The Performance Characteristics of a Surface-Modified Cutting Tool

In the past, many papers have been presented which show that the coating of cutting tools often yields decreased wear rates and reduced coefficients of friction. Although different theories are proposed, covering areas such as hardness theory, diffusion barrier theory, thermal barrier theory, and reduced friction theory, most have not dealt with the question of how and why the coating of tool substrates with hard materials such as Titanium Nitride (TiN), Titanium Carbide (TiC) and Aluminium Oxide (Al203) transforms the performance and life of cutting tools. This project discusses the complex interrelationship that encompasses the thermal barrier function and the relatively low sliding friction coefficient of TiN on an undulating tool surface, and presents the result of an investigation into the cutting characteristics and performance of EDMed surface-modified carbide cutting tool inserts. The tool inserts were coated with TiN by the physical vapour deposition (PVD) method. PVD coating is also known as Ion-plating which is the general term of the coating method in which the film is created by attracting ionized metal vapour in this the metal was Titanium and ionized gas onto negatively biased substrate surface. Coating by PVD was chosen because it is done at a temperature of not more than 5000C whereas chemical Vapour Deposition CVD process is done at very high temperature of about 8500C and in two stages of heating up the substrates. The high temperatures involved in CVD affects the strength of the (tool) substrates. In this study, comparative cutting tests using TiN-coated control specimens with no EDM surface structures and TiN-coated EDMed tools with a crater-like surface topography were carried out on mild steel grade EN-3. Various cutting speeds were investigated, up to an increase of 40% of the tool manufacturer’s recommended speed. Fifteen minutes of cutting were carried out for each insert at the speeds investigated. Conventional tool inserts normally have a tool life of approximately 15 minutes of cutting. After every five cuts (passes) microscopic pictures of the tool wear profiles were taken, in order to monitor the progressive wear on the rake face and on the flank of the insert. The power load was monitored for each cut taken using an on-board meter on the CNC machine to establish the amount of power needed for each stage of operation. The spindle drive for the machine is an 11 KW/hr motor. Results obtained confirmed the advantages of cutting at all speeds investigated using EDMed coated inserts, in terms of reduced tool wear and low power loads. Moreover, the surface finish on the workpiece was consistently better for the EDMed inserts. The thesis discusses the relevance of the finite element method in the analysis of metal cutting processes, so that metal machinists can design, manufacture and deliver goods (tools) to the market quickly and on time without going through the hassle of trial and error approach for new products. Improvements in manufacturing technologies require better knowledge of modelling metal cutting processes. Technically the use of computational models has a great value in reducing or even eliminating the number of experiments traditionally used for tool design, process selection, machinability evaluation, and chip breakage investigations. In this work, much interest in theoretical and experimental investigations of metal machining were given special attention. Finite element analysis (FEA) was given priority in this study to predict tool wear and coating deformations during machining. Particular attention was devoted to the complicated mechanisms usually associated with metal cutting, such as interfacial friction; heat generated due to friction and severe strain in the cutting region, and high strain rates. It is therefore concluded that Roughened contact surface comprising of peaks and valleys coated with hard materials (TiN) provide wear-resisting properties as the coatings get entrapped in the valleys and help reduce friction at chip-tool interface. The contributions to knowledge: a. Relates to a wear-resisting surface structure for application in contact surfaces and structures in metal cutting and forming tools with ability to give wear-resisting surface profile. b. Provide technique for designing tool with roughened surface comprising of peaks and valleys covered in conformal coating with a material such as TiN, TiC etc which is wear-resisting structure with surface roughness profile compose of valleys which entrap residual coating material during wear thereby enabling the entrapped coating material to give improved wear resistance. c. Provide knowledge for increased tool life through wear resistance, hardness and chemical stability at high temperatures because of reduced friction at the tool-chip and work-tool interfaces due to tool coating, which leads to reduced heat generation at the cutting zones. d. Establishes that Undulating surface topographies on cutting tips tend to hold coating materials longer in the valleys, thus giving enhanced protection to the tool and the tool can cut faster by 40% and last 60% longer than conventional tools on the markets today.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

Design of advanced reverse osmosis and nanofiltration membranes for water purification

