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The work presented in this thesis is concerned with the microstructure of zinc oxide varistor materials used in surge protecting devices. This class of material has been characterised with special emphasis on the functional microstructure and the development of the microstructure during sintering. Several different techniques have been used for the analysis, especially scanning electron microscopy (SEM) in combination with electron beam-induced current (EBIC) analysis and in-situ studies of heat-treatment experiments and transmission electron microscopy (TEM) in combination with energy dispersive X-ray spectrometry (EDS) and electron holography. Detailed TEM analyses using primarily centred dark-field imaging of grain boundaries, especially triple and multiple grain junctions, were used to reveal the morphological differences between the various Bi2O3 phases. The triple and multiple grain junctions were found to exhibit distinct differences in morphology, which could be attributed the difference in structure of the crystalline Bi2O3 polymorphs present in the junctions. Electrical measurements were performed on individual ZnO/ZnO grain boundaries using EBIC in the SEM. The EBIC signal was found to depend strongly on the geometric properties of the interface and also on the symmetry of the depletion region at the interface. A symmetric double Schottky barrier was never observed in the experiments, but instead barriers with clear asymmetry in the depletion region. Experimental results together with computer simulations show that reasonably small differences in the deep donor concentrations between grains could be responsible for this effect. Electron holography in the TEM was used to image the electrostatic potential variation across individual ZnO/ZnO interfaces. The sign of the interface charge, the barrier height (about 0.8 eV) and the depletion region width (100 to 150 nm) were determined from holography data. Asymmetries of the depletion region were also found with this technique. The full sintering process of doped ZnO powder granules was studied in-situ in the environmental SEM. The densification and grain growth processes were studied through the sintering cycle. The formation of a functional microstructure in ZnO varistor materials was found to depend strongly on the total pressure.

Hairy prairie-clover (Dalea villosa Nutt. (Spreng) var. villosa), a rare plant species, grows in the Canadian Prairies. Populations of Dalea in Canada are threatened by the loss of sand dune habitat because of changes in land use and altered ecological processes such as grazing and fire. Local populations of Dalea are further threatened by one or more specific threats, including herbivory from native and domestic ungulates and invasion of habitats by exotic plants. The overall objective of this thesis was to gain more knowledge about Dalea and to determine the impact of threats and management practices to the Saskatchewan populations and their habitats. Observational studies were conducted at each of two sites in Saskatchewan supporting Dalea. First, at the Dundurn Sandhills site, structural equation modeling was used to examine landscape, ecological, and management factors associated with high rates of herbivory on Dalea and with reductions in the long-term survival and productivity of Dalea. The conditions which deer (Odocoileus hemionus and Odocoileus virginianus) or cattle (Bos taurus) were responsible for the most intense rates of herbivory to Dalea plants and patches were determined. Generally, deer appeared responsible for the most herbivory, whereas cattle grazing on Dalea increased with stocking densities. At the same time, new hypotheses about ecological processes affecting Dalea productivity in the Dundurn Sandhills were explored. In particular, it appeared that deer may be responding to cattle grazing in Dalea habitat by avoiding those areas, and that mid-season germination and recruitment of many Dalea plants may occur following precipitation events. Second, at the Mortlach site, the costs and benefits of using grazing management to control leafy spurge (Euphorbia esula L. var. esula) were assessed, especially in consideration of the potential negative effects of intense herbivory on Dalea productivity. Aspects of the grazing regime including stocking density and the livestock species influenced herbivory on Dalea and its reproductive output, but there were no apparent links between the abundance of leafy spurge abundance and the reproductive output of Dalea. The findings of these two studies are relevant for the conservation and management of Dalea in Saskatchewan.

