Evaluation of the use of multiple lines for determination of metals in water by inductively coupled plasma optical emission spectrometry with axial viewing

Inductively coupled plasma optical emission spectrometers (ICP DES) allow fast simultaneous measurements of several spectral lines for multiple elements. The combination of signal intensities of two or more emission lines for each element may bring such advantages as improvement of the precision, the minimization of systematic errors caused by spectral interferences and matrix effects. In this work, signal intensities for several spectral lines were combined for the determination of Al, Cd, Co, Cr, Mn, Pb, and Zn in water. Afterwards, parameters for evaluation of the calibration model were calculated to select the combination of emission lines leading to the best accuracy (lowest values of PRESS-Predicted error sum of squares and RMSEP-Root means square error of prediction). Limits of detection (LOD) obtained using multiple lines were 7.1, 0.5, 4.4, 0.042, 3.3, 28 and 6.7 mu g L(-1) (n = 10) for Al, Cd. Co, Cr, Mn, Pb and Zn, respectively, in the presence of concomitants. On the other hand, the LOD established for the most intense emission line were 16. 0.7, 8.4, 0.074. 23, 26 and 9.6 mu g L(-1) (n = 10) for these same elements in the presence of concomitants. The accuracy of the developed procedure was demonstrated using water certified reference material. The use of multiple lines improved the sensitivity making feasible the determination of these analytes according to the target values required for the current environmental legislation for water samples and it was also demonstrated that measurements in multiple lines can also be employed as a tool to verify the accuracy of an analytical procedure in ICP DES. (C) 2009 Elsevier B.V. All rights reserved.

Partial microwave-assisted wet digestion of animal tissue using a baby-bottle sterilizer for analyte determination by inductively coupled plasma optical emission spectrometry

A procedure for partial digestion of bovine tissue is proposed using polytetrafluoroethylene (PTFE) microvessels inside a baby-bottle sterilizer under microwave radiation for multi-element determination by inductively coupled plasma optical emission spectrometry (ICP OES). Samples were directly weighed in laboratory-made polytetrafluoroethylene vessels. Nitric acid and hydrogen peroxide were added to the uncovered vessels, which were positioned inside the baby-bottle sterilizer, containing 500 mL of water. The hydrogen peroxide volume was fixed at 100 mu L The system was placed in a domestic microwave oven and partial digestion was carried out for the determination of Ca, Cu, Fe. Mg, Mn and Zn by inductively coupled plasma optical emission spectrometry. The single-vessel approach was used in the entire procedure, to minimize contamination in trace analysis. Better recoveries and lower residual carbon content (RCC) levels were obtained under the conditions established through a 2(4-1) fractional factorial design: 650 W microwave power, 7 min digestion time, 50 mu L nitric acid and 50 mg sample mass. The digestion efficiency was ascertained according to the residual carbon content determined by inductively coupled plasma optical emission spectrometry. The accuracy of the proposed procedure was checked against two certified reference materials. (C) 2009 Elsevier B.V. All rights reserved.

Fractionation of Zn, Cd and Pb in a Tropical Soil After Nine-Year Sewage Sludge Applications

A long-term field experiment was carried out in the experiment farm of the Sao Paulo State University, Brazil, to evaluate the phytoavailability of Zn, Cd and Pb in a Typic Eutrorthox soil treated with sewage sludge for nine consecutive years, using the sequential extraction and organic matter fractionation methods. During 2005-2006, maize (Zea mays L.) was used as test plants and the experimental design was in randomized complete blocks with four treatments and five replicates. The treatments consisted of four sewage sludge rates (in a dry basis): 0.0 (control, with mineral fertilization), 45.0, 90.0 and 127.5 t ha(-1), annually for nine years. Before maize sowing, the sewage sludge was manually applied to the soil and incorporated at 10 cm depth. Soil samples (0-20 cm layer) for Zn, Cd and Pb analysis were collected 60 days after sowing. The successive applications of sewage sludge to the soil did not affect heavy metal (Cd and Pb) fractions in the soil, with exception of Zn fractions. The Zn, Cd and Pb distributions in the soil were strongly associated with humin and residual fractions, which are characterized by stable chemical bonds. Zinc, Cd and Pb in the soil showed low phytoavailability after nine-year successive applications of sewage sludge to the soil.