Most commercially available reverse osmosis (RO) and nanofiltration (NF) membranes are based on the thin film composite (TFC) aromatic polyamide membranes. However, they have several disadvantages including low resistance to fouling, low chemical and thermal stabilities and limited chlorine tolerance. To address these problems, advanced RO/NF membranes are being developed from polyimides for water and wastewater treatments. The following three projects have resulted from my research. (1) Positively charged and solvent resistant NF membranes. The use of solvent resistant membranes to facilitate small molecule separations has been a long standing industry goal of the chemical and pharmaceutical industries. We developed a solvent resistant membrane by chemically cross-linking of polyimide membrane using polyethylenimine. This membrane showed excellent stability in almost all organic solvents. In addition, this membrane was positively charged due to the amine groups remaining on the surface. As a result, high efficiency (> 95%) and selectivity for multivalent heavy metal removal was achieved. (2) Fouling resistant NF membranes. Antifouling membranes are highly desired for “all” applications because fouling will lead to higher energy demand, increase of cleaning and corresponding down time and reduced life-time of the membrane elements. For fouling prevention, we designed a new membrane system using a coating technique to modify membrane surface properties to avoid adsorption of foulants like humic acid. A layer of water-soluble polymer such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl sulfate (PVS) or sulfonated poly(ether ether ketone) (SPEEK), was adsorbed onto the surface of a positively charged membrane. The resultant membranes have a smooth and almost neutrally charged surface which showed better fouling resistance than both the positively charged NF membranes and commercially available negatively charged NTR-7450 membrane. In addition, these membranes showed high efficiency for removal of multivalent ions (> 95% for both cations and anions). Therefore, these antifouling surfaces can be potentially used for water softening, water desalination and wastewater treatment in a membrane bioreactor (MBR) process. (3) Thermally stable RO membranes. Commercial RO membranes cannot be used at temperature higher than 45°C due to the use of polysulfone substrate, which often limits their applications in industries. We successfully developed polyimides as the membrane substrate for thermally stable RO membranes due to their high thermal resistance. The polyimide-based composite polyamide membranes showed desalination performance comparable to the commercial TFC membrane. However, the key advantage of the polyimide-based membrane is its high thermal stability. As the feed temperature increased from 25oC to 95oC, the water flux increased 5 - 6 times while the salt rejection almost kept constant. This membrane appears to provide a unique solution for hot water desalination and also a feasible way to improve the water productivity by increasing the operating temperature without any drop in salt rejection.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Development of ultra-high-performance concrete (UHPC) using waste glass materials ─ towards innovative eco-friendly concrete

