Organic and total mercury determination in sediments by cold vapor atomic absorption spectrometry: methodology validation and uncertainty measurements

The purpose of the present study was to validate a method for organic Hg determination in sediment. The procedure for organic Hg was adapted from literature, where the organomercurial compounds were extracted with dichloromethane in acid medium and subsequent destruction of organic compounds by bromine chloride. Total Hg was performed according to 3051A USEPA methodology. Mercury quantification for both methodologies was then performed by CVAAS. Methodology validation was verified by analyzing certified reference materials for total Hg and methylmercury. The uncertainties for both methodologies were calculated. The quantification limit of 3.3 µg kg-1 was found for organic Hg by CVAAS.

Simple method for mass production of polypyrrole/carbon nanotubes hybrid artificial muscle

Large scale preparation of hybrid electrical actuators represents an important step for the production of low cost devices. Interfacial polymerization of polypyrrole in the presence of multi-walled carbon nanotubes represents a simple technique in which strong interaction between components is established, providing composite materials with potential applications as actuators due to the synergistic interaction between the individual components, i.e., fast response of carbon nanotubes, high strain of polypyrrole, and diversity in the available geometry of resulting samples.

Method for determining the photocatalytic potential of portland cement mortar containing TiO2 for decomposing the pollutant nitrogen monoxide

Photocatalytic materials can minimize atmospheric pollution by decomposing certain organic and inorganic pollutants using sunlight as an energy source. In this paper, the development of a methodology to measure the photocatalytic potential of mortar containing TiO2 nanoparticles is reported. The results indicate that up to 40% of NOx can be degraded by Portland cement mortar containing 30-50% of TiO2, which validates the method developed for evaluating the photocatalytic potential of materials.

FASES ESTACIONÁRIAS DE LÍQUIDOS IÔNICOS EM CROMATOGRAFIA GASOSA: FUNDAMENTOS, AVANÇOS RECENTES E PERSPECTIVAS

Since their original discovery in 1914, ionic liquids (IL) have been widely examined and explored in chemistry due to their unique physical and chemical properties. Ionic liquids are collectively known as organic salts and have melting points of 100 °C or under. The molten salts most employed in analytical chemistry, including gas chromatography (GC), consist of an organic cation paired with an organic or inorganic anion. This class of materials exhibits negligible vapor pressure and may have their properties (e.g.thermal stability and selectivity) structurally tuned by imparting different moieties to the cation/anion. Currently, there are an estimated 1018possible combinations of IL. In this context, the prospection of highly selective IL-based stationary phases for gas-liquid chromatography has enabled high peak capacity and efficient separations of many critical pairs in complex samples. In this review, we present and discuss fundamental characteristics of ionic liquids and introduce important solvation models for gas-liquid systems. In addition, recent advances and applications of IL in conventional and multidimensional gas chromatography are outlined.

Ba-DOPED ZnO MATERIALS: A DFT SIMULATION TO INVESTIGATE THE DOPING EFFECT ON FERROELECTRICITY

ZnO is a semiconductor material largely employed in the development of several electronic and optical devices due to its unique electronic, optical, piezo-, ferroelectric and structural properties. This study evaluates the properties of Ba-doped wurtzite-ZnO using quantum mechanical simulations based on the Density Functional Theory (DFT) allied to hybrid functional B3LYP. The Ba-doping caused increase in lattice parameters and slight distortions at the unit cell angle in a wurtzite structure. In addition, the doping process presented decrease in the band-gap (Eg) at low percentages suggesting band-gap engineering. For low doping amounts, the wavelength characteristic was observed in the visible range; whereas, for middle and high doping amounts, the wavelength belongs to the Ultraviolet range. The Ba atoms also influence the ferroelectric property, which is improved linearly with the doping amount, except for doping at 100% or wurtzite-BaO. The ferroelectric results indicate the ZnO:Ba is an strong option to replace perovskite materials in ferroelectric and flash-type memory devices.