Obtaining and stability verification of superconducting phases of the Nb-Al and Nb-Sn systems by mechanical alloying and low-temperature heat treatments

The development of Nb(3)Al and Nb(3)Sn superconductors is of great interest for the applied superconductivity area. These intermetallics composites are obtained normally by heat treatment reactions at high temperature. Processes that allow formation of the superconducting phases at lower temperatures (<1000 degrees C), particularly for Nb(3)Al, are of great interest. The present work studies phase formation and stability of Nb(3)Al and Nb(3)Sn superconducting phases using mechanical alloying (high energy ball milling). Our main objective was to form composites near stoichiometry, which could be transformed into the superconducting phases using low-temperature heat treatments. High purity Nb-Sn and Nb-Al powders were mixed to generate the required superconducting phases (Nb-25at.%Sn and Nb-25at.%Al) in an argon atmosphere glove-box. After milling in a Fritsch mill, the samples were compressed in a hydraulic uniaxial press and encapsulated in evacuated quartz tubes for heat treatment. The compressed and heat treated samples were characterized using X-ray diffractometry. Microstructure and chemical analysis were accomplished using scanning electron microscopy and energy dispersive spectrometry. Nb(3)Al XRD peaks were observed after the sintering at 800 degrees C for the sample milled for 30 h. Nb(3)Sn XRD peaks could be observed even before the heat treatment. (C) 2009 Elsevier B.V. All rights reserved.

Determination of nutritional and toxic elements in pasteurized bovine milk from Vale do Paraiba region (Brazil)

Throughout the year of 2004, 54 samples (I L each) were collected from commercial sources in the Vale do Paraiba region (eastern portion of Sao Paulo State, Brazil). The concentrations of (Ca, Cr, Cu, Fe, Mg, Mn, Ni, Se, Zn, Cd and Pb) in these samples were analyzed by two atomic-absorption spectroscopy (AAS) methods. Ca, Cu, Fe, Mg and Zn were determined by flame atomic-absorption spectroscopy (FAAS) and (Cd, Cr, Mn, Ni, Pb and Se) were determined by electrothermal atomic-absorption spectroscopy (ETAAS). Tests to determine and quantify essential, nonessential and toxic elements present in bovine milk are rare in Brazil, especially so for Vale do Paraiba region. Tests were performed on standard NIST-certified milk-powder to validate the reliability of subsequently collected analytical data. Ca presented a lower recovery value (85.3%). The finding for Ca macro-nutrient was found to be below recommended international standards (1300 mg/L) for all samples possibly due to milk heterogeneity and losses in the pasteurization process. Significant results for Pb were found in all milk samples with average values at 0.230 mg/L from a minimum of 0.062 mg/L and maximum of 0.476 mg/L (C) 2009 Elsevier Ltd. All rights reserved.

Spontaneous infiltrations of compound systems of Y(2)O(3), Sm(2)O(3), RE(2)O(3), Al(2)O(3) and AIN in SiC ceramics

Silicon carbide ceramics (SiC) are used in different applications in the engineering area due to the excellent properties, mainly in high temperatures. They are usually obtained by liquid-phase sintering enabling to form volatile products and, consequently, defects. The present work aims at studying the obtention of SiC ceramics by spontaneous infiltration using a eutectic composition of the Al(2)O(3)/Y(2)O(3), AIN/Y(2)O(3), Al(2)O(3)/Sm(2)O(3), AlN/Sm(2)O(3), Al(2)O(3)/RE(2)O(3) and AlN/RE(2)O(3) Systems. RE(2)O(3) is the concentrate of the rare-earth oxide obtained from Xenotime ore. Infiltration tests were carried out in argon atmosphere, graphite crucibles, in several temperatures near the melting point of each system, varying from 2.5 to 60 min. It was observed that Al(2)O(3)/Y(2)O(3), Al(2)O(3)/SM(2)O(3), AlN/SM(2)O(3) and Al(2)O(3)/RE(2)O(3) systems do not infiltrate appropriately and the AlN/Y(2)O(3) and AlN/RE(2)O(3) systems infiltrated spontaneously more than 20 mm; however, the first one presented a higher degree of infiltration, approximately 97%. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Thermal, structural and optical properties of Al(2)CoO(4)-Crocoite composite nanoparticles used as pigments

Al(2)CoO(4)-PbCrO(4) and Al(2)CoO(4)-Pb(2)CrO(5) crystalline powders in different proportions were obtained by the polymeric precursor method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of overlapping decomposition reactions due to different exothermal events, which were identified as H(2)O and NO(x) elimination and polymer pyrolysis. The X-ray diffraction patterns of the xAl(2)CoO(4)-(1 - x)PbCrO(4) and xAl(2)CoO(4)-(1 - x)Pb(2)CrO(5) mixed compounds, with x = 1, 0.75, 0.5, 0.25 and 0, were obtained in the crystalline form with their respective phases, and proved consistent with the nominal compositions. The synthesis of these two systems yielded nine different colors and shades.

