Modifying fish gelatin electrospun membranes for biomedical applications: cross- linking and swelling behavior

Development of suitable membranes is a fundamental requisite for tissue and biomedical engineering applications. This work presents fish gelatin random and aligned electrospun membranes cross-linked with glutaraldehyde (GA). It was observed that the fiber average diameter and the morphology is not influenced by the GA exposure time and presents fibers with an average diameter around 250 nm. Moreover, when the gelatin mats are immersed in a phosphate buffered saline solution (PBS), they can retain as much as 12 times its initial weight of solution almost instantaneously, but the material microstructure of the fiber mats changes from the characteristic fibrous to an almost spherical porous structure. Cross-linked gelatin electrospun fiber mats and films showed a water vapor permeability of 1.37 ± 0.02 and 0.13 ± 0.10 (g.mm)/(m2.h.kPa), respectively. Finally, the processing technique and cross-linking process does not inhibit MC-3T3-E1 cell adhesion. Preliminary cell culture results showed good cell adhesion and proliferation in the cross-linked random and aligned gelatin fiber mats.

Concessão Douro Litoral A32/IC2: passagens inferiores pré-fabricadas no sistema arco "Techspan" e muros ala de suporte de terras no sistema "Terra Armada": ponte sobre o rio Antuã: aplicação da tecnologia "Freyssinet"

O presente relatório visa apresentar o trabalho desenvolvido pelo estagiário na empresa Freyssinet – Terra Armada, S.A. (FTA). O relatório traduz o acompanhamento do estagiário na construção e aplicação da tecnologia Terra Armada em duas passagens inferiores, bem como o acompanhamento dos trabalhos efectuados pela empresa FTA no que diz respeito à aplicação da tecnologia Freyssinet na ponte sobre o rio Antuã, estando ambas as obras abordadas inseridas no Lote 8 – “A32/IC2 Oliveira de Azeméis/IP1 (S. Lourenço) trecho 2 e 3 – a cargo da empresa Alves Ribeiro S.A.. Com a construção dos trechos 2 e 3 da A32 surgiu a necessidade de se restabelecerem algumas ligações, o que fez com que após estudadas as soluções passíveis de serem utilizadas, se tivesse optado pela construção de túneis a céu aberto na execução dos restabelecimentos. Descreve-se neste documento a metodologia utilizada e as tecnologias patenteadas pela empresa Terra Armada, sendo estas compostas pelos Arcos “Techspan” e muros de ala executados com recurso à tecnologia “Terra Armada”. Em relação à ponte sobre o rio Antuã inserida no trecho 2 da empreitada de construção da A32, foi construída com recurso a cimbre auto-lançável e betonada in situ, havendo a necessidade de aplicação de tecnologias patenteadas pela Freyssinet no que diz respeito às actividades de pré-esforço, aparelhos de apoio nas ligações entre o tabuleiro e os pilares e juntas de dilatação na ligação do tabuleiro aos encontros. Apresentam-se os procedimentos de montagem e aplicação das tecnologias anteriormente referidas. No presente relatório estão descritos e explicados detalhadamente os trabalhos executados pela FTA, nomeadamente a aplicação da tecnologia “Terra Armada” no que diz respeito à construção das passagens inferiores, e a aplicação da tecnologia “Freyssinet” aplicada aquando da construção da ponte sobre o rio Antuã.

