Al-based anodic oxide films structure observation using field emission gun scanning electron microscopy

In the present work, the anodic oxide films of Al, Al-Cu 4.5% and Al-Si 6.5% alloys are formed using direct and pulse current. In the case of Al-Cu and Al-Si alloys, the electrolyte used contains sulfuric acid and oxalic acid, meanwhile for Al the electrolyte contains sulfuric acid only. Al-Cu alloy was submitted to a heat treatment in order to decrease the effect of inter metallic phase theta upon the anodic film structure. Fractured samples were observed using a field emission gun scanning electron microscope JSM-6330F at (LME)/Brazilian Synchrotron Light Laboratory (LNLS), Campinas, SP, Brazil. The oxide film images enable evaluation of the pore size and form with a resolution similar to the transmission electron microscope (TEM) resolution. It is also observed that the anodizing process using pulse current produces an irregular structure of pore walls, and by direct cur-rent it is produced a rectilinear pore wall. (c) 2005 Elsevier B.V. All rights reserved.

Soil CO2 emission and its relation to soil properties in sugarcane areas under Slash-and-burn and Green harvest

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of target bias on magnetic field enhanced plasma immersion ion implantation

Recent studies have demonstrated that sheath dynamics in plasma immersion ion implantation (PIII) is significantly affected by an external magnetic field, especially in the case when the magnetic field is parallel to the workpiece surface or intersects it at small angles. In this work we report the results from two-dimensional, particle-in-cell (PIC) computer simulations of magnetic field enhanced plasma immersion implantation system at different bias voltages. The simulations begin with initial low-density nitrogen plasma, which extends with uniform density through a grounded cylindrical chamber. Negative bias voltage is applied to a cylindrical target located on the axis of the vacuum chamber. An axial magnetic field is created by a solenoid installed inside the target holder. A set of simulations at a fixed magnetic field of 0.0025 T at the target surface is performed. Secondary electron emission from the target subjected to ion bombardment is also included. It is found that the plasma density around the cylindrical target increases because of intense background gas ionization by the electrons drifting in the crossed E x B fields. Suppression of the sheath expansion and increase of the implantation current density in front of the high-density plasma region are observed. The effect of target bias on the sheath dynamics and implantation current of the magnetic field enhanced PIII is discussed. (C) 2007 Elsevier B.V. All rights reserved.

Numerical simulation of magnetic field enhanced plasma immersion ion implantation

The behavior of plasma and sheath characteristics under the action of an applied magnetic field is important in many applications including plasma probes and material processing. Plasma immersion ion implantation (PIII) has been developed as a fast and efficient surface modification technique of complex shaped three-dimensional objects. The PIII process relies on the acceleration of ions across a high-voltage plasma sheath that develops around the target. Recent studies have shown that the sheath dynamics is significantly affected by an external magnetic field. In this work we describe a two-dimensional computer simulation of magnetic field enhanced plasma immersion implantation system. Negative bias voltage is applied to a cylindrical target located on the axis of a grounded cylindrical vacuum chamber filled with uniform nitrogen plasma. An axial magnetic field is created by a solenoid installed inside the cylindrical target. The computer code employs the Monte Carlo method for collision of electrons and neutrals in the plasma and a particle-in-cell (PIC) algorithm for simulating the movement of charged particles in the electromagnetic field. Secondary electron emission from the target subjected to ion bombardment is also included. It is found that a high-density plasma region is formed around the cylindrical target due to the intense background gas ionization by the magnetized electrons drifting in the crossed ExB fields. An increase of implantation current density in front of high density plasma region is observed. (C) 2007 Elsevier B.V. All rights reserved.