Flax fibers are often used as reinforcement for thermoset and thermoplastic to produce biocomposite products. These products exhibit numerous advantages such as good mechanical properties, low density, and biodegradability. Thermoplastics are usually reinforced with flax fiber using injection molding technology and limited research has been done on compression molded thermoplastic biocomposite. Therefore, commercial thermoplastic high density polyethylene (HDPE) and polypropylene (PP) were selected for developing compression molded flax reinforced biocomposites in this research project. The main goal of this research was to develop compression molded biocomposite board using Saskatchewan flax fiber and investigate the effect of flax fiber and processing parameters (molding temperature and molding pressure) on the properties of biocomposite. <p>The fiber was cleaned and chemically treated with alkaline and silane solution that modified the fiber surface. Chemical treatments significantly increased the mechanical properties due to better fiber-polymer interfacial adhesion and also reduced the water absorption characteristics. The silane treatment showed better results than alkaline treatment. Differential scanning calorimetry (DSC) test and scanning electron microscopy (SEM) test were performed to study the thermal and morphological properties of the untreated and chemically treated flax fiber. Flax fiber and thermoplastic resin was mixed using a single-screw extruder to ensure homogenous mixing. HDPE- and PP-based biocomposites were developed through compression molding with three different pretreated flax fiber (untreated, alkaline, silane treated fiber), three levels of fiber content, two levels of molding temperature and two levels of molding pressure. <p>Increase in fiber content increased composite color index, density, water absorption, tensile strength, Youngs modulus, bending strength, and flexural modulus. However for the HDPE composites, tensile and bending strength decreased after 20% flax fiber loading. For the PP composites the, tensile and bending strength decreased after 10% flax fiber loading. Analysis of variance (ANOVA) was performed to quantitatively show the significant effects of the process variables (molding temperature, pressure, and fiber content) and their interactions on the response variables (physical and mechanical properties of biocomposites). The duncan multiple range test (DMRT) was also performed to compare the treatment means. Superposition surface methodology was adapted for both HDPE and PP composites to determine the optimum values of process variables.

Heavy metal contamination is a serious concern throughout the world. Increased concentrations in drinking water have many negative impacts on human health. Limestone is an inexpensive and simple media for removing high concentrations of heavy metals from drinking water supplies. Ferric based media is commonly used to remove zinc, cadmium, lead, arsenic and other heavy metals. The drinking water standards set by the US EPA for cadmium, zinc and arsenic are 0.005 mg/L, 5 mg/L and 0.010 mg/L respectively. Bangladesh, parts of India, China and the United States have high concentrations of arsenic in drinking water. Although many technologies exist for heavy metal removal, most of these are complicated and are associated with high costs making them ineffective and unfavorable to be used in impoverished areas. We propose a novel method that combines the benefits of limestone with the capacity of ferric media in an iron-coated limestone based material. Samples of water with various concentrations of zinc and cadmium were prepared and batch tests were performed using both uncoated and iron coated limestone and are compared in removal efficiency. Kinetics studies showed that zinc is removed to a maximum level after 24 hours, while cadmium takes only 15 minutes. The effect of pH on removal of heavy metals was also studied. Metals are analyzed using Inductively Coupled Plasma Emission Spectroscopy (ICP-ES). Limestone is readily available and is also easy to coat with iron, making this material a cost effective and affordable method to be used by developing countries.