Le béton conventionnel (BC) a de nombreux problèmes tels que la corrosion de l’acier d'armature et les faibles résistances des constructions en béton. Par conséquent, la plupart des structures fabriquées avec du BC exigent une maintenance fréquent. Le béton fibré à ultra-hautes performances (BFUP) peut être conçu pour éliminer certaines des faiblesses caractéristiques du BC. Le BFUP est défini à travers le monde comme un béton ayant des propriétés mécaniques, de ductilité et de durabilité supérieures. Le BFUP classique comprend entre 800 kg/m³ et 1000 kg/m³ de ciment, de 25 à 35% massique (%m) de fumée de silice (FS), de 0 à 40%m de poudre de quartz (PQ) et 110-140%m de sable de quartz (SQ) (les pourcentages massiques sont basés sur la masse totale en ciment des mélanges). Le BFUP contient des fibres d'acier pour améliorer sa ductilité et sa résistance aux efforts de traction. Les quantités importantes de ciment utilisées pour produire un BFUP affectent non seulement les coûts de production et la consommation de ressources naturelles comme le calcaire, l'argile, le charbon et l'énergie électrique, mais affectent également négativement les dommages sur l'environnement en raison de la production substantielle de gaz à effet de serre dont le gas carbonique (CO[indice inférieur 2]). Par ailleurs, la distribution granulométrique du ciment présente des vides microscopiques qui peuvent être remplis avec des matières plus fines telles que la FS. Par contre, une grande quantité de FS est nécessaire pour combler ces vides uniquement avec de la FS (25 à 30%m du ciment) ce qui engendre des coûts élevés puisqu’il s’agit d’une ressource limitée. Aussi, la FS diminue de manière significative l’ouvrabilité des BFUP en raison de sa surface spécifique Blaine élevée. L’utilisation du PQ et du SQ est également coûteuse et consomme des ressources naturelles importantes. D’ailleurs, les PQ et SQ sont considérés comme des obstacles pour l’utilisation des BFUP à grande échelle dans le marché du béton, car ils ne parviennent pas à satisfaire les exigences environnementales. D’ailleurs, un rapport d'Environnement Canada stipule que le quartz provoque des dommages environnementaux immédiats et à long terme en raison de son effet biologique. Le BFUP est généralement vendu sur le marché comme un produit préemballé, ce qui limite les modifications de conception par l'utilisateur. Il est normalement transporté sur de longues distances, contrairement aux composantes des BC. Ceci contribue également à la génération de gaz à effet de serre et conduit à un coût plus élevé du produit final. Par conséquent, il existe le besoin de développer d’autres matériaux disponibles localement ayant des fonctions similaires pour remplacer partiellement ou totalement la fumée de silice, le sable de quartz ou la poudre de quartz, et donc de réduire la teneur en ciment dans BFUP, tout en ayant des propriétés comparables ou meilleures. De grandes quantités de déchets verre ne peuvent pas être recyclées en raison de leur fragilité, de leur couleur, ou des coûts élevés de recyclage. La plupart des déchets de verre vont dans les sites d'enfouissement, ce qui est indésirable puisqu’il s’agit d’un matériau non biodégradable et donc moins respectueux de l'environnement. Au cours des dernières années, des études ont été réalisées afin d’utiliser des déchets de verre comme ajout cimentaire alternatif (ACA) ou comme granulats ultrafins dans le béton, en fonction de la distribution granulométrique et de la composition chimique de ceux-ci. Cette thèse présente un nouveau type de béton écologique à base de déchets de verre à ultra-hautes performances (BEVUP) développé à l'Université de Sherbrooke. Les bétons ont été conçus à l’aide de déchets verre de particules de tailles variées et de l’optimisation granulaire de la des matrices granulaires et cimentaires. Les BEVUP peuvent être conçus avec une quantité réduite de ciment (400 à 800 kg/m³), de FS (50 à 220 kg/m³), de PQ (0 à 400 kg/m³), et de SQ (0-1200 kg/m³), tout en intégrant divers produits de déchets de verre: du sable de verre (SV) (0-1200 kg/m³) ayant un diamètre moyen (d[indice inférieur 50]) de 275 µm, une grande quantité de poudre de verre (PV) (200-700 kg/m³) ayant un d50 de 11 µm, une teneur modérée de poudre de verre fine (PVF) (50-200 kg/m³) avec d[indice inférieur] 50 de 3,8 µm. Le BEVUP contient également des fibres d'acier (pour augmenter la résistance à la traction et améliorer la ductilité), du superplastifiants (10-60 kg/m³) ainsi qu’un rapport eau-liant (E/L) aussi bas que celui de BFUP. Le remplacement du ciment et des particules de FS avec des particules de verre non-absorbantes et lisse améliore la rhéologie des BEVUP. De plus, l’utilisation de la PVF en remplacement de la FS réduit la surface spécifique totale nette d’un mélange de FS et de PVF. Puisque la surface spécifique nette des particules diminue, la quantité d’eau nécessaire pour lubrifier les surfaces des particules est moindre, ce qui permet d’obtenir un affaissement supérieur pour un même E/L. Aussi, l'utilisation de déchets de verre dans le béton abaisse la chaleur cumulative d'hydratation, ce qui contribue à minimiser le retrait de fissuration potentiel. En fonction de la composition des BEVUP et de la température de cure, ce type de béton peut atteindre des résistances à la compression allant de 130 à 230 MPa, des résistances à la flexion supérieures à 20 MPa, des résistances à la traction supérieure à 10 MPa et un module d'élasticité supérieur à 40 GPa. Les performances mécaniques de BEVUP sont améliorées grâce à la réactivité du verre amorphe, à l'optimisation granulométrique et la densification des mélanges. Les produits de déchets de verre dans les BEVUP ont un comportement pouzzolanique et réagissent avec la portlandite générée par l'hydratation du ciment. Cependant, ceci n’est pas le cas avec le sable de quartz ni la poudre de quartz dans le BFUP classique, qui réagissent à la température élevée de 400 °C. L'addition des déchets de verre améliore la densification de l'interface entre les particules. Les particules de déchets de verre ont une grande rigidité, ce qui augmente le module d'élasticité du béton. Le BEVUP a également une très bonne durabilité. Sa porosité capillaire est très faible, et le matériau est extrêmement résistant à la pénétration d’ions chlorure (≈ 8 coulombs). Sa résistance à l'abrasion (indice de pertes volumiques) est inférieure à 1,3. Le BEVUP ne subit pratiquement aucune détérioration aux cycles de gel-dégel, même après 1000 cycles. Après une évaluation des BEVUP en laboratoire, une mise à l'échelle a été réalisée avec un malaxeur de béton industriel et une validation en chantier avec de la construction de deux passerelles. Les propriétés mécaniques supérieures des BEVUP a permis de concevoir les passerelles avec des sections réduites d’environ de 60% par rapport aux sections faites de BC. Le BEVUP offre plusieurs avantages économiques et environnementaux. Il réduit le coût de production et l’empreinte carbone des structures construites de béton fibré à ultra-hautes performances (BFUP) classique, en utilisant des matériaux disponibles localement. Il réduit les émissions de CO[indice inférieur 2] associées à la production de clinkers de ciment (50% de remplacement du ciment) et utilise efficacement les ressources naturelles. De plus, la production de BEVUP permet de réduire les quantités de déchets de verre stockés ou mis en décharge qui causent des problèmes environnementaux et pourrait permettre de sauver des millions de dollars qui pourraient être dépensés dans le traitement de ces déchets. Enfin, il offre une solution alternative aux entreprises de construction dans la production de BFUP à moindre coût.