The influence of leukocytospermia on the outcomes of assisted reproductive technology

Background: It is not well established whether the increased number of leukocytes in the seminal fluid impairs the outcomes of assisted reproductive technology (ART). This investigation analysed the outcomes of the intracytoplasmic sperm injection (ICSI) and intracytoplasmic morphologically selected sperm injection (IMSI) cycles in couples in which the male partner exhibited leukocytospermia.Methods: A total of 100 cycles in 100 couples were included in this study. For the ICSI or IMSI procedures, the patients were divided into two groups according to the presence or absence of leukocytospermia and then matched by (female) age:- ICSI: Group I (n = 25): Leukocytospermia - semen samples with a leukocyte count of greater than or equal to 1 x 10(6)/mL; and Group II (n = 25): Non-leukocytospermia - semen samples with a leukocyte count < 1 x 10(6)/mL.- IMSI: Group I (n = 25): Leukocytospermia; and Group II (n = 25): Non-leukocytospermia.The endpoints included the rates of fertilisation, implantation, clinical pregnancy, miscarriage, ongoing pregnancy and live birth. Student's t-tests, Mann-Whitney tests and Chi-square tests were performed, and P < 0.05 was considered significant.Results: The data from the ICSI groups showed that leukocytospermia did not have a negative influence on the rates of fertilisation (Group I: 57.9+/-30.2%, Group II: 61.9+/-27.7%; P = 0.74), implantation (Group I: 12.3%; Group II: 13.5%; P = 0.93), clinical pregnancy (Group I: 24%; Group II: 24%; P = 1.0), miscarriage ( Group I: 0, Group II: 0), ongoing pregnancy (Group I: 24%; Group II: 24%; P = 1.0), or live births (Group I: 24%; Group II: 24%; P = 1.0). Similarly, the data from the IMSI groups also showed that the leukocytospermia did not have a negative influence on the rates of fertilisation (Group I: 67.6+/-24.6%, Group II: 59.5+/-28.1%; P = 0.36), implantation (Group I: 17.5%; Group II: 16.7%; P = 0.90), clinical pregnancy (Group I: 28%; Group II: 24%; P = 1.0), miscarriage (Group I: 14.3%; Group II: 0; P = 0.33), ongoing pregnancy (Group I: 24%; Group II: 24%; P = 1.0), or live births (Group I: 24%, 6/25; Group II: 24%, 6/25; P = 1.0).Conclusions: The results indicate that the leukocytospermia may not have a negative effect on the outcomes of ICSI or IMSI cycles. Nevertheless, it seems that it is necessary to more precisely determine the effects, if any, of seminal leukocytes on fertilisation and implantation processes. Such efforts will help to establish a more reliable leukocyte threshold, which could eventually demonstrate whether there is a negative influence on the ART procedures.

Calculation of the vacuum pressure gradient in field emission displays

The usual design of field-emission displays (FEDs) often results in high vacuum pressure gradients inside the glass plates of the device, and this is the main limitation to the widespread availability of large area FEDs. In this paper, we perform theoretical calculations using the finite element method for determining the pressure distributions in several pumping configurations, including a new FED configuration known as porous FED or pFED. The approach here is capable of clarifying the design issues influencing the final pressure relevant to the field-emission display devices. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Yttrium oxysulfide nanosized spherical particles doped with Yb and Er or Yb and Tm: efficient materials for up-converting phosphor technology field

This work reports on the preparation, structural and luminescent studies of nanosized up-converter phosphors Y2O2S:Yb(4%), Er(0.1%) and Y2O2S:Yb(4%), Tm(0.1%),both from polymeric and basic carbonate precursors. The precursors were submitted to a sulphuration process that was previously developed for oxysulfide preparation from basic carbonate. From XRD data, all phosphors presented the oxysulfide phase and the mean crystallite size estimated from the Scherrer formula in the range of 15-20 nm. Polymeric precursor leads to the smallest crystallite size independent on the doping ion. SEM and TEM results confirmed that basic carbonate leads to spherical particles with narrow size distribution and mean diameter of 150 nm, and polymeric precursor smaller spherical particles with diameter between 20 and 40 nm. Up-conversion studies under 980 nm laser excitation showed that Er-doped phosphors present strong green emission related to H-2(11/2), S-4(3/2) --> I-4(15/2) Er transitions as well as the red ones, F-4(9/2) --> I-4(15/2). Tm-doped samples show strong blue emission assigned to (1)G(4) --> H-3(6) and also the red ones, related to (1)G(4) --> F-3(4). Therefore, the sulphuration method was successfully applied to prepare nanosized and nanostructured blue and green up-converter oxysulfide phosphors starting from basic carbonate and polymeric precursors. (C) 2003 Elsevier B.V. All rights reserved.

