Desenvolvimento de estruturas fibrosas com comportamento auxético

Tese de Doutoramento Engenharia Têxtil

Structural, mechanical and piezoelectric properties of polycrystalline AlN films sputtered on titanium bottom electrodes

Polycrystalline AlN coatings deposited on Ti-electrodes films were sputtered by using nitrogen both as reactive gas and sputtering gas, in order to obtain high purity coatings with appropriate properties to be further integrated into wear resistance coatings as a piezoelectric monitoring wear sensor. The chemical composition, the structure and the morphology of the films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy techniques. These measurements show the formation of highly (101), (102) and (103) oriented AlN films with good piezoelectric and mechanical properties suitable for applications in electronic devices. Through the use of lower nitrogen flow a densification of the AlN coating occurs in the microstructure, with an improvement of the crystallinity along with the increase of the hardness. Thermal stability of aluminum nitride coatings at high temperature was also examined. It was found an improvement of the piezoelectric properties of the highly (10x) oriented AlN films which became c-axis (002) oriented after annealing. The mechanical behavior after heat treatment shows an important enhancement of the surface hardness and Young’s modulus, which decrease rapidly with the increase of the indentation depth until approach constant values close to the substrate properties after annealing. Thus, thermal annealing energy promotes not only the rearrangement of Al–N network, but also the occurrence of a nitriding process of unsaturated Al atoms which cause a surface hardening of the film.

Influence of design parameters on the mechanical behavior and porosity of braided fibrous stents

In spite of all innovations in stent design, commonly used metallic stents present several problems such as corrosion, infection and restenosis, leading to health complications or even death of patients. In this context, the present paper reports a systematic investigation on designing and development of 100% fiber based stents, which can eliminate or minimize the problems with existing metallic stents. For this purpose, braided stents were produced by varying different materials, structural and process parameters such as mono-filament type and diameter, braiding angle and mandrel diameter. The influence of these design parameters on mechanical behavior as well as stent's porosity was thoroughly investigated, and suitable parameters were selected for developing a stentwith mechanical characteristics and porosity matching with the commercial stents. According to the experimental results, the best performance was achieved with a polyester stent designed with 0.27 mm monofilament diameter, braiding angle of 35° and mandrel diameter of 6 mm, providing similar properties to commercial Nitinol stents.

Antibacterial properties of fibrous stents coated with silver oxide nanocoatings

Stents are rigid and perforated tubular structures, which are inserted into blood vessels in order to prevent or inhibit the constriction of blood flow, restoring the normal blood flow, when blood vessels are clogged, being used in 70% of angioplasties. These medical devices assume great importance in the treatment of cardiovascular diseases (CVD) which are the leading cause of death worldwide. In the European Union CVD account for 40% of deaths and assume an estimated annual cost of 196 billion euros[1]. Stents must possess certain requirements, in order to, adequately, perform its function, such as biocompatibility (so that its use does not c ause damage on the health of its user), mechanical strength, radiopacity (so that it is easy to view), longitudinal flexibility, ease of handling, corrosion resistance and having high strength and high radial expansion ability to recover. Stents can be made of different materials, but metals, particularly stainless steel, are the most common. However, metallic stents present several dRawbacks such as corrosion and restenosis, leading to health complications for the patient, or even death. In order to minimize these disadvantages, new materials, like fibrous materials, have been used [2]. Monofilaments present high potential for stents development because, in addition to its biocompatibility, these materials allow the application of various surface treatments, such as antibacterial coatings. Furthermore, monofilament exhibit excellent mechanical properties, like greater stiffness and good results when subjected to compression, tensile and bending forces, since these forces will be directly supported by the monofilament [3]. To minimize the reaction of the human body and Limit the adhesion of microorganisms to the stent surface, some coatings have been developed, including the use of novel metals with antimicrobial properties, like silver. The main objective of this study was the development of fibrous stents, incorporation of silver oxide nanocoating. For the development of the stent, polyester monofilaments with 0.27mm of diameter were used in braiding technology, with a mandrel diameter of 6mm and a braiding angle of 35⁰. The mechanical behaviour of the stent were evaluated by mechanical testing under longitudinal and radial compression, bending. The results of compressive strength tests are according with value from literature: 1.13 to 2.9 N for radial compression and 0. 16-5.28N to longitudinal compression. From literature is also possible to verify that stents must present 75% of unchanged diameter during the bending test and must possess a porosity between 70% and 80% [4]. The produced polyester stent presents values of 1.29N for radial compression, 0.23N for longitudinal compression, 80% of porosity and 85.5% of unchanged diameter, during bending tests. For the antibacterial functionalization, silver oxide nanocoatings were prepared, through reactive magnetron g, with an Ag target in an Ar +O2 atmosphere. In order to evaluate the nanostructure and morphology of the coatings, d ifferent technique s like X-ray diffraction (XRD), scanning electron microscopy (SEM) and and X- ray photoelectron spectroscopy (XPS were used. From the analyses of XRD it is possible to verify that the peaks corresponds to planes of Ag2 O and MATERIAIS 2015 Porto, 21-23 June, 2015 characterize a cubic phase. The presence of Ag2 O is corroborated by XPS spectrum, where it is possible to observe silver, not only, in oxide state, but a lso in mettalic state, and it is possible to verify the presence of silver clusters, confirmed by SEM analysis. Films’ roughness and topography, parameters influencing the wettability of the surface and microorganism adhesion, were measured by Atomic Force Microscopy (AFM), and it was observed that the roughness is very low (under 10 nm). Coatings’ hydrophobicity and surface tension parameters were determined by contact angle measurement, and it was verified the hydrophobic behavior of the coatings. For antibacterial tests were used Staphylococcus epidermidis strain (IE186) and Staphylococcus aureus(ATCC 6538), and halo inhibition zone tests were realized. Ag+release rates were studied by means of inductively coupled plasma mass spectrometry (ICP -MS). The obtained results suggest that silver oxide coatings do not modify significantly surface properties of the substrate, like hydrophobicity and roughness, and present antimicrobial properties for both bacteria used.

