Postbuckling behaviour of a blade-stiffened composite panel loaded in uniaxial compression

The postbuckling behaviour of a panel with blade-stiffeners incorporating tapered flanges was experimentally investigated. A new failure mechanism was identified for this particular type of stiffener. Failure was initiated by mid-plane delamination at the free edge of the postbuckled stiffener web at a node-line. This was consistent with an interlaminar shear stress failure and was calculated from strain gauge measurements using an approximate analysis based on lamination theory and incorporating edge effects. The critical shear stress was found to agree well with the shear strength obtained from a three-point bending test of the web laminate. 

Fast-drying multi-laminate bioadhesive films for transdermal and topical drug delivery

No bioadhesive patch-based system is currently marketed. This is despite an extensive number of literature reports on such systems detailing their advantages over conventional pressure sensitive adhesive-based patches in wet environments and describing successful delivery of a diverse array of drug substances. This lack of proprietary bioadhesive patches is largely due to the fact that such systems are exclusively water-based, meaning drying is difficult. In this paper we describe, for the first time, a novel multiple lamination method for production of bioadhesive patches. In contrast to patches produced using a conventional casting approach, which took 48 hours to dry, bioadhesive films prepared using the novel multiple lamination method were dried in 15?min and were folded into formed patches in a further 10?min. Patches prepared by both methods had comparable physicochemical properties. The multiple lamination method allowed supersaturation of 5-aminolevulinic acid to be achieved in formed patch matrices. However, drug release studies were unable to show an advantage for supersaturation with this particular drug, due to its water high solubility. The multiple lamination method allowed greater than 90% of incorporated nicotine to remain within formed patches, in contrast to the 48% achieved for patches prepared using a conventional casting approach. The procedure described here could readily be adapted for automation by industry. Due to the reduced time, energy and ensuing finance now required, this could lead to bioadhesive patch-based drug delivery systems becoming commercially viable. This would, in turn, mean that pathological conditions occurring in wet or moist areas of the body could now be routinely treated by prolonged site-specific drug delivery, as mediated by a commercially produced bioadhesive patch.

Estudo de falha em placas laminadas usando métodos analíticos e numéricos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Manutenção

Desenvolvimento do Filme Plástico Paper Like

A indústria de transformação de material plástico contribui de forma relevante para o desenvolvimento da economia mundial. Com o objetivo de desenvolvimento dessa indústria, a empresa Pentaplast S. A., situada em Água Longa, Santo Tirso, desenvolve a conceção de novos produtos para novas aplicações. Esta empresa para continuar na posição de destaque que possui, tem que conduzir a sua existência na melhoria contínua e atualização fase ao mercado. Na indústria termoformadora existe uma procura constante de novos materiais, visto ser um mercado muito competitivo. Neste contexto, o presente trabalho tem como objetivo desenvolver um filme plástico com o aspeto de papel para a indústria termoformadora, criando desta forma um impacto no consumidor para a preocupação ambiental. De forma a encontrar soluções para o problema mencionado, conduziu-se ao estudo e desenvolvimento de um novo produto – Paper Like, sendo este, um produto reciclável e adotado às necessidades da termoformação. Para isso, desenvolveu-se o projeto utilizando o processo de termolaminação, com a adição de um aditivo na camada externa, permitindo incorporar ao filme plástico, o aspeto e textura de papel. Foram testados, separadamente, dois aditivos, X e Y, base PET e PE, respetivamente, com diferentes percentagens de incorporação. O aditivo X foi desenvolvido especialmente para este projeto, tendo como base politereftalato de etileno, no entanto com a sua incorporação não se obteve os resultados esperados, somente dava um aspeto mate ao filme extrudidos. O aditivo Y, já existe no mercado mas nunca utilizado em extrusão plana, tem como base polietileno e a sua incorporação permitiu obter um filme com aspeto de papel, comprovando-se a sua compatibilidade com pigmentos, os quais dão diversas cores aos filmes, permitindo assim competir com os filmes tradicionais. Infelizmente a termolaminação do filme com o aditivo Y não foi possível, o que inviabiliza a selagem da embalagem.