Development of an injectable grout for concrete repair and strengthening

This paper deals with the coupled effect of temperature and silica fume addition on rheological, mechanical behaviour and porosity of grouts based on CEMI 42.5R, proportioned with a polycarboxylate-based high range water reducer. Preliminary tests were conducted to focus on the grout best able to fill a fibrous network since the goal of this study was to develop an optimized grout able to be injected in a mat of steel fibers for concrete strengthening. The grout composition was developed based on criteria for fresh state and hardened state properties. For a CEMI 42.5R based grout different high range water reducer dosages (0%, 0.2%, 0.4%, 0.5%, 0.7%) and silica fume (SF) dosages (0%, 2%, 4%) were tested (as replacement of cement by mass). Rheological measurements were used to investigate the effect of polycarboxylates (PCEs) and SF dosage on grout properties, particularly its workability loss, as the mix was to be injected in a matrix of steel fibers for concrete jacketing. The workability behaviour was characterized by the rheological parameters yield stress and plastic viscosity (for different grout temperatures and resting times), as well as the procedures of mini slump cone and funnel flow time. Then, further development focused only on the best grout compositions. The cement substitution by 2% of SF exhibited the best overall behaviour and was considered as the most promising compared to the others compositions tested. Concerning the fresh state analysis, a significant workability loss was detected if grout temperature increased above 35 degrees C. Below this temperature the grout presented a self-levelling behaviour and a life time equal to 45 min. In the hardened state, silica fumes increased not only the grout's porosity but also the grout's compressive strength at later ages, since the pozzolanic contribution to the compressive strength does not occur until 28 d and beyond. (C) 2012 Elsevier Ltd. All rights reserved.

Estudo da estabilidade térmica da pele

Mestrado em Engenharia Química

Controlo de águas do processo e optimização da produção de papel

Na Fábrica de Papel da Ponte Redonda fabricam-se sacos de papel multi-folhas e papel reciclado do tipo Kraft. Tendo em consideração a primeira actividade, é de grande interesse optimizar o processo de fabrico de papel com vista a incorporara a máxima taxa de papel produzido internamente nas diferentes camadas dos sacos de papel. Os papéis de maior interesse são os do tipo Fluting e Liners, tendo sido produzidos em 2010 um total de 4,9 mil toneladas, ou seja 90% de todo o papel fabricado em 2010, correspondendo a a 4 mil toneladas de papéis do tipo Liners e 0,9 mil toneladas para os papéis do tipo Fluting. Nos papéis do tipo Liners incluem-se os papéis do tipo Test-Liner e Kraft-Liner, representando em termos produtivos valores idênticos. No âmbito deste trabalho, em que se pretendeu controlar as águas do processo e optimizar a produção de papel, foram introduzidos uma unidade de flutuação e um sistema que permitisse regular a consistência da suspensão fibrosa à entrada da máquina do papel, e foram ainda estudadas as possibilidades de adição de produtos químicos para melhorar as características da pasta assim como um tratamento microbiológico mais eficaz para todo o processo. Para se avaliar se as medidas implementadas teriam um impacto positivo na qualidade desses dois tipos de papéis, desenvolveu-se o trabalho em duas fases: a primeira envolve a introdução de um sistema de flutuação e de um sistema de controlo de consistência da pasta, assim como a selecção de produtos químicos a adicionar ao processo. A segunda fase consistiu na avaliação do efeito destas medidas nas características do papel fabricado. Para o efeito foram escolhidos dois tipos de papel e de diferentes gramagens, nomeadamente Test-Liner de 80 g/m2 e Fluting de 110 g/m2. Introduziu-se um flutuador com o objectivo de tratar parte das águas do processo de fabrico com vista a serem reutilizadas em determinadas aplicações possíveis para a qualidade da água obtida (lavagens e água do processo), de modo a conseguir-se uma poupança de água, assim como aproveitar-se as lamas resultantes, ricas em fibra de celulose, para utilizá-las como matéria-prima. Foi introduzido um regulador de consistência no processo da Ponte Redonda com o objectivo de alimentar de uma forma constante a consistência da pasta à entrada da máquina do papel proporcionando uma melhor formação da folha, devido à ligação entre fibras, na direcção máquina e direcção transversal. Esse sistema inovador é um Regulador de Consistência que vem proporcionar à máquina do papel uma alimentação em fibra mais constante. O fabrico de papel apenas a partir de fibras de celulose não permitirá obter um papel com as características desejadas para a sua utilização. Para corrigir estas deficiências, são adicionados produtos químicos para atribuir ou melhorar as propriedades dos papéis. Desta forma considerou-se interessante introduzir no processo um agente de retenção numa fase posterior à preparação da pasta e antes da chegada à máquina de papel, de forma a melhorar as características da suspensão fibrosa. Assim foi implementado um sistema cuja eficácia foi avaliada. Concluiu-se que com a sua implementação a máquina de papel apresentou melhores resultados na drenagem e na turbidez da água removida, significando uma água com menor teor de matéria suspensa e dissolvida, devido à melhor agregação das fibras dispersas na suspensão fibrosa, levando a um aumento da drenagem e consequentemente melhor eficiência das prensas e secaria. Foi também elaborado um estudo para introdução de um sistema de tratamento microbiológico em todo o processo de fabrico de papel, devido à existência de microorganismos prejudiciais ao seu fabrico. Concluiu-se que a água clarificada proveniente do flutuador apresentou qualidade aceitável para os objectivos pretendidos. No entanto, considerando a eficiência de 26,5% na remoção de sólidos suspensos será necessário mais algum tempo de utilização da água clarificada, cerca de um ano, para avaliar se esta terá algum efeito prejudicial nos equipamentos. Verificou-se que devido à existência de microrganismos em todo o processo de fabrico de papel será necessário efectuar lavagens aos tinões, tanques e circuitos com alguma regularidade, aproveitando-se as paragens do processo assim como implementar um sistema de tratamento microbiológico mais eficaz. Em resultado das medidas implementadas concluiu-se que os papéis produzidos apresentaram melhorias, tendo-se obtido melhores resultados em todos os ensaios de resistência. No papel do tipo Test-Liner destacam-se os bons resultados nos ensaios de superfície, Cobb60 e rebentamento. No caso do parâmetro do Cobb60, foi um resultado surpreendente visto que por norma este tipo de papéis reciclados não suportam este ensaio. Concluiu-se também que as medidas implementadas proporcionaram uma melhor agregação e ligação entre fibras, e melhor formação da folha na máquina do papel proporcionando aos papéis propriedades físico-mecânicas mais interessantes.

