. "5"7Fe Moessbauer spectroscopy was employed for the study because this technique is specific to Fe and does not suffer interference from other elements. Moreover, both the coordination and oxidation state and the relative abundances of the various Fe-containing phases are able to be monitored. A previous Moessbauer study of Fe in ...
In relation to coal liquefaction reaction, the effect of the coexistence of transferable hydrogen (TH) from process solvent on reduction of radical concentration and the effect of pre-heat treatment on average structure of coals were studied. In experiment, change in radical concentration with temperature rise was measured using the system composed of Yallourn coal and process solvent. The results are as follows. Process solvent with a wide boiling point range of 180-420{degree}C is effective in suppressing an increase in radical concentration even at higher temperature. The effect of hydrogen-donating solvent increases with TH. It was also suggested that high-boiling point constituents in solvent stabilize radicals even over 400{degree}C by vapor phase hydrogenation. The experimental results of pre-heat treatment are as follows. Although the conversion improvement effect of TH is equivalent to that of the model solvent, TH tends to produce ...
The knowledge shown in this work of the relationships between the oxidation stage of chromium, molybdenum and tungsten and their catalytic activity in some hydrocarbon reactions was achieved by the combination of separate investigations of reduction properties and the catalytic activity of the catalysts concerned. To characterize the electronic state of the reduced surfaces, X-ray photo-electronic spectroscopy was mainly used, supplemented by electron spin resonance. The catalyst activity was measured in conventional apparatus (flow, pulse and gradient-free reactors). (orig.) [Deutsch] Die in dieser Arbeit dargestellten Erkenntnisse ueber die Zusammenhaenge zwischen der Oxidationsstufe von Chrom, Molybdaen und Wolfram und ihrer katalytischen Aktivitaet in einigen Kohlenwasserstoffreaktionen wurden durch die Kombination getrennter Untersuchungen ueber Reduktionseigenschaften und katalytische Aktivitaet der betreffenden Katalysatoren erzielt. ...
Following the successful application of hydrostatic pressure in mechanistic investigations of organic reactions, chemists have launched a vigorous effort to apply this tool to substitution reactions of coordination compounds. The authors began to study pressure effects in the NMR spectra of keton-lanthanide combination with the hope that the increase shifts anticipated might enhance the utility of the method, perhaps even expand its applicability to new classes of compounds. 5-Phenyl- and 5-tert-butyladamantan-2-one, piperidine, tetrahydrofuran, and cyclopentanol exhibited pressure-reduced lanthanide-induced shifts with Eu(fod)/sub 3/; Yb(fob)/sub 3/ and the shielding reagent Pr(fod)/sub 3/ showed the same effect with adamantanone. Solvent variations (CD/sub 2/Cl/sub 2/, CCl/sub 4/) caused minor changes in the magnitude of these shifts but did not reverse any. With the objective of learning whether these effects are due to a suppressed ...
The oxidative dehydrodimerization of propylene to C/sub 3/-dimers (1,5-hexadiene and benzene) has been examined at 600/sup 0/C and atmospheric pressure using a (Bi/sub 2/O/sub 3/)/sub 0.85/(La/sub 2/O/sub 3/)/sub 0.15/ oxide ion-conducting catalyst in a reactor where a catalyst disk separates a feed of propylene in helium from air. The surface of the disk exposed to propylene was reoxidized not by gaseous O/sub 2/, but by the dissociative adsorption and reduction of dioxygen at the oxidant side of the disk, followed by oxide ion conduction to replace spent lattice oxygen. Selectivity to C/sub 3/-dimers when using lattice oxide migration to reoxidize the catalyst was considerably greater than when O/sub 2/ was added to the propylene feed under the same reaction conditions. This result supports the proposal that lattice oxygen is predominantly involved in the selective oxidation of propylene to C/sub 3/-dimers, and demonstrates that Bi/sub ...
The manufacture and use of wood/plastic composite (WPC) as an example of wood matrix and wood sawdust/plastic composites (SDP) as an example of plastic matrix are reviewed. The raw material for WPC are mostly vinyl monomers, particularly methyl methacrylate and styrene. The reaction in WPC polymerization is radical polymerization. Researches on the radiation sources mostly resulted in gamma-ray. Electron beam can be applied only to thin products. The future use of WPC may be for furnitures, sporting goods, decorative parts and the like. Vital study on the reduction of manufacturing costs is required, for example, the improvement of reaction and the adoption of continuous process must be considered. The raw materials for SDP are wood sawdust, vinyl monomer (mostly methyl methacrylate) and resins. Electron beam accelerators are the most preferable radiation source because of its high efficiency and safe operation. SDP shows ...
In the past three years, we followed the work plan as we suggested in the proposal and made every efforts to fulfill the project objectives. Based on our large amount of creative and productive work, including both of experimental and theoretic aspects, we received important technical breakthrough on naphthenic acid removal process and obtained deep insight on catalytic decarboxylation chemistry. In detail, we established an integrated methodology to serve for all of the experimental and theoretical work. Our experimental investigation results in discovery of four type effective catalysts to the reaction of decarboxylation of model carboxylic acid compounds. The adsorption experiment revealed the effectiveness of several solid materials to naphthenic acid adsorption and acidity reduction of crude oil, which can be either natural minerals or synthesized materials. The test with crude oil also received promising results, which can be potentially ...
The open circuit potential (OCP) of stainless steels immersed in natural waters generally increases with time. This phenomenon is strongly linked to the formation of a bio-film on the surface. Several studies have proved that the bio-film modifies the reaction of reduction of dissolved oxygen and that it acts mainly on the cathodic processes. One of the hypotheses explaining the action of the bio-film involves certain bacteria which use dissolved oxygen and extracellular enzymes to produce reactive oxygen species. Among this kind of metabolites is hydrogen peroxide H{sub 2}O{sub 2}. This compound interacts with the passive layer of stainless steels and affects their electrochemical behaviour, even when the chloride concentration is low. The aim of this work is to study the influence of an enzymatic reaction (of the oxidoreductase type) on anodic and cathodic processes on AISI 316L stainless steel. Experiments are carried ...
In this study, Cu{sub 2}O/Cu composite particles were synthesized using an innovative chemical reduction method without any template and surfactant. X-ray diffraction (XRD) analysis revealed that the product mainly consisted of Cu{sub 2}O phase coexisting with a Cu phase. FE-SEM images showed that the octahedral shaped particles were Cu{sub 2}O. The electrochemical performance of the Cu{sub 2}O/Cu particles was investigated with regards to the working electrode material in alkaline solution. The particles had a maximum discharge capacity of 222.9 mAh/g at a discharge current density of 60 mA/g and a high value of 109.1 mAh/g after 50 charge-discharge cycles. Cyclic voltammetry revealed that the reaction between Cu{sub 2}O and Cu is the major electrochemical reaction during the charging and discharging process. Electrochemical impedance spectroscopy revealed that the formation of Cu{sub 2}O on the surface of Cu particles ...
Previously we have used atomic force anodisation lithography, with a self-assembled monolayer of hexadecyltrichlorosilane as a resist, to pattern silicon oxide nanostructures onto a p-type silicon (1 0 0) substrate. A condensation reaction was used to immobilise carbon nanotubes with high carboxylic acid functionality directly to the silicon oxide. A further condensation reaction using this surface attached the molecule ferrocenemethanol to the bound nanotubes. These new nanostructures were used as electrodes to observe the oxidation and reduction of ferrocene. However, because the small currents measured are near the detection limits of the electrochemical system used, important electrode kinetics could not to be obtained. A scribing approach made larger regions of oxidised silicon leading to the creation of larger scale patterned arrangements of carbon nanotubes allowing measurement of important electrochemical parameters ...
A microwave-assisted carbothermal reduction and nitridation (CTR/N) method has been used for successful preparation of monophasic #beta#'-SiAlON starting from kaolinite and carbon black. Phase pure #beta#'-SiAlON has been obtained in under 60 min in microwave field. The z value of microwave prepared #beta#'-SiAlON is found to be 2.95, which is very close to the expected value from kaolinite composition. Formation of #beta#'-SiAlON has been monitored with XRD and MASNMR of "2"9Si and "2"7Al; the possible reaction mechanism has been discussed. Kaolinite to #beta#'-SiAlON conversion appears to be a very rapid single-step reaction under microwave irradiation. #beta#'-SiAlON powders have been microwave sintered to 98.7% of theoretical density in 30 min.
One-electron reduction of the square-planar nickel precursor (PNP)NiCl ( 1) (PNP (-) = N[2-P(CHMe 2) 2-4-methylphenyl] 2) with KC 8 effects ligand reorganization of the pincer ligand to assemble a Ni(I) dimer, [Ni(mu 2-PNP)] 2 ( 2), containing a Ni 2N 2 core structure, as inferred by its solid-state X-ray structure. Solution magnetization measurements are consistent with a paramagnetic Ni(I) system likely undergoing a monomer dimer equilibrium. The room-temperature and 4 K solid-state X-band electron paramagnetic resonance (EPR) spectra display anisotropic signals. Low-temperature solid-state X-band EPR data at 4 K reveal rhombic values g z = 1.980(4), g x = 2. 380(4), and g y = 2.225(4), as well as a forbidden signal at g = 4.24 for the Delta M S = 2 half field transition, in accord with 2 having two weakly interacting metal centers. Utilizing an S = 1 model, full spin Hamiltonian simulation of the low-temperature EPR spectrum on the solid sample was achieved by ...
The theoretical and experimental investigation of the mechanism of SO2 and H2S removal by CaCO3 -based sorbents (limestones and dolomites) in pressurized uidized-bed coal combustors (PFBC) and high pressure gasiers, respectively, is the main objective of this study. It is planned to carry out reactivity evolution experiments under simulated high pressure conditions or in high pressure thermogravimetric and, if needed, uidized- bed reactor (high pressure) arrangements. The pore structure of fresh, heat-treated, and half-calcined solids (dolomites) will be analyzed using a variety of methods. Our work will focus on limestones and dolomites whose reaction with SO2 or H2S under atmospheric conditions has been studied by us or other research groups in past studies. Several theoret- ical tools will be employed to analyze the obtained experimental data including a variable diusivity shrinking-core model and models for diusion, reaction, and structure ...
The passive films formed in stainless steels are thin and fine oxide films, a high corrosion resistance can be provided by these films. This study formed SiO2 protective coating on the substrate of SUS 304 stainless steels by chemical vapor deposition using TEOS-O3 system. Firstly, relations of substrate temperature and deposition rate of films, chemical composition, refractive index of films were investigated. Then, the corrosion resistance of SUS 304 stainless steels coated SiO2 films was examined by activation time and an anodic polarization curve in 1 kmol[center dot]m[sup -3] HCl solution. The results were obtained as follows. Thickness of SiO2 films linearly increases with time at the deposition temperature of 473 to 673 K. Si-OH bonds would disappear above the deposition temperature of 573 K, almost perfect SiO2 ...
Molten salt oxidation (MSO) is proposed as a {sup 238}Pu waste treatment technology that should be developed for volume reduction and recovery of {sup 238}Pu and as an alternative to the transport and permanent disposal of {sup 238}Pu waste to the WIPP repository. In MSO technology, molten sodium carbonate salt at 800--900 C in a reaction vessel acts as a reaction media for wastes. The waste material is destroyed when injected into the molten salt, creating harmless carbon dioxide and steam and a small amount of ash in the spent salt. The spent salt can be treated using aqueous separation methods to reuse the salt and to recover 99.9% of the precious {sup 238}Pu that was in the waste. Tests of MSO technology have shown that the volume of combustible TRU waste can be reduced by a factor of at least twenty. Using this factor the present inventory of 574 TRU drums of {sup 238}Pu contaminated wastes is reduced to 30 drums. ...
X-ray emission spectroscopy (XES) and X-ray photoelectron spectroscopy (XPS) methods were employed in the present paper to investigate the electronic structure of face-centred cubic (fcc) molybdenum dioxide, fcc-MoO_2. For the mentioned compound, the XES O K#alpha# and Mo L#beta#_2_,_1_5 bands reflecting the valence O p- and Mo s,d-like states, respectively, were derived and compared on a common energy scale with the XPS valence-band spectrum. For comparison, the similar experimental studies of the electronic structure were made for a usual orthorhombic form of molybdenum trioxide, MoO_3. Band-structure calculations of fcc-MoO_2 were made using the full potential linearized augmented plane wave (FP-LAPW) method. A rather good agreement of the experimental XES and XPS results and the theoretical FP-LAPW data for the electronic properties of fcc-MoO_2 has been ...
The formation of thin SiO_2 layers on silicon and metal silicides was studied by phase- and thickness measurements with Rutherford back-scattering of 2 MeV alfa particles. Thermal oxidation was done in steam and dry oxygen at temperatures between 750 degrees Celsius and 1 100 degrees Celsius, while SiO_2 formation at room temperature was carried out by anodic oxidation. The study of silicon oxidation was done on Si<100>, Si<111> and amorphous silicon substrates. Thermal oxidation of CoSi_2, CrSi_2, NiSi_2, PtSi and TiSi_2 was investigated. The oxidation rates of the silicides were found to be much higher than for silicon. The oxidation process is also diffusion-limited with a higher oxidation rate for steam as compared to dry oxygen. The silicide layers were found to stay intact during thermal oxidation. A certain amount of structural and chemical instability did appear. Chemical instabiliy ...
Chemical-looping combustion is an indirect combustion technology with inherent separation of the greenhouse gas CO{sub 2}. The feasibility of using NiO as an oxygen carrier during chemical-looping combustion of coal has been investigated experimentally at 800-960{degree}C in the present work. The experiments were carried out in a fluidized bed, where the steam acted as the gasification-fluidization medium. Coal gasification and the reaction of oxygen carrier with the water gas take place simultaneously in the reactor. The oxygen carrier particles exhibit high reactivity above 900{degree}C, and the dry basis concentration of CO{sub 2} in the exit gas of the reactor is nearly 95%. The flue gas composition as a function of the reactor temperature and cyclic reduction number is discussed. At 800-960{degree}C, the dry basis concentration of CO{sub 2} in the flue gas presents a monotonously increasing trend, whereas the dry basis concentration of CO, ...
A bottom-up approach is used here to combine carbon nanotubes synthesized by CVD and organically capped platinum nanoparticles electrocatalyst exhibiting a direct electrochemical activity towards oxygen reduction. Both nano-objects are handled in liquid suspension and are associated together in a controlled way. The nanocomposite liquid dispersions can be precisely controlled in terms of platinum nanoparticles to carbon nanotubes weight ratios (NP/NT) which correspond to different coverages of nanotubes by nanoparticles. Electrodes with low to ultra-low platinum loadings can then be prepared on porous fuel cell carbon supports by filtration. The direct electrochemical activity towards aqueous oxygen reductionreaction (ORR) of electrodes with platinum loadings ranging from about 1 to 60 {mu}g/cm{sup 2} is reported without any activation step in order to keep the features of the nanoparticles intact. Before that, we studied ...
The environmental problem of ground level ozone is discussed, and the Canadian strategy for dealing with it is explained. Ozone in the troposphere can cause serious health problems in susceptible persons, and is estimated to cause up to $70 million in crop damage per year. The Canadian Council of Ministers of the Environment (CCME) Plan calls for less than 82 ppB by volume of ozone in any one-hour period in all areas of Canada by 2005. Three areas of Canada regularly exceed this value: the Lower Frazer valley in British Columbia, Saint John in New Brunswick, and the Windsor-Quebec corridor along the lower Great Lakes and the St. Lawrence River. Ozone is formed by a photochemical reaction of ammonia gases, nitrogen oxides, hydrogen sulfide or sulfur dioxide. Historically, ozone control has concentrated on controlling hydrocarbon emissions, but to little effect. In most locations close to large cities, ozone production is nitrogen oxide-limited, and the most recent ...
Randomly oriented ZnO microsheets were successfully self-assembled on TiO2 nanoparticle (TN) film to act as the scattering layer via a cathodic electrodeposition process. The light scattering properties of ZnO microsheets were studied by UV-Vis spectrometer in the 400?800 nm wavelength range. It was found that ZnO microsheets exhibited excellent ability to scatter the incident light for ZnO microsheet-TiO2 nanoparticle (ZT) composite films. The results showed that dye-sensitized solar cells (DSSCs) fabricated with ZT composite films showed higher short-circuit density (J sc) and conversion efficiency than TN-based DSSCs, due to the light scattering properties of ZnO microsheets.
Fe-doped TiO2 hollow spheres (Fe-THs) were synthesized by sol?gel process using carbon spheres as templates. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV?vis diffuse reflectance spectrum (DRS), N2 adsorption?desorption isotherms, Electron paramagnetic resonance (EPR) spectroscopy and Photoluminescence emission spectroscopy (PL). UV?vis spectra showed that Fe3+ doping could extend the absorption edge to the visible region. EPR spectra showed that Fe3+ was incorporated into the crystal lattice of TiO2, which could inhibit the recombination of photo-induced electron?hole pairs and improve the photocatalytic activity. The photocatalytic activities of the prepared samples were evaluated for the degradation of dye Reactive Brillia...
Abstract Superoxide dismutase (SOD) is ubiquitous in aerobic organisms and constitutes the first link in the enzyme scavenging system of reactive oxygen species. In the present study, species and organ diversity of SOD activity in a solution and in an in-gel assay system, as well as the effects of hydrogen peroxide (H2O2) on SOD activity, were investigated. In a solution assay system, SOD activity of jackfruit root, shoot, leaves, axes, and cotyledons, of maize embryos and endosperms, of mung bean leaves and seeds, of sacred lotus axes and cotyledons, and of rice and wheat leaves was increased by 1-15 mmol/L H2 O2. However, SOD activity in rice root and seeds, maize roots and leaves, mung bean roots and shoots, and wheat seeds was decreased by 1-15 mmol/L H2O2. The SOD activity of wheat ro...
Rapid self-aggregation of Ni nanodots on Si substrate covered with a thin SiO_2 buffered layer is investigated. The Ni nanodots can hardly self-aggregate on highly heat-dissipated Si substrate with a thermal conductivity of 148 W/m K. Adding a 200-A-thick SiO_2 buffer with an ultralow thermal conductivity of 1.35 W/m K prevents the formation of NiSi_2 compounds, enhances the heat accumulation, and releases the adhesion at Ni/Si interface, which greatly accelerates the self-assembly of Ni nanodots. Dense Ni nanodots with size and density of 30 nm and 7x10"1"0 cm"-"2, respectively, can be formatted after rapid thermal annealing at 850 deg. C for 22 s.
