Caracterização por XPS de filmes passivos formados sobre aços de baixa liga em meio de bicarbonato

Passive films formed in bicarbonate solutions on carbon steel, chromium steel and high speed steel have been characterized by XPS. The passive films formed on chromium and high speed steels showed superior protective properties than those formed on carbon steel. It was confirmed by XPS that the steel composition influences the passive film composition. Chromium oxide and hydroxide, as well as molybdenum and tungsten oxides and hydroxides are present in the passive film of chromium steel and high speed steel, respectively, besides iron oxide and hydroxide. The more complex composition of the oxide film on high speed steel explains its electrochemical behaviour and highest corrosion resistance.

Síntesis de capas de SiC en substrato de Si mediante implantación iónica

En este trabajo se investiga la síntesis de estructuras SiC/Si mediante implantación iónica de carbono en Si. Las implantaciones se han realizado a energías entre 25 y 300 keV y las dosis en el rango lO^^ylO^^ cm , manteniendo el substrato a temperatura ambiente o 500°C. Algunas estructuras han sido recocidas a 1150°C. Los resultados indican que implantando a temperatura ambiente se forma una capa de SiC amorfa y de composición gradual, que recristaliza formando precipitados de ß-SiC con orientaciones aleatorias después del recocido. Además se forma un capa superficial rica en carbono, debida a la difusión del carbono hacia la superficie durante la implantación, y que desaparece con el recocido. Implantando a 500°C se forma directamente una capa con una muy alta densidad de precipitados de ß-SiC orientados preferencialmente con la matriz de silicio. Dada la estabilidad térmica y química de dicha capa se han realizado membranas de SiC mediante técnicas fotolitográficas y ataque químico selectivo, cuya rugosidad superficial es inferior a 6 nm. Estas membranas muestran unos gradientes de tensiones residuales, que prácticamente desaparecen después del recocido. Los resultados confirman la potencialidad de la implantación iónica para la formación de estructuras microme-cánicas de SiC sobre Si.

Análises térmicas e processo de sinterização da cerâmica KSr2Nb5O15 dopada com CuO

KSr2Nb5O15 is a ferroelectric material. The sintering process of the KSr2Nb5O15 ceramic doped with different amounts of CuO was investigated in this research. It was found that CuO is effective as promoter of the densification process of the KSN ceramic. The developed microstructures were different due to the amount of CuO and secondary phases were observed in the microstructures. However, the results of X - ray diffraction showed that only the tetragonal tungsten bronze (TTB) structure was identified in all the investigated ceramic systems. The thermal behavior of CuO and also of the CuO - KSN phase mixture was investigated by thermal analysis.

Análise cristalográfica da solução sólida com estrutura tipo Tungstênio Bronze de niobato de potássio e estrôncio dopado com ferro

Solid solution of iron doped potassium strontium niobate with KSr2(FeNb4)O15-Δ stoichiometry was prepared by high efficiency ball milling method. Structural characterization was carried out by X-ray diffraction. Crystalline structure was analyzed by the Rietveld refinements using the FullProf software. The results showed a tetragonal system with the tetragonal tungsten bronze structure - TTB (a = 12.4631 (2) Å and c = 3.9322 (6) Å, V = 610.78 (2) ų). In this work, the sites occupancy by the K+, Sr2+ and Fe3+ cations on the TTB structure were determined. NbO6 polihedra distortion and its correlation with the theoretical polarization are discussed.

Análise por componentes principais de espectros nexafs na especiação do molibdênio em catalisadores de hidrotratamento

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination.

Construção de célula eletroquímica para observação de amostras in situ em estereomicroscópio

The electrochemical study of glass like tungsten oxide derivatives requires the construction of special electrodes due to the fact that these glasses are not conductive. Electrodes modified with WO3 change their color when submitted to some potential perturbation. The color change of the electrochromic materials was observed in situ by coupling an electrochemical cell to a stereomicroscope. The constructed cell is versatile and may represent a great contribution to the electrochemical studies of materials, especially in the systems where it is interest to observe the working electrode surface during the electrochemical experiment.

