Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.

Exploring new molecular species on the (1)[H, Se, F] singlet potential energy surface: Energetics, structures, IR spectra, and heats of formation

Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

The reaction of methyl radical with nitrogen atom on the triplet potential energy surface: A CCSD(T)/CBS characterization

CCSD(T)/cc-pVnZ (n = D, T, Q) calculations followed by extrapolations to the CBS limit are used to characterize stationary states of species participating in the N((4)S) + CH(3) (2A ``) reaction on the triplet PES. A mechanistic model is investigated and reaction rates are computed for every step and the overall reaction. Our best CBS estimate (1.93 x 10(10) cm(3) molecule(1) s(1)) for the overall rate constant leading to the formation of H(2)CN + H compares well with the experimental values (8.5 x 10 (11) and 1.3 x 10(10) cm(3) molecule(1) s(1)), thus reducing significantly the discrepancy of a previous theoretical result (9.1 x 10(12) cm(3) molecule(1) s(1)). (C) 2008 Elsevier B.V. All rights reserved.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

Optical Characterization and Optimization of Display Components : Some Applications to Liquid-Crystal-Based and Electrochromics-Based Devices

This dissertation is focused on theoretical and experimental studies of optical properties of materials and multilayer structures composing liquid crystal displays (LCDs) and electrochromic (EC) devices. By applying spectroscopic ellipsometry, we have determined the optical constants of thin films of electrochromic tungsten oxide (WOx) and nickel oxide (NiOy), the films’ thickness and roughness. These films, which were obtained at spattering conditions possess high transmittance that is important for achieving good visibility and high contrast in an EC device. Another application of the general spectroscopic ellipsometry relates to the study of a photo-alignment layer of a mixture of azo-dyes SD-1 and SDA-2. We have found the optical constants of this mixture before and after illuminating it by polarized UV light. The results obtained confirm the diffusion model to explain the formation of the photo-induced order in azo-dye films. We have developed new techniques for fast characterization of twisted nematic LC cells in transmissive and reflective modes. Our techniques are based on the characteristics functions that we have introduced for determination of parameters of non-uniform birefringent media. These characteristic functions are found by simple procedures and can be utilised for simultaneous determination of retardation, its wavelength dispersion, and twist angle, as well as for solving associated optimization problems. Cholesteric LCD that possesses some unique properties, such as bistability and good selective scattering, however, has a disadvantage – relatively high driving voltage (tens of volts). The way we propose to reduce the driving voltage consists of applying a stack of thin (~1µm) LC layers. We have studied the ability of a layer of a surface stabilized ferroelectric liquid crystal coupled with several retardation plates for birefringent color generation. We have demonstrated that in order to accomplish good color characteristics and high brightness of the display, one or two retardation plates are sufficient.

Análise e otimização de superfícies seletivas de Frequência utilizando redes neurais artificiais e algoritmos de otimização natural

The bidimensional periodic structures called frequency selective surfaces have been well investigated because of their filtering properties. Similar to the filters that work at the traditional radiofrequency band, such structures can behave as band-stop or pass-band filters, depending on the elements of the array (patch or aperture, respectively) and can be used for a variety of applications, such as: radomes, dichroic reflectors, waveguide filters, artificial magnetic conductors, microwave absorbers etc. To provide high-performance filtering properties at microwave bands, electromagnetic engineers have investigated various types of periodic structures: reconfigurable frequency selective screens, multilayered selective filters, as well as periodic arrays printed on anisotropic dielectric substrates and composed by fractal elements. In general, there is no closed form solution directly from a given desired frequency response to a corresponding device; thus, the analysis of its scattering characteristics requires the application of rigorous full-wave techniques. Besides that, due to the computational complexity of using a full-wave simulator to evaluate the frequency selective surface scattering variables, many electromagnetic engineers still use trial-and-error process until to achieve a given design criterion. As this procedure is very laborious and human dependent, optimization techniques are required to design practical periodic structures with desired filter specifications. Some authors have been employed neural networks and natural optimization algorithms, such as the genetic algorithms and the particle swarm optimization for the frequency selective surface design and optimization. This work has as objective the accomplishment of a rigorous study about the electromagnetic behavior of the periodic structures, enabling the design of efficient devices applied to microwave band. For this, artificial neural networks are used together with natural optimization techniques, allowing the accurate and efficient investigation of various types of frequency selective surfaces, in a simple and fast manner, becoming a powerful tool for the design and optimization of such structures

Análise do espalhamento espectral em superfícies de estruturas complexas para comunicações móveis

In this work, the transmission line method is explored on the study of the propagation phenomenon in nonhomogeneous walls with finite thickness. It is evaluated the efficiency and applicability of the method, considering materials like gypsum, wood and brick, found in the composition of the structures of walls in question. The results obtained in this work are compared to those available in the literature, for several particular cases. A good agreement is observed, showing that the performed analysis is accurate and efficient in modeling, for instance, the wave propagation through building walls and integrated circuit layers in mobile communication and radar system applications. Later, simulations of resistive sheets devices such as Salisbury screens and Jaumann absorbers and of transmission lines made of metal-insulator-semiconductor (MIS) are made. Thereafter, it is described a study on frequency surface selective structures (FSS). It is proposed the development of devices and microwave integrated circuits (MIC) of such structures, for the accomplishment of experiments. Finally, future works are suggested, for instance, on the development of reflectarrays, frequency selective surfaces with dissimilar elements, and coupled frequency selective surfaces with elements located on different layers