Temporal and spatial variation in temperature experienced by macrofauna at main endeavour Hydrothermal vent field

A significant focus of hydrothermal vent ecological studies has been to understand how species cope with various stressors through physiological tolerance and biochemical resistance. Yet, the environmental conditions experienced by vent species have not been well characterized. This objective requires continuous observations over time intervals that can capture environmental variability at scales that are relevant to animals. We used autonomous temperature logger arrays (four roughly parallel linear arrays of 12 loggers spaced every 10–12 cm) to study spatial and temporal variations in the thermal regime experienced by hydrothermal vent macrofauna at a diffuse flow vent. Hourly temperatures were recorded over eight months from 2010 to 2011 at Grotto vent in the Main Endeavour vent field on the Juan de Fuca Ridge, a focus area of the Ocean Networks Canada cabled observatory. The conspicuous animal assemblages in video footage contained Ridgeia piscesae tubeworms, gastropods (primarily Lepetodrilus fucensis), and polychaetes (polynoid scaleworms and the palm worm Paralvinella palmiformis). Two dimensional spatial gradients in temperature were generally stable over the deployment period. The average temperature recorded by all arrays, and in some individual loggers, revealed distinctive fluctuations in temperature that often corresponded with the tidal cycle. We postulate that this may be related to changes in bottom currents or fluctuations in vent discharge. A marked transient temperature increase lasting over a period of days was observed in April 2011. While the distributions and behavior of Juan de Fuca Ridge vent invertebrates may be partially constrained by environmental temperature and temperature tolerance, except for the one transient high-temperature event, observed fluid temperatures were generally similar to the thermal preferences for some species, and typically well below lethal temperatures for all species. Average temperatures of the four arrays ranged from 4.1 to 11.0 °C during the deployment, indicating that on an hourly timescale the temperature conditions in this tubeworm community were fairly moderate and stable. The generality of these findings and behavioural responses of vent organisms to predictable rhythmicity and non-periodic temperature shifts are areas for further investigation

The experimentally pathogenesis of Aeromonas hydrophila in Astacus leptodactylus with emphasis on temperature in bacterial pathogenesis