Gestão de inventários numa empresa de produção de linhas de costura

Dissertação de mestrado integrado em Engenharia e Gestão Industrial

Melhoria do processo de tingimento numa empresa têxtil

Dissertação de mestrado em Engenharia e Gestão da Qualidade

Single-function approach to calibrating whatman n.º 42 filter paper based on suction versus water content relationships

Several suction–water-content (s-w) calibrations for the filter paper method (FPM) used for soil-suction measurement have been published. Most of the calibrations involve a bilinear function (i.e., two different equations) with an inflection point occurring at 60 kPa

Synthesis of polyhydroxylated compounds from Derythrose: enzymatic inhibition studies

Dissertação de mestrado em Química Medicinal

Estudo da degradação de membranas arquitetónicas

Dissertação de mestrado Internacional em Sustentabilidade do Ambiente Construído

Integração no laboratório da Lameirinho e controlo aos tecidos acabados

Dissertação de mestrado em Técnicas de Caraterização e Análise Química

A change in the treatment of abdominal aortic aneurysms

OBJECTIVE: One of the most exciting potential applications of percutaneous therapy is the treatment of abdominal aneurysms. METHODS: Of 230 patients treated with a self-expanding polyester-lined stent-graft for different aortic pathologies at our institution, we selected 80 abdominal aneurysm cases undergoing treatment (from May 1997 to December 2002). The stent was introduced through the femoral artery, in the hemodynamic laboratory, with the patient under general anesthesia, with systemic heparinization, and induced hypotension. RESULTS: The procedure was successful in 70 (92.9%) cases; 10 patients with exclusion of abdominal aortic aneurysms were documented immediately within the hemodynamic room and 5 patients persisted with a residual leak. Two surgical conversions were necessary. Additional stent-grafts had to be inserted in 3 (3.7%) cases. In the follow-up, 91.4% of patients were alive at a mean follow-up of 15.8 months. CONCLUSION: We believe that stent-grafts are an important tool in improving the treatment of abdominal aneurysms, and this new policy may change the conventional medical management of these patients.