The effect of chemical pretreatments using NaOH, H2O2, and Ca(OH)2 on Empty Palm Fruit Bunches (EPFB) to degrade EPFB lignin before pyrolyis was investigated. Spectrophotometer analysis proved consecutive addition of NaOH and H2O2 decomposed almost 100% of EPFB lignin compared to 44% for the Ca(OH)2, H2O2 system while NaOH and Ca(OH)2 used exclusively could not alter lignin much. Next, the pretreated EPFB was catalytically pyrolyzed. Experimental results indicated the phenolic yields over Al-MCM-41 and HZSM-5 catalysts were 90wt% and 80wt%, respectively compared to 67wt% yield for the untreated sample under the same set of conditions. Meanwhile, the experiments with HY zeolite yielded 70wt% phenols.
We report on the formation of current blocking regions by O2 plasma treatment to reduce current crowding at the active region above the p-type electrodes of GaN-based vertical light emitting diodes (LEDs). The forward voltage and reverse current (at -5 V) of the plasma-treated LEDs slightly increase with increasing aging time. The output power (at 350 mA) of the plasma-treated LEDs is enhanced by 26% as compared to that of reference LEDs and is comparable to that of LEDs with SiO2 current blocking layers. It is shown that the output power (at 700 mA) of the plasma-treated LEDs is degraded by less than 2% of the initial value after 500 h.
AbstractBackground In recent years nano-metaloxides which easily penetrate into the cells with special interest due to their higher chemical reactivity as compared to that of similar materials in the bulk form. Of particular interest are nano-TiO2 and ZnO, which have been widely used for their bactericidal and anticancerous properties. Purpose The aim of the present study was to examine the bactericidal properties of nano-TiO2 and ZnO combined with visible light on S. aureus and S. epidermitis, known for their high prevalence in infected wounds. Study Using the technique of electron-spin resonance (ESR) coupled with spin trapping, we examined the ability of TiO2 and ZnO nanoparticle suspensions in water to produce reactive oxygen species (ROS) with and without visible light irradiation. Th...
Porous SnO2 nanotubes were prepared via electrospinning followed by calcination in air. As anode materials for lithium ion batteries, the porous nanotubes delivered a high discharge capacity of 807mAhg^-^1 after 50cycles. Even after cycled at high rates, the electrode still retained a high fraction of its theoretical capacity. Such excellent performances of porous SnO2 nanotubes could be attributed to the porous and hollow structure which facilitated liquid electrolyte diffusion into the bulk materials and buffered large volume changes during lithium ions insertion/extraction. Furthermore, the nanoparticles of nanotubes provided the shorter diffusion length for lithium ions insertion which benefited in retaining the structural stability and good rate performance. Our results demonstrated t...
In this project, nanocrystalline SnO2 powders were successfully prepared by (a) citrate sol-gel and (b) direct precipitation methods. Powders were characterized using thermal analysis techniques (DTA-TG-DSC), X-ray powder Diffraction (XRD), surface area (BET) and electrical conductivity measurements. XRD patterns showed the presence of the cassiterite structure. SnO2 particles, prepared through sol-gel method exhibit crystallite sizes in the range from 3.1 to 22.3 nm when the gel is heat treated at different temperatures up to 900?C. SnO2 nanocrystallites prepared by the precipitation method are comparatively larger in size. The higher specific surface area was obtained for the powder prepared using sol-gel method and the obtained average grain size (d) is relatively large compared with th...
Abstract Nanocomposites based on SnO2 with carbon scaffold were used as highly porous anode films on Ni substrates. The films were obtained by in situ deposition of the particles without any binder or excess carbon black avoiding any secondary treatment. Compared to similarly prepared uncoated SnO2 nanoparticles as well as conventionally prepared powder samples the capacity loss of the in situ deposited nanocomposite films is significantly reduced. Thus, this newly developed anode material combined with in situ film formation is a promising approach for high capacity anodes in Li-ion batteries. SEM-micrograph of a SnO2/C nanoparticle film.
Surface study techniques were used to investigate films on Type 304 stainless steel which were formed during exposure to high purity water at 288"0C. The results indicated that the film chemistry depended strongly upon the concentration of the dissolved O_2 in the water. Films formed in water having 8 ppm O_2 were stoichiometric mixed oxides; whereas those formed in water with 10 ppb O_2 were highly defective oxyhydroxides. The latter films are not as protective as the stoichiometric oxides. Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) were used to investigate the films. (Auth.).
A superhydrophobic SiO2/nylon 6,6 nanocomposite coating was fabricated by a facile casting process. Compared with the intrinsically hydrophilic pure nylon 6,6, the as-prepared coating displayed a superhydrophobic property in the pH range from 1 to 14. It was also found that the resulting water contact angles of the as-prepared surface were always larger than 159?, but the sliding angles had an obvious decrease from about 33.4??1? as the content of SiO2 nanoparticles increased. In addition, a transition from the transitional superhydrophobic state between Wenzel?s and Cassie?s state to the Cassie?s state was observed.
Chemical looping combustion (CLC) is a novel technology where CO{sub 2} is inherently separated during combustion. Due to the existence of sulfur contaminants in the fossil fuels, the gaseous products of sulfur species and the interaction of sulfur contaminants with oxygen carrier are a big concern in the CLC practice. The reactivity of NiO/Al{sub 2}O{sub 3} oxygen carrier reduction with a gas mixture of CO/H{sub 2} and H{sub 2}S is investigated by means of a thermogravimetric analyzer (TGA) and Fourier Transform Infrared spectrum analyzer in this study. An X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM) are used to evaluate the phase characterization of reacted oxygen carrier, and the formation mechanisms of the gaseous products of sulfur species are elucidated in the process of chemical looping combustion with a gaseous fuel containing hydrogen sulfide. The results show that the rate of NiO ...
Reaction Engineering International (REI) has established a project team of experts to develop a technology for combustion systems which will minimize NO x emissions and minimize carbon in the fly ash. This much need technology will allow users to meet environmental compliance and produce a saleable by-product. This study is concerned with the NO x control technology of choice for pulverized coal fired boilers, ?in-furnace NO x control,? which includes: staged low-NO x burners, reburning, selective non-catalytic reduction (SNCR) and hybrid approaches (e.g., reburning with SNCR). The program has two primary objectives: 1) To improve the performance of ?in-furnace? NO x control processes. 2) To devise new, or improve existing, approaches for maximum ?in-furnace? NO x control and minimum unburned carbon. The program involves: 1) fundamental studies at laboratory- and bench-scale to define NO reduction mechanisms in flames and ...
The series of cubic pyrochlore structure compounds, R_2Mo_2O_7 (R = Nd-Yb, Y; R not= Eu), were prepared as single phase materials by solid state reaction between R_2O_3 and MoO_2 at 1400 "0C in a CO/CO_2 = 1 buffer gas atmosphere. Lattice constants obtained from X-ray powder data compare well with results from previous studies. Magnetic susceptibility and magnetization data were obtained for all samples between 300 K and 4.2 K (700 K for R = Gd) and a range of applied fields. For R = Nd, Sm, and Gd magnetic ordering is observed at 97 K, 93 K and 83 K respectively which is assigned to ferromagnetism on the Mo(IV) sublattice. The Mo(IV) moment in the ordered state is about 1 #mu#/sub B/. At low temperatures, the Gd(III) and Mo(IV) moments are apparently coupled feromagnetically in Gd_2Mo_2O_7 yet the high temperature susceptibility data seem to indicate a ferrimagnetic (antiparallel) Gd(III)-Mo(IV) coupling. The ...
Progress reports are presented for the following two areas: catalytic cracking studies with water-wet silica-alumina catalysts; and Fischer-Tropsch reactor studies where similarities and differences between fixed bed and slurry type reactors are investigated and further experiments conducted to measure mass transfer coefficients and reaction kinetics which are to be used in a model slurry reactor. The following are some of the conclusions. (1) The premise that the presence of liquid water might increase catalytic cracking activity was found to be invalid. It was demonstrated that cracking can occur at previously unobserved low temperatures (though at low conversions) and that an anomaly exists in that one of the catalysts tested shows an entirely different cracking behavior and probably follows a different cracking mechanism. (2) the diameter of a fixed-bed Fischer-Tropsch reactor critically affected the resistance of the reactor to plugging caused by the build up ...
The electrical characteristics of thin TiO2 films prepared by metal?organic chemical vapor deposition grown on a p-type InP substrate were studied. For a TiO2 film of 4.7?nm on InP without and with ammonium sulfide treatment, the leakage currents are 8.8?10?2 and 1.1?10?4?A/cm2 at +2 V bias and 1.6?10?1 and 8.3?10?4?A/cm2 at ?2?V bias. The lower leakage currents of TiO2 with ammonium sulfide treatment arise from the improvement of interface quality. The dielectric constant and effective oxide charge number density are 33 and 2.5?1013?cm2, respectively. The lowest mid-gap interface state density is around 7.6?1011?cm?2?eV?1. The equivalent oxide thickness is 0.52?nm. The breakdown electric field increases with decreasing thickness in the range of 2.5 to 7.6?nm and reaches 9.3?MV/cm at 2.5?n...
Biofumigation with Muscodor albus was investigated to control four fungal decay pathogens (Phytophthora erythroseptica, Sclerotinia sclerotiorum, Botrytis cinerea and Penicillium expansum) and four bacterial pathogens (Erwinia carotovora pv. carotovora, Pseudomonas fluorescens, Escherichia coli, Listeria innocua) in controlled atmosphere conditions (regular air (20.8% O2+0.03% CO2), high CO2 (20.8% O2+15% CO2) or low O2 (1% O2+0.03% CO2)). In vitro experiments involved 48h exposure to M. albus at 3degreeC or 20degreeC, in vivo experiments involved 72h exposure to M. albus at 3degreeC. In vitro biofumigation with M. albus in regular air at 20degreeC killed all the pathogens. Bacterial growth was best controlled by M. albus at 20degreeC regardless of atmospheric conditions whereas fungal gro...
Fine ceramic particles of zirconia toughened alumina (ZTA), titania toughened alumina (TTA), and zirconia-titania toughened alumina (ZTTA) have been synthesized by ultrasonic spray pyrolysis (USP) at various temperatures from starting salt solutions of various compositions aiming for the development of catalytic material. These particles were characterized for properties such as shape, size and size distribution, diffraction pattern, and chemical and phase composition of elements by scanning electron microscopy (SEM), particle size analyzer (PSA), x-ray diffraction (XRD), and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Chemical compositions and sizes of ceramic composites have been controlled by the stoichiometry of salt solutions and the flow rate of spraying solutions. The optimum experimental conditions for the various composite particle synthesis have been proposed.
In this study, SnO2 thin films have been grown using spray pyrolysis technique on glass substrates under a substrate temperature (Ts = 440 oC). The precursors were methanol CH4O and anhydrous tin tetrachloride. XRD analyses yielded strong (1 1 0)-(1 0 1)-(2 0 0) X-ray diffraction peaks which are characteristics to tetragonal crystals. Atomic Force Microscopy (AFM) analyses showed the existence of clusters with particular pyramidal shapes. The main part of this study concerns the optical measurements of transmittance T(?) and reflectance R(?) spectra inside 250-1800 nm domain. Conjoint optical and thermal properties were deduced using the Amlouk-Boubaker Opto-Thermal Expansivity ?AB. The obtained value: ?AB ? 23.4 m3 s-1 helped situating the performance of the as-grown SnO2 compound among most known PV-T oxides like ZnO and TiO2.
The synthesis of narrowly dispersed nanocrystalline TiO_2 was investigated with a surfactant aided solvothermal synthetic method in toluene solutions. When a sufficient amount of titanium isopropoxide, Ti[OCH(CH_3)_2]_4 (TIP), was added to the solution, the shapes of TiO_2 nanoparticles changed from spheres to rods. The aggregated microstructures of the nano-sized TiO_2 in systems of spheres, rods, and mixtures of spheres and rods was studied using TEM. The morphological shape of the aggregation was described in terms of the fractal dimensions. We used a box-counting method to get the fractal dimension of these systems. The fitted fractal dimensions for spheres, sphere/rod mixtures, and rods are D = 1.54, D = 1.81, and D = 1.89, respectively. The fractal dimension changed from 1.54 to 1.9 with the TIP/toluene ratio, indicating that the growth mechanism for ...
Mutant strains of the yeast Saccharomyces cerevisiae which lack functional Cu,Zn superoxide dismutase (SOD-1) do not grow aerobically unless supplemented with methionine. The molecular basis of this...Full Text Available
The antimicrobial effects and quality changes of O2, He, N2 or N2O-enriched active modified atmosphere packaging -MAP- (100 kPa initial gas partial pressure) compared to a chlorinated -100 mg L-1 NaClO- passive MAP (control) in fresh-cut Red Chard baby leaves up to 8 days at 5 degreeC were studied. High O2 MAP (>85 kPa O2) inhibited natural microflora growth during 7 days at 5 degreeC. Regarding control treatment, no differences for He and N2O-enriched MAPs on microbial growth were found although control samples were previously disinfected. Initial total phenolics content (613 mg ChAE kg-1 fw) increased up to 61-93% after 6 days at 5 degreeC under O2, He, and N2-enriched MAPs. Vitamin C content decreased up to 67% after shelf life in control samples while lower decreases were monitored in ...
The alpha emitter plutonium-238 ("2"3"8Pu), which is produced in uranium-fueled, light-water reactors, is used as a thermoelectric power source for space applications. Inhalation of a mixed oxide form of Pu is the most likely mode of exposure of workers and the general public. Occupational exposures to "2"3"8PuO_2 have occurred in association with the fabrication of radioisotope thermoelectric generators. Organs and tissue at risk for deterministic and stochastic effects of "2"3"8Pu-alpha irradiation include the lung, liver, skeleton, and lymphatic tissue. Little has been reported about the effects of inhaled "2"3"8PuO_2 on peripheral blood cell counts in humans. The purpose of this study was to investigate hematological responses after a single inhalation exposure of Beagle dogs to alpha-emitting "2"3"8PuO_2 particles and to extrapolate results to humans.
In this paper, we present the results of Plasma-Enhanced Chemical Vapor Deposition gate-oxide (SiO_2) integrity on ELC (excimer-laser-crystallized), MILC (metal-induced lateral-crystallized) and SPC (solid-phase-crystallized) polysilicon films. We observed that gate oxide strength of poly-Si TFT strongly depends on the crystallization method for the active silicon layer. In the case of ELC films, asperities on the silicon surface reduce the SiO_2 breakdown field significantly. The metallic contaminants in MILC films are responsible for a deleterious impact on gate oxide integrity. Among the three cases, the SiO_2 breakdown field was the highest for the SPC silicon films. The breakdown fields at the 50 % failure points in Weibull plots for the ELC, MILC and SPC cases were 5.1 MV/cm, 6.2 MV/cm, and 8.1 MV/cm, respectively. We conclude that the roughness and ...
The effect of electron and ion beam irradiation on the Sisub(LVV) Auger spectra of SiO_2, Si_3N_4 and Si-oxynitride films was measured by the relative intensity of the 92 eV signal, characteristic for the formation of 'free' silicon during irradiation. While in Si-oxynitride the beam effects were almost negligible, some damage was found in Si_3N_4, but SiO_2 appeared to be extremely sensitive for electron and ion beam irradiation. By low energy electron loss spectroscopy of ion bombarded SiO_2 and Si_3N_4 films new electron states due to broken Si-O and Si-N bonds could be determined within the band gap of the insulators. The measured energy losses were interpreted by means of electron energy level schemes of the amorphous films. (author).
Beagle dogs given a single exposure to "2"3"9PuO_2 or "2"3"8PuO_2 aerosols are being observed for life-span dose-effect relationships. The "2"3"9Pu body burden of the nine dogs that died of pulmonary fibrosis-induced respiratory insufficiency during the first 3 yr after exposure was 1 to 12 #mu#Ci. One of these dogs had a pulmonary tumor. Five additional dogs with body burdens of 0.7 to 1.8 #mu#Ci died due to pulmonary neoplasia 3 to 5 yr after exposure. None of the dogs exposed to "2"3"8Pu have died during the first 3 postexposure yr. Lymphocytopenia was the earliest observed effect after inhalation of "2"3"9PuO_2 or "2"3"8PuO_2, occurring 0.5 to 2 yr after deposition of greater than or equal to 80 nCi plutonium in the lungs.
Sodium benzene sulfonate (BS) was decomposed in aqueous TiO_2 dispersions under highly concentrated solar light illumination to examine the photocatalytic characteristics of a parabolic round concentrator (PRC) reactor to degrade the pollutant without visible light absorption. The effects of such operational parameters as initial concentration, volume of the aqueous BS solution, oxygen purging, and TiO_2 loading on the kinetics of decomposition of BS were investigated. An effective photodegradation necessitates a suitable combination of initial volume and concentration of BS solution. Relative to atmospheric air, oxygen purging significantly accelerates the degradation process at high initial concentrations of BS (0.40 mM or 1.0 mM). Optimal TiO_2 loading was 9 gl "-"1, greater than previously reported. Elimination of TOC (total organic carbon) followed pseudo ...
A general procedure for stabilization of O2-labile enzymes exploiting "salting out" of oxygen from the microenvironment in the molecular layers immediately adjacent to charged surfaces of polyionic...Full Text Available
Monodisperse europium-activated titania hollow phosphors had been synthesized by a facile one-pot hydrothermal method using carbon spheres as hard templates. Samples were characterized by X-ray powder diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive spectrometer and photoluminescence spectrum. The strongest emission intensity was observed with TiO2:Eu0.2 hollow spheres and TiO2:Eu0.2 hollow spheres calcining at 550^oC. Moreover, the strongest excitation of TiO2:Eu0.2 hollow spheres transferred from 400 to 500^oC and the effective nonradiative energy transfer from the TiO2 hollow spheres host matrix to Eu^3^+ ions crystal field states was realized due to changes of crystalline field in the environment around Eu^3^+ ions occupying Ti^4^+ site...
