Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at -0.3 V versus Ag/AgCl(sat) a linear range from 7.5 x 10(-8) to 2.5 x 10(-6) mol L(-1) with detection limit of 3.1 x 10(-8) mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods. (c) 2006 Elsevier B.V. All rights reserved.

Order-disorder transformation in the Ni-4.49 at.% Al alloy

The order-disorder transformation in the Ni-4.49 at.% Al alloy was studied using electrical resistivity measurements, microhardness measurements, differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). The results confirmed the ordering behavior expected for Ni-Al dilute alloys and the suggested relation between resistivity changes and microhardness changes with antiferromagnetic spin ordering. The higher value obtained for the activation energy of vacancy migration was associated with a decrease in the Al concentration gradient near solute-depleted regions. (c) 2005 Elsevier B.V. All rights reserved.

Investigação da Interface Metal-Porcelana da Liga Ni-Cr-Mo Soldada a LASER

The interface formed between the metal and the porcelain of a LASER welded Ni-Cr-Mo alloy was studied. The characterization was carried out through optical microscopy, scanning electron microscopy, X-ray dispersive spectroscopy-EDS and mechanical testing by three-point flexion test-TPE in the region LASER welded with and without the porcelain. The porcelain adhesion with the alloy alone is possible after the oxidation of the metallic surface and subsequent application of an adhesive called opaco. The applied porcelain, on the base metal and fusion zone presented some distinct behaviors. After the TPF test the base metal presented fractures while that in the fusion zone was completely gone. One noticed that the region submitted to the LASER welding showed less porcelain adhesion than the region of the base metal due to the microestructural refinement of the fusion zone. These results can be evidenced by the EDS of the studied regions. The TPF had demonstrated that the Ni-Cr-Mo alloy submitted to the LASER welding, undergone significant alterations in its mechanical properties after the application of the porcelain.

Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determinação direta e simultânea de Al, As, Fe, Mn e Ni em cachaça por espectrometria de absorção atômica em forno de grafite

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

Synthesis, characterization and thermal behaviour of solid-state compounds of 2-methoxybenzoate with some bivalent transition metal ions

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

Synthesis, characterization and thermal behaviour of solid 2-methoxycinnamylidenepyruvate of some bivalent metal ions in CO2 and N2 atmospheres

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

The Ni-Cu-PGE sulfide ores of the komatiite-hosted Fortaleza de Minas deposit, Brazil: Evidence of hydrothermal remobilization

The Fortaleza de Minas Ni-Cu-PGE sulfide deposit is hosted by Archean komatiitic rocks of the Morro do Ferro greenstone belt, near the southwestern margin of the Sa (aFrancisco) over tildeo Francisco craton, Minas Gerais state, Brazil. The deposit contains 6 million tonnes of ore with an average grade of 2.2 wt% Ni, 0.4% Cu, 0.05% Co and 1.2 ppm PGE+Au, and comprises (i) a main orebody, which is metamorphosed, deformed and transposed along a regional shear zone, consisting mainly of disseminated, brecciated and stringer sulfide ores that are interpreted to be of early magmatic origin, and (ii) PGE-rich discordant veins that are hosted in N-S- and NE-SW-trending late faults that cross-cut the main orebody. The discordant PGE-rich ore (up to 4 ppm total PGE) is characterized by thin, discontinuous and irregular veins and lenses of massive sulfides hosted by serpentinite and talc schist, and is relatively undeformed if compared with the early types of ore. It is composed mainly of pyrrhotite, pentlandite, chalcopyrite, magnetite, carbonates, and amphiboles, with minor cobaltite-gersdorffite, sphalerite, ilmenite, and quartz, and rarely maucherite (Ni11Asg), tellurides and platinum-group minerals (PGM). Omeeite, irarsite, sperrylite, and Ni-bearing merenskyite are the main PGM, followed by minor amounts of testibiopalladite and an unknown phase containing Ru, Te, and As. The PGM occur either included in, or at the margins of, sulfides, sulfarsenides, silicates and oxides, or filling fractures in pyrrhotite, pentlandite, and chalcopyrite, suggesting that they started to precipitate with these minerals and continued to precipitate after the sulfides were formed. The mantle-normalized metal distribution of the two samples of discordant veins shows distinct patterns: one richer in Ni-Pd-Ir-Rh-Ru-Os and another with higher amounts of Cu-Pt-Bi. Both are strongly depleted in Cr if compared with the metamorphosed magmatic ore of this deposit, which follows the general Kambalda-type magmatic trend. on the basis of structural, mineralogical and geochemical evidence, we propose that the PGE-rich discordant ore may have formed by remobilization of metals from the deformed, metamorphosed magmatic orebody (which shows a depleted pattern in these elements) by reduced (pyrrhotite - pentlandite - pyrite are stable), neutral to alkaline and carbonic fluids (carbonate-stable). The PGE may have been transported as bisulfide complexes, and precipitated as tellurides (mainly Pd) and arsenides (Pt, Rh, Ru, Os, Ir) in the late N-S and NE-SW-trending faults owing to a decrease in the activity of S caused by the precipitation of sulfides in the veins.

