Thin films generated by plasma immersion ion implantation and deposition of hexamethyldisilazane mixed with nitrogen in different proportions

In this work, it was used a plasma system composed of a cylindrical stainless steel reactor, a radio-frequency (13.56MHz) power source fixed at either 25 W or 70 W, a power source with a negative bias of 10kV and a 100Hz pulse. The system worked at an operational pressure of 80mTorr which consisted of varying concentrations of the monomer HMDSN and gaseous nitrogen in ratios: HMDSN (mTorr)/nitrogen (mTorr) from 70/10 to 20/60 in terms of operational pressure. The structural characterization of the films was done by FTIR spectroscopy. Absorptions were observed between 3500 cm(-1) to 3200 cm(-1), 3000 cm(-1) to 2900 cm(-1), 2500 cm(-1) to 2000 cm(-1), 1500 cm(-1) to 700 cm(-1), corresponding, respectively, to OH radicals, C-H stretching bonds in CH2 and CH3 molecules, C-N bonds, and finally, strain C-H bonds, Si-CH3 and Si-N groups, for both the 70 W and the 25 W. The contact angle for water was approximately 100 degrees and the surface energy is near 25mJ/m(2) which represents a hydrophobic surface, measured by goniometric method. The aging of the film was also analyzed by measuring the contact angle over a period of time. The stabilization was observed after 4 weeks. The refractive index of these materials presents values from 1.73 to 1.65 measured by ultraviolet-visible technique.

Investigation of Plasma Immersion Ion Implantation Process in Magnetic Mirror Geometry

Plasma immersion ion implantation (PIII) with low external magnetic field has been investigated both numerically and experimentally. The static magnetic field considered is essentially nonuniform and is generated by two magnetic coils installed outside the vacuum chamber. Experiments have been conducted to investigate the effect of two of the most important PIII parameters: target voltage and gas pressure. In that context, it was found that the current density increased when the external parameters were varied. Later, the PIII process was analyzed numerically using the 2.5-D computer code KARAT. The numerical results show that the system of crossed E x B fields enhances the PIII process. The simulation showed an increase of the plasma density around the target under the operating and design conditions considered. Consequently, an increase of the ion current density on the target was observed. All these results are explained through the mechanism of gas ionization by collisions with electrons drifting in crossed E x B fields.

Modified LPE system used to diffuse Cd to obtain InSb infrared detectors

We are presenting here p/n junctions obtained with a modified opened liquid-phase epitaxy (LPE) system, used to diffuse indium antimonide (InSb) doped with Cd over InSb doped with Te wafers, in order to make InSb infrared (IR) sensors. This technique has several advantages: the diffusion can be performed in bigger substrate areas improving the device production; this method decreases the device manipulation, decreasing human mistakes and increasing the process reproducibility. The opened LPE in this work produced sensors in the first case with vapor of the diffusion material, coming from a microholed carbon boat full of the diffusion material, over which is positioned the substrate at atmospheric pressure. In the second, the diffusion material is on the bottom of a quartz recipient, and the InSb/Te wafer works as its cover, and vacuum was used. The IR sensors produced with the first method measured 8.9 x 10(7) cm Hz(1/2)/W as detectivity value and higher IR spectral response at 4.6 mu m, and those produced with the second 2.8 x 10(9) cm Hz(1/2)/W, at 4.4 mu m. Besides the electrical-optical properties, the structural properties of diffused layers were investigated by X-ray diffraction (XRD), scanning electron and atomic force microscopy (SEM, AFM), energy-dispersive and secondary ion mass spectroscopy (EDS, SIMS). (C) 2007 Elsevier B.V. All rights reserved.

Hexagonal mesoporous silica modified with 2-mercaptothiazoline for removing mercury from water solution

A method for the attachment of 2-mercaptothiazoline (MTZ) to modified silica gel has been developed. In the first step, a new silylant agent was synthesized, named SiMTZ, by the reaction between MTZ molecule and chloropropyltrimethoxysilane (SiCl). SiMTZ and tetraethylortosilicate were co-condensed in the presence of n-dodecylamine, a neutral surfactant template, to produce a modified ordered hexagonal mesoporous silica named HMTZ. The modified material contained 0.89 +/- 0.03 mmol of 2-mercaptothiazoline per gram of silica. FT-IR, FT-Raman, Si-29- and C-13-NMR spectra were in agreement with the proposed structure of the modified mesoporous silica in the solid state. HMTZ material has been used for divalent mercury adsorption from aqueous solution at 298 I K. The series of adsorption isotherms were adjusted to a modified Langmuir equation. The maximum number of moles of mercury adsorbed gave 2.34 +/- 0.09 mmol/g of material. The same interaction was followed by calorimetric titration on an isoperibol calorimeter. The HMTZ presented a high capacity for the removal of the contaminant mercury from water. The Delta H and Delta G values for the interaction were determined to be -56.34 +/- 1.07 and -2.14 +/- 0.11 kJ mol(-1). This interaction process was accompanied by a decrease of entropy value (- 182 J mol(-1) K-1). Thus, the interaction between mercury and HMTZ resulted in a spontaneous thermodynamic system with a high favorable exothermic enthalpic effect. (c) 2007 Elsevier B.V. All rights reserved.

