Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

Amulti-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.

Properties of tantalum oxynitride thin films produced by magnetron sputtering: the influence of processing parameters

The main purpose of this work is to present and to interpret the change of structure and physical properties of tantalum oxynitride (TaNxOy) thin films, produced by dc reactive magnetron sputtering, by varying the processing parameters. A set of TaNxOy films was prepared by varying the reactive gases flow rate, using a N2/O2 gas mixture with a concentration ratio of 17:3. The different films, obtained by this process, exhibited significant differences. The obtained composition and the interpretation of X-ray diffraction results, shows that, depending on the partial pressure of the reactive gases, the films are: essentially dark grey metallic, when the atomic ratio (N + O)/Ta < 0.1, evidencing a tetragonal β-Ta structure; grey-brownish, when 0.1 < (N + O)/Ta < 1, exhibiting a face-centred cubic (fcc) TaN-like structure; and transparent oxide-type, when (N + O)/Ta > 1, evidencing the existence of Ta2O5, but with an amorphous structure. These transparent films exhibit refractive indexes, in the visible region, always higher than 2.0. The wear resistance of the films is relatively good. The best behaviour was obtained for the films with (N + O)/Ta ≈ 0.5 and (N + O)/Ta ≈ 1.3.

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

Low temperature structural transitions in dipolar hard spheres: the influence on magnetic properties

We investigate the structural chain-to-ring transition at low temperature in a gas of dipolar hard spheres (DRS). Due to the weakening of entropic contribution, ring formation becomes noticeable when the effective dipole-dipole magnetic interaction increases, It results in the redistribution of particles from usually observed flexible chains into flexible rings. The concentration (rho) of DI-IS plays a crucial part in this transition: at a very low rho only chains and rings are observed, whereas even a slight increase of the volume fraction leads to the formation of branched or defect structures. As a result, the fraction of DHS aggregated in defect-free rings turns out to be a non-monotonic function of rho. The average ring size is found to be a slower increasing function of rho when compared Lo that of chains. Both theory and computer simulations confirm the dramatic influence of the ring formation on the rho-dependence of the initial magnetic susceptibility (chi) when the temperature decreases. The rings clue to their zero total dipole moment are irresponsive to a weak magnetic field and drive to the strong decrease of the initial magnetic susceptibility. (C) 2014 Elsevier B.V. All rights reserved.

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.

Molecular simulation of gas adsorption equilibria in nanoporous materials

This work is divided into two distinct parts. The first part consists of the study of the metal organic framework UiO-66Zr, where the aim was to determine the force field that best describes the adsorption equilibrium properties of two different gases, methane and carbon dioxide. The other part of the work focuses on the study of the single wall carbon nanotube topology for ethane adsorption; the aim was to simplify as much as possible the solid-fluid force field model to increase the computational efficiency of the Monte Carlo simulations. The choice of both adsorbents relies on their potential use in adsorption processes, such as the capture and storage of carbon dioxide, natural gas storage, separation of components of biogas, and olefin/paraffin separations. The adsorption studies on the two porous materials were performed by molecular simulation using the grand canonical Monte Carlo (μ,V,T) method, over the temperature range of 298-343 K and pressure range 0.06-70 bar. The calibration curves of pressure and density as a function of chemical potential and temperature for the three adsorbates under study, were obtained Monte Carlo simulation in the canonical ensemble (N,V,T); polynomial fit and interpolation of the obtained data allowed to determine the pressure and gas density at any chemical potential. The adsorption equilibria of methane and carbon dioxide in UiO-66Zr were simulated and compared with the experimental data obtained by Jasmina H. Cavka et al. The results show that the best force field for both gases is a chargeless united-atom force field based on the TraPPE model. Using this validated force field it was possible to estimate the isosteric heats of adsorption and the Henry constants. In the Grand-Canonical Monte Carlo simulations of carbon nanotubes, we conclude that the fastest type of run is obtained with a force field that approximates the nanotube as a smooth cylinder; this approximation gives execution times that are 1.6 times faster than the typical atomistic runs.