Selection of new glass-forming compositions in Al-La system using a combination of topological instability and thermodynamic criteria

A combination of an extension of the topological instability ""lambda criterion"" and a thermodynamic criterion were applied to the Al-La system, indicating the best range of compositions for glass formation. Alloy compositions in this range were prepared by melt-spinning and casting in an arc-melting furnace with a wedge-section copper mold. The GFA of these samples was evaluated by X-ray diffraction, differential scanning calorimetry and scanning electron microscopy. The results indicated that the gamma* parameter of compositions with high GFA is higher, corresponding to a range in which the lambda parameter is greater than 0.1, which are compositions far from Al solid solution. A new alloy was identified with the best GFA reported so far for this system, showing a maximum thickness of 286 mu m in a wedge-section copper mold. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Mechanical properties and cytotoxicity of 3Y-TZP bioceramics reinforced with Al(2)O(3) particles

The influence of Al(2)O(3) addition and sintering parameters on the mechanical properties and cytotoxicity of tetragonal ZrO(2)-3 mol% Y(2)O(3) ceramics was evaluated. Samples containing 0, 10, 20 and 30 wt.% of Al(2)O(3) particles were prepared by cold uniaxial pressing (80 MPa) and sintered in air at 1500, 1550 and 1600 degrees C for 120 min. The effects of the sintering conditions on the microstructure were analyzed by X-ray diffraction analysis and scanning electron microscopy. Hardness and fracture toughness were determined by the Vickers indentation method and the mechanical resistance by four-point bending tests. As a preliminary biological evaluation, ""in vitro"" cytotoxicity tests were realized to determine the cytotoxic level of the ZrO(2)-Al(2)O(3) composites, using the neutral red uptake method with NCTC clones L929 from the American Type Culture Collection (ATCC) bank. Fully dense ceramic materials were obtained with a hardness ranging between 1340 HV and 1585 HV, depending on the amount of Al(2)O(3) in the ZrO(2) matrix. On the other hand, no significant influence of the Al(2)O(3) addition on fracture toughness was observed, exhibiting values near 8 MPa m(1/2) for all compositions and sintering conditions studied. The non-cytotoxic behavior, the elevated fracture toughness, the good bending strength (sigma(f) = 690 MPa) and the elevated Weibull`s modulus (m = 11) exhibited by the material, show that these ceramic composites are highly suitable biomaterials for dental implant applications. (C) 2008 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Properties of Y-TZP/Al(2)O(3) ceramic nanocomposites obtained by high-energy ball milling

In this work, the synthesis of Y(2)O(3) stabilized tetragonal zirconia polycrystals (Y-TZP)-alumina (Al(2)O(3)) powder mixture was performed by high-energy ball milling and the sintering behavior of this composite was investigated. In order to understand the phase transformations occurring during ball milling, samples were collected after different milling times, from 1 to 60 h. The milled powders were compacted by cold uniaxial pressing and sintered at 1400 and 1600 degrees C. Both powders and sintered samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry analysis (EDS) and mechanical properties. Fully dense samples were obtained after sintering at 1600 degrees C, while the samples sintered at 1400 degrees C presented a full density for powder mixtures milled for 30 and 60 h. Fracture toughness and Vickers hardnessvalues of the Y-T-ZP/Al(2)O(3) nanocomposite were improved due to dispersed Al(2)O(3) grains and reduced ZrO(2) grain size. Samples sintered at 1400 degrees C, based on powders milled for 60 h, presented high K(IC) and hardness values near to 8.0 Mpan(1/2) and 15 GPa, respectively (C) 2008 Elsevier B.V. All rights reserved

Crystallographic characterization of silicon nitride ceramics sintered with Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) additions

Silicon nitride ceramics were sintered using Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) (E(2)O(3) denotes a mixed oxide Of Y(2)O(3) and rare-earth oxides) as sintering additives. The intergranular phases formed after sintering was investigated using high-resolution X-ray diffraction (HRXRD). The use of synchrotron radiation enabled high angular resolution and a high signal to background ratio. Besides the appearance Of beta-Si(3)N(4) phase the intergranular phases Y(3)Al(5)O(12) (YAG) and Y(2)SiO(5) were identified in both samples. The refinement of the structural parameters by the Rietveld method indicated similar crystalline structure Of beta-Si(3)N(4) for both systems used as sintering additive. On the other hand, the intergranular phases Y(3)Al(5)O(12) and Y(2)SiO(5) shown a decrease of the lattice parameters, when E(2)O(3) was used as additive, indicating the formation of solid solutions of E(3)Al(5)O(12) and E(2)SiO(5), respectively. (C) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Crystallisation behaviour and glass-forming ability in Al-La-Ni system