Electrical characterization of poly(amide-imide) for application in organic field effect devices

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

Impedance of carrier injection at the metal-organic interface mediated by surface states in electron-only tris(8-hydroxyquinoline) aluminium (Alq(3)) thin layers

Capacitance spectra of thin (< 200 nm) Alq(3) electron-only devices have been measured as a function of bias voltage. Capacitance spectra exhibit a flat response at high frequencies (> 10(3) Hz) and no feature related to the carrier transit time is observed. Toward low frequencies the spectra reach a maximum and develop a negative excess capacitance. Capacitance response along with current-voltage (J-V) characteristics are interpreted in terms of the injection of electrons mediated by surface states at the metal organic interface. A detailed model for the impedance of the injection process is provided that highlights the role of the filling/releasing kinetics of energetically distributed interface states. This approach connects the whole capacitance spectra to the occupancy of interface states, with no additional information about bulk trap levels. Simulations based on the model allow to derive the density of interface states effectively intervening in the carrier injection (similar to 1.5 x 10(12) cm (2)). (C) 2008 Elsevier B.V. All rights reserved.

In-process grinding monitoring by acoustic emission

This work aims to investigate the efficiency of digital signal processing tools of acoustic emission signals in order to detect thermal damages in grinding process. To accomplish such a goal, an experimental work was carried out for 15 runs in a surface grinding machine operating with an aluminum oxide grinding wheel and ABNT 1045. The acoustic emission signals were acquired from a fixed sensor placed on the workpiece holder. A high sampling rate data acquisition system at 2.5 MHz was used to collect the raw acoustic emission instead of root mean square value usually employed. Many statistics have shown effective to detect burn, such as the root mean square (RMS), correlation of the AE, constant false alarm (CFAR), ratio of power (ROP) and mean-value deviance (MVD). However, the CFAR, ROP, Kurtosis and correlation of the AE have been presented more sensitive than the RMS.

Surface finishing of flat pieces when submitted to lapping kinematics on abrasive disc dressed under several overlap factors

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

Material processing by plasma shock wave generated in an inverse Z-pinch plasma expander

The applicability of plasma shock wave for material processing was investigated using modified inverse Z-pinch device. Shock wave expanding speed and plasma spectral analysis were studied using an internal magnetic,probe and spatially collimated light spectroscopy. The material processing capability of the device was shown by many different surface analysis techniques such as AES, IRS, EPM and SEM. The interactions between a plasma shock wave of similar to4x10(6) cm/s speed with a Si substrate surface shows some ion implantation capability using a nitrogen plasma and thin film formation using a methane plasma.

Silicon carbide surface modification by nitrogen plasma expander

Silicon carbide (SiC) has been employed in many different fields such as ballistic armor, thermal coating, high performance mirror substrate, semiconductors devices, among other things. Plasma application over the silicon carbide ceramics is relatively recent and it is able to promote relevant superficial modifications. Plasma expander was used in this work which was supplied by nitrogen and switched by a capacitor bank. Nitrogen plasma was applied over ceramic samples for 20 minutes, in a total medium of 1440 plasma pulses. SiC ceramics were produced by uniaxial pressing method (40 MPa) associated to isostatic pressing (300 MPa) and sintered at 1950 degrees C under argon gas atmosphere. Silicon carbide (beta-sic - BF-12) supplied by HC-Starck and sintering additive (7.6% YAG - Yttrium Aluminum Garnet) were used in order to obtain the ceramics. Before and after the plasma application, the samples were characterized by SEM, AFM, contact angle and surface energy measurement.

Comparative study on the effect of ultrasonic instruments on the root surface in vivo

The present study was designed to investigate the effectiveness of different ultrasonic instruments on the root surface. Fourteen patients with 35 single root teeth designated for extraction were recruited to the present study. Teeth were assigned to four experimental groups: group 1, piezoelectric ultrasonic device; group 2, magnetostrictive ultrasonic device; group 3, hand instrumentation; and group 4, untreated teeth (control). After instrumentation, the teeth were extracted and the presence of residual deposits (roughness and root surfaces characteristics) were analyzed. The results showed that residual deposits were similar in all tested groups: piezoelectric, 8.7%; magnetostrictive, 9.7%; hand instrumentation, 11.1% and control, 76.4%. There were statistically significant differences between control and all the experimental groups (p < 0.0001). With respect to roughness parameters evaluation, R(a) and R(z) of the roots treated with the different instruments showed a similar pattern (p > 0.05), but for R(t) and R(y), a significant difference was observed (p < 0.05) among hand instrumentation and ultrasonic devices. SEM analysis revealed a similar root surface pattern for the ultrasonic devices, but curettes showed many instrumental scratches, deep gouges, and a relatively large amount of dentin was removed. Within the limits of the study, although the instruments produced similar results, root surfaces instrumentated with curettes were rougher and had more root surface tissue removed than with the ultrasonic device.

Solitary waves on a free surface of a heated Maxwell fluid

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)