Compartments of the foot: topographic anatomy

Recent publications have renewed the debate regarding the number of foot compartments. There is also no consensus regarding allocation of individual muscles and communication between compartments. The current study examines the anatomic topography of the foot compartments anew using 32 injections of epoxy-resin and subsequent sheet plastination in 12 cadaveric foot specimens. Six compartments were identified: dorsal, medial, lateral, superficial central, deep forefoot, and deep hindfoot compartments. Communication was evident between the deep hindfoot compartment and the superficial central and deep central forefoot compartments. In the hindfoot, the neurovascular bundles were located in separate tissue sheaths between the central hindfoot compartment and the medial compartment. In the forefoot, the medial and lateral bundles entered the deep central forefoot compartment. The deep central hindfoot compartment housed the quadratus plantae muscle, and after calcaneus fracture could develop an isolated compartment syndrome.

Molecular modeling of EPON 862-DETDA polymer

EPON 862 is an epoxy resin which is cured with the hardening agent DETDA to form a crosslinked epoxy polymer and is used as a component in modern aircraft structures. These crosslinked polymers are often exposed to prolonged periods of temperatures below glass transition range which cause physical aging to occur. Because physical aging can compromise the performance of epoxies and their composites and because experimental techniques cannot provide all of the necessary physical insight that is needed to fully understand physical aging, efficient computational approaches to predict the effects of physical aging on thermo-mechanical properties are needed. In this study, Molecular Dynamics and Molecular Minimization simulations are being used to establish well-equilibrated, validated molecular models of the EPON 862-DETDA epoxy system with a range of crosslink densities using a united-atom force field. These simulations are subsequently used to predict the glass transition temperature, thermal expansion coefficients, and elastic properties of each of the crosslinked systems for validation of the modeling techniques. The results indicate that glass transition temperature and elastic properties increase with increasing levels of crosslink density and the thermal expansion coefficient decreases with crosslink density, both above and below the glass transition temperature. The results also indicate that there may be an upper limit to crosslink density that can be realistically achieved in epoxy systems. After evaluation of the thermo-mechanical properties, a method is developed to efficiently establish molecular models of epoxy resins that represent the corresponding real molecular structure at specific aging times. Although this approach does not model the physical aging process, it is useful in establishing a molecular model that resembles the physically-aged state for further use in predicting thermo-mechanical properties as a function of aging time. An equation has been predicted based on the results which directly correlate aging time to aged volume of the molecular model. This equation can be helpful for modelers who want to study properties of epoxy resins at different levels of aging but have little information about volume shrinkage occurring during physical aging.

Análisis de los modelos de comportamiento de vigas de hormigón armado reforzadas a cortante con polímeros armados con fibras (frp). Validación y calibración experimental