Elemental analysis of wood materials by external millibeam thick target PIXE

PIXE (Particle Induce X-ray Emission spectrometry) was used for analysing stem bark and stem wood of Scots pine, Norway spruce and Silver birch. Thick samples were irradiated, in laboratory atmosphere, with 3 MeV protons and the beam current was measured indirectly using a photo multiplicator (PM) tube. Both point scans and bulk analyses were performed with the 1 mm diameter proton beam. In bulk analyses, whole bark and sectors of discs of the stem wood were dry ashed at 550 ˚C. The ashes were homogenised by shaking and prepared to target pellets for PIXE analyses. This procedure generated representative samples to be analysed, but the enrichment also enabled quantification of some additional trace elements. The ash contents obtained as a product of the sample preparation procedure also showed to be of great importance in the evaluation of results in environmental studies. Spot scans from the pith of pine wood outwards, showed clearly highest concentrations of manganese, calcium and zinc in the first spot irradiated, or 2-3 times higher than in the surrounding wood. For stem wood from the crown part of a pine this higher concentration level was found in the first four spots/mms, including the pith and the two following growth rings. Zinc showed increasing concentrations outwards in sapwood of the pine stem, with the over-all lowest concentrations in the inner half of the sapwood. This could indicate emigration of this element from sapwood being under transformation to heartwood. Point scans across sapwood of pine and spruce showed more distinct variations in concentrations relative to hearth wood. Higher concentrations of e.g. zinc, calcium and manganese were found in earlywood than in denser latewood. Very high concentrations of iron and copper were also seen for some earlywood increments. The ash content of stem bark is up to and order higher than for the stem wood. However, when the elemental concentration in ashes of bark and wood of the same disc were compared, these are very similar – this when trees are growing at spots with no anthropogenic contamination from the atmosphere. The largest difference was obtained for calcium which appeared at two times high concentrations in ashes of bark than in ashes of the wood (ratio of 2). Pine bark is often used in monitoring of atmospheric pollution, where concentrations in bark samples are compared. Here an alternative approach is suggested: Bark and the underlying stem wood of a pine trees are dry ashed and analysed. The elemental concentration in the bark ash is then compared to the concentration of the same element in the wood ash. Comparing bark to wood includes a normalisation for the varying availability of an element from the soil at different sites. When this comparison is done for the ashes of the materials, a normalisation is also obtained for the general and locally different enrichment of inorganic elements from wood to bark. Already a ratio >2 between the concentration in the bark ash and the concentration in the wood ash could indicate atmospheric pollution. For monitoring where bark is used, this way of “inwards” comparison is suggested - instead of comparing to results from analyses of bark from other trees (read reference areas), growing at sites with different soil and, locally, different climate conditions. This approach also enables evaluation of atmospheric pollution from sampling of only relative few individual trees –preferable during forest felling.

Metallien kompleksinmuodostus liuosfaasissa

Liuoksessa metallit muodostavat erilaisia koordinatioyhdisteitä epäorgaanisten ja orgaanisten anionien ja neutraalien molekyylien kanssa. Erityisesti siirtymämetalleilla on voimakas taipumus kompleksiyhdisteiden muodostamiseen elektroneja sisältävien 3-, 4-, ja 5d orbitaaliensa johdosta. Samassa liuoksessa voi samanaikaisesti esiintyä useita erilaisia, mutta samoista lähtöaineista muodostuneita, kompleksiyhdisteitä. Kompleksinmuodostusreaktiot ovat tasapainoreaktioita. Usein tasapainovakiot on esitetty termodynaamisina tasapainovakioina eli ne ovat päteviä standarditilassa. Standarditilan tasapainovakioista voidaan johtaa missä tahansa liuoksessa pätevät vakiot erilaisten Debye-Hückel-teoriasta johdettujen laskentamenetelmien avulla. Metalli-ligandiparin jakautuminen erilaisiksi kompleksiyhdisteiksi voidaan mallintaa kun tunnetaan muodostumisreaktioiden tasapainovakiot. Muodostumisreaktioiden tasapainovakioiden yhtälöistä voidaan johtaa epälineaarinen yhtälöryhmä, joka voidaan ratkaista jollakin numeerisella ratkaisimella. Esimerkiksi Matlab-ohjelmiston sisältämä fsolve-ratkaisin soveltuu tällaiseen tehtävään. Osana tätä työtä on kirjoitettu Matlab-sovellus, jolla voidaan mallintaa kationi-ligandiparin jakautumista koordinaatioyhdisteiksi tunnettujen tasapainovakioiden perusteella.

Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.

