Technological solution for the automatic replacement of the catalytic filaments in HWCVD

The degradation of the catalytic filaments is the main factor limiting the industrial implementation of the hot wire chemical vapor deposition (HWCVD) technique. Up to now, no solution has been found to protect the catalytic filaments used in HWCVD without compromising their catalytic activity. Probably, the definitive solution relies on the automatic replacement of the catalytic filaments. In this work, the results of the validation tests of a new apparatus for the automatic replacement of the catalytic filaments are reported. The functionalities of the different parts have been validated using a 0.2 mm diameter tungsten filament under uc-Si:H deposition conditions.

Fotocromismo em filmes finos de óxidos de tungstênio de diferentes composições

Tungsten oxide thin films with three different compositions were deposited by reactive sputtering in an oxygen-argon plasma. In a system composed of a home made photochemical reactor coupled with an optic fiber spectrophotometer, the photochromic effect was studied in these oxide films as function of UV irradiation time, in ethanol, methanol and formaldehyde atmospheres. It was observed that the photochromic efficiency depends on the vapor chemical nature where the film is irradiated as well as the film composition. Kinetic analysis suggest that two kinds of optical absorption centers should respond by the photochromic effect in these films, one generated at film surface and other inside it, which one presenting a different time constant.

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.

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.

Spectrophotometric study of iron oxidation in the iron(II)/thiocyanate/acetone system and some analytical applications

The possibility of using thiocyanate to determine iron(II) and/or iron(III) in water-acetone mixture has been re-examined as part of a systematic and comparative study involving metallic complexes of pseudohalide ligands. Some parameters that affect the complete oxidation of the ferrous cations, their subsequent complexation and the system stability have been studied to optimize the experimental conditions. Our results show the viability and potentiality of this simply methodology as an alternative analytical procedure to determine iron cations with high sensitivity, precision and accuracy. Studies on the calibration, stability, precision, and effect of various different ions have been carried out by using absorbance values measured at 480 nm. The analytical curve for the total iron determination obeys Beer's law (r = 0.9993), showing a higher sensitivity (molar absorptivity of 2.10x10(4) L cm-1 mol-1) when compared with other traditional systems (ligands) or even with the "similar" azide ion [1.53x10(4) L cm-1 mol-1, for iron-III/azide complexes, in 70% (v/v) tetrahydrofuran/water, at 396 nm]. Under such optimized experimental conditions, it is possible to determine iron in the concentration range from 0.5 to 2 ppm (15-65% T for older equipments, quartz cells of 1.00 cm). Analytical applications have been tested for some different materials (iron ores), also including pharmaceutical products for anemia, and results were compared with atomic absorption determinations. Very good agreement was obtained with these two different techniques, showing the potential of the present experimental conditions for the total iron spectrophotometric determinations (errors < 5%). The possibility of iron speciation was made evident by using another specific and auxiliary method for iron(II) or (III).

Simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation process by GFAAS

A method has been developed for the simultaneous determination of Cd and Pb in antibiotics used in sugar-cane fermentation by GFAAS. The integrated platform of transversely heated graphite atomizer was treated with tungsten to form a coating of tungsten carbide. Six samples of commercial solid antibiotics were analyzed by injecting 20 µL of digested samples into the pretreated graphite platform with co-injection of 5 µL of 1000 mg L-1 Pd as chemical modifier. Samples were mineralized in a closed-vessel microwave-assisted acid-digestion system using nitric acid plus hydrogen peroxide. The pyrolysis and atomization temperatures of the heating program of the atomizer were selected as 600°C and 2200°C, respectively. The calculated characteristic mass for Cd and Pb was 1.6 pg and 42 pg, respectively. Limits of detection (LOD) based on integrated absorbance were 0.02 µg L-1 Cd and 0.7 µg L-1 Pb and the relative standard deviations (n = 10) for Cd and Pb were 5.7% and 8.0%, respectively. The recoveries of Cd and Pb added to the digested samples varied from 91% to 125% (Cd) and 80% to 112% (Pb).

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.

Pretreatment processes in gold recovery by thiosulphate leaching

This thesis describes several different pretreatment processes for gold concentrates and ores. The thesis is divided to theoretical part and experimental part. The theoretical part presents the operating principle of the main pretreatment methods and their suitability for thiosulphate leaching. In the theoretical part also the whole recovery process for gold from ore to elemental gold is presented. In the experimental part the study is focused on pretreatment of sulphidic refractory concentrates with mechanical activation and chemical oxidation under alkaline environment; and their effect on leachability in the thiosulphate leaching. In the experimental part a combined 2-step process, where chemical oxidation under ammoniacal environment is cascaded with thiosulphate leaching in the same conditions, is also tested. The main sulphuric mineral components in the studied refractory concentrate are pyrite (49.4 %) and arsenopyrite (27.7 %). The gold content in the concentrate is 11.3 ppm and silver content is 90 ppm. Without pretreatment the gold conversion in thiosulphate leaching was 30 %, which was analyzed at the time point of 9 hours. At that time the silver conversion was 17 %. By using mechanical activation the gold conversion reached was 59 % and silver conversion 26 %. With chemical oxidation under alkaline environment, where the used chemical was sodium hydroxide, the reached conversion of gold was 72 % and 31 % for silver. In the combined oxidation and leaching experiment the conversion of gold remained at 49 % and 18 % for silver.

CO2 sparging for improving the filtration properties of iron ore slurries

Iron ore treatment processes are usually continuous and high tonnage and filtration equipment has to meet these requirements. In magnetite (Fe3O4) treatment process continuous rotary disc filters are often used for filtration. Carbon dioxide (CO2) treatment is a fairly novel and un-known filtration enhancing process. The interest to use CO2 is quite high because CO2 is a greenhouse gas that is abundant, readily available and capture and use of CO2 would be environmentally beneficial. The focus of this thesis was to investigate if CO2 could be used to enhance the filtration of magnetite with ceramic disc filter. Previous studies have suggested that CO2 could be used to enhance the filtration properties of different iron ores thus increasing the filtration capacity. In the literature part, the basic theory of filtration and the particle properties affecting filtration were discussed. The basic steps of a typical ore treatment process were presented. The reasons why CO2 might enhance the filtration properties of different ores were investigated. A literature survey of earlier studies of CO2 addition as a filter aid was presented and the basic chemical properties and reactions of CO2 were also discussed. The experimental part was done at the LUT Laboratory of Separation Technology using different magnetite samples from the industry. The filtration experiments indicated that CO2 had a positive influence on the filtration properties of magnetite slurry. Zeta potential of untreated and CO2 treated magnetite was measured and CO2 treated magnetite had lower zeta potential values than the untreated magnetite. The filtration capacity was increased while the cake moisture levels were only slightly increased.