Construção de espectrômetro de emissão atômica com atomização eletrotérmica em filamento de tungstênio (WCAES)

It is here discussed the development of a low cost analytical instrument with capacity for metals determination using atomic emission measurements in an electrothermal atomization system with a tungsten coil atomizer. The main goal was to show a new frontier for using this atomizer and to demonstrate that the simple instrumental arrangement here proposed has potential for portability and for solving analytical tasks related to metals determination. Atomic emission of calcium was selected for the adjustment of instrumental parameters and to evaluate the main characteristics of the lab-built instrument. Cobalt was determined in medicines and one alloy to demonstrate its feasibility.

Isolamento do tungstênio da volframita da mina de Igarapé Manteiga (Rondônia - Brasil) por lixiviação ácida

We report results of the efficiency of tungsten extraction from wolframite concentrate (containing 61.5 wt % WO3) from the Igarapé Manteiga mine (state of Rondônia, Brazil) through acid leaching with strong mineral acids at 100 ºC and 400 rpm for 2-4 h. HCl yielded insoluble matter containing the highest WO3 content (90 wt %). This solid was dissolved in concentrated NH3(aq) at 25 ºC and the insoluble matter filtrated. The filtrate was slowly evaporated. 70 wt % of the tungsten present in the starting concentrate material was recovered as ammonium paratungstate (APT).

Processing of spent NiW/Al2O3 catalysts

Spent oxidized (500 ºC, 5 h) commercial NiW/Al2O3 catalysts were processed using two different routes: a) fusion with NaOH (650 ºC, 1 h), the roasted mass was leached in water; b) leaching with HCl or H2SO4 (70 ºC, 1-3 h). HCl was the best leachant. In both routes, soluble tungsten was extracted at pH 1 with Alamine 336 (10 vol.% in kerosene) and stripped with 2 mol L-1 NH4OH (25 ºC, one stage, aqueous/organic ratio = 1 v/v). Tungsten was isolated as ammonium paratungstate at very high yield (> 97.5%). The elements were better separated using the acidic route.

Advanced orbital pipe welding

Since the introduction of automatic orbital welding in pipeline application in 1961, significant improvements have been obtained in orbital pipe welding systems. Requirement of more productive welding systems for pipeline application forces manufacturers to innovate new advanced systems and welding processes for orbital welding method. Various methods have been used to make welding process adaptive, such as visual sensing, passive visual sensing, real-time intelligent control, scan welding technique, multi laser vision sensor, thermal scanning, adaptive image processing, neural network model, machine vision, and optical sensing. Numerous studies are reviewed and discussed in this Master’s thesis and based on a wide range of experiments which already have been accomplished by different researches the vision sensor are reported to be the best choice for adaptive orbital pipe welding system. Also, in this study the most welding processes as well as the most pipe variations welded by orbital welding systems mainly for oil and gas pipeline applications are explained. The welding results show that Gas Metal Arc Welding (GMAW) and its variants like Surface Tension Transfer (STT) and modified short circuit are the most preferred processes in the welding of root pass and can be replaced to the Gas Tungsten Arc Welding (GTAW) in many applications. Furthermore, dual-tandem gas metal arc welding technique is currently considered the most efficient method in the welding of fill pass. Orbital GTAW process mostly is applied for applications ranging from single run welding of thin walled stainless tubes to multi run welding of thick walled pipes. Flux cored arc welding process is faster process with higher deposition rate and recently this process is getting more popular in pipe welding applications. Also, combination of gas metal arc welding and Nd:YAG laser has shown acceptable results in girth welding of land pipelines for oil and gas industry. This Master’s thesis can be implemented as a guideline in welding of pipes and tubes to achieve higher quality and efficiency. Also, this research can be used as a base material for future investigations to supplement present finding.

Eri MAG-hitsausprosessien ja -parametrien vaikutus suurlujuusteräksestä valmistetun otsapienahitsin äärikestävyyteen, muodonmuutoskykyyn ja vauriomuotoon