Embalagens Flexíveis: estudo do processo de reticulação de adesivos e do coeficiente de atrito

A dissertação foi realizada em ambiente industrial, mais precisamente na empresa Monteiro, Ribas – Embalagens Flexíveis, S.A.. Esta empresa dedica-se à impressão e laminagem de filmes, assim como à confeção de sacos. Os seus produtos são direcionados na sua maioria para a indústria alimentar, exportando mais de 50% da sua produção, e dizem respeito a complexos (dois ou mais filmes unidos pela presença de um adesivo) que podem possuir impressão ou não. Estes complexos podem ser enviados para o cliente em bobina ou já em saco. Os objetivos propostos pela empresa diziam respeito a estudos relacionados com a força de laminagem dos complexos, com o coeficiente de atrito dos mesmos e com a identificação dos espetros dos componentes dos adesivos, assim como o estudo do processo de reticulação dos mesmos por espetrofotometria de Infravermelho. Relativamente aos resultados obtidos verificou-se que tanto a tinta como os metalizados influenciam negativamente a força de laminagem. Por sua vez o coeficiente de atrito é afetado por vários fatores. Através dos ensaios experimentais verificou-se que o adesivo, a tinta e o verniz mate favorecem o aumento do valor do COF. Além disso, nos complexos em que se utilizaram filmes de polietileno de maior espessura obtiveram-se valores de COF mais baixos, e no que diz respeito à temperatura e à tensão de enrolamento, verificou-se que valores mais elevados e muito baixos da primeira traduzem-se num aumento do valor do COF e uma tensão de enrolamento maior também tem o mesmo efeito. Relativamente ao tipo de filme impresso, substratos com maior energia superficial atraem mais o agente de deslizamento (slip). Por último, não se conseguiu perceber qual o tipo de adesivo (com ou sem solvente) que tem maior impacto no COF uma vez que em 55% dos casos o valor do COF é superior nas amostras que foram complexadas com adesivo sem solvente e em 45% o COF era superior nas amostras complexadas com adesivo base solvente. No que diz respeito aos espetros obtidos verificou-se que a reticulação dos adesivos é identificada pela diminuição da extensão do pico correspondente à ligação N=C=O.

POCN-type Pincer Complexes of NiII and NiIII : synthesis, reactivities, catalytic activities and physical properties