Los polímeros armados con fibras (FRP) se utilizan en refuerzos de estructuras de hormigón debido sobre todo a sus excelentes propiedades mecánicas, su resistencia a la corrosión y a su ligereza que se traduce en facilidad y ahorro en el transporte, puesta en obra y aplicación, la cual se realiza de forma muy rápida, con pocos operarios y utilizando medios auxiliares ligeros, minimizándose las interrupciones del uso de la estructura y las molestias a los usuarios. Las razones presentadas anteriormente, han despertado un gran inter´es por parte de diferentes grupos de investigación a nivel mundial y que actualmente se encuentran desarrollando nuevas técnicas de aplicación y métodos de cálculo. Sin embargo, las investigaciones realizadas hasta la fecha, muestran un procedimiento bien definido y aceptado en lo referente al cálculo a flexión, lo cual no ocurre con el refuerzo a cortante y aunque se ha demostrado que el refuerzo con FRP es un sistema eficaz para incrementar la capacidad ´ultima frente a esfuerzos cortantes, también se pone de manifiesto la necesidad de más estudios experimentales y teóricos para avanzar en el entendimiento de los mecanismos involucrados para este tipo de refuerzo y establecer un procedimiento de diseño apropiado que maximice las excelentes propiedades de este material. Los modelos que explican el comportamiento del refuerzo a cortante de elementos de hormigón armado son complejos y sin transposición directa a fórmulas ingenieriles. Las normas actualmente en vigor, generalmente, establecen empíricamente la capacidad cortante como la suma de las capacidades del hormigón y el refuerzo transversal de acero. Cuando un elemento es reforzado externamente con FRP, los modelos son evidentemente aun más complejos. Las guías y recomendaciones existentes proponen calcular la capacidad del elemento añadiendo la resistencia aportada por el refuerzo externo de FRP a la ya dada por el hormigón y acero transversal. Sin embargo, la idoneidad de este acercamiento es cuestionable puesto que no tiene en cuenta una posible interacción entre refuerzos. Con base en lo anterior se da origen al tema objeto de este trabajo, el cual está orientado al estudio a cortante de elementos de hormigón armado (HA), reforzados externamente con material compuesto de tejido unidireccional de fibra de carbono y resina epoxi. Inicialmente se hace una completa revisión del estado actual del conocimiento de la resistencia a cortante en elementos de hormigón armado con y sin refuerzo externo de FRP, prestando especial atención en los mecanismos actuantes estudiados hasta la fecha. La bibliografía consultada ha sido exhaustiva y actualizada lo que ha permitido el estudio de los modelos propuestos más importantes, tanto para la descripción del fenómeno de adherencia entre hormigón-FRP como de la valoración del aporte al cortante total hecho por el FRP, a través de sendas bases de datos de ensayos de pull-out y de vigas de hormigón armado ensayadas a cortante. Con base en todo lo anterior, se expusieron los mecanismos actuantes en el aporte a cortante hecho por el FRP en elementos de hormigón armado y la forma como las principales guías de cálculo existentes hasta la fecha los abordan. De igual forma se define un modelo de resistencia de esfuerzos para el FRP y se proponen dos modelos para el cálculo de las tensiones o deformaciones efectivas, de los cuales uno esta basado en el modelo de adherencia propuesto por Oller (2005) y el otro en una regresión multivariante para los mecanismos expuestos. Como complemento del estudio de los trabajos encontrados en la literatura, se lleva acabo un programa experimental que, además de aportar más registros a la exigua base de datos existentes, aporte mayor luz a los puntos que se consideran están deficientemente resueltos. Dentro de este programa se realizaron 32 ensayos sobre 16 vigas de 4.5 m de longitud (dos ensayos por viga), reforzadas a cortante con tejido unidireccional de CFRP. Finalmente, estos estudios han permitido proponer modificaciones a las formulaciones existentes en los códigos y guías en vigor. Abstract Its excellent mechanical properties, as well as its corrosion resistance and light weight, which make it easy to apply and inexpensive to ship to the worksite, are the basis of the extended use of fiber reinforced polymer (FRP) as external strengthening for structures. FRP strengthening is a rapid operation calling for only limited labor and lightweight ancillary equipment, all of which minimizes both the interruption of facility usage and user inconvenience. These advantages have aroused considerable interest in civil engineering science and technology and have led to countless applications the world over. Research studies on the shear strength of FRP-strengthened members have been much fewer in number and more controversial than the research on flexural strengthening, for which a more or less standardized and generally accepted procedure has been established. The research conducted and a host of applications around the world have shown that FRP strengthening is an effective technique for raising ultimate shear strength, but it has also revealed a need for further experimental and theoretical research to advance in the understanding of the mechanisms involved and establish suitable design procedures that optimize the excellent properties of this material The models that explain reinforced concrete (RC) shear strength behavior are complex and cannot be directly transposed to engineering formulas. The standards presently in place generally establish shear capacity empirically as the sum of the capacities of the concrete and the passive reinforcement. When members are externally strengthened with FRP, the models are obviously even more complex. The existing guides and recommendations propose calculating capacity by adding the external strength provided by the FRP to the contributions of the concrete and passive reinforcement. The suitability of this approach is questionable, however, because it fails to consider the interaction between passive reinforcement and external strengthening. The subject of this work is based in above, which is focused on externally shear strengthening for reinforced concrete members with unidirectional carbon fiber sheets bonded with epoxy resin. v Initially a thorough literature review on shear of reinforced concrete beams with and without external FRP strengthening was performed, paying special attention to the acting mechanisms studied to date, which allowed the study of the most important models both to describe the bond phenomenon as well as calculating the FRP shear contribution, through separate databases of pull-out tests and shear tests on reinforced concrete beams externally strengthened with FRP. Based on above, they were exposed the acting mechanisms in a FRP shear strengthening on reinforced concrete beams and how guidelines deal the topic. The same way, it is defined a FRP stress strength model and two more models are proposed for calculating the effective stress, one of these is based on the Oller (2005) bond model and another one is the data best fit, taking into account most of the acting mechanisms. To complement the theoretical part we develop an experimental program that, in addition to providing more records to the meager existing database provide greater understanding to the points considered poorly resolved. The test program included 32 tests of 16 beams (2 per beam) of 4.5 m long, shear strengthened with FRP, externally. Finally, modifications to the existing codes and guidelines are proposed.