Työssä tutkittiin Ruukki Oyj:n suorasammutetusta S960QC-teräksestä valmistetun kuormaakantavan levyjen ristiliitoksen pienahitsien lujuutta, muodonmuutoskykyä ja vaurioitumismekanismia laajaan kokeelliseen aineistoon perustuen. Tärkeimpänä muuttujana koematriisissa olivat eri MAG-hitsausprosessit. Perinteisen kuumakaarihitsauksen vertailukohteena oli Kemppi Oy:n uusi adaptiivinen valokaaren pituutta säätävä WiseFusion-hitsaustoiminto kuuma- ja pulssikaarihitsauksessa. Näiden kolmen hitsausprosessin rinnalla varioitiin erisuuruisia a-mittoja, eri hitsauslisäaineita ja hitsin erikylkisyyttä. Lisäksi juuritunkeuman estämisen vaikutusta hitsien käyttäytymiseen tutkittiin täydentävällä koesarjalla, jossa tunkeuman muodostuminen estettiin levyjen väliin asetetulla volframilevyllä. Työn perimmäisenä tavoitteena oli selvittää syy aiemmassa tutkimuksessa havaitulle pienahitsien vaurioitumiselle leikkautumalla sularajaa pitkin. Sularajan suhteellista pituutta saadaan kasvatettua estämällä hitsin juuritunkeuma ja absoluuttista pituutta saadaan lisää kateettipoikkeaman avulla. Lisäksi tutkimuksessa oli tarkoitus tuoda esille suurlujuusteräksisen liitoksen eri mitoituslähtökohdat (mm. lämmöntuonnin kontrollointi). Tämän vuoksi hitsausparametrit mitattiin jännitteen ja virran hetkellisiin arvoihin perustuen, jolloin kuuma- ja pulssikaarihitsauksen laskennalliset hitsaustehot ovat vertailukelpoisia. Koehitseistä valmistettiin hieet hitsien tarkan geometrian määrittämiseksi ja liitoksen mekaaniset ominaisuudet tutkittiin vetokokeella. Tulosten perusteella sularajavaurio aktivoituu pulssikaarella hitsatuissa koekappaleissa. Tämä aiheutunee pulssi- ja kuumakaarihitsauksen sularajan mikrorakenteiden eroavaisuudesta. Sularajavaurio näyttää huonontavan hitsien muodonmuutoskykyä, mutta jatkokokeita tuloksen verifioimiseksi on tehtävä. S960QC-teräkselle ominaisen pehmenneen vyöhykkeen vaurio ei aktivoitunut, vaikka Ruukin antamat jäähtymisaikasuositukset ylitettiin reilusti.

Arc fusion of self-fluxed nickel alloys

Self-fluxed nickel alloys are usually flame fused after thermal spraying. However, due to the practical aspects of high temperatures reached during flame fusing, large structures such as the hydraulic turbines for power generation, can not be efficiently coated. An alternative is to fuse the sprayed coating with a gas tungsten electric arc. In this case, heating is much more intensive and substrate temperature during and after the fusing operation is much lower, thus reducing the possibility that any problem will occur. In this work, coatings of self-fluxed nickel alloy fused by flame and gas tungsten arc were evaluated as protection of hydraulic turbines against cavitational damage. Several tests were performed, including the ASTM ultrasonically vibration-induced cavitation, optical and scanning electronic microscopic metallography, and hardness tests. The results showed that the arc-fused coating presented better cavitation damage resistance, probably due to its finer microstructure. A field application of this new technique is also described. A self-fluxed Ni alloy was flame sprayed in critical regions of Francis-type hydraulic turbine blades and fused by a gas tungsten arc after spraying. The blades will be inspected during the next two years.