Re-use assessment of thermoset composite wastes as aggregate and filler replacement for concrete-polymer composite materials: a case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.

Ibuprofen-loaded poly(trimethylene carbonate-co-ϵ- caprolactone) electrospun fibres for nerve regeneration

The development of scaffolds that combine the delivery of drugs with the physical support provided by electrospun fibres holds great potential in the field of nerve regeneration. Here it is proposed the incorporation of ibuprofen, a well-known non-steroidal anti-inflammatory drug, in electrospun fibres of the statistical copolymer poly(trimethylene carbonate-co-ε-caprolactone) [P(TMC-CL)] to serve as a drug delivery system to enhance axonal regeneration in the context of a spinal cord lesion, by limiting the inflammatory response. P(TMC-CL) fibres were electrospun from mixtures of dichloromethane (DCM) and dimethylformamide (DMF). The solvent mixture applied influenced fibre morphology, as well as mean fibre diameter, which decreased as the DMF content in solution increased. Ibuprofen-loaded fibres were prepared from P(TMC-CL) solutions containing 5% ibuprofen (w/w of polymer). Increasing drug content to 10% led to jet instability, resulting in the formation of a less homogeneous fibrous mesh. Under the optimized conditions, drug-loading efficiency was above 80%. Confocal Raman mapping showed no preferential distribution of ibuprofen in P(TMC-CL) fibres. Under physiological conditions ibuprofen was released in 24h. The release process being diffusion-dependent for fibres prepared from DCM solutions, in contrast to fibres prepared from DCM-DMF mixtures where burst release occurred. The biological activity of the drug released was demonstrated using human-derived macrophages. The release of prostaglandin E2 to the cell culture medium was reduced when cells were incubated with ibuprofen-loaded P(TMC-CL) fibres, confirming the biological significance of the drug delivery strategy presented. Overall, this study constitutes an important contribution to the design of a P(TMC-CL)-based nerve conduit with anti-inflammatory properties.