Dinámica y cinética de los procesos físicos y químicos del radical OH con compuestos orgánicos volátiles (COVs) de relevancia atmosférica. Dynamics and kinetics of the physical and chemical processes of OH radicals with atmospheric relevant volatile organic compounds (VOCs)

El objetivo del presente proyecto es estudiar los procesos físicos y químicos del radical OH con compuestos orgánicos volátiles (COVs), con los cuales sea factible la formación de agregados de van der Waals (vdW) responsables de la curvatura en los gráficos de Arrhenius, empleando técnicas modernas, complementarias entre si y novedosas en el país. El problema será abordado desde tres perspectivas complementarias: 1) estudios cinéticos, 2) estudios mecanísticos y de distribución de productos y 3) estudios de la dinámica de los procesos físicos y químicos. La finalidad es alcanzar una mejor comprensión de los mecanismos que intervienen en el comportamiento químico de especies presentes en la atmósfera y obtener datos cinéticos de alta calidad que puedan alimentar modelos computacionales capaces de describir la composición de la atmósfera, presente y futura. Los objetivos son estudiar: 1) mediante fotólisis láser pulsada con detección por fluorescencia inducida por láser (PLP-LIF), en reactores de flujo, la cinética de reacción del radical OH(v”=0) con COVs que presentan gráficos de Arrhenius curvos con energías de activación negativas, tales como alcoholes insaturados, alquenos halogenados, éteres halogenados, ésteres alifáticos; 2) en una cámara de simulación de condiciones atmosféricas de gran volumen (4500 L), la identidad y el rendimiento de productos de las reacciones mencionadas, a fines de evaluar su impacto atmosférico y dilucidar los mecanismos de reacción; 3) mediante haces moleculares y espectroscopía láser, la estructura y reactividad de complejos de vdW entre alcoholes insaturados o aromáticos (cresoles) y el radical OH, como modelo de los aductos propuestos como responsables de la desviación al comportamiento de Arrhenius de las reacciones mencionadas; 4) mediante PLP-LIF y expansiones supersónicas, las constantes específicas estado a estado (ksts) de relajación/reacción del radical OH(v”=1-4) vibracionalmente excitado con los COVs mencionados. Los resultados experimentales obtenidos serán contrastados con cálculos ab-initio de estructura electrónica, los cuales apoyarán las interpretaciones, permitirán proponer estructuras de estados de transición y aductos colisionales, como así también calcular las frecuencias de vibración de los complejos de vdW para su posterior asignación en los espectros LIF y REMPI. Asimismo, los mecanismos de reacción propuestos y los parámetros cinéticos medidos experimentalmente serán comparados con aquellos obtenidos por cálculos teóricos. The aim of this project is to study the physical and chemical processes of OH radicals with volatile organic compounds (VOCs) with which the formation of van der Waals (vdW) clusters, responsible for the observed curvature in the Arrhenius plots, might be feasible. The problem will be addressed as follow : 1) kinetic studies; 2) products distribution and mechanistic studies and 3) dynamical studies of the physical and chemical processes. The purpose is to obtain a better understanding of the mechanisms that govern the chemical behavior of species present in the atmosphere and to obtain high quality kinetic data to be used as input to computational models. We will study: 1) the reaction kinetics of OH (v”=0) radicals with VOCs such as unsaturated alcohols, halogenated alkenes, halogenated ethers, aliphatic esters, which show curved Arrhenius plots and negative activation energies, by PLP-LIF, in flow systems; 2) in a large volume (4500 L) atmospheric simulation chamber, reaction products yields in order to evaluate their atmospheric impact and reaction mechanisms; 3) using molecular beams and laser spectroscopy, the structure and reactivity of the vdW complexes formed between the unsaturated or aromatic alcohols and the OH radicals as a model of the adducts proposed as responsible for the non-Arrhenius behavior; 4) the specific state-to-state relaxation/reaction rate constants (ksts) of the vibrationally excited OH (v”=1-4) radical with the VOCs by PLP-LIF and supersonic expansions. Ab-initio calculations will be carried out to support the interpretation of the experimental results, to obtain the transition state and collisional adducts structures, as well as to calculate the vibrational frequencies of the vdW complexes to assign to the LIF and REMPI spectra. Also, the proposed reaction mechanisms and the experimentally measured kinetic parameters will be compared with those obtained from theoretical calculations.