May 31, 2011 ... Synthesis and Structural Characterization of a Novel Indium Mercapto Derivative [Clln(SCH2(CO)O)2]2-[(4-MepyH)2]2+. 284. System Mass ...
Six uranyl coordination compounds, UO_2(OH)(PYCA) (1), UO_2(PYCA)_2(H_2O).2H_2O (2), UO_2(PIC)_2 (3), UO_2(H_2O)_2(NIC)_2 (4), UO_2(OH)(HINIC)(INIC) (5), and UO_2(PYTAC)_2(H_2O)_2 (6) were grown as single crystals via hydrothermal synthesis (PYCA - pyrazine-2-carboxylate, PIC - picolinate, NIC - nicotinate, INIC - iso-nicotinate, and PYTAC - 2-(pyridin-4-yl)thiazole-5-carboxylate) to study their optical properties. All six compounds have been identified via single crystal X-ray diffraction and fully characterized via powder X-ray diffraction, infrared spectroscopy, UV-Vis spectroscopy, and fluorescence spectroscopy. Three of the complexes, 1, 3, and 6, represent new structures, and their synthesis and structural characterization is detailed within. The structures of 2, 4, and 5 have previously been reported in the ...
A mixture of powders of silica and aluminum nitride is subjected to high-energy ball milling for different milling times. This material is subsequently compacted by uniaxial pressing and sintered at 1450 deg. C. The resulting pellets are crushed and analysed by X-ray diffraction. For short milling times, the amount of phase transformation is minimal and the resulting material mostly consists of cristobalite and aluminum nitride. For long milling times, nanocrystalline #beta#-SiAl_2O_2N_2 is mainly produced.
An in vitro system for studying Pu uptake by, and removal from, macrophages was developed to provide data for the actinide therapy program. We have shown that "2"3"9PuO_2 particle uptake in vitro resembles the process in vivo with respect to the intracellular localization of phagocytized particles. At the end of 7 days of culture of Pu-loaded cells, 54% of the cells were viable even though 71% of the cells in the culture initially contained enough "2"3"9PuO_2 to deliver more than 53 intracellular #alpha#-disintegrations.
Isobaric molar heat capacities of powder and microsphere form of Li2TiO3 (s) and powder form of LiAlO2 (s) and Li2ZrO3 (s) were measured using a heat flux type differential scanning calorimeter in the temperature range 320 - 870 K. Specific heat capacities of LiAlO2 (s) was found to be much larger compared to those of Li2TiO3 (s) and Li2ZrO3 (s). (author)
Conduction-band electrons, formed by pulse radiolysis of Degussa P25 TiO_2 particles, have been monitored by time-resolved microwave conductivity and found to undergo equilibrium localization and eventual recombination at the particle surface. In the presence of isopropyl alcohol recombination is retarded due to surface hole scavenging. The particle bulk can then be pumped with mobile electrons, which survive for seconds.
Adult and newborn rats were exposed to "2"3"9PuO_2 aerosols of four different size distributions. Rats of both ages were killed at intervals between 1 hr and 60 days postexposure. There were marked age- and particle-related size differences in deposition, although retention was similar throughout. The differences in deposition are attributable to relatively greater deposition of larger particles in the upper respiratory tracts of newborns.
FT-IR spectra of the products obtained in each step of the tetramethyltin (TMT)/3-wt.% Re_2O_7/Al_2O_3-SiO_2 and TMT/Al_2O_3-SiO_2 system preparation are presented and discussed. The obtained spectra show that TMT reacts with alumina-silica hydroxyl groups already at room temperature, yielding surface methyltin compounds; NH_4ReO_4 reacts with alumina-silica surface at temperatures up to 423 K, yielding rhenium surface species and ammonia, which is strongly bonded by acidic sites of the Broensted kind. FT-IR spectrum of the system (TMT)/3-wt.% Re_2O_7/Al_2O_3-SiO_2 indicated the absence of surface methyl tin compounds observed on the surface system TMT/Al_2O_3-SiO_2 , and the presence of physically adsorbed TMT; after 5 h of evacuation of the TMT/3-wt.% Re_2O_7/Al_2O_3-SiO_2 ...
In the present work, a new kind of myoglobin (Mb)/Au nanoparticles composite film was fabricated on pyrolytic graphite (PG) electrodes. Oppositely charged chitosan (CS) and silica (SiO(2)) nanoparticles were alternately adsorbed on the PG surface by the electrostatic interaction between them, forming {CS/SiO(2)}(5) layer-by-layer films. Mb and HAuCl(4) in solution were then simultaneously loaded into {CS/SiO(2)}(5) films. The loaded Au(III) in the films were electrochemically reduced into Au nanoparticles, forming nanocomposite films, designated as {CS/SiO(2)}(5)-Mb-Au. Various techniques such as cyclic voltammetry (CV), square wave voltammetry (SWV), quartz crystal microbalance (QCM), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) analysis were used to ...
Ab initio calculations of the electronic structure were performed for the silver palladium oxide, Ag_2PdO_2, by the full potential mixed linearized augmented plane wave and augmented plane wave plus local orbitals method (mixed LAPW/APW+lo) within the density functional theory and using the generalized gradient approximation (GGA96, Phys. Rev. Lett. 77 (1996) 3865) for the exchange-correlation potential. The lattice parameters were calculated from the ground-state total energy versus volume curve, and are in good agreement with the available experimental results. Our calculations of band structure predicted that the compound Ag_2PdO_2 has indirect band gap, and the Pd 4d states strongly hybridize with the O2p states all over the valence bands and conduction bands. The valence bands are composed mainly of Ag, Pd 4d states and O ...
Proton and alpha particle spectral shapes and multiplicities have been measured in coincidence with evaporation residues from {sup 28}Si+{sup 165}Ho and {sup 16}O + {sup 197}Au, {sup 208}Pb fusion reactions. Our experiments used 145 to 220 MeV {sup 28}Si and 115 and 140 MeV {sup 16}O beams produced with the Stony Brook LINAC. ER`s were separated using an electrostatic deflector and detected with large area surface barrier detectors. Light charged particles were detected at forward and backward angles with fourteen single NaI detectors. In the context of the statistical model, charged particle spectra yield information about emission barriers and compound nucleus equilibrium level densities. These are significant ingredients in calculations determining fission timescales from other observables such as pre-scission neutron multiplicities or fusion-evaporation excitation functions. Results will also be compared to analyses of pre-scission charged particles from ...
This report summarizes the findings of a five-month LDRD project funded through Sandia's NTM Investment Area. The project was aimed at providing the foundation for the development of advanced functional materials through the application of ultrathin coatings of microporous or mesoporous materials onto the surface of substrates such as silicon wafers. Prior art teaches that layers of microporous materials such as zeolites may be applied as, e.g., sensor platforms or gas separation membranes. These layers, however, are typically several microns to several hundred microns thick. For many potential applications, vast improvements in the response of a device could be realized if the thickness of the porous layer were reduced to tens of nanometers. However, a basic understanding of how to synthesize or fabricate such ultra-thin layers is lacking. This report describes traditional and novel approaches to the growth of layers of microporous materials on silicon wafers. The novel approaches ...
For reduction of the amount of waste plastics, the paper summarized the actual recycling state and the present recycling technology in Japan. A total plastic discharge amount of Japan in 1995 is 8.84 million tons, approximately 60% of all the production amount, 950,000 tons of which are recycled. Reutilized are pallets and containers in the physical distribution field. Recycling is a cascade recycling to the usage field where the degree of the required properties is lower than that of products used in virgin. As to making it a chemical material, chemical recycling technology by depolymerization has been developed. Thermal recycling is a strong method where combustion heat energy of waste plastics is used for steam production and power generation. The thermal recycling is divided into a direct combustion method and a method of use as fuel. Keys to promote and settle recycling are summarized to the following five: promotion of the government environmental policies, ...
Our work deals with accumulative roll bonding (ARB) of pure Mg sheet (0.9mm thickness) and of Al5052 sheet (0.5mm). A stacking of Al-Mg-Al was firstly rolled to 50% reduction at 400"0C and secondly ARB has been processed up to 3 cycles. In such multilayers as well as highly mixed composites of two-phased system texture development, phase reactions and strain accumulation are of basic interest, which needs a combination of different experimental methods for characterization. The present paper deals with the global texture evolution measured by thermal neutrons to average always over the whole sample thickness, SEM and optical microscopy indicates the macroscopic development of Mg and Al layers. The initial materials show typical and strong basal plane texture of hexagonal Mg (17.9mrd) and a recrystallization texture of cubic Al (8.5mrd). Co-deformation of Al/Mg/Al leads to strong decrease of both textures, whereas Mg has always a much stronger ...
Thallium-201 diethyldithiocarbamate (DDC) behaves like a chemical microsphere and is trapped by spontaneous decomposition in the brain in proportion to regional perfusion. They have shown that the technetium-99m analog, Tc-99m DDC (1), is unsuitable for cerebral perfusion imaging because it does not decompose rapidly enough to be trapped in the brain. With the goal of turning this greater stability of 1 into an advantage, a series of dithiocarbamates with lipophilic or amine groups designed to enhance cerebral uptake and retention was prepared from the following amines by reaction with carbon disulfide and sodium hydroxide: pyrrolidine (2), piperazine (3), 4-benzylpiperazine (4), and 4-(1-piperidino)piperidine (5). These ligands (5 mg) were labelled with Tc-99m in > 95% efficiency (ITLC-SG, saline) by reduction of pertechnetate at room temperature with formamidine sulfinic acid at alkaline pH. In preliminary studies, 4 and 5 show a trend of ...
The effect of flame temperature on the Moza-Austin sticking test has been evaluated by increasing the adiabatic flame temperature used to melt the pellet and make it drop. It was found that the variation of apparent contact angle with substrate temperature, for an oxidized steel substrate, was almost independent of flame temperature over the range of 1750-2500 C. However, the strength of adhesion to the substrate increased with higher flame temperature at each substrate temperature. The adhesion force of a drop frozen on the substrate at constant temperature also increased with time up to about one h. This indicated that the adhesion was not caused solely by mechanical anchoring of solidified glass in the pores of the oxide layer. Reduction of the substrate temperature to lower temperatures after attachment of the drop caused lower strength of adhesion, but this was partially restored by raising the temperature. This also suggested a continuing solid-state ...
A series of silylated Co/SBA-15 catalysts were prepared via the reaction of surface Si-OH of SBA-15 with hexamethyldisilazane (HMDS) under anhydrous, vapor-phase conditions, and then characterized by FT-IR, N2 physisorption, TG, XRD, and TPR-MS. The results showed that organic modification led to a silylated SBA-15 surface composed of stable hydrophobic Si-(CH3)3 species even after calcinations and H2 reduction at 673 K. Furthermore, the hydrophobic surface strongly influenced both metal dispersion and reducibility. Compared with non-silylated Co/SBA, Co/S-SBA (impregnation after silylation) showed a high activity, due to the better cobalt reducibility on the hydrophobic support. However, S-Co/SBA (silylation after impregnation) had the lowest FT activity among all the catalysts, due to the lower cobalt reducibility along with the steric hindrance of grafted -Si(CH3)3 for the re-adsorption of ?-olefins. -- Graphical abstract: The silylation of ...
Thin, lightweight, and flexible gas-diffusion electrodes (GDEs) based on freestanding entangled networks of single-walled carbon nanotubes (SWNTs) decorated with Ag nanoparticles (AgNPs) are tested as the air-breathing cathode in a zinc-air battery. The SWNT networks provide a highly porous surface for active oxygen absorption and diffusion. The high conductivity of SWNTs coupled with the catalytic activity of AgNPs for oxygen reduction leads to an improvement in the performance of the zinc-air cell. By modulating the pH value and the reaction time, different sizes of AgNPs are decorated uniformly on the SWNTs, as revealed by transmission electron microscopy and powder X-ray diffraction. AgNPs with sizes of 3-5 nm double the capacity and specific energy of a zinc-air battery as compared with bare SWNTs. The simplified, lightweight architecture shows significant advantages over conventional carbon-based GDEs in terms of weight, thickness and ...
An assay method for ATP sulfurylase is presented which employs Na/sub 2/(35)SO/sub 4/ as a substrate and measures the production of labeled adenosine 5'-phosphosulfate and 3'-phosphoadenosine 5'-phosphosulfate by low-voltage, hanging paper strip electrophoresis. The method is applicable to crude bacterial or mammalian extracts and accurately measures picomole amounts of product(s). Na/sub 2/(/sup 75/)SeO/sub 4/ can also be employed as a substrate, if the unstable radioactive product, adenosine 5'-phosphoselenate, is converted to elemental /sup 75/Se degrees by inclusion of reduced glutathione in the reaction mixture. The same paper strip electrophoretic technique can then be used to separate /sup 75/Se degrees from the radiolabeled substrate. The method also has utility for measuring any direct reduction by crude microbial extracts of radioactive selenate to selenite, independent of ATP sulfurylase.
Reductive quenching of two photoexcited ruthenium(II) complexes by an anionic electron donor, 2,2{prime}-azinobis(3-ethyl-benzothiazoline-6-sulfonate) (ABTS{sup 2{minus}}), in aqueous solution was examined by laser flash photolysis before and after adding positively charged colloidal (250-{angstrom} diameter) alumina-coated silica particles. The kinetics and quantum yields of electron transfer with an anionic sensitizer, RuL{sub 3}{sup 4{minus}} (L = bathophenanthroline disulfonate), and a cationic one, Ru(bpy){sub 3}{sup 2+} (bpy = 2,2{prime}-bipyridine), were compared. Coadsorption of ABTS{sup 2{minus}} and RuL{sub 3}{sup 4{minus}} by the particles greatly enhanced the rate of quenching such that only the reaction occurring on the surfaces of the particles was observed. Electron transfer from ABTS{sup 2{minus}} to RuL{sub 3}{sup 4-*} occurred by a static (nondiffusional) process, and the quenching efficiency was maximal when there was close ...
Laser-induced change is studied of the optical absorption and luminescence due to F-H pairs generated by an electron pulse in SrF_2. It is found that laser irradiation near 2.34 eV at a delay of 26 #mu#s after an electron pulse by which F-H pairs are generated reduces the component I of the pairs that has a decay time of 59 #mu#s and optical absorption bands at 2.34 and 4.13 eV and enhances the component II that has a decay time of 7.7 ms and has optical absorption bands at 2.7 and 3.35 eV. Laser irradiation near 2.7 eV at a delay of 4 ms after the electron pulse is found to induce the reverse reaction. Studies of dichroism of the laser-induced reduction and enhancement of the optical absorption bands and the luminescence reveal that the direction of the #SIGMA#-#SIGMA# transition of the F_2"- molecular ion is converted by the transformation from I to II and vice versa. It is suggested that the component I corresponds to the F-H pairs at ...
A permeable reactive mixture has been developed using low cost, readily available materials that is capable of providing effective, long-term phosphorous treatment in areas impacted by on-land wastewater disposal. The reactive mixture creates a geochemical environment suitable for P-attenuation by both adsorption and precipitation reactions. Potential benefits include significant reductions in phosphorous loading to receiving groundwater and surface water systems, and the accumulation of P-mass in a finite and accessible volume of material. The mixture may be applied as a component within surface treatment systems or in subsurface applications such as horizontal or vertical permeable reactive walls. The mixture averaged > 90% treatment efficiency over 3.6 years of continuous-flow laboratory column experiments. The mixture was further evaluated at the pilot-scale to treat municipal wastewater, and the field-scale to treat a well-characterized ...
#beta#-SiAlON was synthesized from a zeolite by NH_3 gas nitridation and its formation mechanism was investigated using X-ray diffraction and "2"9Si and "2"7Al NMR spectroscopy. It was revealed that most of the Si and Al atoms react to form #beta#-SiAlON via amorphous forms of Si-Al-O-N and O-SiAlON. Nitridation using NH_3 gas is an effective means of preventing mullite formation and promoting the introduction of nitrogen into aluminosilicate materials at lower temperatures than temperatures required by the carbothermal reduction nitridation process. Further, the NMR spectra showed that the siliceous part of the system changed into low z-value of Si_6_-_zAl_zO_zN_8_-_z (#beta#-SiAlON) and the incorporation of Al components into the #beta#-SiAlON was promoted in the later stages of the reaction. (author)
Micronutrient deficiencies in flooded rice have been recognized with increasing frequency in recent years. Zinc deficiency is the most widespread disorder, followed by Fe, Mn, and Cu deficiencies. Boron and Mo deficiencies have not been reported in field culture. The peculiar characteristics of a flooded soil are: 1) a layer of standing water; 2) absence of oxygen; 3) a soil profile largely in a reduced chemical state; 4) the presence of large biological carbon dioxide excesses; 5) the presence of high concentrations of soluble Fe"+"+ and Mn"+"+; 6) alteration of soil pH; 7) the presence of toxic substances; 8) increased soluble Na"+, K"+, Ca"+"+, Mg"+"+, NH_4"+, HCO_3"-, H_2PO_4"-, and Si(OH)_4 in the soil solution. Micronutrient availability in flooded soils is affected by: 1) increased solubility of relatively insoluble minerals due to dilution effects; 2) pH changes in relation to solubility and plant availability; 3) changes in oxidation-reduction equilibria; ...
A highly efficient integrated energy conversion system is built based on a methane catalytic decomposition reactor (MCDR) together with a direct carbon fuel cell (DCFC) and an internal reforming solid oxide fuel cell (IRSOFC). In the MCDR, methane is decomposed to pure carbon and hydrogen. Carbon is used as the fuel of DCFC to generate power and produce pure carbon dioxide. The hydrogen and unconverted methane are used as the fuel in the IRSOFC. A gas turbine cycle is also used to produce more power output from the thermal energy generated in the IRSOFC. The output performance and efficiency of both the DCFC and IRSOFC are investigated and compared by development of exact models of them. It is found that this system has a unique loading flexibility due to the good high-loading property of DCFC and the good low loading property of IRSOFC. The effects of temperature, pressure, current densities, and methane conversion on the performance of the fuel cells and the system are discussed. The ...