This thesis aims to investigate the formation of deposits from thermally degraded biodiesel on a hot metal surface under the influence of sodium or copper contaminations. Biodiesel or Fatty Acid Methyl Esters (FAMEs) is a widely utilized biofuel with the potential to replace fossil fuels, however, issues regarding the thermal and oxidative stability prevent the progress of biodiesel for utilization as vehicle fuel. The thermal degradation of biodiesel causes formation of deposits often occurring in the fuel injectors, which could result in reduced engine efficiency, increased emissions and engine wear. However, still have no standard method for evaluation of a fuels’ tendency to form deposits been developed. In this study biodiesel deposits have been formed on aluminum test tubes utilizing a Hot Liquid Process Simulator (HLPS), an instrument based on the principle of the Jet Fuel Thermal Oxidation Tester (JFTOT). Quantitative and qualitative analyses have been made utilizing an array of techniques including Scanning Electron Microscopy (SEM), Gas Chromatography Mass Spectrometry (GCMS) and Attenuated Total Reflectance Fourier Transform Infrared Spectrometry (ATR-FTIR). A multi-factorial trial investigating the effects of sodium hydroxide and copper contaminations at trace levels and the impact of a paraffin inhibitor copolymer additive on three different FAME products, two derived from rapeseed oil and one from waste cooking oil as well as a biodiesel blend with mineral diesel, was conducted.The results exhibited that FAMEs are the major precursor to deposit formation in diesel fuel. The SEM analyses exploited the nature of FAME deposits forming porous structures on hot metal surfaces. Sodium hydroxide proved to participate in the deposit formation by forming carboxylic salts. However, the copper contamination exhibited no enhancing effect on the deposits, possibly due to interference of the blank oil in which copper was received. The paraffin inhibitor functioning as a crystal modifier had significant reducing effect on the deposit formation for all biodiesel samples except for the FAME product derived from waste cooking oil. Further studies are needed in order to investigate the influence of glycerin and water residues to the biodiesel deposit formation. Mechanisms involving oxidative or thermal peroxide formation, polymerization and disintegration have been suggested as degradation pathways for biodiesel. The involvement of oxidation intermediates, peroxides, was confirmed by the experiments performed in this thesis. However, the mechanisms of biodiesel deposit formation are complex and hard to study as the deposits are seemingly insoluble. Nevertheless, ATR-FTIR in combination with JFTOT-processing has potential as standard method for evaluation of deposit forming tendencies of biodiesel.

L'ús de materials híbrids ha estat demostrat que és una aposta important en moltes àrees de la ciència i particularment, dels processos de separació. En aquest treball s'ha utilitzat el carbó activat per obtenir membranes compostes. Les membranes de naturalesa carbonosa ofereixen el potencial de combinar la senzilla utilització dels polímers amb les bones propietats de separació dels tamisos moleculars carbonosos. Tanmateix, la incorporació del carbó activat respon a una segona motivació corresponent al seu ús com a suport per obtenir reactors de membrana enzimàtics (EMR). D'aquesta manera s'aconsegueix obtenir en un únic procés una operació de separació i una de reacció, fet que es coneix com intensificació de processos, i que respon a una de les principals tendències de la recerca actual. En la primera etapa del treball es van sintetitzar membranes polimèriques de polisulfona mitjançant el mètode de precipitació per immersió, i en primer terme, es va estudiar l'efecte de la concentració de polímer, i el tipus de solvent a utilitzar. Determinades aquestes condicions, es va realitzar un estudi més profund considerant la variació de la composició del bany de coagulació. La caracterització va incloure la microscòpia electrònica d'escombratge (SEM), la microscòpia de força atòmica, la tècnica experimental de rebuig de sòlids i l'angle de contacte. També es van caracteritzar les membranes mecànicament. Els resultats van demostrar que amb la variació de la concentració del bany de coagulació s'obtenen membranes amb morfologies molt diferents, aptes per processos de micro i ultrafiltració, les quals ofereixen un rang de tall d'entre 25 i 700 kDa (mesurat amb dextrans). El mètode de SEM és un dels més versàtils ja que permet caracteritzar morfològicament tota la superfície de la membrana, de manera relativament ràpida i senzilla i sobretot podent-la examinar globalment. Tanmateix, els resultats són qualitatius, i en aquest treball es va desenvolupar una eina informàtica (IFME®) que permet obtenir resultats quantitatius, ràpids i sistemàtics. Relatiu al mètode experimental, cal destacar que el rendiment de les membranes es veu decisivament afectat pel disseny del mòdul: un mal disseny pot implicar un inadequat flux sobre la mateixa i l'aparició de fenòmens com l'embrutiment o la polarització que implica una sensible reducció del flux de permeat i una modificació del tall de la membrana. És per això, que es van considerar diversos mòduls, i per cada un d'ells es va realitzar un estudi de la dinàmica de fluid (CFD) per tal d'estudiar-ne el seu comportament i optimitzar-lo en els casos necessaris.La segona etapa va consistir en l'obtenció i caracterització de membranes compostes mitjançant l'ús de carbó activat (mateixos mètodes). Se'n van obtenir de dos tipus: les formades per una i dues capes. En les primeres, el carbó