An evaluation of septic tank effluent movement in soil and groundwater systems

Recent studies have shown that septic tank systems are a major source of groundwater pollution. Many public health workers feel that the most cri^cal aspect of the use of septic tanks as a means of sewage disposal is the contamination of private water wells with attendant human health hazards. In this study the movement and attenuation of septic tank effluents in a range of soil/overburden types and hydrogeological situations was investigated. The suitability of a number of chemical and biological tracer materials to monitor the movement of septic tank effluent constituents to groundwater sources was also examined. The investigation was divided into three separate but inteiTelated sections. In the first section of the study the movement of septic tank effluent from two soil treatment systems was investigated by direct measurements of soil nutrient concentrations and enteric bacterial numbers in the soil beneath and downgradient of the test systems. Two sites with different soil types and hydrogeological characteristics were used. The results indicated that the attenuation of the effluent in both of the treatment systems was incomplete. Migration of nitrate, ammonium, phosphate and fecal bacteria to a depth of 50 cm beneath the inverts of the distribution tiles was demonstrated on all sampling occasions. The lateral migration of the pollutants was less pronounced, although on occasions high nutrients levels and fecal bacterial numbers were detected at a lateral distance of 4.0 m downgradient of the test systems. There was evidence that the degree and extent of effluent migration was increased after periods of heavy or prolonged rainfall when the attenuating properties of the treatment systems were reduced as a result of saturation of the soil. The second part of the study examined the contamination of groundwaters downgradient of septic tank soil treatment systems. Three test sites were used in the investigation. The sites were chosen because of differences in the thicknesses and nature of the unsaturated zone available for effluent attenuation at each of the locations. A series of groundwater monitoring boreholes were installed downgradient of the test systems at each of the sites and these were sampled regularly to assess the efficiency of the overburden material in reducing the polluting potential of the wastewater. Effluent attenuation in the septic tank treatment systems was shown to be incomplete, resulting in chemical and microbiological contamination of the groundwaters downgradient of the systems. The nature and severity of groundwater contamination was dependent on the composition and thickness of the unsaturated zone and the extent of weathering in the underlying saturated bedrock. The movement of septic tank effluent through soil/overburdens to groundwater sources was investigated by adding a range of chemical and biological tracer materials to the three septic tank systems used in section two of the study. The results demonstrated that a single tracer type cannot be used to accurately monitor the movement of all effluent constituents through soils to groundwater. The combined use of lithium bromide and endospores of Bacillus globigii was found to give an accurate indication of the movement of both the chemical and biological effluent constituents.

Groundwater vulnerability and protection in County Tipperary (South Riding), Ireland

The aim of the project was to determine the extent and quality of the groundwater in Tipperary South Riding with a view to developing a groundwater protection plan which would allow the Local Authority to manage, protect and develop the groundwater as efficiently as possible. The geology of the area varies with topography. The low-lying areas of the county comprise mainly Carboniferous limestones while the elevated regions consist of sandstones and shales of Upper Carboniferous, Devonian and Silurian ages. Deformation of these rocks decreases in magnitude moving northwards over the area; the Southern Synclines having suffered the effects of the Hercynian orogeny and the northern region exhibiting Caledonian orogenic trends. Quaternary (subsoil) deposits are found throughout the area and are of variable thickness and permeability. Till is the most widespread deposit with discontinuous pockets of sand and gravel in various proportions, and some marl, alluvium and peat in places. The principal aquifers of the area are the Kiltorcan sandstone formation and various limestone units within the Carboniferous succession. 50 % of south Tipperary constitutes either regionally or locally important aquifers. Secondary permeabilities created by structural deformation, dolomitisation, karstification and weathering processes create high transmissivities and often have large well yields. Specific baseflow analysis highlighted the complexity of the aquifers and proved that the lower part of the Suir river system is a major groundwater resource region. The hydrochemistry and water quality of the local authority groundwater sources was examined briefly. The majority of south Tipperary is underlain by limestone or Quaternary deposits derived from limestone and, consequently, calcium/magnesium bicarbonate waters predominate. The quality of the groundwater in south Tipperary demonstrates that the main concern originates from the presence of E.coli, and Total coliforms. The primary sources of contamination are from farmyard wastes and septic tanks. The vulnerability of groundwater to diffuse and point sources of pollution has been found to be dependent on the overlying soil, subsoil and the thickness of the unsaturated zone. A conceptual rather than quantitative approach is used and it is found that approximately 60% of south Tipperary is designated as being extremely or highly vulnerable. The groundwater protection plan was devised subsequent to an understanding of the aquifer systems, an assessment of the vulnerability, and a review of the Irish planning system and environmental law. It is recommended that the plan be integrated into the county development plan for legislative purposes. A series of acceptability matrices were devised to restrict potentially polluting activities in vulnerable areas while maintaining a balance between protection of the groundwater resource and the need to site essential developments.