Printed low-voltage organic transistors on plastics and paper

The main advantage of organic electronics over the more widespread inorganic counterparts lies not in the electrical performance, but rather in the solution processability that opens up for low-cost flexible electronics (e.g. displays, sensors and smart tags) fabricated by using printing techniques. Replacing the commonly used laboratory-scale fabrication techniques with mass-printing techniques is, however, truly challenging, especially when low-voltage operation is required. In this thesis it is, nevertheless, demonstrated that low-voltage organic transistors can be fully printed with a similar performance to that of transistors made by laboratory scale techniques. The use of an ion-modulated type of organic field effect transistor (OFET) not only enabled low-voltage operation and printability, but was also found to result in low sensitivity to the surface roughness of the substrate. This allows not only the use of low-cost plastic substrates, but even the use of paper as a substrate. However, while absorption into the porous paper surface is advantageous in a graphical printing process, by reducing the spreading and the coffee-stain effect and by improving the adhesion, it provides great challenges when applying thin electrically active layers. In spite of these difficulties we were able to demonstrate the first low-voltage OFET to be fabricated on paper. We have also shown that low-cost incandescent lamps can be used for sintering printed metal-nanoparticles, and that the process was especially suitable on paper and compatible with a roll-to-roll manufacturing process.

Feasibility study of metal to polymer hybrid joining

The increasing demand for lightweight components has led to a huge exploitation of non-metallic materials such as polymers, fibers and elastomers in industrial and manufacturing processes. Recent trends towards cost effectiveness, weight reduction and production flexibility in industrial production and manufacturing processes has led to a growing interest in hybrid components where two or more dissimilar materials coexist to achieving specifically optimized characteristics. The importance of this research is to serve as a bridge to understanding the theories behind various joining techniques and the adaptation of the process for metal to polymer hybrid joints. Moreso, it helps companies to select the most productive and yet economical joining process for realization of lightweight metal to polymer hybrid components. This thesis is a literature review analyzing various materials that has been published on various joining methods for metal to polymer hybrid joints on the feasibility and eventual realization of the joint between these dissimilar materials. This study is aimed at theoretically evaluating the feasibility of joining processes between metal and plastic components by exploiting exhaustively joining and welding sources.

Laser-TIG hybrid welding process

Joining processes and techniques need to meet the trend of new applications and the development of new materials. The application in connection with thick and thin plates in industrial fields is wide and the joining technology is in very urgent need. The laser-TIG hybrid welding technology can play the respective advantages of both of them. One major advantage of the hybrid laser-TIG welding technology is its efficient use of laser energy. Additionally, it can develop into a high and new advanced welding technology and become a hot spot in both the application and research area. This thesis investigated laser –TIG hybrid welding with the aim of enlightening the reader on its advantages, disadvantages and future areas of improvement. The main objective is to investigate laser-TIG hybrid on the welding of various metals (steels, magnesium, aluminium etc.). In addition, it elaborates on various possible combinations on hybrid laser-TIG welding technology and their benefits. The possibility of using laser-TIG hybrid in welding of thick materials was investigated. The method applied in carrying out this research is by using literature review. The results showed that hybrid laser-TIG is applicable to almost all weldable metals. Also it proves to be effective in welding refractive metals. The possibility of welding with or without filler materials is of economic advantage especially in welding of materials with no filler material. Thick plate’s hybrid laser-TIG welding is showing great prospects although it normally finds its used in welding thin materials in the range of 0.4 to 0.8 mm. The findings show that laser-TIG hybrid welding can be a versatile welding process and therefore will be increasingly used industrially due to its numerous advantages and the development of new TIG arc that enhances its capabilities.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Optimization of parameters for fiber laser-MAG hybrid welding in shipbuilding applications