The crystallisation behaviour for alloys in the Al-rich corner in the Al-La-Ni system is reported in this paper Alloys were selected based on the topological instability criterion (lambda criterion) calculated from the alloy composition and metallic radii of the alloying elements and aluminum Amorphous ribbons were produced by melt-spinning and the crystallisation reactions were analysed by X-ray diffraction and calorimetry The results showed that increasing the values of lambda from 0.072 to 0.16 resulted in the following changes in the crystallisation behaviour, as predicted by the lambda criterion (a) nanocrystallisation of alpha-Al for the alloy composition corresponding to lambda = 0 072 and (b) detection of the glass transition temperature, T(g), for the alloys with composition close to lambda approximate to 0.1 line. For compositions corresponding to both ends of the lambda approximate to 0 1 line (near the binaries lines) T(g) could be detected only in the ""intermediary"" central region, and the alloy we produced in this region was considered the best glass former for the Al-rich corner Also, except for the alloys with the highest NI content, crystallisation proceeded by two distinct exothermic peaks which are typical of nanocrystallisation transformation. These behaviours are discussed in terms of compositional (lambda parameter) and topological aspects to account for cluster formation in the amorphous phase. Crown Copyright (C) 2009 Published by Elsevier B V All rights reserved

Dynamic behavior analysis of drill-threading process when machining AISI Al-Si-Cu(4) alloy

Conventional threading operations involve two distinct machining processes: drilling and threading. Therefore, it is time consuming for the tools must be changed and the workpiece has to be moved to another machine. This paper presents an analysis of the combined process (drilling followed by threading) using a single tool for both operations: the tap-milling tool. Before presenting the methodology used to evaluate this hybrid tool, the ODS (operating deflection shapes) basics is shortly described. ODS and finite element modeling (FEM) were used during this research to optimize the process aiming to achieve higher stable machining conditions and increasing the tool life. Both methods allowed the determination of the natural frequencies and displacements of the machining center and optimize the workpiece fixture system. The results showed that there is an excellent correlation between the dynamic stability of the machining center-tool holder and the tool life, avoiding a tool premature catastrophic failure. Nevertheless, evidence showed that the tool is very sensitive to work conditions. Undoubtedly, the use of ODS and FEM eliminate empiric decisions concerning the optimization of machining conditions and increase drastically the tool life. After the ODS and FEM studies, it was possible to optimize the process and work material fixture system and machine more than 30,000 threaded holes without reaching the tool life limit and catastrophic fail.

Oxidation and abrasive wear of Fe-Si and Fe-Al intermetallic alloys

In the present work, intermetallic alloys Fe-Si and Fe-Al (Fe(3)Si-C-Cr and Fe(3)Al-C), produced by induction melting, were evaluated regarding their oxidation and abrasive resistance. The tests performed were quasi-isothermal oxidation, cyclic oxidation, and dry sand/rubber wheel abrasion. As reference, the ASTM A297-HH grade stainless steel was tested in the same conditions. In the oxidation tests, the Fe-Al based alloy presented the lowest oxidation rate, and the Fe-Si based alloy achieved the best results in the abrasion test, showing better performance than the HH type stainless steel.

Design and Characterization of Novel Wear Resistant Multilayer CVD Coatings with Improved Adhesion Between Al(2)O(3) and Ti(C,N)

Multilayer CVD coatings for high speed cutting applications were designed to achieve high wear and heat resistance during machining of steel alloys. In this work the microstructure and cutting performance of these novel multilayer CVD coatings are investigated and compared with standard CVD multilayer coatings. 3D-FIB tomography is used to characterize the microstructure of the layers, especially the transition between the Ti(C,N) and the Al(2)O(3) layer. The 3D reconstruction of the surface of the Ti(C,N) layer shows the formation of protruded Ti(C,N) grains with a very particular architecture, which penetrate into the Al(2)O(3) top-layer, providing a mechanical anchoring between both layers. Cemented carbides coated with the novel CVD multilayer present reduced crater and flank wear as well as improved adherence between the Al(2)O(3) top-layer and the Ti(C,N) layer leading to a dramatic improvement of cutting performance.