In this study, four hundred freshwater Crayfish (A. leptodactylus) with average weight of 25-40g were purchased from Aras dam reservoirs in west Azerbayjan province and transported to Iranian Artemia Research Center of Uromya province in September 2010. (One hundred crayfish extra purchased for probably mortality). Before implement of experiment the Crayfish were acclimated for ten days. These experiments was designed in four group treatments (Number, 1,2,3,4) and one control group (Number 5) in triplicate with 20 Crayfish in each repetition prepared of glass aquarium with size (50x40x30cm). Many of infected Crayfish were used for isolation of bacteria. Haemolymph sample had been gathered from infected Crayfish with cutting their antennules and transferred to TSA medium (tryptic soy agar) and then A. hydrophila were determined in order to biochemical test. The treatments and repetitions has exposed to A. hydrophila. The concentrations of the bacteria in 4 treatments were respectively 3 x 108 (T=10-15°C), 3x106 (T=25°C), 3 x 106 and 3 x 104 Cfu mL-1 (T=10- i5oc) (4, 2, 3 and 1) that were prepared in individual containers for exposure of treatments. The control (5) prepared without any bacteria and disinfected by oxytetracycline antibiotic with concentration 100 ppm for 24 hours. The hemolymph samples were withdrawn from abdominal second segments of Crayfish for measuring of THC and TPC in interval hours (2, 6, 12, 24, 48, 96, 144, 240 and 336). For histopatological studies the crayfish samples fixed in Davidson fixative. The results indicated that interval 2 hours after experiment the difference of THC value between treatment 4 with control and treatments 1,2, and 3 was significant (P< 0.05). After 48 hours of experiment the difference of THC value between control group with treatment 1 ,2 and 3 was significant (P< 0.05). The interval 336 hours after experiment also the difference of THC value between treatment 2 with treatments 1, 3 and 4 was significant (P< 0.05). The finding of TPP value showed that the last time after challenge (336 h) there was significant difference between treatment 2 with treatment 4 and control group (P< 0.05). In histopathology studying, in hepatopancreas observed hemocyte aggregated and necrosis withof peknosis nucleus that with increased concentration of bacteria and temperature, The value of hemocyte has increased. Gill revealed necrosis and cell death especially with increased concentration of bacteria and temperature. In lower concentration of bacteria in heart no difference observed, but with increased concentration of bacteria (3 x 108) the low aggregation of hemocyte observed in heart. In treatment 3 x 106 with high temperature also distributed of high hemocyte in heart was observed. In digestive system didn't appear any difference in treatments land 3 but in concentration of 3 x 108 Cfu m1-1 and 3 x 106 (T=25°C) in digestive system was revealed the low aggregation of hemocyte.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Caracterização termo-mecânica de interconectores metálicos recobertos com filmes de LaCrO3

The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 º C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests.

Adição do resíduo de biomassa da cana-de-açúcar em pastas para cimentação de poços petrolíferos produtores de óleos pesados

The Potiguar basin has large fields of viscous oil where the used method for recovering is based on vapor injection; this operation is carried out by injecting vapor in the oilwell directly, without the protection of a revetment through thermal insulation, what causes its dilation and, consequently, cracks in the cement placed on the annular, and lost of hydraulic insulation; this crack is occasioned by the phenomenon of retrogression of the compressive resistance due to the conversion of the hydrated calcium silicate in phases calcium-rich, caused by the high temperatures in the wells, subjected to thermal recuperation. This work has evaluated the application of composite pastes with addition of residue of biomass of ground sugar-cane bagasse as anti-retrogression mineral admixture for cementation of oil-wells subjected to thermal recuperation. The addition of the mineral residue was carried out considering a relative amount of 10, 20, 30, 40 and 59% in relation to cement mass, trying to improve the microstructure of the paste, still being developed a reference paste only with cement and a paste with addition of 40% of silica flour - renowned material in the oil industry as anti-retrogression additive. Pozzolanic activity of the ash was evaluated through XRD, TG/DTG, as the resistance to compression, and it was also determined the physical and mechanical behavior of the pastes when submitted to cure at low temperatures (22 and 38º C); besides it was evaluated the behavior of the pastes when submitted to two cycles of cure at high temperature (280ºC) and pressure (7 MPa). It was verified that the ash of the sugar-cane biomass presents pozzolanic reaction and has great efficiency in decrease the permeability of the paste by filler effect, as well as that addition of ash in a relative amount of 10, 20 e 30% increases cured compressive resistance at low temperatures. It was also showed that the ash in a relative amount of 40% and 59% has very significant efficiency as anti-retrogression additive, since it prevents the decrease of compressive resistance and forms hydrated calcium silicate type xenotlita and tobermorita which have more resistance and stability in high temperatures