The Arctic region becoming very active area of the industrial developments since it may contain approximately 15-25% of the hydrocarbon and other valuable natural resources which are in great demand nowadays. Harsh operation conditions make the Arctic region difficult to access due to low temperatures which can drop below -50 °C in winter and various additional loads. As a result, newer and modified metallic materials are implemented which can cause certain problems in welding them properly. Steel is still the most widely used material in the Arctic regions due to high mechanical properties, cheapness and manufacturability. Moreover, with recent steel manufacturing development it is possible to make up to 1100 MPa yield strength microalloyed high strength steel which can be operated at temperatures -60 °C possessing reasonable weldability, ductility and suitable impact toughness which is the most crucial property for the Arctic usability. For many years, the arc welding was the most dominant joining method of the metallic materials. Recently, other joining methods are successfully implemented into welding manufacturing due to growing industrial demands and one of them is the laser-arc hybrid welding. The laser-arc hybrid welding successfully combines the advantages and eliminates the disadvantages of the both joining methods therefore produce less distortions, reduce the need of edge preparation, generates narrower heat-affected zone, and increase welding speed or productivity significantly. Moreover, due to easy implementation of the filler wire, accordingly the mechanical properties of the joints can be manipulated in order to produce suitable quality. Moreover, with laser-arc hybrid welding it is possible to achieve matching weld metal compared to the base material even with the low alloying welding wires without excessive softening of the HAZ in the high strength steels. As a result, the laser-arc welding methods can be the most desired and dominating welding technology nowadays, and which is already operating in automotive and shipbuilding industries with a great success. However, in the future it can be extended to offshore, pipe-laying, and heavy equipment industries for arctic environment. CO2 and Nd:YAG laser sources in combination with gas metal arc source have been used widely in the past two decades. Recently, the fiber laser sources offered high power outputs with excellent beam quality, very high electrical efficiency, low maintenance expenses, and higher mobility due to fiber optics. As a result, fiber laser-arc hybrid process offers even more extended advantages and applications. However, the information about fiber or disk laser-arc hybrid welding is very limited. The objectives of the Master’s thesis are concentrated on the study of fiber laser-MAG hybrid welding parameters in order to understand resulting mechanical properties and quality of the welds. In this work only ferrous materials are reviewed. The qualitative methodological approach has been used to achieve the objectives. This study demonstrates that laser-arc hybrid welding is suitable for welding of many types, thicknesses and strength of steels with acceptable mechanical properties along very high productivity. New developments of the fiber laser-arc hybrid process offers extended capabilities over CO2 laser combined with the arc. This work can be used as guideline in hybrid welding technology with comprehensive study the effect of welding parameter on joint quality.

Population density and weed infestation in organic no-tillage corn cropping system under different soil covers

Currently, one of the biggest challenges faced by organic no-tillage farming is weed control. Thus, the use of cropping practices that help in the control of weeds is extremely important. The objective of this study was to evaluate population density and level of weed infestation in an organic no-tillage corn cropping system under different soil covers. The experiment was conducted in a randomized block design with six repetitions and five treatments, consisting of three soil covers in an organic no-tillage system, and an organic and a conventional system, both without soil cover. The treatments with soil cover used a grass species represented by the black oat, a leguminous species represented by the white lupine, and intercropping between both species. Corn was sown with spacing of 1.0 m between rows and 0.20 m between plants, using the commercial hybrid AG 1051. Infestation in corn was evaluated at stages V5 and V10, and weed density was evaluated at stage V5. The use of black oat straw alone or intercropped with white lupine, in the organic no-tillage corn cropping system, reduced the percentage of weed infestation and absolute weed density. Management-intensive systems and systems without soil cover showed higher relative densities for species Oxalis spp., Galinsoga quadriradiata and Stachys arvensis. The species Cyperus rotundus showed the highest relative density on organic no-tillage corn cropping systems. Black oat straw in the organic no-tillage cropping system limited the productive potential of corn.

Decentralized management of organic household wastes in the Kathmandu Valley using small-scale composting reactors

The sustainable management of municipal solid waste in the Kathmandu Valley has always been a challenging task. Solid waste generation has gone rapidly high in the Kathmandu Valley over the last decade due to booming population and rapid urbaniza-tion. Finding appropriate landfill sites for the disposal of solid wastes generated from the households of the Kathmandu Valley has always been a major problem for Nepalese government. 65 % of total generated wastes from the households of Nepal consist of organic materials. As large fractions of generated household wastes are organic in na-ture, composting can be considered as one of the best sustainable ways to recycle organ-ic wastes generated from the households of Nepal. Model Community Society Development (MCDS), a non-governmental organization of Nepal carried out its small-scale project in five households of the Kathmandu Valley by installing composting reactors. This thesis is based on this small-scale project and has used secondary data provided by MCDS Nepal for carrying out the study. Proper man-agement of organic wastes can be done at household levels through the use of compost-ing reactors. The end product compost can be used as soil conditioners for agricultural purposes such as organic farming, roof-top farming and gardening. The overall average organic waste generation in the Kathmandu Valley is found to be 0,23 kg/person/day and the total amount of organic household wastes generated in the Kathmandu Valley is around 210 Gg/yr. Produced composts from five composting reac-tors contain high amount of moistures but have sufficient amount of nutrients required for the fertility of land and plant growth. Installation of five composting reactors in five households have prevented 2,74 Mg of organic wastes going into the landfills, thus re-ducing 107 kg of methane emissions which is equivalent to 2,7 Mg of carbondioxide.