Preliminary studies of laser-induced breakdown spectrometry for the determination of Ba, Cd, Cr and Pb in toys

The performance of laser-induced breakdown spectrometry (LIBS) for the determination of Ba, Cd, Cr and Pb in toys has been evaluated by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with intensified charge-coupled device detector. Samples were purchased in different cities of Sao Paulo State market and analyzed directly without sample preparation. Laser-induced breakdown spectrometry experimental conditions (number of pulses, delay time. integration time gate and pulse energy) were optimized by using a Doehlert design. Laser-induced breakdown spectrometry signals correlated reasonably well with inductively coupled plasma optical emission spectrometry (ICP OES) concentrations after microwave-assisted acid digestion of selected samples. Thermal analysis was used for polymer identification and scanning electron microscopy to Visualize differences in crater geometry of different polymers employed for toy fabrication. Results indicate that laser-induced breakdown spectrometry can be proposed as a rapid screening method for investigation of potentially toxic elements in toys. The unique application of laser-induced breakdown spectrometry for identification of contaminants in successive layers of ink and polymer is also demonstrated. (C) 2009 Elsevier B.V. All rights reserved.

Sources of particulate matter: emission profile of biomass burning

Biomass burning is an important source of atmospheric Particulate Matter (PM) in Brazil: the burning of forests in the northwest and of sugar cane plantations in the southeast are important examples. The objective of this work is the measurement of the PM emission profile of burning of sugar cane and other characteristic vegetative burning in the region of Sao Carlos-SP/Brazil. Samples of PM(10) and PM(2.5) were collected in different conditions, including small laboratory controlled burnings and real ones. The samples were analysed by X-Ray Fluorescence (XRF) and 14 chemical elements quantified. t-Student tests were performed to compare the obtained profiles, using as a reference a vegetative burn profile taken from the USEPA data bank SPECIATE. All measured profiles presented significant amounts of Cl and K, which are confirmed as tracers of sugar cane foliage burning.

A new monitor for routine thermal and epithermal neutron fluence rate monitoring in k(0) INAA

The Zr-Au set for monitoring the thermal and epithermal neutron fluence rate and the epithermal spectrum parameter a is not always practicable for routine application of INAA in well-thermalized facilities. An alternative set consisting of Cr, Au and Mo provides values for the thermal neutron fluence rate, f and alpha that are not significantly different from those found via the Zr-Au method and the Cd-covered Zr-method. The IRMM standard SMELS-II was analyzed using the (Au-Cr-Mo) monitor and a good agreement was obtained. (C) 2008 Elsevier Ltd. All rights reserved.

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.

Exploring the emission intensities of ICP OES aided by chemometrics in the geographical discrimination of mineral waters

A rapid method for classification of mineral waters is proposed. The discrimination power was evaluated by a novel combination of chemometric data analysis and qualitative multi-elemental fingerprints of mineral water samples acquired from different regions of the Brazilian territory. The classification of mineral waters was assessed using only the wavelength emission intensities obtained by inductively coupled plasma optical emission spectrometry (ICP OES), monitoring different lines of Al, B, Ba, Ca, Cl, Cu, Co, Cr, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Si, Sr, Ti, V, and Zn, and Be, Dy, Gd, In, La, Sc and Y as internal standards. Data acquisition was done under robust (RC) and non-robust (NRC) conditions. Also, the combination of signal intensities of two or more emission lines for each element were evaluated instead of the individual lines. The performance of two classification-k-nearest neighbor (kNN) and soft independent modeling of class analogy (SIMCA)-and preprocessing algorithms, autoscaling and Pareto scaling, were evaluated for the ability to differentiate between the various samples in each approach tested (combination of robust or non-robust conditions with use of individual lines or sum of the intensities of emission lines). It was shown that qualitative ICP OES fingerprinting in combination with multivariate analysis is a promising analytical tool that has potential to become a recognized procedure for rapid authenticity and adulteration testing of mineral water samples or other material whose physicochemical properties (or origin) are directly related to mineral content.