Reactive milling of NiO + Al powder mixture resulted in the formation of NiAl-Al_2O_3 nanocomposite powders, with a crystallite size of about 20 nm. The Hall-Williamson analysis revealed that NiAl showed an orientation dependent crystallite size after short processing time and orientation dependent internal strain after long milling time. Both anisotropies were removed by heating the powders in the differential scanning calorimetry. Calorimetric studies showed one exothermic effect attributed to the reductionreaction of NiO and endothermic one associated with melting of Al. Two methods were applied for powders compaction: resistance sintering and pulse electric discharge. In both cases the densities of abut 90% of the theoretical value were achieved. A significant increase in average NiAl crystallites size in compacted samples was observed, up to several hundreds of nanometers.(author)
For ages, herbs have been used as medicine and food. Nowadays, the interest in phytotherapeutics is increasing as well as the consumer attention. Some biochemical compounds synthesized by plants as alkaloids, phenolics, flavonoids, essential oils, tannins and vitamins, influence the composition of these plant pharmacologicals, which may produce various reactions in the human body. The microbial contamination in these raw plant materials is common, and the radiation processing is one appropriate technique for the reduction of microorganism. In herbs used as food products, the changes in total #beta#-carotene and flavonoids upon the radiation treatment were tested. The powdered and dehydrated herbs were irradiated with "6"0Co gamma rays applying doses of 0, 10, 20 and 30 kGy. The botanical species investigated were rosemary (Rosmarinus officinalis Linne), watercress (Nasturtium officinale R. Br), artichoke (Cynara scolymus Linne) and sweet basil ...
Stereoselective methods for synthesising iminoalditols are still needed, as this class of compounds is known to contain strong glycosidase inhibitors. We have for some time investigated (1) the possibilities for using 2-amino-6-bromo-2,6-dideoxy-aldonolactones as starting materials for such compounds, since a substitution at C-6 by the 2-amino group should lead to the target molecules. We have found that treatment of mentioned 2-aminolacones with aqueous base gave 5- or 6-membered iminoalditols depending of the stereochemistry of the lactone, while under non aqueous conditions only formation of 6-membered iminoalditols were observed. The use of triethylamine in methanol thus gave methylesters of 6-membered iminouronic acids. Reduction of the ester group with sodium borohydride gave the target compounds. The mechanisms of the reactions will be discussed as well as specific results obtained. (1) Lundt, I. Top. Curr. Chem. 1997, 187, 117-156
Early effects of boron neutron capture therapy (BNCT) on malignant glioma are characterized by reduction of the enhancement area and regression of the peritumoral edema radiologically. The aim of this study was to investigate the early histological changes of tumors and inflammatory cells after BNCT in the rat brain. Rats were treated with BNCT using boronophenylalanine (BPA) 7 days after implantation of C6 glioma cells. The tumors were assessed with magnetic resonance imaging and histopathological examination at 4 days after BNCT. The mean tumor volumes were 39#+-#2 mm"3 in the BNCT group and 134#+-#18 mm"3 in the control group. In the BNCT group, tumor cells showed a less pleomorphic appearance with atypical nuclei and mitotic figures. The Ki-67 labeling index was 6.5%#+-#4.7% in the BNCT and 35%#+-#3.8% in the control group. The reactions of the inflammatory cells were examined with ED-1 as macrophage marker and OX42 as microglia marker. ...
A novel bioelectrochemical membrane reactor (BEMR), which takes advantage of a membrane bioreactor (MBR) and microbial fuel cells (MFC), is developed for wastewater treatment and energy recovery. In this system, stainless steel mesh with biofilm formed on it serves as both the cathode and the filtration material. Oxygen reductionreactions are effectively catalyzed by the microorganisms attached on the mesh. The effluent turbidity from the BEMR system was low during most of the operation period, and the chemical oxygen demand and NH(4)(+)-N removal efficiencies averaged 92.4% and 95.6%, respectively. With an increase in hydraulic retention time and a decrease in loading rate, the system performance was enhanced. In this BEMR process, a maximum power density of 4.35 W/m(3) and a current density of 18.32 A/m(3) were obtained at a hydraulic retention time of 150 min and external resister of 100 ?. The Coulombic efficiency was 8.2%. Though the ...
The industrial standard process for the purification of natural gas is to remove acid gases, mainly hydrogen sulfide and carbon dioxide, by the absorption and reaction of these gases with alkanolamines. The natural gas industry requires vapor-liquid equilibrium (VLE) data to develop more energy efficient amine mixtures. Some energy reductions have been realized in the past decade by applying such amine systems as hindered amines, methyldiethanolamine (MDEA), and MDEA based amine mixtures. However, the lack of reliable and accurate VLE data impedes the commercial application of these more efficient alkanolamine systems. The first objective of this project is to improve the accuracy of vapor-liquid equilibrium measurements at low hydrogen sulfide concentrations. The second objective is to make VLE measurements for amine mixtures. By improving the accuracy of the VLE data on MDEA and other amines, energy savings can be implemented in the many ...
The industrial standard process for the purification of natural gas is to remove acid gases, mainly hydrogen sulfide and carbon dioxide, by the absorption and reaction of these gases with alkanolamines. Inadequate data for vapor -- liquid equilibrium (VLE) hinder the industry from converting operations to more energy efficient amine mixtures and conserving energy. Some energy reductions have been realized in the past decade by applying such amine systems as ``hindered`` amines, methyldiethanolamine (MDEA), and MDEA based amine mixtures. However, the lack of reliable and accurate fundamental VLE data impedes the commercial application of these more efficient alkanolamine systems. The first project objective is to improve the accuracy of vapor -- liquid equilibrium measurements at low hydrogen sulfide concentrations. The second project objective is to measure the VLE for amine mixtures. By improving the accuracy of the VLE measurements on MDEA ...
The industrial standard process for the purification of natural gas is to remove acid gases, mainly hydrogen sulfide and carbon dioxide, by the absorption and reaction of these gases with alkanolamines. Inadequate data for vapor -- liquid equilibrium (VLE) hinder the industry from converting operations to more energy efficient amine mixtures and conserving energy. Some energy reductions have been realized in the past decade by applying such amine systems as hindered'' amines, methyldiethanolamine (MDEA), and MDEA based amine mixtures. However, the lack of reliable and accurate fundamental VLE data impedes the commercial application of these more efficient alkanolamine systems. The first project objective is to improve the accuracy of vapor -- liquid equilibrium measurements at low hydrogen sulfide concentrations. The second project objective is to measure the VLE for amine mixtures. By improving the accuracy of the VLE ...
10%Pt/C catalysts were prepared by liquid reduction method. PTFE and Pt/ C catalysts were adhered to porous metal and hydrophobic Pt/C/PTFE catalysts were prepared. The structure and size of Pt crystal particles of Pt/C catalysts were analyzed by XRD, and their mean size was 3.1 nm. The dispersion state of Pt/C and PTFE was analyzed by SEM, and they had good dispersion mostly, but PTFE membrane could be observed on local parts of Pt/C/PTFE surface. Because of low hydrophobicity, Pt/C/ PTFE catalysts have low activity when the mass ratio of PTFE and Pt/C is 0.5: 1, and their catalytic activity increases markedly when the ratio is 1:1. When the ratio increases again, more Pt active sites would be covered by PTFE and interior diffusion effect would increase, which result in the decrease of catalytic activity of Pt/C/PTFE. By PTFE pretreatment of porous metal carrier, the activity of Pt/C/PTFE catalysts decreases when the mass ratio of PTFE and Pt/C is 0.5:1, and their ...
Epidemiological studies have revealed that butyrate and 17?-estradiol (E2) may decrease the incidence of colorectal cancer (CRC). In peripheral tissue, E2 can be produced locally by 17?-hydroxysteroid dehydrogenase 1 (HSD17B1) estrone (E1) reduction. Using quantitative real-time polymerase chain reaction and western blotting analysis, we found that sodium butyrate significantly upregulates HSD17B1 long and short transcripts and protein levels in HT29 and SW707 CRC cells. Chromatin immunoprecipitation analysis showed that upregulation of these transcript levels correlated with an increase in binding of Polymerase II to proximal and distal promoters of HSD17B1. Moreover, we observed that upregulation of HSD17B1 protein levels was associated with increased conversion of E1 to E2 in HT29 and S...
In this paper we have proposed a novel gas turbine cycle with hydrogen-fueled chemical-looping combustion, and the system study on two hydrogen-fueled power plants, the new gas turbine cycle and an advanced gas turbine cycle with H{sub 2}/O{sub 2} combustion, has been investigated with the aid of exergy principle (EUD methodology). The hydrogen fueled chemical-looping combustion in the new gas turbine cycle consists of two successive reactions: hydrogen fuel is reacted with metal oxide (reduction of metal oxide), and then instead of air or pure oxygen, the reduced metal is successively oxidized by the saturated air. As a result, the new hydrogen-fueled gas turbine cycle has a breakthrough performance, with at least about 12 percentage-point higher efficiency compared to the gas turbine cycle with H{sub 2}/O{sub 2} combustion, and will be environmentally superior due to complete elimination of NO{sub x} formation. The promising results obtained ...
Metal nanoparticles have many potential technological applications. Biological routes to the synthesis of these particles have been proposed including production by vascular plants, known as phytoextraction. While many studies have looked at metal uptake by plants, particularly with regard to phytoremediation and hyperaccumulation, few have distinguished between metal deposition and metal salt accumulation. This work describes the uptake of AgNO{sub 3}, Na{sub 3}Ag(S{sub 2}O{sub 3}){sub 2}, and Ag(NH{sub 3}){sub 2}NO{sub 3} solutions by hydroponically grown Brassica juncea and the quantitative measurement of the conversion of these salts to silver metal nanoparticles. Using X-ray absorption near edge spectroscopy (XANES) to determine the metal speciation within the plants, combined with atomic absorption spectroscopy (AAS) for total Ag, the quantity of reduction of Ag{sup I} to Ag{sup 0} is reported. Transmission electron microscopy (TEM) showed Ag particles of ...
Aluminum is a principal element in alkaline nuclear sludge waste stored in high level waste (HLW) tanks at the Savannah River Site. The mass of sludge in a HLW tank can be reduced through the caustic leaching of aluminum, i.e. converting aluminum oxides (gibbsite) and oxide-hydroxides (boehmite) into soluble hydroxides through reaction with a hot caustic solution. The temperature limits outlined by the chemistry control program for HLW tanks to prevent caustic stress corrosion cracking (CSCC) in concentrated hydroxide solutions will potentially be exceeded during the sludge mass reduction (SMR) campaign. Corrosion testing was performed to determine the potential for CSCC under expected conditions. The experimental test program, developed based upon previous test results and expected conditions during the current SMR campaign, consisted of electrochemical and mechanical testing to determine the susceptibility of ASTM A516 carbon steel to CSCC in ...
The novel optical, electronic, and/or magnetic properties of metal and semiconductor nanoparticles have resulted in extensive research on new methods for their preparation. An ideal preparation method would allow the particle size, size distribution, crystallinity, and particle shape to be easily controlled, and would be applicable to a wide variety of material systems. Numerous preparation methods have been reported, each with its inherent advantages and disadvantages; however, an ideal method has yet to emerge. The most widely applied methods for nanoparticle preparation include the sonochemical reduction of organometallic reagents,(1&2) the solvothermal method of Alivisatos,(3) reactions in microemulsions,(4-6) the polyol method (reduction by alcohols),(7-9) and the use of polymer and solgel materials as hosts.(10-13) In addition to these methods, there are a variety of methods that take advantage of the unique ...
Data on the reactions of thiocyanogen and thiocyanogen halides with unsaturated compounds are systematised. The kinetic and stereo- and regiochemical regularities of these reactions are analysed. The bibliography includes 81 references.
This paper illustrates how the techniques developed by the authors for capital cost targeting of mass exchange networks can be applied to determination of capital investment targets for reduction in effluent for existing systems involving mass exchange. The results is an impact diagram which shows the relationship between effluent reduction and capital investment, indicating a region of limiting return on investment as well as the maximum possible reduction in effluent. (au)
A new study on the pressure-induced phase transitions of TiO_2 has been performed using all-electron density-functional theory based computations with the projector augmented wave and the linearized augmented plane wave methods considering five experimentally observed structures. The static results yield a picture that is consistent with experiments, i.e., phase transitions with pressure are predicted as rutile #-># monoclinic baddeleyite (MI) #-># orthorhombic I (OI) #-># cotunnite (OII) on compression, and OII #-># OI #-># MI #-># columbite (TiO_2II) on decompression. The elasticities of these five polymorphs are compared. Except for the baddeleyite structure, which is considerably softer than the other polymorphs, all phases show a zero pressure bulk modulus in the range of 200-240 GPa, consistent with compression results and the single crystal elastic constant; on the basis of ...
Fe_5_0Pt_5_0 nanodots dispersed in a SiO_2 film (Fe_5_0Pt_5_0 nanodot film) were formed by a self-assembled nanodot deposition (SAND) method in which Fe_5_0Pt_5_0 and SiO_2 are cosputtered in a high vacuum rf magnetron sputtering equipment. Fe_5_0Pt_5_0 pellets are laid on a SiO_2 target in a sputtering chamber to form the Fe_5_0Pt_5_0 nanodot film in the SAND method. The size and density of Fe_5_0Pt_5_0 nanodot were controlled by changing the ratio of the total area of Fe_5_0Pt_5_0 pellets to that of SiO_2 target. The Fe_5_0Pt_5_0 nanodot size decreases and its density increases when the ratio decreases. As-deposited Fe_5_0Pt_5_0 nanodots self-assembled to a face-centered-cubic phase of single-crystal structure. The Fe_5_0Pt_5_0 nanodot films were annealed to evaluate the nanodot size controllability, the magnetic ...
The cytotoxicity of 15-nm and 46-nm silica nanoparticles was investigated by using crystalline silica (Min-U-Sil 5) as a positive control in cultured human bronchoalveolar carcinoma-derived cells. Exposure to 15-nm or 46-nm SiO_2 nanoparticles for 48 h at dosage levels between 10 and 100 #mu#g/ml decreased cell viability in a dose-dependent manner. Both SiO_2 nanoparticles were more cytotoxic than Min-U-Sil 5; however, the cytotoxicities of 15-nm and 46-nm silica nanoparticles were not significantly different. The 15-nm SiO_2 nanoparticles were used to determine time-dependent cytotoxicity and oxidative stress responses. Cell viability decreased significantly as a function of both nanoparticle dosage (10-100 #mu#g/ml) and exposure time (24 h, 48 h, and 72 h). Indicators of oxidative stress and cytotoxicity, including total reactive oxygen species (ROS), ...
Growth of Ru- and RuO_2-composite (ROC) nanodots on atomic-layer-deposited Al_2O_3 film has been studied for the first time using ion-beam sputtering followed by post-deposition annealing (PDA). X-ray photoelectron spectroscopy analyses reveal that RuO_2 and Ru co-exist before annealing, and around 10% RuO_2 is reduced to metallic Ru after PDA at 900 deg. C for 15 s. Scanning electron microscopy measurements show that well-defined spherical ROC nanodots are not formed till the PDA temperature is raised to 900 deg. C. The mean diameter of the nanodots enlarges with increasing PDA temperature whereas the nanodot density decreases, which is attributed to coalescence process between adjacent nanodots. It is further illustrated that the resulting nanodot size and density are weakly dependent on the annealing time, but are markedly influenced by the decomposition of ...
Influence of alkali elements on formation, composition, solubility and region of stability of complex hafnium sulfates, separated in the HfO"2-H"2SO"4-Me"2SO"4-H"2O (Me-Na, K, Rb, Cs and NH"4 group) systems is studied. In all cases hafnium forms the complex sulfates of three types differing by basicity or ratio HfO"2:SO"3 1:1, 1:1.5, 1:2. Three basic and three medium sulfates are crystallized in the systems with sodium; with rubidium, cesium and ammonium - two basic and two medium sulfates and with potassium - two basic and one medium salts. Anhydrous salts do not form in the investigated systems. Potassium salt approximately 0.3% according to HfO"2 is characterized by minimum solubility from the salts of 2HfOSO"4x(1-3)Me"2SO"4x(4-6)xH"2O while solubility of the same salts with rubidium, cesium and sodium increases from (0.25-1.0); (0.5-1.5) till (1.0-5)% ...
Analyses of process system properties were continued for important chemical materials involved in the several processes under consideration for semiconductor and solar cell grade silicon production. Major activities were devoted to physical, thermodynamic and transport property data for silicon. Property data are reported for vapor pressure heat of vaporization, heat of sublimation, liquid heat capacity and solid heat capacity as a function of temperature to permit rapid usage in engineering. Chemical engineering analysis of the HSC process (Hemlock Semiconductor Corporation) for production of silicon was initiated. The process is based on hydrogen reduction of dichlorosilane (DCS) to produce the polysilicon. The chemical vapor deposition reaction for DCS is faster in rate than the conventional process route which utilizes trichlorosilane (TCS) as the silicon raw material. Status and progress are reported for primary activities of base case ...
A zinc-air battery using zinc regeneration electrolysis with propanol oxidation as a counter electrode reaction is reported in this paper. It possesses functions of both zincate reduction and electrochemical preparation, showing the potential for increasing the electronic energy utilization. Charge/discharge tests and scanning electron microscopy (SEM) micrographs reveal that when a nickel sheet plated with the high-H{sub 2}-overpotential metal, cadmium, was used as the negative substrate electrode, the dendritic formation and hydrogen evolution are suppressed effectively, and granular zinc deposits become larger but relatively dense with the increase of charge time. The performance of batteries is favorable even if the charge time is as long as 5 h at the current density of 20 mA cm{sup -2}. Better discharge performance is achieved using a 'cavity-opening' configuration for the discharge cell rather than a ...
The first quarter 1982 report summarizes the operating and test data obtained at the six ton per day Advanced Coal Liquefaction Research and Development Facility in Wilsonville, Alabama. The Wilsonville R and D Facility was in operation 52% of the period with scheduled shutdowns accounting for 33% of the downtime. Illinois 6 coal from the Burning Star No. 2 mine was processed during Run 236. The three process units of the Wilsonville facility were operated in a non-integrated mode to evaluate process parameters and to test equipment and operating modifications. Data were obtained in the following areas: In the SRC Unit: operation at low severity reaction conditions for single stage liquefaction with a high LSRC recycle rate using Illinois 6 coal; process solvent activity control; and preliminary feeding tests with hydrotreated SRC as a replacement for LSRC in the process solvent. In the CSD Unit: operation with T102 Vacuum Column bottoms produced at low severity ...