On-line determination of Sb(III) and total Sb using baker's yeast immobilized on polyurethane foam and hydride generation inductively coupled plasma optical emission spectrometry

The yeast Saccharomyces cerevisiae was immobilized in cubes of polyurethane foam and the ability of this immobilized material to separate Sb(III) and Sb(V) was investigated. A method based on sequential determination of total Sb (after on-line reduction of Sb(V) to Sb(III) with thiourea) and Sb(Ill) (after on-line solid-liquid phase extraction) by hydride generation inductively coupled plasma optical emission spectrometry is proposed. A flow system assembled with solenoid valves was used to manage all stages of the process. The effects of pH, sample loading and elution flow rates on solid-liquid phase extraction of Sb(III) were evaluated. Also, the parameters related to online pre-reduction (reaction coil and flow rates) were optimized. Detection limits of 0.8 and 0.15 mu g L-1 were obtained for total Sb and Sb (III), respectively. The proposed method was applied to the analysis of river water and effluent samples. The results obtained for the determination of total Sb were in agreement with expected values, including the river water Standard Reference Material 1640 certified by the National Institute of Standards and Technology (NIST). Recoveries of Sb(III) and Sb(V) in spiked samples were between 81 19 and I I I 15% when 120 s of sample loading were used. (c) 2006 Elsevier B.V. All rights reserved.

Effect of tannin levels in sorghum silage and concentrate supplementation on apparent digestibility and methane emission in beef cattle

This study evaluated the effect of diets containing sorghum silages with higher (HT) and lower-tannin (LT) concentrations supplemented with concentrate or urea on intake, digestibility, ruminal digestibility, methane emission and rumen parameters in beef cattle. Four treatments were distributed according to a 2 x 2 factorial arrangement in a duplicate 4 x 4 Latin square: LT sorghum silage + urea, LT sorghum silage + concentrate, HT sorghum silage + urea, and HT sorghum silage + concentrate. Total digestibility of the organic matter was higher when concentrate was included in the diet (0.749 and 0.753 in the LT and HT treatments, respectively). It was observed lower ruminal apparent digested matter of neutral detergent fiber in HT diets. There was no effect of tannin levels on digestibility and methane emission. The supplementation with concentrate in the LT diet decreased gas losses as a function of gross energy intake in comparison to the supplementation of the diet with urea. These results suggest the potential of concentrate supplementation to minimize energy loss as methane emission by ruminants and increase the efficiency of energy utilization. (c) 2006 Elsevier B.V. All rights reserved.

Distributed feedback multipeak laser emission in Rhodamine 6G doped organic-inorganic hybrids

Organic-inorganic hybrid materials were prepared from an ureasil precursor (ureapropyltriethoxysilane designated as UPTES) and acrylic acid modified zirconium (IV) n-propoxide. Thin films containing rhodamine 6G (Rh6G) were prepared by spin-coating on glass substrates with different Zr:Si molar ratios (Zr:Si = 75:25, 50:50 and 25:75). Refractive index, thickness, number of propagating modes and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm wavelengths by the prism coupling technique. Distributed feedback (DFB) laser effect was observed and studied as a function of films thickness and refractive index.

Multiwavelength visible and white light generation by upconversion emission in Ho/Tm/Yb triply doped fluorogermanate glass-ceramic

Energy transfer excited multiwavelength visible upconversion emission and white light generation is described in a single sample of PbGeO(3)-PbF(2)-CdF(2) glass-ceramic triply doped With Ho/Tm/Yb under single infrared laser excitation. Blue (475 nm), green (540 mn), and red (650 nm), upconversion luminescence signals are generated, and the emissions are assigned, respectively, to thulium ((1)G(4)-(3)H(6)), and holmium ((5)S(2);(5)F(4)) -> (5)I(8), (5)F(5) -> (5)I(8)) ions transitions, both excited via successive energy transfers from ytterbium ions. It is experimentally shown that with a proper combination of the rare earth ions contents, white light may be produced, with the simultaneous generation of fluorescence with controllable intensities at the wavelengths of the three primary colours in a single sample and using a single near-infrared excitation source.