Nutritional composition, quality and spoilage capacity of orange roughy (Hoplostethus atlanticus) from the North East Atlantic

The nutritional composition o f orange roughy (collected from the Northeast Atlantic near the Rockall Trough) was studied on a seasonal basis. In addition samples were aged and stability assessed. Protein levels (16.68-16.21% w/w) were found to be slightly higher than those recorded for the N ew Zealand species o f orange roughy and compared favourably with protein values for fish muscle in general. Statistically results show a significant seasonal variation with no variation from fish to fish or in the location within the fish. Lipid content (3.6-4.5% w/w) was found to be much lower than that recorded for New Zealand. As with protein statistically results show a significant seasonal variation and no variation from fish to fish or in the location within the fish. Moisture levels (77.3_79.6%w/w) compared favourably with values obtained from other studies. Again statistically results show a significant seasonal variation with no variation from fish to fish or within the fish. Iodine values (74.63-79.54) indicate the likely presence o f a high level o f mono unsaturated fatty acids. Statistically results show no significant seasonal variation and no sample variation or variation within fish. Thin layer chromatography o f the extracted fat showed the major type to be wax esters with a much lower amount o f triglycerides and smaller amounts of polar lipids, free sterols and free fatty acids. Total fatty acid composition was found to be very similar to that recorded from other studies and showed that most o f the oils extracted from the fish muscle contained a high percentage o f mono unsaturates namely 16:1,18:1, 20:1 and 22:1 (85.63 - 91.14% ) with 16:1 present in the smallest amounts and 18:1 the major one. The only saturated fatty M.Sc. in Biochemistry III Nutritional Composition, Quality and Spoilage Capacity of Specific Deep Sea Fish acids present in significant quantities were 14:0, 16:0 and 18:0, the total varied from a seasonal average high o f 4.05 % to an average low o f 2.27%. The polyunsaturated fatty acids linoleic and arachidonic acid were present in small quantities varying in total from 0.89% to 1.50%. Docosapentaenoic acid (D P A ) was found only in trace quantities in spring, autumn and winter samples and undetected in summer. Levels o f Eicosapentaenoic acid (EPA ) and Docosahexaenoic acid (D H A ) were also found in very low percentages and varied on a seasonal basis with average values ranging from 0.41% in summer to 1.03 % in autumn for EPA and from 1.44 % in summer to3.20 % in autumn for D H A . Again statistically results show a significant seasonal variation with no variation from fish to fish or location within the fish. Levels o f freshness were measured using the Thiobarbituric acid (T B A ), Total volatile base nitrogen (T V B -N ) and Trimethylamine (T M A ) techniques. The quality o f the fish upon arrival was excellent and well below legal/acceptable lim its.T V B -N values ranged from 6.88-8.91 mg/lOOg and T M A values from 4.82-6.46 mg/lOOg Values for T B A ranged from 0.18-0.35 mg Malonaldehyde/kg fish. The summer values were higher than the other seasons. Seasonal variation was significant for all methods with no variation from fish to fish or within the fish. Fish aged at +4°C in air did not exceed the T V B N lim it o f 35mg/100g until day 6 whereas the T V B N lim it was extended to 8 days for fish aged at +4°C in vacuum. However the T M A lim it o f 12mg/100g was reached on day 4 for fish stored at +4°C in air and on day 5 for vacuum packed samples stored at +4°C . Fish stored at -5°C in air and vacuum packed did not reach the T V B N lim it until day 61 but the T M A limit was reached on day 24 for fish stored at -5°C in air and was extended to 31 days for vacuum packed fish stored at-5°C. Prolonged storage at -18°C caused some deterioration o f the frozen fish muscle. Upon thawing the shelf life o f fish stored for 12 months was much shorter than that stored for 6 M.Sc. in Biochemistry IV Nutritional Composition, Quality and Spoilage Capacity of Specific Deep Sea Fish months. This in turn deteriorated faster than fresh fish held at refridgeration temperature in air. Orange roughy were found to be a good source of protein with moisture levels similar to that o f other fish. They were o f medium fat content but have a very poor content o f the essential omega 3 and omega 6 fatty acids. Orange roughy can be stored at -18°C but its subsequent refridgerated shelf life will be shorter than that o f unfrozen orange roughy stored at refridgeration temperature. Orange roughy are a very important part o f the ecosystem. Their composition is less nutritionally beneficial than more readily available fish for human consumption and therefore should not be fished at all