Power semiconductor nonlinearities in active du/dt output filtering

This doctoral thesis introduces an improved control principle for active du/dt output filtering in variable-speed AC drives, together with performance comparisons with previous filtering methods. The effects of power semiconductor nonlinearities on the output filtering performance are investigated. The nonlinearities include the timing deviation and the voltage pulse waveform distortion in the variable-speed AC drive output bridge. Active du/dt output filtering (ADUDT) is a method to mitigate motor overvoltages in variable-speed AC drives with long motor cables. It is a quite recent addition to the du/dt reduction methods available. This thesis improves on the existing control method for the filter, and concentrates on the lowvoltage (below 1 kV AC) two-level voltage-source inverter implementation of the method. The ADUDT uses narrow voltage pulses having a duration in the order of a microsecond from an IGBT (insulated gate bipolar transistor) inverter to control the output voltage of a tuned LC filter circuit. The filter output voltage has thus increased slope transition times at the rising and falling edges, with an opportunity of no overshoot. The effect of the longer slope transition times is a reduction in the du/dt of the voltage fed to the motor cable. Lower du/dt values result in a reduction in the overvoltage effects on the motor terminals. Compared with traditional output filtering methods to accomplish this task, the active du/dt filtering provides lower inductance values and a smaller physical size of the filter itself. The filter circuit weight can also be reduced. However, the power semiconductor nonlinearities skew the filter control pulse pattern, resulting in control deviation. This deviation introduces unwanted overshoot and resonance in the filter. The controlmethod proposed in this thesis is able to directly compensate for the dead time-induced zero-current clamping (ZCC) effect in the pulse pattern. It gives more flexibility to the pattern structure, which could help in the timing deviation compensation design. Previous studies have shown that when a motor load current flows in the filter circuit and the inverter, the phase leg blanking times distort the voltage pulse sequence fed to the filter input. These blanking times are caused by excessively large dead time values between the IGBT control pulses. Moreover, the various switching timing distortions, present in realworld electronics when operating with a microsecond timescale, bring additional skew to the control. Left uncompensated, this results in distortion of the filter input voltage and a filter self-induced overvoltage in the form of an overshoot. This overshoot adds to the voltage appearing at the motor terminals, thus increasing the transient voltage amplitude at the motor. This doctoral thesis investigates the magnitude of such timing deviation effects. If the motor load current is left uncompensated in the control, the filter output voltage can overshoot up to double the input voltage amplitude. IGBT nonlinearities were observed to cause a smaller overshoot, in the order of 30%. This thesis introduces an improved ADUDT control method that is able to compensate for phase leg blanking times, giving flexibility to the pulse pattern structure and dead times. The control method is still sensitive to timing deviations, and their effect is investigated. A simple approach of using a fixed delay compensation value was tried in the test setup measurements. The ADUDT method with the new control algorithm was found to work in an actual motor drive application. Judging by the simulation results, with the delay compensation, the method should ultimately enable an output voltage performance and a du/dt reduction that are free from residual overshoot effects. The proposed control algorithm is not strictly required for successful ADUDT operation: It is possible to precalculate the pulse patterns by iteration and then for instance store them into a look-up table inside the control electronics. Rather, the newly developed control method is a mathematical tool for solving the ADUDT control pulses. It does not contain the timing deviation compensation (from the logic-level command to the phase leg output voltage), and as such is not able to remove the timing deviation effects that cause error and overshoot in the filter. When the timing deviation compensation has to be tuned-in in the control pattern, the precalculated iteration method could prove simpler and equally good (or even better) compared with the mathematical solution with a separate timing compensation module. One of the key findings in this thesis is the conclusion that the correctness of the pulse pattern structure, in the sense of ZCC and predicted pulse timings, cannot be separated from the timing deviations. The usefulness of the correctly calculated pattern is reduced by the voltage edge timing errors. The doctoral thesis provides an introductory background chapter on variable-speed AC drives and the problem of motor overvoltages and takes a look at traditional solutions for overvoltage mitigation. Previous results related to the active du/dt filtering are discussed. The basic operation principle and design of the filter have been studied previously. The effect of load current in the filter and the basic idea of compensation have been presented in the past. However, there was no direct way of including the dead time in the control (except for solving the pulse pattern manually by iteration), and the magnitude of nonlinearity effects had not been investigated. The enhanced control principle with the dead time handling capability and a case study of the test setup timing deviations are the main contributions of this doctoral thesis. The simulation and experimental setup results show that the proposed control method can be used in an actual drive. Loss measurements and a comparison of active du/dt output filtering with traditional output filtering methods are also presented in the work. Two different ADUDT filter designs are included, with ferrite core and air core inductors. Other filters included in the tests were a passive du/dtfilter and a passive sine filter. The loss measurements incorporated a silicon carbide diode-equipped IGBT module, and the results show lower losses with these new device technologies. The new control principle was measured in a 43 A load current motor drive system and was able to bring the filter output peak voltage from 980 V (the previous control principle) down to 680 V in a 540 V average DC link voltage variable-speed drive. A 200 m motor cable was used, and the filter losses for the active du/dt methods were 111W–126 W versus 184 W for the passive du/dt. In terms of inverter and filter losses, the active du/dt filtering method had a 1.82-fold increase in losses compared with an all-passive traditional du/dt output filter. The filter mass with the active du/dt method was 17% (2.4 kg, air-core inductors) compared with 14 kg of the passive du/dt method filter. Silicon carbide freewheeling diodes were found to reduce the inverter losses in the active du/dt filtering by 18% compared with the same IGBT module with silicon diodes. For a 200 m cable length, the average peak voltage at the motor terminals was 1050 V with no filter, 960 V for the all-passive du/dt filter, and 700 V for the active du/dt filtering applying the new control principle.