Gas tungsten arc welding of NiTi shape memory alloy

Shape memory alloys are characterized by the ability of recovering their initial shape after being deformed and by superelasticity. Since the discovery of these alloys, a new field of interest emerged not only for the scientific community but also to many industries. However, these alloys present poor machinability which constitute a constrain in the design of complex components for new applications. Thus, the demand for joining techniques able to join these alloys without compromising their properties became of great importance to enlarge the complexity of existing applications. Literature shows that these alloys are joined mainly using laser welding. In the present study, similar NiTi butt joints, were produced using TIG welding. The welds were performed in 1.5 mm thick plates across the rolling direction. A special fixture and gas assist device was designed and manufactured. Also a robot arm was adapted to accommodate the welding torch to assure the repeatability of the welding parameters. Welds were successfully achieved without macroscopic defects, such as pores and distortions. Very superficial oxidation was seen on the top surface due to insufficient shielding gas flow on the weld face. The welded joints were mechanically tested and structurally characterized. Testing methods were used to evaluate macro and microstructure, as well as the phase transformation temperatures, the mechanical single and cyclic behaviour and the shape recovery ability. Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), microhardness measurements were techniques also used to evaluate the welded joints. A depletion in Ni in the fusion zone was seen, as well as a shift in Ms temperature. For strain values of 4% the accumulated irrecoverable strain was of about 30% and increased with the strain imposed during cycling. Nevertheless, a complete recovery of initial shape was observed when testing the shape memory effect on a dedicated device that introduces a deformation of 6.7%. That is, the welding procedure does not remove the ability of the specimens to recover their initial shape.

Magnetotransport properties of metal/LaAlO3/SrTiO3 heterostructures

The quasi two-dimensional electron gas (q2DEG) hosted in the interface of an epitaxially grown lanthanum aluminate (LaAlO3) thin film with a TiO2-termi-nated strontium titanate (SrTiO3) substrate (001) has been massively studied in the last few years. The confinement of mobile electrons to within a few nanome-ters from the interface, superconductive behavior at low temperatures and elec-tron mobility exceeding 1000 cm2/(V.s) make this system an interesting candi-date to explore the physics of spin injection and transport. However, due to the critical thickness for conduction of 4 unit cells (uc) of LaAlO3, a high tunneling resistance hampers electrical access to the q2DEG, preventing proper injection of spin polarized current. Recently, our group found that depositing a thin overlayer of Co on LaAlO3 reduces the critical thickness, enabling conduction with only 1 uc of LaAlO3. Two scenarios arise to explain this phenomenon: a pinning of the Fermi level in the metal, inducing charge transfer in the SrTiO3; the creation of oxygen vacancies at the interface between LaAlO3 and the metal, leading to an n-type doping of the SrTiO3. In this dissertation, we will report on magnetotransport of metal/LaAlO3/SrTiO3 (metal: Ti, Ta, Co, Py, Au, Pt, Pd) heterostructures with 2 uc of LaAlO3 studied at low temperatures (2 K) and high magnetic fields (9 T). We have analyzed the transport properties of the gas, namely, the carrier concen-tration, mobility and magnetotransport regime and we will discuss the results in the light of the two scenarios mentioned above.

Structural, mechanical and piezoelectric properties of polycrystalline AlN films sputtered on titanium bottom electrodes

Polycrystalline AlN coatings deposited on Ti-electrodes films were sputtered by using nitrogen both as reactive gas and sputtering gas, in order to obtain high purity coatings with appropriate properties to be further integrated into wear resistance coatings as a piezoelectric monitoring wear sensor. The chemical composition, the structure and the morphology of the films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy techniques. These measurements show the formation of highly (101), (102) and (103) oriented AlN films with good piezoelectric and mechanical properties suitable for applications in electronic devices. Through the use of lower nitrogen flow a densification of the AlN coating occurs in the microstructure, with an improvement of the crystallinity along with the increase of the hardness. Thermal stability of aluminum nitride coatings at high temperature was also examined. It was found an improvement of the piezoelectric properties of the highly (10x) oriented AlN films which became c-axis (002) oriented after annealing. The mechanical behavior after heat treatment shows an important enhancement of the surface hardness and Young’s modulus, which decrease rapidly with the increase of the indentation depth until approach constant values close to the substrate properties after annealing. Thus, thermal annealing energy promotes not only the rearrangement of Al–N network, but also the occurrence of a nitriding process of unsaturated Al atoms which cause a surface hardening of the film.

Optical properties of zirconium oxynitride films: the effect of composition, electronic and crystalline structures

tThis work is devoted to the investigation of zirconium oxynitride (ZrOxNy) films with varied opticalresponses prompted by the variations in their compositional and structural properties. The films wereprepared by dc reactive magnetron sputtering of Zr, using Ar and a reactive gas mixture of N2+ O2(17:3).The colour of the films changed from metallic-like, very bright yellow-pale and golden yellow, for low gasflows to red-brownish for intermediate gas flows. Associated to this colour change there was a significantdecrease of brightness. With further increase of the reactive gas flow, the colour of the samples changedfrom red-brownish to dark blue or even to interference colourations. The variations in composition dis-closed the existence of four different zones, which were found to be closely related with the variationsin the crystalline structure. XRD analysis revealed the change from a B1 NaCl face-centred cubic zirco-nium nitride-type phase for films prepared with low reactive gas flows, towards a poorly crystallizedover-stoichiometric nitride phase, which may be similar to that of Zr3N4with some probable oxygeninclusions within nitrogen positions, for films prepared with intermediate reactive gas flows. For highreactive gas flows, the films developed an oxynitride-type phase, similar to that of -Zr2ON2with someoxygen atoms occupying some of the nitrogen positions, evolving to a ZrO2monoclinic type structurewithin the zone where films were prepared with relatively high reactive gas flows. The analysis carriedout by reflected electron energy loss spectroscopy (REELS) revealed a continuous depopulation of thed-band and an opening of an energy gap between the valence band (2p) and the Fermi level close to 5 eV.The ZrN-based coatings (zone I and II) presented intrinsic colourations, with a decrease in brightness anda colour change from bright yellow to golden yellow, red brownish and dark blue. Associated to thesechanges, there was also a shift of the reflectivity minimum to lower energies, with the increase of thenon-metallic content. The samples lying in the two last zones (zone III, oxynitride and zone IV, oxide films)revealed a typical semi-transparent-optical behaviour showing interference-like colourations only dueto the complete depopulation of the d band at the Fermi level. The samples lying in these zones presentedalso an increase of the optical bandgap from 2 to 3.6 eV.