Cette thèse décrit la synthèse, la caractérisation, les réactivités, et les propriétés physiques de complexes divalents et trivalents de Ni formés à partir de nouveaux ligands «pincer» de type POCN. Les ligands POCN de type amine sont préparés d’une façon simple et efficace via l’amination réductrice de 3-hydroxybenzaldéhyde avec NaBH4 et plusieurs amines, suivie par la phosphination de l’amino alcool résultant pour installer la fonction phosphinite (OPR2); le ligand POCN de type imine 1,3-(i-Pr)2PC6H4C(H)=N(CH2Ph) est préparé de façon similaire en faisant usage de PhCH2NH2 en l’absence de NaBH4. La réaction de ces ligands «pincer» de type POCN avec NiBr2(CH3CN)x en présence d’une base résulte en un bon rendement de la cyclométalation du lien C-H situé en ortho aux fonctions amine et phosphinite. Il fut découvert que la base est essentielle pour la propreté et le haut rendement de la formation des complexes «pincer» désirés. Nous avons préparé des complexes «pincer» plan- carrés de type POCN, (POCNRR΄)NiBr, possédant des fonctions amines secondaires et tertiaires qui démontrent des réactivités différentes selon les substituants R et R΄. Par exemple, les complexes possédant des fonctions amines tertiaires ArCH2NR2 (NR2= NMe2, NEt2, and morpholinyl) démontrent des propriétés rédox intéressantes et pourraient être convertis en leurs analogues trivalents (POCNR2)NiBr2 lorsque réagis avec Br2 ou N-bromosuccinimide (NBS). Les complexes trivalents paramagnétiques à 17 électrons adoptent une géométrie de type plan-carré déformée, les atomes de Br occupant les positions axiale et équatoriale. Les analyses «DSC» et «TGA» des ces composés ont démontré qu’ils sont thermiquement stables jusqu’à ~170 °C; tandis que la spectroscopie d’absorption en solution a démontré qu’ils se décomposent thermiquement à beaucoup plus basse température pour regénérer les complexes divalents ne possédant qu’un seul Br; l’encombrement stérique des substitutants amines accélère cette route de décomposition de façon significative. Les analogues NMe2 et N(morpholinyl) de ces espèces de NiIII sont actifs pour catalyser la réaction d’addition de Kharasch, de CX4 à des oléfines telles que le styrène, tandis qu’il fut découvert que l’analogue le moins thermiquement stable (POCNEt2)Ni est complètement inerte pour catalyser cette réaction. Les complexes (POCNRH)NiBr possédant des fonctions amines secondaires permettent l’accès à des fonctions amines substituées de façon non symétrique via leur réaction avec des halogénures d’alkyle. Un autre avantage important de ces complexes réside dans la possibilité de déprotonation pour préparer des complexes POCN de type amide. De telles tentatives pour déprotoner les fonctions NRH nous ont permis de préparer des espèces dimériques possédant des ligands amides pontants. La nature dimérique des ces complexes [P,C,N,N-(2,6-(i-Pr)2PC6H3CH2NR)Ni]2 (R= PhCH2 et Ph) fut établie par des études de diffraction des rayons-X qui ont démontré différentes géométries pour les cœurs Ni2N2 selon le substituant N : l’analogue (PhCH2)N possède une orientation syn des substitutants benzyles et un arrangement ressemblant à celui du cyclobutane du Ni et des atomes d’azote, tandis que l’analogue PhN adopte un arrangement de type diamant quasi-planaire des atomes du Ni et des atomes d’azote et une orientation anti des substituants phényles. Les espèces dimériques ne se dissocient pas en présence d’alcools, mais elles promouvoient l’alcoolyse catalytique de l’acrylonitrile. De façon intéressante, les rendements de ces réactions sont plus élevés avec les alcools possédant des fonctions O-H plus acides, avec un nombre de «turnover» catalytique pouvant atteindre 2000 dans le cas de m-cresol. Nous croyons que ces réactions d’alcoolyse procèdent par activation hétérolytique de l’alcool par l’espèce dimérique via des liaisons hydrogènes avec une ou deux des fonctions amides du dimère. Les espèces dimériques de Ni (II) s’oxydent facilement électrochimiquement et par reaction avec NBS ou Br2. De façon surprenante, l’oxydation chimique mène à l’isolation de nouveaux produits monomériques dans lesquels le centre métallique et le ligand sont oxydés. Le mécanisme d’oxydation fut aussi investigué par RMN, «UV-vis-NIR», «DFT» et spectroélectrochimie.

An ichnofabric approach to the depositional interpretation of the intensely burrowed Bateig Limestone, Miocene, SE Spain