Glass pipette-carbon fiber microelectrodes for evoked potential recordings

Current methods for recording field potentials with tungsten electrodes make it virtually impossible to use the same recording electrode also as a lesioning electrode, for example for histological confirmation of the recorded site, because the lesioning procedure usually wears off the tungsten tip. Therefore, the electrode would have to be replaced after each lesioning procedure, which is a very high cost solution to the problem. We present here a low cost, easy to make, high quality glass pipette-carbon fiber microelectrode that shows resistive, signal/noise and electrochemical coupling advantages over tungsten electrodes. Also, currently used carbon fiber microelectrodes often show problems with electrical continuity, especially regarding electrochemical applications using a carbon-powder/resin mixture, with consequent low performance, besides the inconvenience of handling such a mixture. We propose here a new method for manufacturing glass pipette-carbon fiber microelectrodes with several advantages when recording intracerebral field potentials

Surface studies of limestones and dolostones : characterisation using various techniques and batch dissolution experiments with hydrochloric acid solutions

In this thesis, stepwise titration with hydrochloric acid was used to obtain chemical reactivities and dissolution rates of ground limestones and dolostones of varying geological backgrounds (sedimentary, metamorphic or magmatic). Two different ways of conducting the calculations were used: 1) a first order mathematical model was used to calculate extrapolated initial reactivities (and dissolution rates) at pH 4, and 2) a second order mathematical model was used to acquire integrated mean specific chemical reaction constants (and dissolution rates) at pH 5. The calculations of the reactivities and dissolution rates were based on rate of change of pH and particle size distributions of the sample powders obtained by laser diffraction. The initial dissolution rates at pH 4 were repeatedly higher than previously reported literature values, whereas the dissolution rates at pH 5 were consistent with former observations. Reactivities and dissolution rates varied substantially for dolostones, whereas for limestones and calcareous rocks, the variation can be primarily explained by relatively large sample standard deviations. A list of the dolostone samples in a decreasing order of initial reactivity at pH 4 is: 1) metamorphic dolostones with calcite/dolomite ratio higher than about 6% 2) sedimentary dolostones without calcite 3) metamorphic dolostones with calcite/dolomite ratio lower than about 6% The reactivities and dissolution rates were accompanied by a wide range of experimental techniques to characterise the samples, to reveal how different rocks changed during the dissolution process, and to find out which factors had an influence on their chemical reactivities. An emphasis was put on chemical and morphological changes taking place at the surfaces of the particles via X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM). Supporting chemical information was obtained with X-Ray Fluorescence (XRF) measurements of the samples, and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) measurements of the solutions used in the reactivity experiments. Information on mineral (modal) compositions and their occurrence was provided by X-Ray Diffraction (XRD), Energy Dispersive X-ray analysis (EDX) and studying thin sections with a petrographic microscope. BET (Brunauer, Emmet, Teller) surface areas were determined from nitrogen physisorption data. Factors increasing chemical reactivity of dolostones and calcareous rocks were found to be sedimentary origin, higher calcite concentration and smaller quartz concentration. Also, it is assumed that finer grain size and larger BET surface areas increase the reactivity although no certain correlation was found in this thesis. Atomic concentrations did not correlate with the reactivities. Sedimentary dolostones, unlike metamorphic ones, were found to have porous surface structures after dissolution. In addition, conventional (XPS) and synchrotron based (HRXPS) X-ray Photoelectron Spectroscopy were used to study bonding environments on calcite and dolomite surfaces. Both samples are insulators, which is why neutralisation measures such as electron flood gun and a conductive mask were used. Surface core level shifts of 0.7 ± 0.1 eV for Ca 2p spectrum of calcite and 0.75 ± 0.05 eV for Mg 2p and Ca 3s spectra of dolomite were obtained. Some satellite features of Ca 2p, C 1s and O 1s spectra have been suggested to be bulk plasmons. The origin of carbide bonds was suggested to be beam assisted interaction with hydrocarbons found on the surface. The results presented in this thesis are of particular importance for choosing raw materials for wet Flue Gas Desulphurisation (FGD) and construction industry. Wet FGD benefits from high reactivity, whereas construction industry can take advantage of slow reactivity of carbonate rocks often used in the facades of fine buildings. Information on chemical bonding environments may help to create more accurate models for water-rock interactions of carbonates.