Optimisation of environmental gas cleaning routes for solid wastes cogeneration systems. Part II - Analysis of waste incineration combined gas/steam cycle

In the first paper of this paper (Part I), conditions were presented for the gas cleaning technological route for environomic optimisation of a cogeneration system based in a thermal cycle with municipal solid waste incineration. In this second part, an environomic analysis is presented of a cogeneration system comprising a combined cycle composed of a gas cycle burning natural gas with a heat recovery steam generator with no supplementary burning and a steam cycle burning municipal solid wastes (MSW) to which will be added a pure back pressure steam turbine (another one) of pure condensation. This analysis aims to select, concerning some scenarios, the best atmospheric pollutant emission control routes (rc) according to the investment cost minimisation, operation and social damage criteria. In this study, a comparison is also performed with the results obtained in the Case Study presented in Part I. (c) 2007 Elsevier Ltd. All rights reserved.

Composites from Brazilian natural fibers with polypropylene: mechanical and thermal properties

Brazil has a well established ethanol production program based on sugarcane. Sugarcane bagasse and straw are the main by-products that may be used as reinforcement in natural fiber composites. Current work evaluated the influence of fiber insertion within a polypropylene (PP) matrix by tensile, TGA and DSC measurements. Thus, the mechanical properties, weight loss, degradation, melting and crystallization temperatures, heat of melting and crystallization and percentage of crystallinity were attained. Fiber insertion in the matrix improved the tensile modulus and changed the thermal stability of composites (intermediary between neat fibers and PP). The incorporation of natural fibers in PP promoted also apparent T(c) and Delta H(c) increases. As a Conclusion, the fibers added to polypropylene increased the nucleating ability, accelerating the crystallization process, improving the mechanical properties and consequently the fiber/matrix interaction.

Thermal expansion of the V(5)Si(3) and T(2) phases of the V-Si-B system investigated by high-temperature X-ray diffraction

The thermal expansion anisotropy of the V(5)Si(3) and T(2)-phase of the V-Si-B system were determined by high-temperature X-ray diffraction from 298 to 1273 K. Alloys with nominal compositions V(62.5)Si(37.5) (V5Si3 phase) and V(63)Si(12)B(25) (T(2)-phase) were prepared from high-purity materials through arc-melting followed by heat-treatment at 1873 K by 24 h, under argon atmosphere. The V(5)Si(3) phase exhibits thermal expansion anisotropy equals to 1.3, with thermal expansion coefficients along the a and c-axis equal to 9.3 x 10(-6) K(-1) and 11.7 x 10(-6) K(-1), respectively. Similarly, the thermal expansion anisotropy value of the T(2)-phase is 0.9 with thermal expansion coefficients equal to 8.8 x 10(-6) K(-1) and 8.3 x 10(-6) K(-1) along the, a and c-axis respectively. Compared to other isostructural silicides of the 5:3 type and the Ti(5)Si(3) phase, the V(5)Si(3) phase presents lower thermal expansion anisotropy. The T(2)-phase present in the V-Si-B system exhibits low thermal expansion anisotropy, as the T(2)-phase of the Mo-Si-B, Nb-Si-B and W-Si-B systems. (C) 2009 Elsevier Ltd. 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.

Lightweight composite concrete produced with water treatment sludge and sawdust: Thermal properties and potential application

The main objective of this study was to evaluate the potential application of a lightweight concrete produced with lightweight coarse aggregate made of the water treatment sludge and sawdust (lightweight composite), by determining the thermal properties and possible environmental impact of future residue of this concrete. Two types of concrete were prepared: concrete produced with the lightweight composite dosed with cement/sand/composite/water in a mass ratio of 1:2.5:0.67:0.6 and conventional concrete dosed with cement/sand/crushed stone/water in a mass ratio of 1:4.8:5.8:0.8. The thermal properties were determined by the hot wire parallel technique. The possible environmental impact was measured using the procedures and guidelines of the Brazilian Association of Technical Standards - ABNT. The concrete produced with the lightweight composite presented a 23% lower thermal conductivity than the conventional concrete. The concrete produced with the lightweight composite presented a set of thermal properties suitable for the application of this concrete in non-structural sealing elements. The concentration of aluminum in the solubilized extract of the concrete produced with the lightweight composite was much lower than the concentration of aluminum in the water treatment sludge, confirming the possible reduction of environmental impact of this composite for use in concrete. (C) 2010 Elsevier Ltd. All rights reserved.

