CIMBNC- Combination and interactions of three kinds of nanoclays structural modifiers, for the colored bio-nanocomposites optimization

Biopolymers do not have competitive prices, which has prevented their industrial exploitation on a global scale so far. In this context, Using nanoclays, improvements in certain biopolymer properties, mainly mechanical and thermal, have been achieved. However, research has been much less focused on changing optical properties through the incorporation of nanoclays. At the same time, current research has focused on obtaining nanopigments, by organic dyes adsoptions into different nanoclays in order to achieve sustainable colouring and high performance materials. By combining advances in these lines of research, biodegradable composites with optimal mechanical and optical properties can be obtained. The aim of this work is to find the optimal formulation of naturally sourced nanopigments, incorporate them into a biological origin epoxy resin, and obtain a significant improvement in their mechanical, and optical properties. We combine three structural modifiers in the nanopigment synthesis: surfactant, silane and mordant salt. The latter was selected in order to replicate the mordant textile dyeing with natural dyes. Using a Taguchi’s desing L8, we look for the effect of the presence of the modifiers, the pH acidification, and the interactions effect between the synthesis factors. Three natural dyes were selected: chlorophyll, beta-carotene, and beetroot extract. Furthermore we use two kinds of laminar nanoclays, differentiated by the ion exchange charge: montmorillonite, and hydrotalcite. Then the thermal, mechanical and colorimetric characterization of the bionanocomposite materials was carried out. The optimal conditions to obtain the best bionanocomposite materials are using acid pH, and modifying the nanoclays with mordant and surfactant.

Avaliação in vitro da microinfiltração marginal de resinas de polimerização aumentada pela técnica directa

Dissertação para obtenção do grau de Mestre no Instituto Superior de Ciências da Saúde Egas Moniz

Nanostructures, Semicrytalline Morphology, and Nanoscale Confinement Effect on the Crystallization Kinetics in Self-Organized Block Copolymer/Thermoset Blends

This work reports the first instance of self-organized thermoset blends containing diblock copolymers with a crystallizable thermoset-immiscible block. Nanostructured thermoset blends of bisphenol A-type epoxy resin (ER) and a low-molecular-weight (M-n = 1400) amphiphilic polyethylene-block-poly(ethylene oxide) (EEO) symmetric diblock copolymer were prepared using 4,4'-methylenedianiline (MDA) as curing agent and were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC). All the MDA-cured ER/EEO blends do not show macroscopic phase separation but exhibit microstructures. The ER selectively mixes with the epoxy-miscible PEO block in the EEO diblock copolymer whereas the crystallizable PE blocks that are immiscible with ER form separate microdomains at nanoscales in the blends. The PE crystals with size on nanoscales are formed and restricted within the individual spherical micelles in the nanostructured ER/EEO blends with EEO content up to 30 wt %. The spherical micelles are highly aggregated in the blends containing 40 and 50 wt % EEO. The PE dentritic crystallites exist in the blend containing 50 wt % EEO whereas the blends with even higher EEO content are completely volume-filled with PE spherulites. The semicrystalline microphase-separated lamellae in the symmetric EEO diblock copolymer are swollen in the blend with decreasing EEO content, followed by a structural transition to aggregated spherical micellar phase morphology and, eventually, spherical micellar phase morphology at the lowest EEO contents. Three morphological regimes are identified, corresponding precisely to the three regimes of crystallization kinetics of the PE blocks. The nanoscale confinement effect on the crystallization kinetics in nanostructured thermoset blends is revealed for the first time. This new phenomenon is explained on the basis of homogeneous nucleation controlled crystallization within nanoscale confined environments in the block copolymer/thermoset blends.

Infrared microspectroscopic mapping of the homogeneity of extruded blends: Application to starch/polyester blends

Blends of starch and a biodegradable polyester, produced by an extrusion process, which included a cross-linker/compatibilizer (maleic anhydride) and an initiator (dicumyl peroxide), were studied by infrared (IR) microspectroscopy using an attenuated total reflectance (ATR) objective. Extruded material, which had a diameter of about 3 mm, was sectioned and embedded in epoxy resin prior to IR analysis. Spectra were collected in a grid pattern across the sectioned face of the sample. Measurement of various band parameters from the spectra allowed IR maps to be constructed containing semi-quantitative information about the distribution of blend components. These maps showed the quality of the blend on a microscopic scale and showed how it varied with different concentrations of compatibilizer and initiator. (c) 2005 Elsevier Ltd. All rights reserved.