In situ application of a cellulose bag and an ion exchanger for differentiation of labile and inert metal species in aquatic systems

This work involved the development and application of a new analytical procedure for in-situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory. The in-situ application involved immersing the DM-Cell-PAB system in two different rivers, enabling us to study the relative lability of metal species (Cu, Cd, Fe, Mn, and Ni) as a function of time and quantity of exchanger. The procedure is simple and opens up a new perspective for understanding environmental phenomena relating to the complexation, transport, stability, and lability of metal species in aquatic systems rich in organic matter.

Numerical simulation of magnetic-field-enhanced plasma immersion ion implantation in cylindrical geometry

Recent studies have demonstrated that the sheath dynamics in plasma immersion ion implantation (PIII) is significantly affected by an external magnetic field. In this paper, a two-dimensional computer simulation of a magnetic-field-enhanced PHI system is described. Negative bias voltage is applied to a cylindrical target located on the axis of a grounded vacuum chamber filled with uniform molecular nitrogen plasma. A static magnetic field is created by a small coil installed inside the target holder. The vacuum chamber is filled with background nitrogen gas to form a plasma in which collisions of electrons and neutrals are simulated by the Monte Carlo algorithm. It is found that a high-density plasma is formed around the target due to the intense background gas ionization by the magnetized electrons drifting in the crossed E x B fields. The effect of the magnetic field intensity, the target bias, and the gas pressure on the sheath dynamics and implantation current of the PHI system is investigated.

Biosotption of lanthanum using Sargassum fluitans in batch system

Separation and purification of lanthanum from other rare-earth (RE) elements are highly complex processes comprising several steps of extraction using organic solvents or ion-exchange resins at high costs. In order to study the biosorption process as an alternative for conventional lanthanum recovery, this work investigated some basic aspects of lanthanum-Sargassum biomass interactions in batch equilibrium contact. The dynamics of biosorption, influence of pH, and the desorption of this RE were investigated. Maximum biosorption coefficient (q(max)) increased from 0.05 at pH 2 to 0.53 mmol g(-1) at pH 5 for lanthanum sulfate. When lanthanum chloride was used, a higher q(max) at pH 5 (0.73 mmol g(-1)) was observed as compared to the sulfate salt (q(max) = 0.53 mmol g(-1)) at the same pH. Adsorption and desorption curves pointed out a complete recovery of metal adsorbed in the Sargassum fluitans biomass, showing a reversibility of this process and indicating the potential of biosorption for lanthanum removal and recovery. (C) 2002 Elsevier B.V. B.V. All rights reserved.

The effect of EU3+ ion doping concentration in Gd2O3 fine spherical particles

This work reports on the preparation of Gd2O3, cubic system, with spherical particles, narrow size distribution, whether or not doped with 1-5 at.% of Eu3+ and the influence of Eu3+ concentration on optical and morphological properties. Average diameter and size distribution particle analyses were performed for all samples from SEM results. Doped samples were also investigated by luminescence spectroscopy and emission kinetic measurements. All oxide samples present a particle average diameter distribution range from 110 to 150 nm and a decrease of particle average diameter with the presence of Eu3+. The particle size decrease is almost the same for all samples with different doping ion concentration. Therefore, the presence of doping ion may be inhibiting particle growth after the nucleation process. From spectroscopic studies, the doping ion distribution in the surface of oxide samples can be considered homogeneous because concentration quenching is not observed, as well as a significant difference among the calculated lifetime for each sample. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Study of an organically modified clay: Selective adsorption of heavy metal ions and voltammetric determination of mercury(II)

In this work, a hydrophilic clay, Na-montmorillonite from Wyoming, USA, was rendered organophilic by exchanging the inorganic interlayer cations for hexaclecyltrimethylammonium ions (HDTA), with the formulae of [(CH3)(3)N(C16H33)](+) ion. Based on fact that organo-clay has high affinities for non-ionic organic molecules, 1,3,4-thiadiazole-2,5-dithiol was loaded oil the HDTA-montmorillonite surface, resulting in the 1,3,4-thiadiazole-2,5-dithiol-HDTA-montmorillonite complex (TDD-organo-clay).The following properties of TDD-organo-clay are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II).The main point of this paper is the construction of a selective sensor, a carbon paste electrode modified with TDD-organo-clay, its properties and its application to the determination of mercury(II) ions, as this element belongs to the most toxic metals. The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination. (c) 2005 Elsevier B.V. All rights reserved.