es va addicionar juntament amb el polímer i el solvent, de manera que quedava una mescla homogènia a partir de la qual s'obtenia la membrana. En les de dues, el carbó es va addicionar a la part superior del film un cop estava format, però abans d'obtenir la membrana. Els resultats van mostrar que l'addició de carbó activat no modificava les propietats morfològiques de les membranes, i conseqüentment, la seva capacitat de separació, malgrat les funcionalitzava.En la darrera etapa es van desenvolupar dos tipus d'EMRs. Un primer utilitzant enzim sòlid que es va immobilitzar entre dues capes de membrana (sense enllaç químic), i un segon que va incloure un complex enzimàtic líquid enllaçat químicament al carbó activat de dues maneres: directament a ell i mitjançant l'ús d'un ió metàl·lic, Cu(II), (tècnica IMAC). D'aquest darrer tipus, se'n van obtenir dos configuracions: d'una capa, on el complex es va addicionar juntament amb el polímer i el solvent obtenint una mescla homogènia de tots els components, i de dues capes, addicionant el complex damunt el film polimèric, però abans d'introduir-lo al bany de coagulació i obtenir la membrana. Totes les membranes enzimàtiques obtingudes van mostrar una adequada immobilització de l'enzim i una bona reactivitat i per tant, es va aconseguir un bon equilibri entre la velocitat de reacció i la de separació. Els reactors monocapa obtinguts amb l'enzim líquid són els que van oferir un rendiment global millor, ja que permeten l'obtenció d'aquells components més desitjats, mantenen inalterada la capacitat de separació de la membrana, són vàlids també per processos difusius i són sistemes molt compactes. / The utilization of hydride materials has been demonstrated to be an important approach in many fields of science, and particularly, in separation processes. In this work, activated carbon was used to obtain composite membranes. They offer the potential of combine the simple utilization of polymers with the functional properties of carbon materials. Nevertheless, the incorporation of the activated carbon responds also to a second objective: the production of enzymatic membrane reactors by taking advantage of its adsorption capability. Therefore it is possible to obtain a single unit which carries out two processes: separation and reaction. This is process intensification, which is one of the main research trends. In the first stage, polysulfone membranes were synthesized by immersion precipitation. Firstly, the effect of its concentration in the polymeric mixture was studied. Secondly, the type of solvent was also investigated. When the best conditions of these variables were encountered, the effect of the composition of the coagulation bath was deeply studied. The characterization included methods as the scanning electron microscopy (SEM), the force atomic microscopy, the experimental related to solid exclusion and the contact angle. Membranes were also mechanical characterized by strain-stress tests. Results demonstrated that with the variation of the coagulation bath it is possible to obtain a wide range of membrane morphologies with a cut-off range from 25 to 700 kDa (measured with dextrans). The SEM is one of the most versatile method because allows to characterize morphologically almost all the membrane surface, in a quick and simple way. But the results obtained are qualitative, and in this work, a software (IFME®) was developed to obtain quantitative results, quickly and systematically. Related to the experimental, the global performance of membranes depends also on the module design: a wrong design could imply a non-adequate flux flow over the membrane, which facilitates the phenomena of fouling and polarization that reduces the permeate flow. For this reason, several modules were considered, used and also simulated with computational fluid dynamics, and in those necessary cases, were also optimized. The second stage consisted on the synthesis and characterization of composite membranes by adding activated carbon (same techniques). Two types of composite membranes were obtained. A single-layered one, which the activated carbon was added to the polymeric solution at the beginning of the process and, therefore, a homogeneous film and membrane were obtained, and a two-layered one. The activated carbon was added over the surface of the film obtained before immersing it in the coagulation bath, and therefore, producing the membrane. Results showed that the addition of the carbon did not modify the morphology of the membranes and therefore, their separation capability, but it added functionality to the membrane.The last stage of the work consisted on the synthesis of two types of EMR. The first one contained a solid enzyme which was immobilized between two membrane layers (without chemical bind). The second one contained an enzymatic liquid complex with was bounded directly to the activated carbon and by using an ion metal (IMAC technique). Related to this second type of enzyme, two different EMR configurations were obtained: a single-layered one (adding the complex to the polymeric mixture) and two-layered one (adding the complex over the obtained film before producing the membrane). All the configurations demonstrated a successfully immobilization of the enzyme and also proper reactivity results (a good equilibrium between the kinetics of the reaction and the membrane flux was achieved). The monolayer enzymatic membrane reactor was the one which showed best overall results, since the desired reaction products could be obtained, the separation capability of the membrane was not altered, the system is also valid for diffusive processes and the system is very compact.