COMPARAÇÃO DAS FORÇAS DE DEFLEXÃO LIBERADAS ENTRE OS FIOS ORTODÔNTICOS ESTÉTICOS E SUA RELAÇÃO COM O REVESTIMENTO

O objetivo do presente estudo consistiu em comparar as forças de deflexão in vitro entre fios estéticos e fio NiTi, para verificar a força máxima e da região platô e determinar sua correlação com o diâmetro do fio com e sem revestimento. Foram realizados dez ensaios de sete marcas comerciais de arcos précontornados, sendo seis fios estéticos (Invu (I), Optis (O), Flexy Super Elastic Esthetic (FSEE), Niticosmetic (N), Orthocosmetic Elastinol (OE) e Pro Form Coated Nitanium (PFCN)) e um fio NiTi superelástico (Nitinol Super Elastic (NSE)), aplicando-se o teste de curvatura de três pontos, associado a máquina de ensaios universal EMIC. Desenvolveu-se um dispositivo com braquetes cerâmicos (Transcend), cujos fios foram presos por elásticos modulares, sendo obtidos os valores da força de deflexão em 3,0, 2,0 e 1,0mm. O diâmetro dos fios com e sem revestimento foram mensurados com o especímetro digital Micromaster. A análise de variância a um critério (p<0,05) mostrou diferença significante entre os fios e o teste post-hoc de Tukey determinou que a força de deflexão em 3mm para o O

ANÁLISE MICROSCÓPICA E DA RUGOSIDADE DE SUPERFÍCIE DE FIOS ORTODÔNTICOS ESTÉTICOS, ANTES E APÓS DEFLEXÃO

O objetivo deste estudo foi avaliar a topografia de superfície dos fios estéticos, antes e após teste de deflexão. A amostra foi composta por 70 corpos de prova de fios 0,014 redondos, sendo 10 de cada uma das marcas comerciais avaliadas: Orthocosmetic Elastinol (Masel), Flexy Super Elastic Esthetic (Orthometric), InVu (TP Orthodontics) e ProForm Nitanium (Ortho Organizers) fios de NiTi revestidos por Teflon®; Optis (TP Orthodontics) fio de resina reforçado por fibra de vidro ou FRP; Niticosmetic (Tecnident) fio de NiTi revestido por resina epoxídica; e Nitinol SE (3M Unitek) fio de NiTi superelástico, usado para controle. A topografia de superfície de cada fio foi avaliada por rugosímetro e por microscópio óptico, antes e após ser submetido a ensaio de deflexão, no lado em que a força foi aplicada e no lado oposto a este. Cada fio foi defletido em 3,1mm, a uma velocidade de 1mm/min, com célula de carga de 5N a 36⁰C + 1⁰C. A análise de variância a três critérios (p<0,05) mostrou diferença significante entre os fios e o teste de Tukey mostrou que o fio Optis (TP Orthodontics) apresentou aumento nos parâmetros de rugosidade Ra, Rt e Rz, após a deflexão. O fio Niticosmetic (Tecnident) apresentou aumento na rugosidade média (Ra). O fio InVu (TP Orthodontics) foi o único que mostrou aumento na rugosidade no lado em que a força foi aplicada. A análise visual por meio de microscopia óptica revelou alterações na superfície em todos os fios estéticos após o teste de deflexão, desde delaminações do revestimento, observadas nos fios Orthocosmetic Elastinol e InVu, riscos permanentes na superfície, como visto nos fios Flexy Super Elastic Esthetic, Niticosmetic e ProForm Nitanium, e até mesmo fratura incompleta, no fio Optis. Concluiu-se que o fio Niticosmetic apresentou topografia de superfície similar ao fio metálico, e os demais fios estéticos apresentaram maior rugosidade e alterações visuaisna superfície.