The foraminiferal-rich pelagic Bateig Limestone forms several varieties of the important building stones quarried at Bateig Hill in southeastern Spain. Three principal ichnofabrics (Bichordites, mottled-Palaeophycus and mottled-Ophiomorpha) are recognized, which are present in at least two (possibly up to four) repeated successions (cycles). Each succession begins with an erosional event. The Bichordites ichnofabric represents a new type of facies, formed as thin turbidity/grain flow, stratiform units derived from sediment slips off a fault into deep water. Each slipped unit became almost completely bioturbated by infaunal echinoids, colonizing by lateral migration. Because of the thinness of the units, successive colonizations tended to truncate the underlying burrows giving rise to a pseudo-stratification. As the Bichordites ichnofabric accumulated on the fault apron, thus reducing the effective height of the fault scarp, the substrate gradually came under the influence of currents traversing the shelf. This led to a change in hydraulic regime, and to the mottled-Palaeophycus and mottled-Ophiomorpha ichnofabrics in sediment deposited under bed load transport, and associated with laminar and cross-stratified beds and local muddy intervals. Reactivation of the fault triggered erosion and channeling and a return to grain flow sedimentation, and to the Bichordites ichnofabric of the succeeding cycle. The highest unit of the Bateig Limestone is formed entirely of cross-stratified calcarenites with occasional Ophiomorpha (Ophiomorpha-primary lamination ichnofabric) and is similar to many shallow marine facies but they still bear a significant content of pelagic foraminifera. The sedimentary setting bears resemblance with that described for the Pleistocene Monte Torre Paleostrait and the modem Strait of Messina (Italy), where the narrow morphology of the depositional area enhanced tidal currents and allowed for high-energy sandy deposition in relatively deep areas. More data on the Miocene paleogeography of the Bateig area should provide further testing for this hypothesis. The ichnofacies and stacking of the Bateig Limestone differ from the classic Seilacherian model in that they reflect changes in hydraulic process and are associated with faulting and subsidence and changes in sediment supply. Recognition of the unusual ichnofabrics and their relationships provides a clear indication of the overall dynamic setting. (c) 2006 Elsevier B.V. All rights reserved.

The interpretation of symptoms of starvation/severe dietary restraint in eating disorder patients

The aims of the study were to test the hypotheses that some symptoms of starvation/severe dietary restraint are interpreted by patients with eating disorders in terms or control. Sixty-nine women satisfying the Diagnostic and Statistical Manual of Mental Disorders - IV edition (DSM-IV) criteria for a clinical eating disorder and 107 controls participated in the Study. All the participants completed an ambiguous scenarios paradigm, the Eating Disorder Lamination Questionnaire (EDE-Q) and the Beck Depression Inventory (BDI). Significantly more eating disorder patients than non clinical participants interpreted the starvation/dietary restraint symptoms of hunger, heightened satiety, and dizziness in terms of control. The data give further Support to the recent cognitive-behavioural theory of eating disorders suggesting that eating disorder patients interpret some starvation/dietary restraint symptoms in terms of control.

A laminated polymer film formulation for enteric delivery of live vaccine and probiotic bacteria

Live bacterial cells (LBC) are administered orally as attenuated vaccines, to deliver biopharmaceutical agents, and as probiotics to improve gastrointestinal health. However, LBC present unique formulation challenges and must survive gastrointestinal antimicrobial defenses including gastric acid after administration. We present a simple new formulation concept, termed Polymer Film Laminate (PFL). LBC are ambient dried onto cast acid-resistant enteric polymer films that are then laminated together to produce a solid oral dosage form. LBC of a model live bacterial vaccine and a probiotic were dried directly onto a cast film of enteric polymer. The effectiveness at protecting dried cells in a simulated gastric fluid (pH 2.0) depended on the composition of enteric polymer film used, with a blend of ethylcellulose plus Eudragit L100 55 providing greater protection from acid than Eudragit alone. However, although PFL made from blended polymers films completely released low molecular weight dye into intestinal conditions (pH 7.0), they failed to release LBC. In contrast, PFL made from Eudragit alone successfully protected dried probiotic or vaccine LBC from simulated gastric fluid for 2h, and subsequently released all viable cells within 60min of transfer into simulated intestinal fluid. Release kinetics could be controlled by modifying the lamination method.