Net heats of reaction were measured in an isothermal calorimeter for both single phase (organic) and two phase (organic and aqueous) TBP/HNO{sub 3} reacting solutions at temperatures above 100 C. The oxidation rate constant was determined to be 5.4E-4 min{sup {minus}1} at 110 C for an open ``vented`` system as compared to 1.33 E-3 min{sup {minus}1} in the closed system. The heat released per unit material oxidized was also reduced. The oxidation in both phases was found to be first order in nitric acid and pseudo-zero order in butylnitrate and water. The hydrolysis (esterification) rate constant determined by Nichols` (1.33E-3 min{sup {minus}1}) fit the experimental data from this work well. Forced evaporation of the volatile components by the product gases from oxidation resulted in a cooling mechanism which more than balanced the heat from the oxidation reaction in the two-phased systems. Rate expressions were derived and rate constants ...
This study is a contribution to the growing body of work on the influence of changes in the composition of an acrylic bone cement on various properties of the curing and cured material. The focus is on one commercially-available acrylic bone cement brand, Surgical Simplex P, and three variants of it and a series of properties, namely, setting time, maximum exotherm temperature, activation energy and frequency factor for the polymerization reaction, diffusion coefficient for the uptake of phosphate buffered saline, at 37 degrees C, ultimate compressive strength (UCS), plane-strain fracture toughness, fatigue life (under fully-reversed tension-compression stress), hardness (H) and elastic modulus (both determined using quasi-static nanoindentation), and the variation of the storage and loss moduli with frequency of the applied force in a dynamic nanoindentation test. It was found that (a) a 68% reduction in the volume of the activator, N,N ...
Marker experiments for studying the mass transport through a palladium silicide layer on a crystalline substrate during thermal oxidation at 700 to 850 deg C have been reported recently. In this work argon gas embedded in amorphous silicon during sputtering was implemented as the inert marker and the oxidation of PdSi was processed above 900 deg C. At this high-temperature oxidation silicon-rich silicide PdSisub(y), with y exceeding 5, may be obtained. This can be anticipated by considering the Pd-Si phase diagram which shows the liquid phase may appear at an annealing temperature above 892 deg C. As a result, a non-stoichiometric and non-uniform silicide layer may develop at the sample surface. Marker analysis showed that both palladium and silicon dissociated at the Pdsub(x)Si/ SiO_2 interface and moved to the substrate with the silicon being the dominant diffuser. The Rutherford backscattering spectra (RBS) showing the oxide film and ...
Lithium-ion batteries are now considered to be the technology of choice for future hybrid electric and full electric vehicles to address global warming. LiCoO2 has been the most widely used cathode material in commercial lithium-ion batteries. Since LiCoO2 has economic and environmental issues, intensive research has been directed towards the development of alternative low cost, environmentally friendly cathode materials as possible replacement of LiCoO2. Among them, spinel LiNi0.5Mn1.5O4 material is one of the promising and attractive cathode materials for next generation lithium-ion batteries because of its high voltage (4.7V), acceptable stability, and good cycling performance. Research advances in high voltage spinel LiNi0.5Mn1.5O4 are reviewed in this paper. Developments in synthesis,...
Results of our systematic NMR study in high T_c cuprates are reviewed. The antiferromagnetic spin fluctuations (AFSF) decrease in the order of La_1_._8_5Sr_0_._1_5CuO_4. YBa_2Cu_3O_7 and Tl_2Ba_2CuO_6_+_y. 1/T_1 of "6"3Cu in the CuO_2 plane in the normal state follows essentially a Curie-Weiss law at high temperature and T_1T = const. law at low temperature. The temperature dependence of 1/T_1 and the Knight shift together with their impurity effect in the superconducting state strongly suggest d-wave pairing implying the AFSF to be responsible for the occurrence of superconductivity. From the NQR frequency measurement the density of Cu 3d and O2p holes decreases and increases, respectively, in the order of La, Y and Tl compounds, which is consistent with the change of AFSF. The relation between T_c and #nu#_Q, and their pressure dependence suggest that there exists and optimum value of the ratio of Cu ...
Focused ion beam (FIB) milling techniques are presented aiming at the manipulation of both tin dioxide (SnO_2) inverted opals and polystyrene (PS) direct opals. Different SnO_2 opals are considered in order to estimate the regularity of their bulk after the production. A SnO_2 mesoporous monolith is FIB micromachined to make it suitable for optical applications. PS direct opals are structured by FIB milling at different scales. Ordered arrays of PS opals are modified by selectively removing a single sphere. In performing this task, we discuss the effects on the FIB milling due to the gas-assisted enhanced etching and to the binding of the nearest neighbours. Techniques to achieve imaging of PS opals in absence of a conductive coating are also brought up. Furthermore, isolated PS spheres are drilled with or without enhanced etching in order to produce controlled ...
We report on studies of field-effect transistor (FET) and transparent thin-film transistor (TFT) devices based on lightly Ta-doped SnO2 nano-wires. The nanowire-based devices exhibit uniform characteristics with average field-effect mobilities exceeding 100 cm2/V x s. Prototype nano-wire-based TFT (NW-TFT) devices on glass substrates showed excellent optical transparency and transistor performance in terms of transconductance, bias voltage range, and on/off ratio. High on-currents and field-effect mobilities were obtained from the NW-TFT devices even at low nanowire coverage. The SnO2 nanowire-based TFT approach offers a number of desirable properties such as low growth cost, high electron mobility, and optical transparency and low operation voltage, and may lead to large-scale applications of transparent electronics on diverse substrates. PMID:17595151
The linearized-augmented-plane-wave (LAPW) method for thin films is generalized by removing the remaining shape approximation to the potential inside the atomic spheres. A new technique for solving Poisson's equation for a general charge density and potential is described and implemented in the film LAPW method. In the resulting full-potential LAPW method (FLAPW), all contributions to the potential are completely taken into account in the Hamiltonian matrix elements. The accuracy of the method: already well known for clean metal surfaces: is demonstrated for the case of a nearly free (noninteracting) O_2 molecule which is a severe test case of the method because of its large anisotropic charge distribution. Detailed comparisons show that the accuracy of the FLAPW results for O_2 exceeds that of existing state-of-the-art local-density linear-combination-of-atomic-orbitals (LCAO)-type calculations, and ...
Use of high plutonia MOX as fuel is contemplated from the point of view of rapid disposition of plutonium and economic power generation. The fuel pellets are subjected to steep thermal gradients #approx# 1700 K drop across a radius of #approx# 2.5mm. This leads to evaporation-condensation of the fuel constituents to cooler regions. Vaporization depends on fuel compositions such as Pu fraction, Oxygen-to-Metal (O/M) ratio and local temperature. Knowledge of vapour chemistry is essential in understanding the fuel behavior. The vaporization behaviour of MOX was analyzed in this work using thermochemical methods. The vapour phase consisted of nine species; O, O_2, Pu, PuO, PuO_2, U, UO, UO_2 and UO_3. Oxygen formed part of the vapour phase along with other species and oxygen potential was not controlled independently. The vapour pressures were estimated at 2000 K as a function of (O/M) for several ...
The addition of paraquat (methyl viologen) to a growing culture of Escherichia coli K-12 led within 1 hr to a 10- to 20-fold increase in the level of endonuclease IV, a DNase for apurinic/apyrimidinic sites. The induction was blocked by chloramphenicol. Increases of 3-fold or more were also seen with plumbagin, menadione, and phenazine methosulfate. H_2O_2 produced no more than a 2-fold increase in endonuclease IV activity. The following agents had no significant effect: streptonigrin, nitrofurantoin, tert-butyl hydroperoxide, #gamma# rays, 260-nm UV radiation, methyl methanesulfonate, mitomycin C, and ascorbate. Paraquat, plumbagin, menadione, and phenazine methosulfate are known to generate superoxide radical anions via redox cycling in vivo. A mutant lacking superoxide dismutase was unusually sensitive to induction by paraquat. In addition, endonuclease IV could be induced by merely growing the mutant in pure ...
The irradiation behavior of Li_2TiO_3 under a fusion reactor environment was simulated by simultaneous irradiation of Li_2TiO_3 by the triple ion beams and the respective single ion beams of O"2"+, He"+ and H"+. The microstructural changes in Li_2TiO_3 caused by the irradiation were measured by FT-IR photoacoustic spectroscopy. The results suggest that the amount of TiO_2 formed is proportional to the dpa and that the method of irradiation does not affect the dependence of formation of TiO_2. On the other hand, the amount of defects and/or radiolytic products generated by irradiation, which is considered to trap hydrogen near the surface, is found to be affected by the method of irradiation. Such phenomena are believed to affect the tritium release behavior from Li_2TiO_3, and durability of Li_2TiO_3 and compatibility of Li_2TiO_3 with other components of the ...
The effect of hydrostatic pressure applied at high temperature on photoluminescence of Si-implanted SiO_2 films was studied. A 'blue'-shift of PL spectrum from the SiO_2 films implanted with Si"+ ions to total dose of 1.2x10"1"7 cm"-"2 with increase in hydrostatic pressure was observed. For the films implanted with Si"+ions to a total dose of 4.8x10"1"6 cm"-"2 high temperature annealing under high hydrostatic pressure (12 kbar) causes a 'red'-shift of photoluminescence spectrum. The 'red' photoluminescence bands are attributed to Si nanocrystals while the 'blue' ones are related to Si nanocrystals of reduced size or chains of silicon atoms or Si-Si defects. A decrease in size of Si nanocluster occurs in result of the pressure-induced decrease in the diffusion of silicon atoms. (author)
Si nanocrystal floating gate MOS capacitors were formed on p-Si (100) wafers by thermal plasma jet (TPJ) annealing of SiO2/SiOx /SiO2/Si(100) stacked structure. The chemical composition of SiOx layer was controlled by changing the SiH4, He, and O2 gas flow ratio during plasma enhanced chemical vapour deposition. The MOS capacitors showed clear hysteresis in capacitance-voltage (CV) characteristics after TPJ annealing. The hysteresis width shows maximum value when initial composition x =1.7, which shows the maximum photoluminescence (PL) intensity. The maximum hysteresis width of 6.8 V was observed with gate voltage swept between 20 and -20 V in x = 1.7 sample. The result means 7.4 x 1012 cm-2 carriers are injected to or emitted from Si nanocrystals. The duration of 1 V shift in flatband vo...
In the MnIII complex of the title compound, [MnIII(C18H12N4O2)(H2O)2]ClO4, the MnIII atom is coordinated by four N atoms from the bpb2- [1,2-bis(pyridine-2-carboxamido)benzene] ligand located in the equatorial plane and two O atoms of water molecules at axial positions, yielding a distorted MnN4O2 octahedral coordination geometry. The bpb2- ligand is nearly planar, with a maximum deviation of 0.2311 (3) A from the mean plane. The MnIII complex cation and the perchlorate anion, both of which are located on twofold rotation axes, are connected by O-H...O and C-H...O hydrogen bonds into a three-dimensional supramolecular network structure.
A magnetic core/shell Fe3O4/FeMnOx catalyst was prepared by a simple oxidation-precipitation method. The catalyst was characterized by X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry. The characterization studies verified that Fe3O4 core was coated with a layer of Fe-Mn oxide. The Fe3O4/FeMnOx was found to be an effective and stable heterogeneous catalyst for the discoloration of methylene blue (MB) in aqueous solution by H2O2. The high catalytic activity is due to the FeMnOx shell, which not only increased the surface hydroxyl groups, but also enhanced the interfacial electron transfer. The discoloration of MB could be due to the decomposition of H2O2 into ?OH ...
The work scope of 'Biological Research for the Radiation Protection' had contained the research about ornithine decarboxylase and its controlling proteins, thioredoxin, peroxiredoxin, S-adenosymethionine decarboxylase, and glutamate decarboxylase 67KD effect on the cell death triggered ionizing radiation and H_2O_2(toxic agents). In this study, to elucidate the role of these proteins in the ionizing radiation (or H_2O_2)-induced apoptotic cell death, we utilized sensesed (or antisensed) cells, which overexpress (or down-regulate) RNAs associated with these proteins biosynthesis, and investigated the effects of these genes on the cytotoxicity caused by ionizing radiation and H_2O_2(or paraquat). We also investigated whether genisteine(or thiamine) may enhance the cytotoxic efficacy of tumor cells caused by ionizing radiation (may enhance the preventing effect ...
A dialyzable factor(s) in human serum is known to stimulate gonococcal oxygen consumption. Its effect on other human pathogens was investigated. A 10% serum solution increased peak O2 consumption for Escherichia coli and Staphylococcus aureus to 157% (P less than 0.05) and 199% (P less than 0.02), respectively, of their O2 consumption when suspended in Hanks balanced salt solution, compared with a 356% increase for Neisseria gonorrhoeae with serum. Dialyzed serum lacked stimulatory capacity. Bacteria, serum, and neutrophils are often incubated to evaluate neutrophil bactericidal activity. Samples of 10(8) N. gonorrhoeae, S. aureus, and E. coli turned resazurin colorless (anaerobic conditions, Eh less than -42 mV) after 7.4, 13.3, and 15.1 min, respectively. Because neutrophil formation of reactive oxygen intermediates requires ambient O2, the effect of live ...
Woolfolk, C. A. (University of Washington, Seattle). Reduction of inorganic compounds with molecular hydrogen by Micrococcus lactilyticus. II. Stoichiometry with inorganic...Full Text Available
Mixed additions of Sm_2O_3 and Y_2O_3 were used in the formation of zirconia-containing O'-sialon composites, where Sm_2O_3 was used for the purpose of densification and Y_2O_3 for zirconia stabilization. Dense ZrO_2/O' -sialon composites were produced at 1500 deg C. by sintering in nitrogen for 4 hours. Tetragonal zirconia remained in the product and t#->#m transformation was observed when the sample was ground into powder. However, the improvement in fracture toughness was not significant and this was attributed to the weakened transformability of the tetragonal zirconia phase in the nitrogen-based materials. 18 refs., 4 tabs., 2 figs.
In this paper, multilayer oxide nanorods were deposited in the nanopores of anodic aluminum oxide (AAO) via solution infiltration followed by heat treatment. The nanorods have a core-shell structure. First, the shell (nanotube) with the thickness of about 40nm was made of TiO"2 through the hydrolysis of (NH"4)"2TiF"6. Second, silver nanoparticles with the diameter of about 3nm were added into the TiO"2 layer through thermal decomposition of AgNO"3 at elevated temperatures. Then, cylindrical cores (nanorods) of CoO and ZnO with 200nm diameter were prepared, respectively. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and composition of the nanorods. UV-vis light absorption measurements in the wavelength range from 350 to...
We have performed extended X-ray absorption fine structure (EXAFS) analysis for artificial Cr-goethite to elucidate the local structure around Cr in Cr-goethite. The spectra were obtained using synchrotron radiation X-rays at the Photon Factory in Tsukuba. The first shell contributions were isolated by Fourier filtering EXAFS data, and the inverse Fourier transformed single-shell data were analyzed using a curve fitting method. The results show that Cr is coordinated with (7#+-#1)O"2"- ions. The protective characteristics of the Cr-goethite protective rust layer on weathering steel can be interpreted in terms of the O"2"- coordination around Cr"3"+ resulting in the creation of negative fixed charge in the Cr-goethite particles. (author)
The synthesis of dense sintered sialon with external additives selected from the system Y_2O_3-AlN-SiO_2 is reported. The highest density (3.21 g/cm"3) was achieved at 1750 degrees C at 90 min of sintering with 5 wt% additive. The degree of sialon substitution increased with the amount of liquid; the YSiO_2N crystalline phase formed concurrently. Strength degradation occurred above 1000 degrees C. The fracture toughness of the material sintered with a lower amount of sintering aid remained relatively unchanged to 1200 degrees C. The material with more additive exhibited decreased toughness above 1000 degrees C.
The X-ray storage phosphor CsBr:Eu2+ in form of needle image plates is believed to be a promising alternative to the granular BaFBr:Eu2+ with regard to PSL yield and spatial resolution. Unfortunately, CsBr:Eu2+ exhibits poor radiation hardness, which is caused by a migration of europium ions initiated by naturally existing defect centers like (Eu2+-VCs)-centers and X-ray generated MEu-centers. It will be shown that the formation of (Eu2+-O2?)-dipoles at the expense of (Eu2+-VCs)-dipoles, incorporated by thermal annealing in O2-containing and humid atmosphere, does not improve the radiation stability. There is, however, a strong improvement in the radiation hardness by codoping of CsBr:Eu2+ with lithium ions, which is accompanied by a complete suppression of the previously observed MEu-cent...
Twelve powders of TiO_2-Y_2O_3-ZrO_2 solid solution of the methodically changed composition were prepared by a coprecipitation-calcination technique. After mixing with phenol-formaldehyde resin, the powders were calcinated for 2 hours at 1200"oC in vacuum. The resultant composite powders contained TiC and non-reacted carbon. Green compacts were sintered in vacuum at 1500"oC for 2 hours. A temperature increase was stopped at 1200"oC to react remains of carbon. There were two carbides in the composites TiC and ZrC. TiC non-stoichiometry depended on carbon content in the system. Phase composition of the depended on of titania and yttria in zirconia solid solution. The majority of the samples showed two tetragonal zirconia phases differing in lattice parameter and tetragonality. (author)
The irradiation behavior of Li_2TiO_3 under a fusion reactor environment was simulated by simultaneous irradiation of Li_2TiO_3 by the triple ion beams and the respective single ion beams of O"2"+, He"+ and H"+. The microstructural changes in Li_2TiO_3 caused by the irradiation were measured by Raman spectroscopy and FT-IR photoacoustic spectroscopy. The results suggest that the formation of TiO_2 due to displacements by irradiation occurs, and the irradiation defects generated by irradiation trap hydrogen and increase the amount of hydroxyl near the surface. Such phenomena are believed to significantly affect the chemical form of the released tritium and the tritium inventory in the breeding materials of a fusion reactor.