On-line redox speciation analysis of antimony using L-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Atmospheric emission of reactive nitrogen during biofuel ethanol production

This paper evaluates emissions to the atmosphere of biologically available nitrogen compounds in a region characterized by intensive sugar cane biofuel ethanol production. Large emissions of NH(3) and NO,, as well as particulate nitrate and ammonium, occur at the harvest when the crop is burned, with the amount of nitrogen released equivalent to similar to 35% of annual fertilizer-N application. Nitrogen oxides concentrations show a positive association with fire frequency, indicating that biomass burning is a major emission source, with mean concentrations of NO, doubling in the dry season relative to the wet season. During the dry season biomass burning is a source of NH3, with other sources (wastes, soil, biogenic) predominant during the wet season. Estimated NO(2)-N, NH(3)-N, NO(3)(-)-N and NH(4)(+)-N emission fluxes from sugar cane burning in a planted area,of ca. 2.2 x 10(6) ha are 11.0, 1.1, 0.2, and 1.2 Gg N yr(-1), respectively.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

A preliminary physicochemical, exergetic and economic study of hydrogen production utilizing glycerol

This work has as objective to demonstrate technical and economic viability of hydrogen production utilizing glycerol. The volume of this substance, which was initially produced by synthetic ways (from oil-derived products), has increased dramatically due mainly to biodiesel production through transesterification process which has glycerol as main residue. The surplus amount of glycerol has been generally utilized to feed poultry or as fuel in boilers, beyond other applications such as production of soaps, chemical products for food industry, explosives, and others. The difficulty to allocate this additional amount of glycerol has become it in an enormous environment problem, in contrary to the objective of biodiesel chain, which is to diminish environmental impact substituting oil and its derivatives, which release more emissions than biofuels, do not contribute to CO2-cycle and are not renewable sources. Beyond to utilize glycerol in combustion processes, this material could be utilized for hydrogen production. However, a small quantity of works (theoretical and experimental) and reports concerning this theme could be encountered. Firstly, the produced glycerol must be purified since non-reacted amounts of materials, inclusively catalysts, contribute to deactivate catalysts utilized in hydrogen production processes. The volume of non-reacted reactants and non-utilized catalysts during transesterification process could be reutilized. Various technologies of thermochemical generation of hydrogen that utilizes glycerol (and other fuels) were evaluated and the greatest performances and their conditions are encountered as soon as the most efficient technology of hydrogen production. Firstly, a physicochemical analysis must be performed. This step has as objective to evaluate the necessary amount of reactants to produce a determined volume of hydrogen and determine thermodynamic conditions (such as temperature and pressure) where the major performances of hydrogen production could be encountered. The calculations are based on the process where advance degrees are found and hence, fractions of products (especially hydrogen, however, CO2, CO, CH4 and solid carbon could be also encountered) are calculated. To produce 1 Nm3/h of gaseous hydrogen (necessary for a PEMFC - Proton Exchange Membrane Fuel Cell - containing an electric efficiency of about 40%, to generate 1 kWh), 0,558 kg/h of glycerol is necessary in global steam reforming, 0,978 kg/h of glycerol in partial oxidation and cracking processes, and 0,782 kg/h of glycerol in autothermal reforming process. The dry reforming process could not be performed to produce hydrogen utilizing glycerol, in contrary to the utilization of methane, ethanol, and other hydrocarbons. In this study, steam reforming process was preferred due mainly to higher efficiencies of production and the need of minor amount of glycerol as cited above. In the global steam reforming of glycerine, for one mole of glycerol, three moles of water are necessary to produce three moles of CO2 and seven moles of H2. The response reactions process was utilized to predict steam reforming process more accurately. In this mean, the production of solid carbon, CO, and CH4, beyond CO2 and hydrogen was predicted. However, traces of acetaldehyde (C2H2), ethylene (C2H4), ethylene glycol, acetone, and others were encountered in some experimental studies. The rates of determined products obviously depend on the adopted catalysts (and its physical and chemical properties) and thermodynamic conditions of hydrogen production. Eight reactions of steam reforming and cracking were predicted considering only the determined products. In the case of steam reforming at 600°C, the advance degree of this reactor could attain its maximum