Fabrication and integration of planar electrodes for contactless conductivity detection on polyester-toner electrophoresis microchips

In this report, we describe the microfabrication and integration of planar electrodes for contactless conductivity detection on polyester-toner (PT) electrophoresis microchips using toner masks. Planar electrodes were fabricated by three simple steps: (i) drawing and laser-printing the electrode geometry on polyester films, (ii) sputtering deposition onto substrates, and (iii) removal of toner layer by a lift-off process. The polyester film with anchored electrodes was integrated to PT electrophoresis microchannels by lamination at 120 degrees C in less than 1 min. The electrodes were designed in an antiparallel configuration with 750 mu m width and 750 gm gap between them. The best results were recorded with a frequency of 400 kHz and 10 V-PP using a sinusoidal wave. The analytical performance of the proposed microchip was evaluated by electrophoretic separation of potassium, sodium and lithium in 150 mu m wide x 6 mu m deep microchannels. Under an electric field of 250 V/cm the analytes were successfully separated in less than 90 s with efficiencies ranging from 7000 to 13 000 plates. The detection limits (S/N = 3) found for K+, Na+, and Li+ were 3.1, 4.3, and 7.2 mu mol/L, respectively. Besides the low-cost and instrumental simplicity, the integrated PT chip eliminates the problem of manual alignment and gluing of the electrodes, permitting more robustness and better reproducibility, therefore, more suitable for mass production of electrophoresis microchips.

Plásticos reforçados a base de tecidos híbridos: efeitos da anisotropia e geometria normativa na caracterização mecânica e da fratura

As most current studies, reinforced plastics have been, in recent years, a viable alternative in building structural elements of medium and large, since the lightness accompanied by high performance possible. The design of hybrid polymer composites (combination of different types of reinforcements) may enable structural applications thereof, facing the most severe service conditions. Within this class of composite materials, reinforced the underlying tissues hybrid high performance are taking space when your application requires high load bearing and high rigidity. The objective of this research work is to study the challenges in designing these fabrics bring these materials as to its mechanical characterization and fracture mechanisms involved. Some parameters associated with the process and / or form of hybridization stand out as influential factors in the final performance of the material such as the presence of anisotropy, so the fabric weave, the process of making the same, normative geometry of the specimens, among others. This sense, four laminates were developed based hybrid reinforcement fabrics involving AS4 carbon fiber, kevlar and glass 49-E as the matrix epoxy vinyl ester resin (DERAKANE 411-350). All laminates were formed each with four layers of reinforcements. Depending on the hybrid fabric, all the influencing factors mentioned above have been studied for laminates. All laminates were manufactured industrially used being the lamination process manual (hand-lay-up). All mechanical characterization and study of the mechanism of fracture (fracture mechanics) was developed for laminates subjected to uniaxial tensile test, bending in three and uniaxial compression. The analysis of fracture mechanisms were held involving the macroscopic, optical microscopy and scanning electron microscopy

Influência da umidade nas propriedades mecânicas dos compósitos poliméricos híbridos (sisal/ vidro)

This study aims to evaluate the mechanical properties of polymer matrix composites reinforced with sisal fabric bidirectional tissue (Agave sisalana,) and E-glass fibers, containing the following configuration: a polymer matrix hybrid composite (Polyester Resin orthophalic) reinforced with three (3) layers of glass fibers and alternating-2 (two) layers of bidirectional sisal fabric, and finally a composite of polymer matrix reinforced with five (5) layers of glass fiber mat-type E. For this purpose as first step, the preparation of by sisal, since they are not on the market. The composites were made by manual lamination (Hand lay-up) and evaluated for tensile properties and three point bending both in the dry, and wet conditions aswele as immersed in oil. Macroscopic and microscopic characteristics of the materialsweve awalysed, after the completion of the mechanical tests. After the studies, it was proven that the sisal fiber decreases the tensile stiffness of the material above 50% for both situations studied the tensile strength of the material decreases by approximately 40% for the cases mentioned, and when compared to the specific strength stiffness values drop to 14.6% and 29.02% respectively for the dry state only. Constants for bending the values were are to approximately 50% to 25% for strength and stiffness of the material for the cases dry, wet and immersed in oil. Under the influence of tension fluids do not interfere in the stiffness of the material for the bending tests, the same does not occur with the resistance, and these values are modified only in the cases stiffness and flexural strength