Electrothermal AAS determination of Ni in soft drinks using Co as the internal standard

A method for the direct determination of Ni in soft drinks by graphite furnace atomic absorption spectrometry using a transversely heated graphite atomizer (THGA), Zeeman-effect background corrector, and Co as the internal standard (IS) is proposed. Magnesium nitrate was used to stabilize both Ni and Co. All diluted samples (1+1) in 0.2% (v/v) HNO3 and reference solutions [5.0-50 mu g L-1 Ni in 0.2% (v/v) HNO3] were spiked with 50 mu g L-1 Co. For a 20-mu L sample dispensed into the atomizer, correlations between the ratio of absorbance of Ni to absorbance of Co and the analyte concentration were close to 0.9996. The relative standard deviation of the measurements varied from 0.5 to 3.4% and 1.0 to 7.0% (n=12) with and without IS, respectively. Recoveries within 98-104% for Ni spikes were obtained using IS. The characteristic mass was calculated as 43 pg Ni and the limit of detection was 1.4 mu g L-1. The accuracy of the method was checked for the direct determination of Ni in soft drinks and the results obtained with IS were better than those without IS.

Spin reversal and magnetization jumps in ErMexMn1-xO3 perovskites (Me = Ni, Co)

The erbium-based manganite ErMnO3 has been partially substituted at the manganese site by the transition-metal elements Ni and Co. The perovskite orthorhombic structure is found from x(Ni) = 0.2-0.5 in the nickel-based solid solution ErNixMn1-xO3, while it can be extended up to x(Co) = 0.7 in the case of cobalt, provided that the synthesis is performed under oxygenation conditions to favor the presence of Co3+. Presence of different magnetic entities (i.e., Er3+, Ni2+, Co2+, Co3+, Mn3+, and Mn4+) leads to quite unusual magnetic properties, characterized by the coexistence of antiferromagnetic and ferromagnetic interactions. In ErNixMn1-xO3, a critical concentration x(crit)(Ni) = 1/3 separates two regimes: spin-canted AF interactions predominate at x < x(crit), while the ferromagnetic behavior is enhanced for x > x(crit). Spin reversal phenomena are present both in the nickel- and cobalt-based compounds. A phenomenological model based on two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall magnetic moment at low temperatures. In this model, the ferromagnetic transition-metal lattice, which orders at T-c, creates a strong local field at the erbium site, polarizing the Er moments in a direction opposite to the applied field. At low temperatures, when the contribution of the paramagnetic erbium sublattice, which varies as T-1, gets larger than the ferromagnetic contribution, the total magnetic moment changes its sign, leading to an overall ferrimagnetic state. The half-substituted compound ErCo0.50Mn0.50O3 was studied in detail, since the magnetization loops present two well-identified anomalies: an intersection of the magnetization branches at low fields, and magnetization jumps at high fields. The influence of the oxidizing conditions was studied in other compositions close to the 50/50 = Mn/Co substitution rate. These anomalies are clearly connected to the spin inversion phenomena and to the simultaneous presence of Co2+ and Co3+ magnetic moments. Dynamical aspects should be considered to well identify the high-field anomaly, since it depends on the magnetic field sweep rate. (C) 2006 Elsevier B.V. All rights reserved.

Simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by GFAAS

A method has been developed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by graphite furnace atomic absorption spectrometry (GFAAS) using a transversely heated graphite atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of analytes during the pyrolysis and atomization stages using the mixture Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3, and diluted ethanol (1 + 1, v/v) containing different nitric acid concentrations. With 5 rhog Pd + 3 mug Mg as the modifiers, pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1200 C and 2200degreesC respectively. For 20 muL of diluted sample (10 muL ethanol + 10 muL of 0.28 mol L-1 HNO3) dispensed into the graphite tube, analytical curves in the 2.0 - 50 mug L-1 Al, As, Cu, Fe, Mn, Ni ranges were established. The calculated characteristic masses were - 37 pg Al, 73 pg As, 31 pg Cu, 16 pg Fe, 9 pg Mn, and 44 pg Ni, and the lifetime of the tube was around 2 50 firings. The limits of detection (LOD) based on integrated absorbance were 1.2 mug L-1 Al, 2.5 mug L-1 As. 0.22 mug L-1 Cu, 1.6 L-1 Fe 0.20 mug L-1 Mn 1.1 mug L-1 Ni. The relatively standard deviations (n = 12) were less than or equal to 3%, less than or equal to 6%, less than or equal to 2%, less than or equal to 3.4%, less than or equal to 1.3%, and less than or equal to 2% for Al, As, Cu, Fe, Mn, and Ni, respectively, the recoveries of Al, As, Cu, Fe, Mn and Ni added to fuel ethanol samples varied from 77% to 112%, 92% to 114%, 104% to 113%, 73% to 116%, 91% to 122% and 93% to 116%, respectively. Accuracy was checked for Al, As, Cu, Fe, Mn, and Ni determination in 20 samples purchased at local gas stations in Araraquara city, Brazil. A paired t-test showed that the results were in agreement at the 95% confidence level with those obtained by single-element GFAAS.