All-atom molecular dynamics simulations were used to study the morphology of polymer/inorganic composite particles prepared by heterocoagulation. The results were also compared to those of our previous study of the preparation of TiO2/poly(acrylic acid-co-methyl methacrylate) and Fe3O4/polystyrene composite particles. In the simulation system, polymer or inorganic particles were simulated by surface-charge-modified C60 or Na atoms. Through a combination of analysis of the radial distribution functions of charged atoms and snapshots of the equilibrated structure, three kinds of particle distributions were observed under different conditions. When the polymer and inorganic particles had opposite surface charges and their sizes were very different, the composite morphology showed a core-shell...
A 340-watt CO_2 laser is being used to generate PuO_2-UO_2 condensation aerosol from the surface of a Liquid Metal Fast Breeder Reactor (LMFBR) fuel pellet. A wide range of concentrations is achieved by varying the laser power, pulse width, and/or pulse period. The resulting aerosol is composed of branch chain-like aggregates, with the primary particle size ranging between 0.005 and 0.15 #mu#m. X-ray diffraction analyses show that these aerosols condense into a face-centered cubic crystal structure. The activity mean aerodynamic diameter (AMAD), for most power levels, is approximately 0.85 #mu#m with a geometric standard deviation of 1.5.
A poly(ether urethane) (PEUR)/poly(ethylene oxide) (PEO)/SiO2 based nanocomposite polymer is prepared and employed in the construction of high efficiency all-solid-state dye-sensitized nanocrystalline solar cells. The introduction of low-molecular weight PEUR prepolymer into PEO electrolyte has greatly enhance the electrolyte performance by both improving the interfacial contact properties of electrode/electrolyte and decreasing the PEO crystallization, which were confirmed by XRD and SEM characteristics. The effects of polymer composition, nano SiO2 content on the ionic conductivity and I3- ions diffusion of polymer-blend electrolyte are investigated. The optimized composition yields an energy conversion efficiency of 3.71% under irradiation by white light (100 mW cm-2).
Herein, we demonstrate the structure of the PS colloidal crystals which were fabricated on the hydrophilic/hydrophobic Si wafers by a spin-coating technique. Monodisperse PS colloids are spin-coated onto self-assembled monolayers of 3-(aminopropyl)triethoxysilane and propyltrimethoxysilane coated Si wafers. PS spheres organized as ordered close-packed face-centered cubic structure with (111) planes on the hydrophilic surface while they gathered without the crystal structure on the hydrophobic surface. This paper also reports a simple and rapid method to fabricate the close-packed structure of hollow TiO2 spheres. The colloidal crystal of TiO2 hollow spheres was prepared using the PS sphere template on the hydrophobic surface. The mechanism for the growing multilayers of self-assembled PS p...
To improve the friction and wear behavior of carbon fabric reinforced polymer composites (CFRP), nano-SiO2 was deposited on the fabric surface. The friction and wear behavior of the resulting composites were investigated on a model ring-on-block test rig. Experimental results revealed that fiber surface treatment contributed to largely improve the tribological properties of the CFRP composites. Scanning electron microscope (SEM) investigation showed that the worn surface of the surface modified CFRP composite was smoother under given load and sliding rate. Field emission scanning electron microscopy (FESEM), FTIR and X-ray photoelectron spectroscopy (XPS) studies of the carbon fiber surface showed that nanostructured Sio2 thin film can be obtained by SiO2 sols deposition, which improved th...
The antioxidant properties of magnolol and honokiol were evaluated in the experimental systems of reducing ONOO^- and ^1O"2, bleaching @b-carotene in linoleic acid (LH) emulsion, and trapping 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS^+?) and 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and then were applied to inhibit the oxidation of DNA induced by Cu^2^+/glutathione (GSH) and 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH). Magnolol and honokiol were active to reduce ONOO^- and ^1O"2. Honokiol showed a little higher activity to protect LH and to inhibit Cu^2^+/GSH-induced oxidation of DNA than magnolol. In addition, honokiol exhibited higher activities to trap ABTS^+? and DPPH than magnolol. In particular, honokiol trapped 2.5 radicals while magnolol o...
The purpose of the present study is to develop a new method for chemical state analysis by means of EPMA(Electron probe microanalyser). The measured X-ray intensity of Si-K#beta# characteristic X-ray spectra were read-out by a 16 bit microcomputer with a RS-232C interface. And using the curve fitting method the quantitative analysis of chemical compositions in a ternary compound that constituted of the same element has been established. The present method was applied to analyse of the friction and wear properties of Si-base ceramics sliding materials. It was found that the wear debris contains both the compositions of the sliding materials and SiO_2, and the SiO_2 contents in wear debris was changed with relative humidity. The results clearly showed that the proposed method is very useful for determing the compositions in the ternary compound. (author).
The formation of a porous coating is the decisive feature for the bio-compatibility of silica-free calcium phosphate glass ceramics on alloy surfaces like the #beta#-Ti structured Ti-29Nb-13Ta-4.6Zr used in this work. The ceramic composition is highly important: 50CaO-40P_2O_5-7Na_2O-3TiO_2 glass powder produces a pore-free coating unable to bind hydroxyapatite, whereas 60CaO-30P_2O_5-7Na_2O-3TiO_2 glass incorporates pores from which a crystalline hydroxyapatite phase can grow over the surface from simulated body fluid (see Figure). (Abstract Copyright [2003], Wiley Periodicals, Inc.)
Abstract Acute lung injury (ALI) in sepsis is characterized by an increase in microvascular permeability, resulting in pulmonary edema. Several studies have suggested that angiopoietin-1 and -2 play a contributory role in the pathogenesis of ALI. Polymyxin B-immobilized fiber column hemoperfusion is effective for sepsis-induced ALI. We investigated the angiopoietin levels before and after direct hemoperfusion with polymyxin B-immobilized fiber column (PMX) therapy. Enzyme-linked immunoassay was used to measure the serum angiopoietin-1 and -2 levels in 25 patients with septic shock treated with PMX. Eleven of the 25 patients were diagnosed with ALI. There was a significant positive correlation between the angiopoietin-1 level and the PaO2/FiO2 ratio, but there was a significant inverse corr...
An experiment has been performed to investigate the chemical reaction between the liquid phases of the eutectic lithium-lead (Li/sub 17/Pb/sub 83/) and water. The reactants and products were constrained within a closed reaction vessel, allowing the extent of reaction to be determined from the partial pressure of the hydrogen reaction product. The data from the tests showed that the extent of reaction did not depend upon the water temperature. The data also indicated that the extent of reaction passed through a maximum as the initial liquid metal temperature was varied from 350 to 500 C, and a model was developed to explain this behavior. 11 refs., 3 figs.
I discuss several examples of critical phenomena in O(N) models where topological excitations play an important role at criticality. I focus particular attention on the O(2) model in 3D, where recent measurements of the vortex string length distribution in equilibrium suggest the existence of a quantitative picture of the critical behavior in terms of defects. The compatibility of this perspective with renormalization group predictions is examined.
Model phosphate-metal solvation complexes have been studied by ab-initio self-consistent-field techniques. The complexes studied include (RO)2PO2-(R = H or CH3) with Li+, Na+, K+, Be++, Mg++, Ca++,...Full Text Available
The application of kinetic probes that allow one to determine relative reactivities of biologically relevant substrates with oxidizing intermediates in the Fenton reagent (H2O2 plus Fe2+ in acidic aqueous...Full Text Available
Vacuum glazing consists of an evacuated space between two sheets of glass. Vacuum glazing has a large effect on energy savings in houses and buildings. Vacuum glazing can achieve higher insulating performance than conventional insulated glazing. Nippon Sheet Glass has successfully developed conventional vacuum glazing. In this study we investigated an advanced form of vacuum glazing. Its thermal insulation ability is equivalent to 100 mm thick glass wool thermal insulation. This vacuum glazing contained a SnO_2:F low emissivity surface. The influence of the residual gas in a vacuum space on heat flow is important to performance. For long-term thermal stability, it is very important to maintain vacuum stability. To understand this better, we studied the behavior of outgassing from the inside glass surfaces exposed to an external energy source. We have studied the behavior of outgassing from a glass surface using a Nd:YAG laser (operated at 355 ...
Halide complexes of astatine cations At"+ and AtO"+ were prepared and their rate of migration was measured. The complexes are of the type AtX_2"- and AtOX_2"- (X = Cl"-, Br"-, I"-). The bromo complexes, AtBr_2"- and AtOBr_2"-, have a higher stability than the chloro complexes. The hydrolysis in weakly alkaline solution of AtX_2"- resulted At"-, and that of AtOX_2"- AtO_2"-. (author).
The objective of this work is to develop sealing materials for solid oxide fuel cells (SOFCs). A suitable sealant must form strong, dense bonds with SOFC components, be chemically and mechanically compatible with the components, be stable at 1000 degrees C in the operating environment of the SOFC (H_2 and H_2O on the anode side, O_2 on the cathode side), and must be nonconductive.
Technology of plasma sputtering, structure and properties of zirconium dioxide coatings were studied. Necessity of void number increase to enhance coating heat-resistance is shown. Optimal powder particle size (20-60 #mu#m) providing optimal coating porosity was determined. Weight part of stabilizating oxide (Y_2O_3) in ZrO_2 for formation in coating of microcracks serving as barriers for macro-cracks propagation was determined.
The complex phase relationships near the BaO-poor region of the quaternary Ba-Sm-Y-Cu-O oxide system prepared in pure air (pO2=22 kPa, 950 oC) and in 0.1% O2 (pO2=100 Pa, 810 oC) have been determined. This investigation also included the subsolidus compatibilities in ten subsystems (Ba-Sm-Y-O, Ba-Sm-Cu-O, Ba-Y-Cu-O, Sm-Y-Cu-O, Ba-Sm-O, Ba-Y-O, Ba-Cu-O, Sm-Y-O, Sm-Cu-O, and Y-Cu-O), and the homogeneity range of five solid solutions (Ba(SmxY2-x)CuO5, (Sm,Y)2O3, (Sm,Y)2CuO4, (Y,Sm)2Cu2O5, and Ba(Sm,Y)2O4). The single phase range of the superconductor solid solution, (Ba2-xSmx)(Sm1-yYy)Cu3O6+z, and the phase compatibilities in its vicinity, which are particularly important for processing, are described in detail. The phase equilibrium data of the Ba-Sm-Y-Cu-O system will enable the improvement of the intrinsic superconducting properties of second-generation wires, ...
Bacterial plasmids contain specific genes for resistances to toxic heavy metal ions including Ag+, AsO2-, AsO4(3-), Cd2+, Co2+, CrO4(2-), Cu2+, Hg2+, Ni2+, Pb2+, Sb3+, and Zn2+. Recent progress with...Full Text Available
Bovine microvascular endothelial cells (MEC) were able to degrade the H2O2 generated by phorbol myristate acetate-activated bovine neutrophils or by glucose oxidase with a maximal capacity of 4.0 +/-...Full Text Available
... Three prototype reactors were constructed and the photocatalysts used were TiO2 for hydroxyl radical generation, dyes such as methylene blue and rose bengal for singlet oxygen generation, and ferric chloride/hydrogen peroxide in Photo-Fenton OH radical generation. Singlet oxygen was effective against some of the pesticides but reacted slowly or not at all with others. All pesticides were degraded by OH radical generating agents (such as methylene blue)...
In monocytes, sulfatide, a lipid from Mycobacterium tuberculosis, blocked priming for enhanced release of superoxide (O2-) by the macrophage activating factors lipopolysaccharide, gamma interferon,...Full Text Available
A combined application of several microtechniques is presented and discussed with the Ti/TiO_2 and Zr/ZrO_2-systems as an example. All measurements were carried out on single grains of technical materials in order to detect and quantify the effect of substrate microstructure on the properties of anodic passive films formed potentiodynamically in 0.5 M H_2SO_4 (dU/dt = 20 mVs"-"1). Anisotropy-micro-ellipsometry (AME) was employed to determine the crystallographic orientation of the substrate grains along with passive film thickness and crystallinity in dependence on the anodization potential. Both the isotropic (amorphous) TiO_2- and the anisotropic (crystalline) ZrO_2-films exhibit a systematic dependence of film thickness on the grain orientation. Local LASER-scanning photocurrent measurements (#lambda#=257 nm) on the ...
Magnetic properties of layer ferromagnets against the thickness are investigated. Two new compounds served for studies: Bisub(6)Tisub(2)Nbsub(0,5)Fesub(2,5)Osub(18) and Bi_7Ti_3Fe_3O_2_1. The Moessbauer effect and the magnetic susceptibility measurements were applied in the experiment. The Faraday method was used in magnetic measurements in fields from 1 to 9,5 kOe. The results of Moessbauer measurements show that temperature dependence of the spectra is typical for compounds with superparamagnetic properties. The magnetic fields Hsub(n) on Fe"5"7 nuclei in Bisub(6)Tisub(2)Nbsub(0,5)Fesub(2,5)Osub(18) and Bi_7Ti_3Fe_3O_2_1 are similar and equal to 520+-10 kOe. Therefore it may be concluded that relaxation times of nuclear spins in these compounds are equal or close to each other. The lines of quadrupole splitting appear in spectra together at 20 K. The results of magnetic measurements show that the ...
We have investigated the growth behaviors of high temperature compatible ZrO_2 insulation coatings on Ag and AgMg sheathed Bi_2Sr_2Ca_1Cu_2O_x superconducting tapes depending on number of dipping and thermal conditions. The coatings were fabricated on long-length superconducting tape substrates using a solution derived from Zr tetrabutoxide, solvent and chelating agent for high magnetic field magnets. The layer-on-layer growth behaviors were characterized by environmental scanning electron microscope (ESEM), energy dispersive spectroscopy (EDS), X-ray maps and X-ray diffraction (XRD). This research showed that the ZrO_2 coatings were regularly grown on Ag-based tape substrates and coating thickness increased with increasing number of dipping. It was found that ceramic oxides formed at temperature range 450 and 550 deg. C. The final coating thickness changed between 6 and 8 #mu#m after annealing process. ...
The ecological effects of acid mine drainage were investigated during the summer of 1993 on St. Kevin Gulch, a headwater stream near Leadville, Colorado. The stream currently receives acidic water from an abandoned mine. The pH downstream of the mine is between 3.5 and 4.5, and several metals exceed concentrations toxic to aquatic organisms. Zinc is present at especially high concentrations (1 to 10 mg/L) Furthermore, the stream bottom is covered with a thick layer of iron hydroxide precipitates. Effects on stream biota have been dramatic. Aquatic flora in the affected reach is limited to a green filamentous alga, Ulothrix subtilissima. Macroinvertebrate densities are significantly lower in the affected reach (mean = 99 indiv/m"2; SD = 88 indiv/M"2) compared to an upstream (pristine) reference reach (mean = 1,735 indiv/m"2; SD = 652 indiv/M"2). Functional processes were also studied in the stream. Net primary production (NPP) was measured during midday with recirculating chambers. ...
Transient enhanced diffusion (TED) and dose loss (pile-up) are investigated for phosphorus-implanted samples covered with both oxide and nitride films. P ions were implanted into p-type (1 0 0) CZ-Si (dose 5x10"1"3 cm"-"3, 100 keV) through a chemical vapor deposition (CVD) Si_3N_4 film. For a half of samples, Si_3N_4 was etched off and SiO_2 films were grown by CVD. Both samples were annealed for 20-360 min at 700 deg. C. Diffusivity of P and the dose loss were estimated based on the secondary-ion mass spectrometry (SIMS) P profiles. Both Si/Si_3N_4 and Si/SiO_2 interfaces were investigated with transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS). There is no significant difference in P diffusivity between the SiO_2 and Si_3N_4 films for the present annealing condition of 700 deg. C for 20-360 min. Regarding dose loss, a distinct ...
By means of ESCA the composition and the thickness of passive films formed on austenitic stainless steels were investigated after the attack of nitric acid at various temperatures and acid concentrations. The outermost layers of the oxide film consist of SiO_2, then a layer rich of Cr-oxid follows, containing also some Mo in the four- and sixvalent state. Ni does not contribute to the oxide film. Cr is also enriched in the metal just below the oxide film. (orig.).
Four advanced oxidation processes (UV/TiO2, UV/IO4^-, UV/S2O8^2^-, and UV/H2O2) were tested for their ability to mineralize naphthenic acids to inorganic carbon in a model oil sands process water containing high dissolved and suspended solids at pH values ranging from 8 to 12. A medium pressure mercury (Hg) lamp was used, and a Quartz immersion well surrounded the lamp. The treatment goal of 5mg/L naphthenic acids (3.4mg/L total organic carbon (TOC)) was achieved under four conditions: UV/S2O8^2^- (20mM) at pH 8 and 10, and UV/H2O2 (50mM) at pH 8 (all with the Quartz immersion well). Values of electrical energy required to meet the treatment goal were about equal for UV/S2O8^2^- (20mM) and UV/H2O2 (50mM) at pH 8, but three to four times larger for treatment by UV/S2O8^2^- (20mM) at pH 10. ...
Depth sensing indentation tests were carried out to obtain load-penetration depth curves of SiAlON-ZrO_2 ceramics under different peak loads ranging from 200 to 1800 mN. The values of indentation hardness (H_O_P, H_C_C) and reduced elastic modulus (E_O_P, E_C_C) were calculated by using Oliver-Pharr (OP) and Cheng-Cheng (CC) methods. The experimental results revealed that the indentation hardness and reduced elastic modulus exhibit peak-load dependence, i.e. indentation size effect. Both indentation hardness and reduced elastic modulus values were obtained by considering indenter tip roundness and machine compliance. These values obtained from the OP method are higher than from the CC method. On the other hand, h_f/h_m ratios were used to clarify the indentation deformation behaviour of the SiAlON-ZrO_2 ceramic. The experimental h_f/h_m values were lower than the reported critical value (0.7) for all ...
The costs of greenhouse gas emission-reductions vary among countries depending on emission levels, technologies used, past emission-reduction achievements, path of economic development, fuel mix, and initial endowment of hydrocarbon resources. The criterion of cost-effectiveness therefore suggests that the ways should be found to encourage emission reductions in the countries where the required costs of reduction of additional unit of emissions are the lowest. These countries usually face crucial capital constraints and have other development priorities than investing in reduction of greenhouse gas emissions. Developed countries could invest their resources in the former Soviet Union and the east European countries to achieve the same level of reduction of greenhouse gases with lower costs than they could in their own countries.