The incidence of corpora amylacea (CA) in the optic nerve of patients with Alzheimer's disease

Corpora amylacea (CA) are spherical or ovoid bodies 50-50 microns in diameter. They have been described in normal elderly brain as well as in a number of neurodegenerative disorders. In this study, the incidence of CA in the optic nerves of Alzheimer's disease (AD) patients was compared with normal elderly controls. Samples of optic nerves (MRC Brain Bank, Institute of Psychiatry) were taken from 12 AD patients (age range 69-94 years) and 18 controls (43-82 years). Optic nerves were fixed in 2% buffered glutaraldehyde, post-fixed in osmium tetroxide, embedded in epoxy resin and then sectioned to a thickness of 2 microns. Sections were stained with toluidine blue. CA were present in all of the optic nerves examined. In addition, a number of similarly stained but more irregularly shaped bodies were present. Fewer CA were found in the optic nerves of AD patients compared with controls. By contrast, the number or irregularly shaped bodies was increased in AD. In AD, there may be a preferential decline in the large diameter fibres which may mediate the M-cell pathway. Hence, the decline in the incidence of CA in AD may be associated with a reduction in these fibres. It is also possible that the irregualrly shaped bodies are a degeneration product of the CA.

Interlamellar modification of smectite clays

Clay minerals, both natural and synthetic, have a wide range of applications. Smectite clays are not true insulators, their slight conductivity has been utilized by the paper industry in the development of mildly conducting paper. In particular, the synthetic hectorite clay, laponite, is employed to produce paper which is used in automated drawing offices where electro graphic printing is common. The primary objective of this thesis was to modify smectite clays, particularly laponite, to achieve enhanced conductivity. The primary objective was more readily achieved if the subsidiary objective of understanding the mechanism of conductivity was defined. The cyclic voltammograms of some cobalt complexes were studied in free solution and as clay modified electrodes to investigate the origin of electroactivity in clay modified electrodes. The electroactivity of clay modified electrodes prepared using our method can be attributed to ion pairs sorbed to the surface of the electrode, in excess of the cationic exchange capacity. However, some new observations were made concerning the co-ordination chemistry of the tri-2-pyridylamine complexes used which needed clarification. The a.c. conductivity of pressed discs of laponite RD was studied over the frequency range 12Hz- 100kHz using three electrode systems namely silver-loaded epoxy resin (paste), stainless-steel and aluminium. The a. c. conductivity of laponite consists of two components, reactive (minor) and ionic (major) which can be observed almost independently by utilizing the different electrode systems. When the temperature is increased the conductivity of laponite increases and the activation energy for conductivity can be calculated. Measurement of the conductivity of thin films of laponite RD in two crystal planes shows a degree of anisotropy in the a.c. conductivity. Powder X-ray diffraction and 119Sn Mossbauer spectroscopy studies have shown that attempts to intercalate some phenyltin compounds into laponite RD under ambient conditions result in the formation of tin(IV) oxide pillars. 119Sn Mossbauer data indicate that the order of effectiveness of conversion to pillars is in the order: Ph3SnCl > (Ph3Sn)2O, Ph2SnCl2 The organic product of the pillaring process was identified by 13C m.a.s.n.m.r. spectroscopy as trapped in the pillared lattice. This pillaring reaction is much more rapid when carried out in Teflon containers in a simple domestic microwave oven. These pillared clays are novel materials since the pillaring is achieved via neutral precursors rather than sacrificial reaction of the exchangeable cation. The pillaring reaction depends on electrophilic attack on the aryl tin bond by Brønsted acid sites within the clay. Two methods of interlamellar modification were identified which lead to enhanced conductivity of laponite, namely ion exchange and tin(IV) oxide pillaring. A monoionic potassium exchanged laponite shows a four fold increase in a.c. conductivity compared to sodium exchanged laponite RD. The increased conductivity is due to the appearence of an ionic component. The conductivity is independent of relative humidity and increases with temperature. Tin(IV) oxide pillared laponite RD samples show a significant increase in conductivity. Samples prepared from Ph2SnCl2 show an increase in excess of an order of magnitude. The conductivity of tin(IV) oxide pillared laponite samples is dominated by an ionic component.