Self-standing curved crystals for X and Gamma rays focusing

The efficiency of a Laue lens for X and Gamma ray focusing in the energy range 60 ÷ 600 keV is closely linked to the diffraction efficiency of the single crystals composing the lens. A powerful focusing system is crucial for applications like medical imaging and X ray astronomy where wide beams must be focused. Mosaic crystals with a high density, such as Cu or Au, and bent crystals with curved diffracting planes (CDP) are considered for the realization of a focusing system for X rays, owing to their high diffraction efficiency. In this work, a comparison of the efficiency of CDP crystals and mosaic crystals was performed on the basis of the theory of X-ray diffraction. Si, GaAs and Ge CDP crystals with optimized thicknesses and moderate radii of curvature of several tens of metres demonstrate comparable or superior performance with respect to the higher atomic number mosaic crystals generally used. A simplified approach for calculating the integrated reflectivity of the crystals is applied. A bending technique used during this work to realize CDP crystals consists in a controlled surface damaging induced by a mechanical lapping process. A compressive strained layer of few micrometres in thickness is generated and causes the convex curvature of the damaged side of the crystal. Another new bending technique is developed and the main results are shown. The process consists on a film deposition of a selected bi-component epoxy resin on one side of crystal, made uniform in thickness by mean of a spin-coater. Choosing the speed of spin-coating, so changing the thickness of the film, a control of radius of curvature can be obtained. Moreover the possibility to combine the two bending technique to obtain CDP crystal with a stronger curvature in rather thick crystals was demonstrated. Detailed characterization of Si, and GaAs CDP crystals at low and high x-ray energies are performed on flat and bent crystals obtained with the damaging and the resin deposition technique. As expected an increase of diffraction efficiency in asymmetrical diffraction geometry in CDP crystals with respect to the flat ones is observed. On the other hand an unexpected increase of the integrated intensity in symmetrical geometry, not predicted by the theory, is observed in all the measurements performed with different set up. The experimental trend of the integrated reflectivity as a function of the radius of curvature is in a good agreement with that predicted by the theory of bent perfect crystals, so it is possible to conclude that the surface damage has a limited effect on the crystal reflectivity. A study of the integrated reflectivity in the energy range of interest (100÷350 keV) in CDP crystals realized with damaging and resin deposition technique at symmetrical and asymmetrical geometries was performed at ILL Institute. Also at these energies the diffraction efficiency of bent crystals was much larger (a 12 time increase is observed for bent crystals in asymmetrical 111 geometry) than that measured in flat crystals. The diffraction efficiency of CDP crystals realized with both techniques tends to coincide with that of flat crystals at very high energies (> 200 keV). This suggesting that also real flat perfect crystals can be considered as strongly bent or mosaic crystals at very high X ray energies.

Avaliação in vivo e in vitro de diferentes protocolos no tratamento da hipersensibilidade dentinária cervical