The main compositions of iron-base amorphous self-fluxing alloy powders of 150 mesh, used in this work, are Fe, Cr, Ni, W, Mo, B, Si and C. The ranges of each element in at% are (65-70)Fe, (3-5)Cr, (2-4)Ni, (2-4)W, (1-2)Mo, (10-14)B, (4-7)Si and (2-3)C. The atomic ratio of metal-metalloid is about 80:20, so this alloy is abbreviated as M_8_0X_2_0. The material on which coatings were deposited is 1020 steel, austenitized for 1h at 880 C, water quenched, and tempered at 180 C for 1h. This heat treatment resulted in a low carbon martensite structure with a hardness of HRC35-45. After cleaning, shot blasting and preheating the steel to about 200 C, the authors sprayed a thin Ni-Al alloy layer of about 0.1--0.15mm in thickness onto the specimen by means of an oxygen-acetylene torch to provide better bonding of the coating with substrate. Then the M_8_0X_2_0 and M_8_0X_2_0+8%CeO_2 alloy coatings were sprayed to a thickness of about 0.6--0.8mm. The ...
Interest in finding out passive ways to keep the variation in the indoor climate within the comfort zone is gaining in popularity. One possible solution is the use of the moisture-buffering property of materials. In this study, the effects of the ventilation system and moisture-buffering properties of the building fabric on the stability of the indoor temperature and humidity are analysed by means of long-term field measurements. Indoor climate measurements were carried out in 170 detached houses (248 rooms). Temperature and relative humidity were measured continuously in bedrooms and living rooms at one-hour intervals over a one-year period. In general, it may be concluded that in this study, the ventilation had a greater effect on the indoor climate than the properties of the building fabric. The dampening effect of hygroscopic materials was remarkably less in the field measurements than it was in simulations in different studies. This indicates that completely non-hygroscopic and ...
Semiclassical analysis of heavy ion induced transfer reactions are discussed for the quasielastic region. Some unique aspects of these reactions are shown, the variety of features which can be understood semiclassically is demonstrated, and some open problems are indicated. 28 refs., 16 figs. (LEW)
Carbon capture and storage have been receiving increasing interest lately, mainly as an option to reduce CO{sub 2} emissions from the power sector. The concept could be adapted for production of H{sub 2} as well, which would provide a carbon free energy carrier that could be used for example as transportation fuel. In this doctoral thesis, the option to use chemical-looping technologies to produce H{sub 2} from fossil fuels with CO{sub 2} capture is explored. In chemical-looping combustion, direct contact between fuel and combustion air is avoided. Instead, a solid oxygen carrier performs the task of bringing oxygen from the air to the fuel. Thus, the resulting CO{sub 2} and H{sub 2}O are not diluted with N{sub 2}, and pure CO{sub 2} can easily be recovered by cooling and condensation. The heat of reaction is the same as for ordinary combustion. Chemical-looping reforming uses the same basic principles as chemical-looping combustion, but operates at under ...
Transient enhanced diffusion (TED) from implantation of 5thinspkeVthinspB{sub 10}H{sub 14} and 0.5 keV B ions has been quantified and compared for nominal boron doses of 10{sup 14} and 10{sup 15}thinspcm{sup {minus}2}. Boron diffusivity during annealing was extracted from secondary ion mass spectroscopy depth profiles of diffused marker layers in boron doping-superlattices and the actual implanted B dose was independently measured by nuclear reaction analysis. Comparable enhancements were observed from both ions. Transmission electron microscopy analysis revealed that both boron- and decaborane-implanted samples were amorphized at a nominal 10{sup 15}thinspcm{sup {minus}2}thinspB dose. A comparison with data from low energy Si implants revealed a similar dependence of diffusivity enhancement on implant dose. These findings are consistent with the understanding that TED is caused by the interstitial supersaturation resulting from a number of excess interstitials ...
Transient enhanced diffusion (TED) from implantation of 5keVB_1_0H_1_4 and 0.5 keV B ions has been quantified and compared for nominal boron doses of 10"1"4 and 10"1"5cm"-"2. Boron diffusivity during annealing was extracted from secondary ion mass spectroscopy depth profiles of diffused marker layers in boron doping-superlattices and the actual implanted B dose was independently measured by nuclear reaction analysis. Comparable enhancements were observed from both ions. Transmission electron microscopy analysis revealed that both boron- and decaborane-implanted samples were amorphized at a nominal 10"1"5cm"-"2B dose. A comparison with data from low energy Si implants revealed a similar dependence of diffusivity enhancement on implant dose. These findings are consistent with the understanding that TED is caused by the interstitial supersaturation resulting from a number of excess interstitials approximately equal to the number of implanted atoms which can become ...
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was ...
Coal liquefaction investigations required the availability of model compounds for mechanistic investigations. Towards this end, IITRI was funded to develop an approach for the synthesis of one of the target compound. This study was carried out in several phases as outlined here. Initial synthetic investigations on obtaining 2-tetrolol was carried out using high pressure and temperature reduction with Raney nickel catalyst. The next step consisted in incorporation of a hydroxymethyelene group at the C-3 position. This was successfully carried out utilizing 2-tetrolol, formaldehyde, and calcium oxide. An alternate improved method was developed using 3-carboxyl-2-naphthol. This required less time, gave a cheer product in higher yield. Efforts at the introduction of a chloromethylene group only yielded polymeric material or starting material in spite of protection the phenolic group by various groups. They synthesis of 3, 5-dimethyl-6- bromobenzyl chloride was ...
(methine-{sup 3}H)1,1-Di-(4-chlorophenyl)-2,2,2-trichloroethane ((methine-{sup 3}H)DDT) and its di-(4-nitrophenyl) analog, both of high purity with a moderately high specific activity were prepared. Chloro-benzene was condensed with (1-{sup 3}H)1-(4-chlorophenyl)-2,2,2-trichloro-ethanol, which has been synthesized by sodium boro({sup 3}H)hydride reduction of 4-chlorophenyl trichloromethyl ketone. The purified ({sup 3}H)DDT had a specific activity of 0.77 Ci/mmol (28.49 GBq/mmol). (methine-{sup 3}H)1,1-Diphenyl-2,2,2-trichloroethane was similarly synthesized and was nitrated to give (methine-{sup 3}H)1,1-di-(4-nitrophenyl)-2,2,2-trichloro-ethane of 1.63 Ci/mmol (60.31 GBq/mmol). Dehydrochlorination with housefly enzyme (glutathione-dependent DDT dehydrochlorinase) showed a remarkable isotope effect. For DDT, the observed tritium isotope effect on V{sub max}/K{sub m} was 11.51{plus minus}0.52. For the nitro-analog, the value was 11.3{plus minus}1.2. We measured ...
The central benzodiazepine receptor tracer [N-methyl-"1"1C]iomazenil (Ro 16-0154) was synthesized by alkylation of the desmethyl precursor noriomazenil with ["1"1C]methyl iodide. The ["1"1C]CH_3I (prepared by reduction of ["1"1C]CO_2 with LiAlH_4 followed by reaction with HI) was reacted with noriomazenil inN,N -dimethylformamide and Bu_4N"+OH"- for 1 min at 80 deg. C and purified by HPLC (C_1_8, 34% CH_3CN/H_2O, 7 mL/min). The product was obtained with synthesis time 35 #+-# 5 min (mean #+-# SD, n = 7), radiochemical yield (EOB) 36 #+-# 16%, radiochemical purity 99 #+-# 1%, and specific activity 5100 #+-# 2800 mCi/#mu#mol. Absorbed radiation doses were calculated from previously acquired human biodistribution data. The urinary bladder wall received the highest dose (0.099 mGy/MBq) for 4.8 h voiding interval and the effective dose equivalent was 0.015 mSv/MBq. After i.v. injection of ["1"1C]iomazenil in an adult baboon or healthy human ...
Sulfur poisoning from engine fuel and lube is one of the most recognizable degradation mechanisms of a NOx adsorber catalyst system for diesel emission reduction. Even with the availability of 15 ppm sulfur diesel fuel, NOx adsorber will be deactivated without an effective sulfur management. Two general pathways are currently being explored for sulfur management: (1) the use of a disposable SOx trap that can be replaced or rejuvenated offline periodically, and (2) the use of diesel fuel injection in the exhaust and high temperature de-sulfation approach to remove the sulfur poisons to recover the NOx trapping efficiency. The major concern of the de-sulfation process is the many prolonged high temperature rich cycles that catalyst will encounter during its useful life. It is shown that NOx adsorber catalyst suffers some loss of its trapping capacity upon high temperature lean-rich exposure. With the use of a disposable SOx trap to remove large portion of the sulfur ...
porous silica ceramics were prepared(with HCL catalyst)using H{sub 2}O/TEOS molar ratios of 2.6-59.0, with the EtOH/TEOS ratio fixed. After preparing 9 kinds of sol, the followings were investigated; measurement of the gelation time, thermal analyses by TG/DTA, property analyses of the intermediates by FT-IR and X-ray diffractometry with dried samples, analyses of SiO{sub 2} polymer by FT-IR, the investigation of specific surface area and pore size distribution by N{sub 2}-adsorption isotherm, and structural change of SiO{sub 2} polymer and pore morphology by TEM observation, with samples heat-treated to 500 deg. C. In the concentrations of investigated compositions and catalyst, gelation time showed a minimum at ca. 11 moles of water per one mole of TEOS, the highest degree of polymerization at ca.8-18 moles, and the largest specific surface area at ca. 11 moles, which means that the polymerization proceeded fastest at ca. 11 moles of water. In conclusion, the more water used, the ...
Tritium is produced in large quantities at heavy water nuclear power reactors via the neutron activation reaction "2H(n,#gamma#)"3H. At Wolsung nuclear power plant which has a CANDU reactor, the tritium concentrations in coolant and in moderator systems are 1.5 Ci/Kg-D_2O and 35 Ci/kg-D_2O, respectively, after 12 years of operation. The airborne tritium concentration in main access area is normally less than 5 MPCa except short-term peaks. The average tritium concentrations in main access controlled areas are normally less than 100 MPCa. Tritium is mainly present in the air of workplace of CANDU reactors as a tritiated water vapour. Airborne tritiated water vapour enters the workers body via inhalation and absorption through skin and can result in a significant dose. The occupational doses from tritium at Wolsung NPP have been maintained below 1 man-Sv per year so far. The tritium contribution to the total plant man-Sv changes between 30 percent and 50 percent. For ...
Structural and functional alterations in hepatocytes of the European eel, Anguilla anguilla, following a 4-week-exposure to 5, 50, and 250 micrograms/liter dinitro-o-cresol (DNOC) were investigated by means of electron microscopy and biochemistry and compared to liver pathology in eels exposed to the chemical spill into the Rhine river at Basle in November 1986. Whereas phenological parameters (growth, condition factor) are unaffected, ultrastructural and biochemical alterations are detectable at greater than or equal to 50 and 5 micrograms/liter DNOC, respectively. Structural modifications include: rounding-up of the nuclei; fractionation and reduction of the rough endoplasmic reticulum; proliferation of the smooth endoplasmic reticulum (SER), mitochondria, peroxisomes, and lysosomes; bundles of rod-shaped SER profiles; annulate lamellae; membrane whorls within mitochondria; crystallization of the peroxisomal matrix and glycogen bodies; glycogen depletion and ...
The structure of hydroxylated oxide films (passive films) formed on Cr(110) in 0.5 M H{sub 2}SO{sub 4} at +0.35, +0.55, and +0.75 V/SHE has been investigated by in situ scanning tunneling microscopy (STM). Cathodic reduction pretreatments at {minus}0.54, {minus}0.64, and {minus}0.74 V/SHE destroy the well-defined topography of the single-crystal electrode and they have been excluded from the passivation procedure. Two different passive film structures have been observed, depending on the potential and time of passivation. At low potential (+0.35 V/SHE), the passive film, consisting mostly of chromium hydroxide, has a noncrystalline and granular structure whose roughness suggests local variations of thickness of ca. {+-} 0.5 nm. A similar structure is observed at higher potential (+0.55 V/SHE), but only for a short polarization time. For longer polarization at 0.55 V/SHE, and at higher potentials (+0.75 V/SHE), a crystalline structure is formed; the higher the ...
Roller compacted concretes (RCC) were developed for the Norwegian Skjerka hydropower project. RCCs were developed to have a high-volume fly ash content to address environmental issues, including the reduction of carbon dioxide emissions associated with dam construction. They also makes good use of waste product and conserve natural resources. This study examined a series of mixtures to determine the appropriateness of using RCC as a competing alternative to the traditional rock fill dam proposed for the Skjerka hydropower project. The main advantage of RCC is speed, allowing a relatively large dam to be constructed in just one summer season, saving financial costs and providing early return on the investment. In addition, fly ash can be used in the structure, using clean and renewable energy. Several procedures to proportion RCC mixtures were proposed, including the optimal paste volume method which is based on the assumption that an optimal RCC should have just ...
For large transmission steel towers to be built in a mountainous area, caisson type pile foundations are often applied. The works for construction of this kind of foundation are manned operations such as drilling, arranging reinforcements, concrete laying, etc. in a narrow vertical pit which is 3m in diameter and about 20m in depth, but securing labour force of good quality for such works becomes increasingly difficult. In order to cope with the above situation and achieve reduction of costs, shortening of construction period, improvement of safety, saving of manpower, etc. a power supply company and construction companies have developed jointly a method of unmanned construction in a caisson type pile foundation pit. This method consists of the use of a caisson type pile full size excavator (this consists of an excavator proper, a vacuum soil discharging device, a monitor/controller, a load crane and a reaction pad, and performs continuously ...
The fixed bed pilot plant, the catalyst testing procedure, and the calculations for conversion and selectivities were previously described in the technical progress report covering the period of 3/16/88 to 6/16/88 for Contract DE-AC22-87PC79812. Conversions and hydrocarbon selectivities were calculated using data from an on-line gas chromatography (GC) analyzer. Alcohol selectivities were calculated using data from an on-line boiling point GC analyzer which analyzed the liquid product. The catalysts were prepared via the steps of impregnation, calcination, and reduction on a special Y-zeolite-derived support. The impregnation step consisted of evaporation of metal salts on to the support from an aqueous solution. For one catalyst (No. 6531-188) the metal salts were evaporated on to the support from a reverse micelle solution containing the metal salts. All the catalysts were calcined for four hours at 450{degree}C. The calcined catalysts were loaded in the reactor ...
Plasma-deposited thin films prepared at room temperature, ranging from 46 to 250 A of PdAu on #approx#45-50 A Si-oxide and Si-oxynitride films grown on Si wafers were studied. Grazing incidence X-ray diffraction, X-ray reflectivity, and XPS depth profile techniques were used to characterize the thin films. A reactive interface involving Pd- and Au-silicides is formed, linking the thin film to the Si-oxide and Si-oxynitride films: a small fraction of Pd and Au atoms from PdAu migrate into the Si substrate, first penetrating the oxide layer, and the small fraction of Si atoms from the oxide layer migrate into the PdAu film and form a silicide interlayer consisting of a reactive interface made up of mixtures of Au- and Pd-silicides interspersed within the matrix of PdAu and substrate. The concentration profiles of these silicides have a maximum at the interface with decay on both sides. The density and the face-centered cubic (fcc) lattice parameter of the film are determined to be ...
Red mud is a solid waste produced in the process of alumina extraction from bauxite. In this paper, recovery iron from Bayer red mud was studied with direct reduction roasting process followed by magnetic separation, and then building materials were prepared from alumosilicate residues. After analysis of chemical composition and crystalline phase, the effects of different parameters on recovery efficiency of iron were carried out. The optimum reaction parameters were proposed as the following: ratio of carbon powder: red mud at 18:100, ratio of additives: red mud at 6:100, roasting at 1300 deg. C for 110 min. With these optimum parameters, total content of iron in concentrated materials was 88.77%, metallization ratio of 97.69% and recovery ratio of 81.40%. Then brick specimens were prepared with alumosilicate residues and hydrated lime. Mean compressive strength of specimens was 24.10 MPa. It was indicated that main mineral phase transformed ...
The overall objective of this project was to develop a new approach for the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrated coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and a technical assessment including an economic evaluation. Heterofunctional solvents were the most effective in swelling coals. Also solvent blends such as isopropanol/water were more effective than pure solvents alone. Impregnating slurry catalysts simultaneously during coal swelling showed that better uptake was achieved with nonswelling solvent and higher impregnation temperature. Some enhancement in initial coal conversion was seen liquefying SO{sub 2}-treated Black Thunder coal with slurry catalysts, and also when hydrogen donor liquefaction solvents were used. Noncatalytic ...
The shrinking core model is examined for gas-solid noncatalytic reactions with a self-inhibited rate form and it is shown that multiple reaction pathways are possible for solid particles reacted under identical conditions. The observed reaction rate can have up to two discontinuities (jumps) during reaction for particles of spherical and cylindrical shape. The geometric instability analysis reveals that the reaction interface is stable under a very limited set of conditions only for solid particles of slab geometry. For a sphere or cylinder at large Biot numbers the reaction interface is always potentially unstable. This model provides a plausible explanation for gas-solid reactions which exhibit erratic shrinking core behavior.
The effects of temperatures, durations of treatment, and derivations from spermatophores or spermaries on in vitro acrosome reaction of the spermatozoa in the Chinese mitten crab Eriocheir sinensis...Full Text Available
Major advances in 'Energy and Materials Cycles' have been achieved in the removal of heavy metals from the solid residues of municipal waste incineration. It has been conclusively shown that the oxidation/reduction conditions established during the thermal treatment of filter ash have a decisive influence on the evaporation of groups of heavy metals. With respect to biomass gasification, studies have been carried out with respect to the best way of extracting pure hydrogen from the low calorific value gas that is typically obtained from a biomass gasifier. The overarching goal of the laboratory 'High Temperature Solar Technology' is the use of solar energy for the production of solar fuels, or for the reduction of CO{sub 2} emissions in large scale industrial processes that are conventionally carried out with the use of fossil fuels. In a short-term project targeted at the solar production of lime, highly ...