Melamine phosphate as a component of intumescent coatings

Melamine orthophosphate has been shown to exhibit variations in its chemical constitution, and crystal shape and size, dependent upon the method of production. These crystal types have been incorporated with epoxy resin to produce intumescent coatings, which have been tested on a small scale fire testing device, designed and calibrated within this project. The factors influencing performance in three fire test regimes are the percentage loading of melamine phosphate, its chemical constitution, crystal size and shape, thermal degradation, and state of agglomeration . and dispersion in the coating, determined by the method of incorporation into the coating. When melamine phosphate is heat treated at 210ºC, a process designed to reduce its solubility, the performance of coatings produced with such material is profoundly affected, depending mainly on crystal size and shape alone. Consideration of heat transfer across the chars produced has allowed a quantitative evaluation of the thermal resistance of chars throughout a test. An optimum production route for melamine phosphate has been suggested, taking into account the requirements for weatherability of coatings as well as performance in a fire.

Interactions between organic polymers and cement hydration products

Organic substances, particularly polymers, are finding increasing use in modifying the properties of cements and concrete. Although a significant amount of research has been conducted into the modification of the mechanical properties of cements by polymers, little is known about the nature of the interface and interactions taking place between the two phases. This thesis addresses the problem of elucidating such interactions. Relevant literature is reviewed, covering the general use of polymers with cements, the chemistry of cements and polymers, adhesion and known interactions between polymers and both cements and related minerals. Although several polymer systems were studied, two in particular were selected, as being well characterized. These were: - 1) polymethyl methacrylate (PMMA), the polymer derived from methyl methacrylate (MMA), and 2) an amine-cured epoxy resin system. By this approach, a methodology was developed for the examination of other polymer/cement interactions. Experiments were conducted in five main areas:- 1) polymer-cement adhesion and the feasibility of revealing interfacial regions mechanically, 2) chemical reactions between polymers and cements, 3) characterization of cement adhesion surfaces, 4) interactions affecting overall polymerisation rates, and 5) studies of polymer impregnated cements. The following conclusions were reached:- 1) The PMMA/cement interface contains calcium methacrylate as an interfacial reaction product, water being a reactant. Calcium methacrylate is detrimental to the properties of PMMA/cement composites, being highly water-soluble. 2) The pore surface of cement accelerates the polymerisation of MMA, leading to an increased molecular weight compared to polymerisation of pure MMA, minerals in hydrated cement powders having the opposite effect. 3) The investigation of reaction products presents a number of experimental problems, selection of appropriate techniques depending upon the system studied. For the two systems examined in detail, ion chromatography proved particularly useful; DTA, IRS and XPS indicated reactions, though the data was hard to interpret; XRD proving inconclusive. 4) It is impractical to reveal interfacial regions mechanically, but may be accomplished by chemical means.

Desenvolvimento de um painel sanduíche com carga de particulado oriundo de resíduo lignocelulósico para aplicação em produtos na área de equipamentos de proteção

This work aims to study and investigate the use of a hybrid composite polymer formed with blanket aramid (Kevlar 29) fiber blanket flax fiber and particulate dry endocarp of coconut (Cocos nucifera Linn), using as matrix an epoxy resin based thermoset for use in areas of protective equipment. Besides such material is used an aluminum plate, joined to the composite by means of glue based on epoxy and araldite commercial. The manufacturing process adopted was manual lamination (Hand Lay Up) to manufacture the hybrid composite. After the composite is prepared, an aluminum plate is subjected to pressure and glued to cure the adhesive. Layers of veil will also be used to separate the particulate from the linen blanket layer without disturbing the alignment of the fibers of the blankets. To characterize the mechanical and physical behavior was manufactured a plate of 800 x 600 mm of the hybrid composite, which were removed specimens for tests of water absorption to saturation; density; impact test (Charpy) and two test specimens for ballistic testing 220 mm x 200 mm to make a comparative study between the dry state and saturated water absorption and thus see the ballistic performance of these two conditions. The test was applied to make a comparative study of fracture in these two conditions, caused by penetrating ballistic missile (38 and 380). To test the impact (Charpy) will analyze the absorbed energy, fracture appearance and lateral contraction, also in dry condition and saturation of absorbed water, thereby analyzing situations where the impact load is relevant, such as bumps and shocks produced by stone, metal or wooden bars among others. The proposed configuration, along with the tests, has the purpose, application in the fields of equipment against ballistic impact, such as helmets; bullet proof vests; shields; protective packaging and other items to be identified in this research.