Este estudo possui duas partes distintas: 1. in vivo (randomizado e longitudinal) que teve como objetivo avaliar protocolos de tratamento para hipersensibilidade dentinária com laser de baixa potência (com diferentes dosagens), laser de alta potência e agente dessensibilizante, por um período de 12 e 18 meses; e 2. in vitro que teve como objetivo analisar a perda de estrutura de dois dentifrícios distintos (Colgate Total 12 e Colgate Pró Alívio) e analisar a permeabilidade dentinária dos tratamentos da etapa 01, associados aos dentifrícios, após diferentes ciclos de abrasão. Na parte in vivo, as lesões cervicais não cariosas de 32 voluntários, previamente submetidos aos critérios de elegibilidade ou exclusão, foram divididas em nove grupos (n=10): G1: Gluma Desensitizer (Heraeus Kulzer), G2: Laser de baixa potência com baixa dosagem (Photon Lase, DMC) (três pontos de irradiação vestibulares e um ponto apical: 30 mW, 10 J/cm2, 9 seg por ponto com o comprimento de onda de 810nm). Foram realizadas três sessões com um intervalo de 72 horas), G3: Laser de baixa potência com alta dosagem (um ponto cervical e um ponto apical: 100 mW, 90 J/cm2, 11 seg por ponto com o comprimento de onda de 810nm. Foram realizadas três sessões com um intervalo de 72 horas), G4: Laser de baixa potência com baixa dosagem + Gluma Desensitizer, G5: Laser de baixa potência com alta dosagem + Gluma Desensitizer, G6: Laser de Nd:YAG (Power LaserTM ST6, Lares Research®), em contato com a superfície dental: 1,0W, 10 Hz e 100 mJ, ? 85 J/cm2, com o comprimento de onda de 1064nm, G7: Laser de Nd:YAG + Gluma Desensitizer, G8: Laser de Nd:YAG + Laser de baixa potência com baixa dosagem, G9: Laser de Nd:YAG + Laser de baixa potência com alta dosagem. O nível de sensibilidade de cada voluntário foi avaliado através da escala visual analógica de dor (VAS) com auxílio do ar da seringa tríplice e exploração com sonda após 12 e 18 meses do tratamento. Na parte 02, in vitro, foram utilizados terceiros molares humanos não irrompidos e recém-extraídos. Todos foram limpos e tiveram suas raízes separadas das coroas. As raízes foram seccionadas em quadrados de dentina com dimensões de 4x4x2 mm, os quais foram embutidos em resina Epoxi e devidamente polidos até uma curvatura de 0,3 ?m, analisados em perfilometria ótica. Estes foram imersos em solução de EDTA 17% por 2min para abertura dos túbulos e armazenados em uma solução de Soro Fetal Bovino diluído em salina tamponada com fosfato. Os espécimes foram divididos aleatoriamente em 12 grupos (n=10) G1: Sem tratamento de superfície, sem dentifrício; G2: Nd:YAG/sem dentifrício; G3: Gluma/sem dentifrício; G4: Nd:YAG + Gluma/sem dentifrício; G5: Sem tratamento de superfície/Colgate Total 12; G6: Nd:YAG/Colgate Total 12; G7: Gluma/Colgate Total 12; G8: Nd:YAG + Gluma/Colgate Total 12; G9: Sem tratamento de superfície/Colgate Pró Alívio; G10: Nd:YAG/Colgate Pró Alívio; G11: Gluma/Colgate Pró Alívio; G12: Nd:YAG + Gluma/Colgate Pró Alívio. Em seguida, as superfícies receberam a aplicação de fitas adesivas nas duas margens, mantendo uma área central de teste exposta de 4 x 1 mm, onde foram realizados os tratamentos de superfície e os ciclos de abrasão correspondentes a 1, 7, 30 e 90 dias de escovação (52 ciclos, 210 segundos de contato com o slurry; 361 ciclos, 1470 segundos de contato com o slurry; 1545 ciclos, 6300 segundos de contato com o slurry; 4635 ciclos, 18900 segundos de contato com o slurry, respectivamente). A cada etapa de abrasão, foi realizada análise em Perfilometria Ótica. Para as analises de permeabilidade e Microscopia Eletrônica de Varredura, foram utilizadas amostras circulares de 6 mm de diâmetro e 1 mm de espessura de dentina obtidas das coroas dentais. Estas foram divididas aleatoriamente nos mesmos grupos já descritos anteriormente, sendo que 120 espécimes foram utilizados para permeabilidade (n=10) e 36 para MEV (n=3). Ambas as análises foram realizadas após imersão no EDTA; após tratamentos para a sensibilidade; pós 1 dia, 7 dias, 30 dias e 90 dias de escovação. Após análise estatística pode-se concluir que, in vivo, todos os tratamentos foram eficazes para a redução da hipersensibilidade dentinária. Ainda que o nível da sensibilidade dos pacientes aumentou numericamente, estes não são considerados estatisticamente diferentes a partir de 12 meses. Portanto, até a avaliação de 18 meses, podemos concluir que não houve um aumento na sensibilidade dentinária desde a sua diminuição pós-tratamento. In vitro, pode-se concluir que todos os tratamentos foram capazes de diminuir a permeabilidade dentinária. O dentifrício Total 12 apresentou-se como o mais abrasivo em comparação com o dentifrício Pro Alivio, pois este último promoveu uma perda de estrutura menor, porém ambos não apresentaram aumento na permeabilidade nos tempos de escovação. As microscopias eletrônicas de varredura mostram a formação da smear layer, obliterando os túbulos para ambos os dentifricios. Como conclusão, pode-se afirmar que todos os agentes dessensibilizantes foram efetivos, mesmo apresentando estratégias de ação diferentes. Os dentifrícios são igualmente interessantes para o uso caseiro por ocasionarem oclusão tubular e a associação de tratamentos (caseiro e de consultório) parece ser uma alternativa eficaz no tratamento da hipersensibilidade dentinária.

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.