Permian stromatolites associated with bivalve coquina beds-Angatuba, SP, Brazil (Teresina Formation, Parana Basin)

Silicified stromatolites have been described in the Permian Teresina Formation, Passa Dois Group, of the Parana Basin. These stromatolites occur as blocks in the Fazenda Monte Alegre area at the headwaters of the creek known as Corrego Catanduva in the municipality of Angatuba. These blocks originate from the Serra de Angatuba region and were recognized in a road that was cut in the midst of sandstones and siltites. The stromatolites are isolated bioherms that are domed to subspherical with a flat base in profile and a rounded to lenticular shape in plan view. The stromatolites exhibit a reddish coloration and are composed of microcrystalline quartz. Lamination is continuous, non-columnar, and anastomosed, showing parallel to divergent growth; however, divergent columns also occur, especially at the tops of the bioherms. The lamination is fine and well preserved, with alternating light and dark laminas. Microfossils of filamentous cyanobacteria are preserved and were related to the genera Microcoleus and Rivularia. Silicified bivalves occur in association with the stromatolites and are preserved in the form of coquina beds and rare isolated specimens within the bioherms. The described specimens belong to the Pinzonella illusa biozone, with representatives of the species Pinzonella illusa, Angatubia cowperesioides, and Houldausiella elongata. The formation environment of these stromatolites is associated with tidal plains of shallow, brackish, relatively calm, warm waters of good luminosity with the presence of weak currents. There was likely a low level of predation, and the environment may have been hypersaline. The coquina beds associated with the stromatolites indicate a probable proximal tempestite, i.e., they were formed near the coastline. The stromatolites were originally composed of carbonates, although these were replaced by silica during early diagenesis.

Evolutionary Changes in the Complexity of the Tectum of Nontetrapods: A Cladistic Approach

Background: The tectum is a structure localized in the roof of the midbrain in vertebrates, and is taken to be highly conserved in evolution. The present article assessed three hypotheses concerning the evolution of lamination and citoarchitecture of the tectum of nontetrapod animals: 1) There is a significant degree of phylogenetic inertia in both traits studied (number of cellular layers and number of cell classes in tectum); 2) Both traits are positively correlated accross evolution after correction for phylogeny; and 3) Different developmental pathways should generate different patterns of lamination and cytoarchitecture.Methodology/Principal Findings: The hypotheses were tested using analytical-computational tools for phylogenetic hypothesis testing. Both traits presented a considerably large phylogenetic signal and were positively associated. However, no difference was found between two clades classified as per the general developmental pathways of their brains.Conclusions/Significance: The evidence amassed points to more variation in the tectum than would be expected by phylogeny in three species from the taxa analysed; this variation is not better explained by differences in the main course of development, as would be predicted by the developmental clade hypothesis. Those findings shed new light on the evolution of an functionally important structure in nontetrapods, the most basal radiations of vertebrates.

Logística reversa numa empresa de laminação de vidros: um estudo de caso

Este trabalho apresenta uma aplicação da Logística Reversa numa empresa multinacional que atua na área de laminação de vidros no Brasil. Na empresa estudada, a sucata gerada pelos seus clientes pode ser usada para realimentar o seu processo de produção. Inicialmente, são discutidos os principais aspectos relacionados ao tema, tais como, definição de Logística Reversa, ciclo de vida do produto, motivos e destinos do retorno, além dos fatores que influenciam a eficiência de um processo de Logística Reversa. A seguir, ilustradas pelo estudo de caso, são apresentadas e comentadas as etapas para uma implementação de um sistema de Logística Reversa ser bem sucedida. Finalmente, comentam-se as dificuldades, ganhos e vantagens competitivas obtidas por empresas que adotaram soluções da Logística Reversa, em particular na empresa em que o estudo de caso foi desenvolvido.