Abstract Methods for tephrochronology are evaluated, in the following way: Lake sediments &lt;500 years old from three small Antarctic lakes were analysed for identification of tephras. Subsamples were analysed for a) grain size, and identification and concentration of volcanogenic grains, b) identification of tephra horizons, c) element abundance by EPMA WDS/EDS and LA-ICP-MS, and d) possible correlations between lakes and volcanoes. Volcanogenic minerals and shards were found all through the sediment cores in all three lakes, in different abundances. A high background population of volcanogenic mineral grains, in all samples, made the identification of tephra horizons difficult, and shards could only be distinguished by certainty after chemical analysis of elements. The tephra layers commonly could not be seen by the naked eye, and, hence they are regarded as cryptotephras. Because of the small size of recent eruptions in the research area, and the travel distance of ash, most shards are small and difficult to analyse. Nine possible tephra horizons have been recorded in the three lakes, and preliminary correlations have been made. But because of analytical problems, the proposed correlations between the lakes and possible volcanic sources are preliminary.

Flax fibers are often used as reinforcement for thermoset and thermoplastic to produce biocomposite products. These products exhibit numerous advantages such as good mechanical properties, low density, and biodegradability. Thermoplastics are usually reinforced with flax fiber using injection molding technology and limited research has been done on compression molded thermoplastic biocomposite. Therefore, commercial thermoplastic high density polyethylene (HDPE) and polypropylene (PP) were selected for developing compression molded flax reinforced biocomposites in this research project. The main goal of this research was to develop compression molded biocomposite board using Saskatchewan flax fiber and investigate the effect of flax fiber and processing parameters (molding temperature and molding pressure) on the properties of biocomposite. <p>The fiber was cleaned and chemically treated with alkaline and silane solution that modified the fiber surface. Chemical treatments significantly increased the mechanical properties due to better fiber-polymer interfacial adhesion and also reduced the water absorption characteristics. The silane treatment showed better results than alkaline treatment. Differential scanning calorimetry (DSC) test and scanning electron microscopy (SEM) test were performed to study the thermal and morphological properties of the untreated and chemically treated flax fiber. Flax fiber and thermoplastic resin was mixed using a single-screw extruder to ensure homogenous mixing. HDPE- and PP-based biocomposites were developed through compression molding with three different pretreated flax fiber (untreated, alkaline, silane treated fiber), three levels of fiber content, two levels of molding temperature and two levels of molding pressure. <p>Increase in fiber content increased composite color index, density, water absorption, tensile strength, Youngs modulus, bending strength, and flexural modulus. However for the HDPE composites, tensile and bending strength decreased after 20% flax fiber loading. For the PP composites the, tensile and bending strength decreased after 10% flax fiber loading. Analysis of variance (ANOVA) was performed to quantitatively show the significant effects of the process variables (molding temperature, pressure, and fiber content) and their interactions on the response variables (physical and mechanical properties of biocomposites). The duncan multiple range test (DMRT) was also performed to compare the treatment means. Superposition surface methodology was adapted for both HDPE and PP composites to determine the optimum values of process variables.

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