Reversible intermittent flow-injection determination of mercury in sediments and vinasses by cold vapor atomic absorption spectrometry

A reversible intermittent pow-injection procedure is proposed for the automated determination of mercury in sediments and vinasses by cold vapor atomic absorption spectrometry, CVAAS. Solutions of sample and stannous chloride are carried by two air streams and sequentially injected into the generator/separator chamber in a segmented asynchronous merging zone configuration. The intermittent flow in the forward direction carries the mercury vapor through the flow cell, and in the backward direction, if aspirates the the remaining solution from the vessel to waste. We investigated composition and concentration of reagents, pow rates, commutation times, reactor configuration, and conditions for mercury release. The accuracy was checked by mercury determination in a certified sediment and spiked vinasses and river waters. The system handles about 100 samples per hour (0.50-5.00 mu g L-1), consuming ca. 2.5 mL of sample and 50 mg of SnCl2 per determination; Good recoveries (92-103%) were obtained with spiked samples. Results are precise (RSD <3% for 2.5 mu g Hg L-1, n = 12) and in agreement with values for certified reference material at 95% confidence level. (C) 1999 John Wiley & Sons, Inc.

Chronopotentiometric stripping analysis using gold electrodes, an efficient technique for mercury quantification in natural waters

This paper proposes a simple methodology for mercury quantification in natural water by stripping chronopotentiometry at constant current, using gold (film) electrodes constructed from recordable CDs in stationary cell. The proposed method allows the direct measurement of labile mercury in natural waters. To quantify total mercury, a robust and low cost UV irradiation system was developed for the degradation of organic constituents of water. The proposed system presents such advantages as excellent sensitivity, low cost, versatility, and smaller dimensions (portability for on-field applications) when compared with other techniques (ICP, GFAAS, fluorimetry) traditionally utilized for mercury quantification. A large linear region of responses was observed, situated over the range 0.02 - 200 μ g L-1. Various experimental parameters were optimized and the system allowed quantifications in natural samples, with detection limit of 8 ng L-1 and excellent reproducibility (RSD of 1.4% for 48 repetitive measurements using a 10 μ g L-1 mercury solution). Different metal ions were evaluated, including copper, as possible interferences on stripping mercury signals. Applications of the new method were demonstrated for the analysis of certified and groundwater samples spiked with a known amount of mercury and for the quantification of methylmercury in synthetic oceanic water, originally utilized for fishes contamination experiment.

The non-adiabatic hyperspherical approach to the two-dimensional D- ion in the presence of a magnetic field

We have used the adiabatic hyperspherical approach to determine the energies and wave functions of the ground state and first excited states of a two-dimensional D- ion in the presence of a magnetic field. Using a modified hyperspherical angular variable, potential energy curves are analytically obtained, allowing an accurate determination of the energy levels of this system. Upper and lower bounds for the ground-state energy have been determined by a non-adiabatic procedure, as the purpose is to improve the accuracy of method. The results are shown to be comparable to the best variational calculations reported in the literature.

Reduction of mercury(II) by tropical river humic substances (Rio Negro) - A possible process of the mercury cycle in Brazil

The evolution of elemental Hg from its environmental compounds has already been supposed to be an important process within the global mercury cycle. The present study characterizes the abiotic reduction of Hg(II) ions by typical river humic substances (HS) conventionally pre-isolated by the adsorbent XAD 8 from the Rio Negro near Manaus, Brazil. For the investigation of this reduction process a special reaction and Hg(0) trapping unit combined with cold-vapor atomic absorption spectrometry (CVAAS) was developed. Preconcentration of traces of mercury(II), if required, was obtained by a home-made FIA system using microcolumns filled with the Hg(II)-selective collector CheliteS(R) (Serva Company). The effect of environmentally relevant parameters such as the pH value, the Hg(II)/HS ratio and the HS concentration on the I-IE;(II) reduction process was studied as a function of the time. The Hg(0) production was highest at pH 8.0 and in the case of decreasing HS amounts (0.5 mg) when about 65% of initially 1.0 mug Hg(H) was reduced within 50 h. Moreover, the reduction efficiency of HS towards HE;(II) strongly depended on the HS concentration but hardly on the Hg(II)/HS ratio. The reduction kinetics followed a relatively slow two-step first-order mechanism with formal rate constants of about 0.1 and 0.02 h(-1), respectively. Based on these findings the possible relevance of the abiotic evolution of mercury in humic-rich aquatic environments is considered. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Er3+-doped germanate glasses for active waveguides prepared by Ag+/K+ <-> Na+ ion-exchange

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Groundwater geochemical evolution in the northern portion of the Guarani Aquifer System (Brazil) and its relationship to diagenetic features

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)