Síntese e caracterização de TaC e óxido misto de tântalo e cobre nanoestruturados a partir do precursor oxálico de tântalo através de reações gás-sólido e sólido-sólido a baixa temperatura

The research and development of nanostructured materials have been growing significantly in the last years. These materials have properties that were significantly modified as compared to conventional materials due to the extremely small dimensions of the crystallites. The tantalum carbide (TaC) is an extremely hard material that has high hardness, high melting point, high chemical stability, good resistance to chemical attack and thermal shock and excellent resistance to oxidation and corrosion. The Compounds of Tantalum impregnated with copper also have excellent dielectric and magnetic properties. Therefore, this study aimed to obtain TaC and mixed tantalum oxide and nanostructured copper from the precursor of tris (oxalate) hydrate ammonium oxitantalato, through gas-solid reaction and solid-solid respectively at low temperature (1000 ° C) and short reaction time. The materials obtained were characterized by X-ray diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), Spectroscopy X-Ray Fluorescence (XRF), infrared spectroscopy (IR), thermogravimetric (TG), thermal analysis (DTA) and BET. Through the XRD analyses and the Reitiveld refinement of the TaC with S = 1.1584, we observed the formation of pure tantalum carbide and cubic structure with average crystallite size on the order of 12.5 nanometers. From the synthesis made of mixed oxide of tantalum and copper were formed two distinct phases: CuTa10O26 and Ta2O5, although the latter has been formed in lesser amounts

Biodiesel production from Jathropha curcas l. oil using chemical or enzymatic catalysts

Doutoramento em Engenharia dos Biossistemas - Instituto Superior de Agronomia - UL

Síntese e caracterização de CuNb2O6 e CuNbC através de reação sólido- sólido e gás- sólido a baixa temperatura

The refractory metal carbides have proven important in the development of engineering materials due to their properties such as high hardness, high melting point, high thermal conductivity and high chemical stability. The niobium carbide presents these characteristics. The compounds of niobium impregnated with copper also have excellent dielectric and magnetic properties, and furthermore, the Cu doping increases the catalytic activity in the oxidation processes of hydrogen. This study aimed to the synthesis of nanostructured materials CuNbC and niobium and copper oxide from precursor tris(oxalate) oxiniobate ammonium hydrate through gas-solid and solid-solid reaction, respectively. Both reactions were carried out at low temperature (1000°C) and short reaction time (2 hours). The niobium carbide was produced with 5 % and 11% of copper, and the niobium oxide with 5% of copper. The materials were characterized by X-Ray Diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF), infrared spectroscopy (IR), thermogravimetric (TG) and differential thermal analysis (DTA , BET and particle size Laser. From the XRD analysis and Rietveld refinement of CuNbC with S = 1.23, we observed the formation of niobium carbide and metallic copper with cubic structure. For the synthesis of mixed oxide made of niobium and copper, the formation of two distinct phases was observed: CuNb2O6 and Nb2O5, although the latter was present in small amounts

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test

Evolution of surface properties of ornamental granitoids exposed to high temperatures

Granite submitted to high temperatures may lead to the loss of aesthetic values even before structural damage is caused. Thirteen granitoids were exposed to target temperatures, 200 °C, 400 °C, 600 °C, 800 °C and 1000 °C. Damage characterisation, including roughness, colour and oxidation of chromogen elements by means of X-ray photoelectron spectroscopy (XPS) was assessed. Altered granitoids are more resistant to structural failure but redden rapidly. Black mica-rich granitoids turn into yellow with a maximum at 800 °C. Alkali feldspar-rich granitoids redden progressively due to iron oxidation. Roughness varies progressively in mica-rich granitoids, while in mica-poor granitoids, an increase in roughness precedes catastrophic failure.