Influência do retardante de chamas nas propriedades mecânicas e flamabilidade em compósitos poliméricos de epóxi/fibra de curauá

Currently, there is a great search for materials derived from renewable sources. The vegetable fibers as reinforcement for polymer matrixes, has been used as an alternative to replace synthetic fibres, being biodegradable and of low cost. The present work aims to develop a composite material with epoxy resin reinforced with curauá fibre with the addition of alumina trihydrate (aluminum hydroxide, Al(OH)3) as a flame retardant, which was used in proportions of 10 %, 20% and 30% of the total volume of the composite. The curauá fibers have gone through a cleaning process with an alkaline bath of sodium hydroxide (NaOH ), parallelized by hand and cut carding according to the default length . They were molded composites with fibers 30cm. Composites were molded in a Lossy Mold with unidirectional fibres in the proportion of 20% of the total volume of the composite. The composites were prepared in the Chemical Processing Laboratory of the Textile Engineering Department at UFRN. To measure the performance of the material, tests for the resistance to traction and flexion were carried out. with samples that were later analyzed in the Electronic Microscopy Apparatus (SEM ). The composites showed good mechanical properties by the addition of flame retardant and in some cases, leaving the composite more vulnerable to breakage. These mechanical results were analyzed by chi-square statistical test at the 5% significance level to check for possible differences between the composite groups. Flammability testing was conducted based on the standard Underwriters Laboratory 94 and the material showed a satisfactory result taking their average burn rate (mm / min) decreasing with increasing addition of the flame retardant composite.

Estudo das propriedades mecânicas de laminados com cortiça micro-aglomerada

Esta tese desenvolveu-se a partir de uma proposta de uma conceituada empresa portuguesa especializada em kayaks e consistiu em desenvolver um laminado de base natural e com núcleo de cortiça, capaz de se assemelhar em termos mecanicos aos de fibra de vidro e resina epóxi já utilizados. Após uma alargada pesquisa de materiais e fornecedores, procedeu-se ao fabrico de várias placas diferentes. Os materiais de base foram o núcleo de cortiça, peles em fibra de linho e bio-resina epóxi. De modo a avaliar as respostas mecânicas em regime estático e dinamico, foram realizados ensaios de flexão e impacto. As conclusões obtidas após exaustiva análise dos resultados permitem concluir que os laminados naturais podem oferecer propriedades mecânicas interessantes e quiça rivalizar com os seus concorrentes sintéticos, mantendo as óbvias vantagens em termos de responsabilidade ambiental. Ficam também directrizes para o caso de se pretender o fabrico de um protótipo utilizando estes materiais.

Caracterização do ciclo da marcha em amputado transtibial com prótese inteligente

This work presents an application of optical fiber sensors based on Bragg gratings integrated to a transtibial prosthesis tube manufactured with a polymeric composite systrem of epoxy resin reinforced with glass fiber. The main objective of this study is to characterize the sensors applied to the gait cycle and changes in the gravity center of a transtibial amputee, trough the analysis of deformation and strengh of the transtibial prosthesis tube. For this investigation it is produced a tube of the composite material described above using the molding method of resin transfer (RTM) with four optical sensors. The prosthesis in which the original tube is replaced is classified as endoskeletal, has vacuum fitting, aluminium conector tube and carbon fiber foot cushioning. The volunteer for the tests was a man of 41 years old, 1.65 meters tall, 72 kilograms and left-handed. His amputation occurred due to trauma (surgical section is in the medial level, and was made below the left lower limb knee). He has been a transtibial prosthesis user for two years and eight months. The characterization of the optical sensors and analysis of mechanical deformation and tube resistance occurred through the gait cycle and the variation of the center of gravity of the body by the following tests: stand up, support leg without the prosthesis, support in the leg with the prosthesis, walk forward and walk backward. Besides the characterization of optical sensors during the gait cycle and the variation of the gravity center in a transtibial amputated, the results also showed a high degree of integration of the sensors in the composite and a high mechanical strength of the material.

Desenvolvimento de fontes radioativas seladas imobilizadas em resina epóxi para verificação de detectores utilizados em medicina nuclear

Dissertação (Mestrado em Tecnologia Nuclear)