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P) = I0¿exp(¿P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature.

Properties of nitrogen doped silicon films deposited by low-pressure chemical vapor deposition from silane and ammonia

Nitrogen doped silicon (NIDOS) films have been deposited by low-pressure chemical vapor deposition from silane SiH4 and ammonia NH3 at high temperature (750°C) and the influences of the NH3/SiH4 gas ratio on the films deposition rate, refractive index, stoichiometry, microstructure, electrical conductivity, and thermomechanical stress are studied. The chemical species derived from silylene SiH2 into the gaseous phase are shown to be responsible for the deposition of NIDOS and/or (silicon rich) silicon nitride. The competition between these two deposition phenomena leads finally to very high deposition rates (100 nm/min) for low NH3/SiH4 gas ratio (R¿0.1). Moreover, complex variations of NIDOS film properties are evidenced and related to the dual behavior of the nitrogen atom into silicon, either n-type substitutional impurity or insulative intersticial impurity, according to the Si¿N atomic bound. Finally, the use of NIDOS deposition for the realization of microelectromechanical systems is investigated.

Liquid-gas phase transition in nuclear matter from realistic many-body approaches

The existence of a liquid-gas phase transition for hot nuclear systems at subsaturation densities is a well-established prediction of finite-temperature nuclear many-body theory. In this paper, we discuss for the first time the properties of such a phase transition for homogeneous nuclear matter within the self-consistent Green's function approach. We find a substantial decrease of the critical temperature with respect to the Brueckner-Hartree-Fock approximation. Even within the same approximation, the use of two different realistic nucleon-nucleon interactions gives rise to large differences in the properties of the critical point.

Gas collisions and pressure quenching of the photoluminescence of silicon nanopowder grown by plasma-enhanced chemical vapor deposition

The quenching of the photoluminescence of Si nanopowder grown by plasma-enhanced chemical vapor deposition due to pressure was measured for various gases ( H2, O2, N2, He, Ne, Ar, and Kr) and at different temperatures. The characteristic pressure, P0, of the general dependence I(P) = I0¿exp(¿P/P0) is gas and temperature dependent. However, when the number of gas collisions is taken as the variable instead of pressure, then the quenching is the same within a gas family (mono- or diatomic) and it is temperature independent. So it is concluded that the effect depends on the number of gas collisions irrespective of the nature of the gas or its temperature.

Plasma-enhanced chemical vapor deposition of boron nitride thin films from B2H6-H2-NH3 and B2H6-N2 gas mixtures

Highly transparent and stoichiometric boron nitride (BN) films were deposited on both electrodes (anode and cathode) of a radio-frequency parallel-plate plasma reactor by the glow discharge decomposition of two gas mixtures: B2H6-H2-NH3 and B2H6-N2. The chemical, optical, and structural properties of the films, as well as their stability under long exposition to humid atmosphere, were analyzed by x-ray photoelectron, infrared, and Raman spectroscopies; scanning and transmission electron microscopies; and optical transmittance spectrophotometry. It was found that the BN films grown on the anode using the B2H6-H2-NH3 mixture were smooth, dense, adhered well to substrates, and had a textured hexagonal structure with the basal planes perpendicular to the film surface. These films were chemically stable to moisture, even after an exposition period of two years. In contrast, the films grown on the anode from the B2H6-N2 mixture showed tensile stress failure and were very unstable in the presence of moisture. However, the films grown on the cathode from B2H6-H2-NH3 gases suffered from compressive stress failure on exposure to air; whereas with B2H6-N2 gases, adherent and stable cathodic BN films were obtained with the same crystallographic texture as anodic films prepared from the B2H6-H2-NH3 mixture. These results are discussed in terms of the origin of film stress, the effects of ion bombardment on the growing films, and the surface chemical effects of hydrogen atoms present in the gas discharge.