Thermal diffusivity of polymers by modified angstrom method

The nature of the molecular structure of plastics makes the properties of such materials markedly temperature dependent. In addition, the continuous increase in the utilization of polymeric materials in many specific applications has demanded knowledge of their physical properties, both during their processing as raw material, as well as over the working temperature range of the final polymer product. Thermal conductivity, thermal diffusivity and specific heat, namely the thermal properties, are the three most important physical properties of a material that are needed for heat transfer calculations. Recently, among several different methods for the determination of the thermal diffusivity and thermal conductivity, transient techniques have become the preferable way for measuring thermal properties of materials. In this work, a very simple and low cost variation of the well known Angstrom method is employed in the experimental determination of the thermal diffusivity of some selected polymers. Cylindrical shaped samples 3 cm diameter and 7 cm high were prepared by cutting from long cylindrical commercial bars. The reproducibility is very good, and the results obtained were checked against results obtained by the hot wire technique, laser flash technique, and when possible, they were also compared with data found in the literature. Thermal conductivity may be then derived from the thermal diffusivity with the knowledge of the bulk density and the specific heat, easily obtained by differential scanning calorimetry. (C) 2009 Elsevier Ltd. All rights reserved.

Thermal characterization of a cross-flow heat exchanger with a new flow arrangement

The objective of the present paper is to thermally characterize a cross-flow heat exchanger featuring a new cross-flow arrangement, which may find application in contemporary refrigeration and automobile industries. The new flow arrangement is peculiar in the sense that it possesses two fluid circuits extending in the form of two tube rows, each with two tube lines. To assess the heat exchanger performance, it is compared against that for the standard two-pass counter-cross-flow arrangement. The two-part comparison is based on the thermal effectiveness and the heat exchanger efficiency for several combinations of the heat capacity rate ratio, C*, and the number of transfer units, NTU. In addition, a third comparison is made in terms of the so-called ""heat exchanger reversibility norm"" (HERN) through the influence of various parameters such as the inlet temperature ratio, T, and the heat capacity rate ratio, C*, for several fixed NTU values. The proposed new flow arrangement delivers higher thermal effectiveness and higher heat exchanger efficiency, resulting in lesser entropy generation over a wide range of C* and NTU values. These metrics are quantified with respect to the arrangement widely used in refrigeration industry due to its high effectiveness, namely, the standard two-pass counter-cross-flow heat exchanger. The new flow arrangement seems to be a promising avenue in situations where cross-flow heat exchangers for single-phase fluid have to be used in refrigeration units. (c) 2009 Elsevier Masson SAS. All rights reserved.

Thermal error evaluation and modelling of a CNC cylindrical grinding machine

With the relentless quest for improved performance driving ever tighter tolerances for manufacturing, machine tools are sometimes unable to meet the desired requirements. One option to improve the tolerances of machine tools is to compensate for their errors. Among all possible sources of machine tool error, thermally induced errors are, in general for newer machines, the most important. The present work demonstrates the evaluation and modelling of the behaviour of the thermal errors of a CNC cylindrical grinding machine during its warm-up period.

INFLUENCE OF ROOF MATERIAL ON THERMAL COMFORT IN BROILER HOUSINGS IN THE STATE OF SAO PAULO

This paper presents a different roof tiles influence study on the thermal comfort for broiler housings. The research was conducted at UNESP`s Experimental Campus at Dracena, state of Sao Paulo, Brazil. Four prototypes in real scale were built, each with an area of 28 m(2). The prototype was covered with roof tiles made of recycled long-life packing material, ceramic tiles, ceramic tiles painted with white coating, and fiber/cement tiles. Temperatures inside the structures were recorded in the winter 2007 over a 90-day period. The results obtained indicated that recycled tile thermal behavior was similar to ceramic tiles. However for the winter period all the prototypes had presented comfort thermal index not in the broilers thermo neutral zone.