value, i.e., overall volume of reactants could be obtained whether this reaction is maintained at 1 atm. As soon as temperature of this reaction increases the advance degree also increase, in contrary to the pressure, where advance degree decrease as soon as pressure increase. The fact of temperature of reforming is relatively small, lower costs of installation could be attained, especially cheaper thermocouples and smaller amount of thermo insulators and materials for its assembling. Utilizing the response reactions process in steam reforming, the predicted volumes of products, for the production of 1 Nm3/h of H2 and thermodynamic conditions as cited previously, were 0,264 kg/h of CO (13% of molar fraction of reaction products), 0,038 kg/h of CH4 (3% of molar fraction), 0,028 kg/h of C (3% of molar fraction), and 0,623 kg/h of CO2 (20% of molar fraction). Through process of water-gas shift reactions (WGSR) an additional amount of hydrogen could be produced utilizing mainly the volumes of produced CO and CH4. The overall results (steam reforming plus WGSR) could be similar to global steam reforming. An attention must to be taking into account due to the possibility to produce an additional amount of CH4 (through methanation process) and solid carbon (through Boudouard process). The production of solid carbon must to be avoided because this reactant diminishes (filling the pores) and even deactivate active area of catalysts. To avoid solid carbon production, an additional amount of water is suggested. This method could be also utilized to diminish the volume of CO (through WGSR process) since this product is prejudicial for the activity of low temperature fuel cells (such as PEMFC). In some works, more three or even six moles of water are suggested. A net energy balance of studied hydrogen production processes (at 1 atm only) was developed. In this balance, low heat value of reactant and products and utilized energy for the process (heat supply) were cited. In the case of steam reforming utilizing response reactions, global steam reforming, and cracking processes, the maximum net energy was detected at 700°C. Partial oxidation and autothermal reforming obtained negative net energy in all cited temperatures despite to be exothermic reactions. For global steam reforming, the major value was 114 kJ/h. In the case of steam reforming, the highest value of net energy was detected in this temperature (-170 kJ/h). The major values were detected in the cracking process (up to 2586 kJ/h). The exergetic analysis has as objective, associated with physicochemical analysis, to determine conditions where reactions could be performed at higher efficiencies with lower losses. This study was performed through calculations of exergetic and rational efficiencies, and irreversibilities. In this analysis, as in the previously performed physicochemical analysis, conditions such as temperature of 600°C and pressure of 1 atm for global steam reforming process were suggested due to lower irreversibility and higher efficiencies. Subsequently, higher irreversibilities and lower efficiencies were detected in autothermal reforming, partial oxidation and cracking process. Comparing global reaction of steam reforming with more-accurate steam reforming, it was verified that efficiencies were diminished and irreversibilities were increased. These results could be altered with introduction of WGSR process. An economic analysis could be performed to evaluate the cost of generated hydrogen and determine means to diminish the costs. This analysis suggests an annual period of operation between 5000-7000 hours, interest rates of up to 20% per annum (considering Brazilian conditions), and pay-back of up to 20 years. Another considerations must to be take into account such as tariffs of utilized glycerol and electricity (to be utilized as heat source and (or) for own process as pumps, lamps, valves, and other devices), installation (estimated as US$ 15.000 for a plant of 1 Nm3/h) and maintenance cost. The adoption of emission trading schemes such as carbon credits could be performed since this is a process with potential of mitigates environment impact. Not considering credit carbons, the minor cost of calculated H2 was 0,16288 US$/kWh if glycerol is also utilized as heat sources and 0,17677 US$/kWh if electricity is utilized as heat sources. The range of considered tariff of glycerol was 0-0,1 US$/kWh (taking as basis LHV of H2) and the tariff of electricity is US$ 0,0867 US$/kWh, with demand cost of 12,49 US$/kW. The costs of electricity were obtained by Companhia Bandeirante, localized in São Paulo State. The differences among costs of hydrogen production utilizing glycerol and electricity as heat source was in a range between 0,3-5,8%. This technology in this moment is not mature. However, it allows the employment generation with the additional utilization of glycerol, especially with plants associated with biodiesel plants. The produced hydrogen and electricity could be utilized in own process, increasing its final performance.