The purpose of this study was to determine whether resistance exercise training-induced reductions in inflammation are mediated via melanocortin 3 receptor expression in obese (BMI 32.7 ± 3.7)...Full Text Available
Objectives To evaluate the extent to which intensive care units participating in the initial Keystone ICU project sustained reductions in rates of catheter related bloodstream infections.Design...Full Text Available
BackgroundLung volume reduction surgery is effective at improving lung function, quality of life, and mortality in carefully selected individuals with advanced emphysema. Recently,...Full Text Available
Nitrate reduction was studied as a function of carbohydrate concentration in detached primary leaves of barley (Hordeum vulgare L. cv Numar) seedlings under aerobic conditions in light...Full Text Available
Nitrogenase activity was measured by the C2H2reduction method in large soil cores (29 cm in diameter by 20 cm in depth) of maize (Zea mays) and sorghum (Sorghum...Full Text Available
We proposed a faster pedigree-based generalized multifactor dimensionality reduction algorithm, called PedG-MDR II (PII), to detect gene-gene interactions underlying complex traits. Inherited...Full Text Available
In this letter a method to estimate the visco-elastic response of monolithic ceramics to cyclic loading conditions at high temperatures is proposed. A relation is observed between the visco-elastic energy dissipation measured for two silicon nitride materials, and the structural characteristics of their respective intergranular phases. Some consequences for the fatigue resistance of the tested materials, and of non-transforming monolithic ceramics in general, are discussed. Two batches (G for glassy and C for crystalline) of SiAlON have been studied. The G-batch is obtained by pressureless sintering of silicon nitride powder with Y_2O_3 (6 wt%) and 6AlN-SiO_2 (5 wt%) as sintering additives. The main phase after sintering is #beta#-sialon. Upon cooling from the sintering temperature the amorphous intergranular residues of the sintering additives and of SiO_2, which is unavoidably present as a thin layer ...
ObjectivesWe have developed a life cycle perspective inspired conceptual model (CM) that suggests the importance of terrestrial ecosystems as a major repository of ZnO, TiO2, and Ag (Tier 1) manufactured nanomaterials (MNMs) introduced via the land application of MNM-containing biosolids. We propose to investigate the transport, fate, behavior, bioavailability, and effects of MNMs in(to) agroecosystems under environmentally realistic scenarios organized around three key hypotheses: Hypothesis (H1) Surface [continued...]DescriptionWe have developed a life cycle perspective inspired conceptual model (CM) that suggests the importance of terrestrial ecosystems as a major repository of ZnO, TiO2, and Ag (Tier 1) manufactured nanomaterials (MNMs) introduced via the land application of MNM-containing biosolids. We propose to investigate the transport, fate, behavior, bioavailability, and effects of MNMs in(to) ...
New tetradentate N(2)O(2) donor Schiff bases and their mononuclear Co(II), Ni(II), Cu(II), and Pd(II) complexes were synthesized and characterized extensively by IR, (1)H-, (13)C-NMR, mass, ESR, conductivity measurements, elemental and thermal analysis. Specifically the magnetic and electronic spectral measurements demonstrate the octahedral structures of cobalt(II), nickel(II) complexes and square planar geometries of copper(II), palladium(II) complexes. All the ligands and complexes were screened for their in vitro antibacterial activity against two gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus) and two gram-negative bacteria (Escherichia coli, Klebsiella pneumonia). In this study, Pd(II) complexes exhibited potent antibacterial activity against B. subtilis, S. aureus whereas other metal complexes also exerted good activity towards all tested strains even than standard drugs streptomycin and ampicillin. PMID:21297294
This work estimates the power requirements for using photochemical processes driven by space nuclear power to counteract the Earth's ozone layer depletion. The total quantity of ozone (O_3) in the Earth's atmosphere is estimated to be about 4.7 x 10"3"7 molecules. The ozone production and destruction rates in the stratosphere are both on the order of 4.9 x 10"3"1 molecules/s, differing by a small fraction so that the net depletion rate is about 0.16 to 0.26% per year. The delivered optical power requirement for offsetting this depletion is estimated to be on the order of 3 GW. If the power were produced by satellite reactors at 800 km altitude (orbit decay time #approx# 300 years), some means of efficient power beaming would be needed to deliver the power to stratospheric levels (10--50 km). Ultraviolet radiation at 140--150 nm could have higher absorption rates in O_2 (leading to production of atomic oxygen, which can combine with ...
Site-selective spectroscopy fluorescence experiments (emission and excitation) in the near-infrared region associated with the "4I_1_5_/_2_4I_1_1_/_2 transitions of Er"3"+ ions have been successfully used to show the presence of two different Er"3"+ centres in the Bi_1_2SiO_2_0 piezoelectric crystal. Green (545-570 nm), red (650-690 nm) and near-infrared (850-890 nm) up-converted emissions have been observed and resolved for each type of centre under excitation up to the "4_I_1_1_/_2 state. The Stark energy level schemes of the three lower energy states of Er"3"+ ions have been determined and compared for both centres, showing two quite different crystalline field environments. The mechanisms responsible for the up-conversion process (excited state absorption and/or energy transfer up-conversion) are also analysed. (author)
Total-dose irradiation seriously damages MOS devices and their circuit performance. Threshold voltage shifts, transconductance degradation and increase in off-state leakage current are generally observed for irradiated devices. These instabilities are essentially due to positive and/or negative charge trapping in SiO_2 and interface trap generation at the SiO_2/Si interface. Radiation hardening of CMOS VLSIs is to eliminate these trapping effects, and for this purpose, special considerations for fabrication processes and layout design are necessary. In this paper, basic mechanisms for radiation-induced charge trapping and related effects on MOS devices are reviewed. Also discussed are radiation-hardening technologies from both fabrication-process and layout-design viewpoints. Using these technologies, 1 #mu#m radiation-hard CMOS gate arrays have been successfully developed. Experimental data taken for ...
Abstract Lithium-indium oxide is one of the candidate materials as solid-state scintillators for solar neutrinos due to an inverse --decay of 115In to 115Sn. On the other hand, when doped with rare-earth ions such as Eu3+ or Sm3+, it becomes a promising phosphor material. In this report we present a simple solid-state procedure for preparation of LiInO2:Eu3+ powders. X-ray diffraction confirmed prod-uct in tetragonal structural form (space group: I41/amd) and no impurity phases were detected. Then, high resolution photoluminescence emission measurements were performed at room and low temperatures to find 5D0 - 7FJ. Emission kinetics from 5D0 level exhibited pure single exponential behavior with lifetime of about 1.5 ms. Maximum energy splitting of 7F1 manifold is recorded as a function of ...
The excellent high temperature strength and thermal conductivity of molybdenum-base alloys provide attractive features for components in advanced magnetic and inertial fusion devices. Refractory metal alloys react readily with oxygen and other gases. Oxidized molybdenum in turn is susceptible to losses from volatile molybdenum trioxide species, (MoO3)m, in air and the hydroxide, MoO2(OH)2, formed from water vapor. Transport of radioactivity by the volatilization, migration, and re-deposition of these volatile species during a potential accident involving a loss of vacuum or inert environment represents a safety issue. In this report we present experimental results on the oxidation, volatilization and re-deposition of molybdenum from TZM in flowing air between 400 and 800°C. These results are compared with calculations obtained from a vaporization mass transfer model using chemical thermodynamic data for vapor pressures of MoO3(g) over ...
A series of new non-discoid chiral copper(ii)-salen type complexes, [Cu((4-CnH2n+1O)2salen)], n = 14, 16, 18 and salen = N,N'-cyclohexane bis (salicylideneiminato), containing 4-substituted alkoxy tails in the side aromatic rings and a cyclohexane spacer, have been prepared and their mesogenic properties investigated. The compounds were characterised by Fourier transform infra-red spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy, UV-vis spectroscopy and fast atom bombardment mass spectrometry. Mesomorphic properties of these compounds were studied by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction (XRD). The ligands are non-mesogenic but the complexes exhibited enantiotropic rectangular columnar mesophases (Colr) with extended temperat...
The band structure (BS) of crystalline Bi_2Se_2Te both pure as well as deposited on Si or SiO_2 (substrates) was calculated for the first time. The calculation approach consists of an orthogonalization of the plane wave basis set with respect to the core-like orbitals and the application of the Perdew-Alder exchange-correlation scheme. In addition, a virtual crystal approach was applied. Experimental ellipsometric spectra were used as a criterion of the advantages of the different calculation techniques. The results of traditional one-electron methods of BS calculations, using norm-conserving pseudo-potential (NCPP), and full linear augmented plane wave (FLAPW), were compared with the experimental data. Better agreement with experiment is achieved when the NCPP wave functions are orthogonalized to the 4dBi core-like states. Concerning the LMTO and the FLAPW all-electron methods, only appropriate application of the virtual crystal approximation ...
An x-ray fluorescence spectrometer was designed and fabricated which nondestructively determines the thickness of aluminum cladding at small suspected thin spots in the inner or outer surface of actinide reactor tubes. The analysis method is based on the difference in absorption of actinide L/sub #alpha#/ and L/sub #beta#/ fluorescent x-rays in passing through the cladding. Calibration plots of the logarithm of the L/sub #beta#//L/sub #alpha#/ x-ray intensity ratio versus cladding thickness are linear to at least 40 mils for U-Al, U_3O_8-Al, and PuO_2-Al substrates. Accuracy and precision of the experimentally determined cladding thickness and evaluated for both uranium and plutonium substrates. Experimental thickness data are reported for 618 quality assurance analyses on six Mark 41 PuO_2-Al target tubes. An x-ray fluorescence cladding thickness monitor operated with a computer-controlled fluoroscope ...
The composite of doped lanthanum gallate (La_0_._9Sr_0_._1Ga_0_._8Mg_0_._2O_2_._8_5, LSGM) and doped ceria (Ce_0_._8Sm_0_._2O_1_._9, CSO) was investigated as an electrolyte for solid oxide fuel cell (SOFC). The LSGM-CSO composite was examined by X-ray diffraction (XRD) and impedance spectroscopy. It was found that the sintered LSGM-CSO composite contains mainly fluorite CeO_2 phase and a minority impurity phase, Sm_3Ga_5O_1_2. The LSGM-CSO composite electrolyte shows a small grain boundary response in the impedance spectroscopy as compared to LSGM and CSO pellets. The composite electrolyte exhibits the highest conductivity in the temperature range of 250-600 "oC, compared to LSGM and CSO. The LSGM-CSO composite can be expected to be an attractive intermediate temperature electrolyte material for solid oxide fuel cells.
This study examined the oxygen permeation behavior of Ce0.9Gd0.1O2-d (Gadolinium-Doped Ceria, GDC)/Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF) composite membranes fabricated using a conventional sintering technique. GDC/BSCF composite membranes with a relative density >95% could be obtained when a green compact of BSCF and GDC was sintered at 1150^oC for 5h. It appears that GDC serves as a grain growth inhibitor because the average grain size of the composite decreased with increasing GDC content. The oxygen permeability of the BSCF and GDC/BSCF composite membranes strongly depends on the grain size and membrane thickness. The addition of GDC to BSCF resulted in a small grain size, low thermal expansion coefficient and high hardness. However, it is believed that oxygen permeation was blocked by GDC, a...
The effects of the dopants, Mg"2"+, Sr"2"+, Sc"3"+, Yb"3"+, Gd"3"+, La"3"+, Ti"4"+, Zr"4"+, Ce"4"+, and Nb"5"+, on the grain boundary mobility of dense Y_2O_3 have been investigated from 1,500 to 1,650 C. Parabolic grain growth has been observed in all cases over a grain size from 0.31 to 12.5 microm. Together with atmospheric effects, the results suggest that interstitial transport is the rate-limiting step for diffusive processes in Y_2O_3, which is also the case in CeO_2. The effect of solute drag cannot be ascertained but the anomalous effect of undersized dopants (Ti and Nb) on diffusion enhancement, previously reported in CeO_2, is again confirmed. Indications of very large binding energies between aliovalent dopants and oxygen defects are also observed. Overall, the most effective grain growth inhibitor is Zr"4"+, while the most potent grain growth promoter is Sr"2"+, both at 1.0% concentration.
Functionalizing nanoparticle surfaces is essential for achieving homogeneous dispersions of monodisperse particles in polymer nanocomposites for successful utilization in engineering applications. Functionalization reduces the surface energy of the nanoparticles, thereby limiting the tendency to agglomerate. Moreover, reactive groups on the surface can also participate in the polymerization, creating covalent bonds between the inorganic and organic phases. In this paper, a fluidized bed inductively coupled plasma (FB-ICP) reactor is used to break apart the agglomerates and functionalize commercial TiO2 nanoparticle powders in a batch of several grams. The fluidized bed could be implemented into a continuous flow reactor, potentially making this a viable method to treat larger quantities of commercial powders. The particles are treated with acrylic acid (AA) and tetraethylorthosilicate (TEOS) plasma and the functionalized particles were ...
X-ray magnetic diffraction (XMD) technique was applied to an orbital ordering compound of ferromagnetic YTiO_3 for the first time. The orbital-magnetic form factor #mu# _L(k) and the spin-magnetic form factor #mu# _S(k) were independently measured by utilizing the LS separation ability of the XMD. The #mu# _L(k) was measured for ten reciprocal-lattice points. No significant values of the #mu# _L(k) were observed for most of the reciprocal-lattice points within the estimated statistical errors, which suggested quenching of the orbital moment. The #mu# _S(k) was measured for 22 reciprocal-lattice points. Fourier synthesis of the #mu# _S(k) gave the spin density distribution m _S(r) in the real space. The obtained m _S(r) map shows the characteristic feature of the electron distribution of 3d electron in the t_2_g state of a Ti atom coordinated by O"2"- ions, in which the electrons are distributed away from the negative ...
BaTiO_3 compacts, when fluxed with < 2 vol% of a complex borate glass phase, were sintered to near theoretical density at temperatures < 1175 degrees C in 2 h. Microstructural analysis showed a uniform grain size < 1.0 #mu#m with 0.75 wt% ZrO_2 added to the flux phase as a grain growth inhibitor. TEM analysis revealed a microcrystalline grain-boundary phase with the ZrO_2 resident along the grain boundaries. These samples displayed an essentially flat dielectric profile, low dissipation factors (< 2%) over the range 25 degrees to 125 degrees C, a near linear dependence (#approx# #+-# 15%) between 25 degrees and - 55 degrees C, and significantly increased voltage stability. X-ray diffraction analysis of these small-grained materials indicates a suppression of the tetragonal structure toward a more cubic modification.
Ion bombardment during deposition can significantly modify the film properties. In the partially ionized beam deposition, ions derived from the depositing material, i.e., the self-ions, are used during deposition. Cu films were deposited on SiO_2 substrates at room temperature using 1% Cu self-ions with an energy ranging between 0--4 keV. We studied the microstructures of the Cu films using x-ray diffraction and transmission electron microscopy, measured the impurity level inside the films using secondary ion mass spectrometry, and performed the resistivity measurements using a four point probe. The results indicate that there is an optimum ion energy around 2 keV at which, the integrated x-ray intensity ratio I(111)/I(200) reaches its maximum value indicating a strong left-angle 111 right-angle texture, while the impurity concentration and resisitivity are minimum. The correlation between the structural, compositional and electrical properties ...
A dense silica glass was prepared by consolidating a highly dispersed silicic acid powder (particle size 1H magic-angle spinning (MAS) NMR confirmed an increase in hydroxyl groups in the sample prepared by SPS relative to that of the conventional SiO2 reference glass. Aside from the comparably high water content, we conclude from the similarity of the IR-reflectance and the 29Si MAS NMR spectra of the SPS sample and the corresponding spectra of the conventionally prepared silica glass, that the short- and medium-range order is virtually the same in both materials. Raman spectroscopy, however, suggests that the number of three- and four-membered rings is significantly smaller in the SPS sample compared to the conventionally prepared sample. Based on these results we conclude that it is possible to prepare glasses by compacting amorphous powders by the SPS process. The SPS process may therefore enable the preparation of glasses with compositions ...
Complex formation between neptunium(IV) and neptunium(V) ions with thiosemicarbazidodiacetic acid in solution has been studied spectrophotometrically. Under the conditions employed herein complexes of composition 1:2 and 1:1, in the form Np(HR)_2 and NpO_2R"2"-, respectively, are formed. Stability constants for these complexes have been calculated and their molar extinction coefficients have been determined, and are equal to (1.33 +/- 0.25) x 10"7, log #beta# = 7.11 +/- 0.8, element of/sub K/ = 96 +/- 3 liter/mole x cm for Np(HR)_2, and (2.34 +/- 0.2) x 10"3, log #beta# = 3.36 +/- 0.036, element of/sub K/ = 235 +/- 1 liter/mole x cm for NpO_2R"2"-. Spectrophotometric titration has also shown that in basic solutions thiosemicarbazidodiacetic acid behaves as a tribasic acid; it third ionization constant has been determined and is equal to 10/sup -9.2/.
We have constructed a 27-kDa hTERT C-terminal polypeptide (hTERTC27) devoid of domains required for telomerase activity and demonstrated that it is capable of nuclear translocation/telomere-end targeting. Here we showed that expression of a low level of hTERTC27 renders hTERT positive HeLa cells sensitive to H(2)O(2)-induced oxidative stress and subsequent cell senescence. The senescence-associated gene, the cyclin/cdk inhibitor p21(Waf1), was up-regulated. This occurs without changing the expression of endogenous hTERT, causing significant telomere shortening or inhibiting telomerase activity. Results from this study suggest for the first time that in addition to telomerase activity, the C-terminus of hTERT also plays a role in hTERT-mediated cellular resistance to oxidative stress. PMID:12565825
... operation, experimental data reduction, and application of PES results to studies related to estuarine and coastal sediment transport problems are ...
... is to develop a systematic program of energy consumption reductions in compliance with the stated goals of the Army Facilities Energy Plan (AFEP ...
... projects that will result in the reduction of energy consumption in compliance with the objectives set forth in the Army Facilities Energy Plan, without ...
... be easily replaceable, and its compartment or container ... in a simple, efficient manner for storage or disposal. ... and enters the reactor at approximatel ...