Distribution of Cr, Ni, Cu, Cd and Pb in different molecular size of humic fractions extracted from water and sediment samples collected at Anhumas reservoir - Araraquara/SP

In this work was studied the distribution of Cr, Ni, Cu, Cd and Pb in humic fractions with different molecular size. The HS were extracted from waters (AHS), surface sediments (HESS), interface water sediment (HSIS) and bottom sediment (HSBS) collected in the Anhumas surface water collection reservoir, located in the district of Araraquara - São Paulo State Brazil. The humic substances were extracted by procedures recommended by International Humic Substances Society (IHSS). After purification by dialysis, the humic substances were fractionated using a multistage tangential flow ultrafiltration system. The fractionation patterns of HS characterized a mass distribution relatively uniform among the fractions with different molecular sizes, with larger values in the fractions F-2 (20.8%) and F-4 (23.8%), Except for the ions Pb(II) and Cu(II), which presented relatively higher concentrations in the fractions F-2 and F-4, respectively. In general, chromium, nickel, cadmium and lead have similar distributions in the five fractions with larger and medium molecular sizes (F-1 to F-5). With relation to the mass distributions in the different humic substances fractions extracted from sediment samples collected at three depth, they presented 42-48% of HS in the fractions with larger molecular sizes (F-1 and F-2), 29-31% in the middle fractions (F-3 and F-4) and 13-20% in the fractions with smaller molecular sizes (F-5 and F-6). In general, the metallic ions presented distributions similar among the respective fractions F-1 to F-6, Exceptions for Pb(II) and M(II) in surface sediment with concentrations relatively smaller in the fractions F-2 and F-4, respectively,

Thermal decomposition of crystalline Ni-II-Cr-III layered double hydroxide: A structural study of the segregation process

A structural study of the thermal evolution of Ni0.69Cr0.31(OH)(2)(CO3)(0.155)(.)nH(2)O into NiO and tetragonal NiCr2O4 is reported. The characteristic structural parameters of the two coexisting crystalline phases, as well as their relative abundance, were determined by Rietveld refinement of powder x-ray diffraction (PXRD) patterns. The results of the simulations allowed us to elucidate the mechanism of the demixing process of the oxides. It is demonstrated that nucleation of a metastable nickel chromite within the common oxygen framework of the parent Cr-III-doped bunsenite is the initial step of the cationic redistribution. The role that trivalent cations play in the segregation of crystalline spinels is also discussed.

Mixed ionic-electronic YSZ/Ni composite for SOFC anodes with high electrical conductivity

The preparation of the ZrO(2):8 mol % Y(2)O(3)/NiO (YSZ/NiO) composites by a modified liquid mixture technique is reported. Nanometric NiO particles dispersed over the yttria-stabilized zirconia (YSZ) were prepared, resulting in dense sintered specimens with no solid solution formation between the oxides. Such a feature allowed for the electrical characterization of the composites in a wide range of relative volume fraction, temperature, and oxygen partial pressure. The main results indicate that the composites have high electrical conductivity, and the transport properties in these mixed ionic-electronic (MIEC) composites are strongly dependent on the relative volume fraction of the phases, microstructure, and temperature. These parameters should hence be taken into consideration for the optimized design of MIEC composites for electrochemical applications. In this context, the composite was reduced under H(2) for the preparation of high-conductivity YSZ/Ni cermets for use as solid oxide fuel cell anode material with relatively low metal content. (c) 2005 the Electrochemical Society. [DOI:10.1149/1.2149312] All rights reserved.

Solid-state compounds of 2-chlorobenzylidenepyruvate with some bivalent metal ions - Synthesis, characterization and thermal behaviour

Solid-state M-2-Cl-BP, where M stands for Mn, Fe, Co, Ni, Cu, Zn and Pb and 2-Cl-BP is 2-chlorobenzylidenepyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), simultaneous thermogravimetry and differential thermal analysis (TG-DTA), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.