Geodynamics of the eastern sector of the Arrábida chain (W Portugal)

N.º4, p.263-267

analytical model and measurements of the target erosion depth profile of balanced and unbalanced planar magnetron cathodes

The erosion depth profile of planar targets in balanced and unbalanced magnetron cathodes with cylindrical symmetry is measured along the target radius. The magnetic fields have rotational symmetry. The horizontal and vertical components of the magnetic field B are measured at points above the cathode target with z = 2 x 10(-3) m. The experimental data reveal that the target erosion depth profile is a function of the angle. made by B with a horizontal line defined by z = 2 x 10(-3) m. To explain this dependence a simplified model of the discharge is developed. In the scope of the model, the pathway lengths of the secondary electrons in the pre-sheath region are calculated by analytical integration of the Lorentz differential equations. Weighting these lengths by using the distribution law of the mean free path of the secondary electrons, we estimate the densities of the ionizing events over the cathode and the relative flux of the sputtered atoms. The expression so deduced correlates for the first time the erosion depth profile of the target with the angle theta. The model shows reasonably good fittings to the experimental target erosion depth profiles confirming that ionization occurs mainly in the pre-sheath zone.

New recycling approaches for thermoset polymeric composite wastes – an experimental study on polyester based concrete materials filled with fibre reinforced plastic recyclates

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

Hybrid thermoset polymeric composites – an Innovation towards sustainability

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

A case study on the improvement of eco-efficiency ratios: application to a composite processing industry

The World Business Council for Sustainable Development (WBCSD) defines Eco-Efficiency as follows: ‘Eco- Efficiency is achieved by the delivery of competitively priced-goods and services that satisfy human needs and bring quality of life, while progressively reducing ecological impacts and resource intensity throughout the life-cycle to a level at least in line with the earth’s estimated carrying capacity’. Eco-Efficiency is under this point of view a key concept for sustainable development, bringing together economic and ecological progress. Measuring the Eco-Efficiency of a company, factory or business, is a complex process that involves the measurement and control of several and relevant parameters or indicators, globally applied to all companies in general, or specific according to the nature and specificities of the business itself. In this study, an attempt was made in order to measure and evaluate the eco-efficiency of a pultruded composite processing company. For this purpose the recommendations of WBCSD [1] and the directives of ISO 14301 standard [2] were followed and applied. The analysis was restricted to the main business branch of the company: the production and sale of standard GFRP pultrusion profiles. The main general indicators of eco-efficiency, as well as the specific indicators, were defined and determined according to ISO 14031 recommendations. With basis on indicators’ figures, the value profile, the environmental profile, and the pertinent eco-efficiency’s ratios were established and analyzed. In order to evaluate potential improvements on company eco-performance, new indicators values and ecoefficiency ratios were estimated taking into account the implementation of new proceedings and procedures, both in upstream and downstream of the production process, namely: a) Adoption of new heating system for pultrusion die in the manufacturing process, more effective and with minor heat losses; b) Implementation of new software for stock management (raw materials and final products) that minimize production failures and delivery delays to final consumer; c) Recycling approach, with partial waste reuse of scrap material derived from manufacturing, cutting and assembly processes of GFRP profiles. In particular, the last approach seems to significantly improve the eco-efficient performance of the company. Currently, by-products and wastes generated in the manufacturing process of GFRP profiles are landfilled, with supplementary added costs to this company traduced by transport of scrap, landfill taxes and required test analysis to waste materials. However, mechanical recycling of GFRP waste materials, with reduction to powdered and fibrous particulates, constitutes a recycling process that can be easily attained on heavy-duty cutting mills. The posterior reuse of obtained recyclates, either into a close-looping process, as filler replacement of resin matrix of GFRP profiles, or as reinforcement of other composite materials produced by the company, will drive to both costs reduction in raw materials and landfill process, and minimization of waste landfill. These features lead to significant improvements on the sequent assessed eco-efficiency ratios of the present case study, yielding to a more sustainable product and manufacturing process of pultruded GFRP profiles.

Recycling of pultrusion production waste into innovative concrete-polymer composite solutions

In this study, the added value resultant from the incorporation of pultrusion production waste into polymer based concretes was assessed. For this purpose, different types of thermoset composite scrap material, proceeding from GFRP pultrusion manufacturing process, were mechanical shredded and milled into a fibrous-powdered material. Resultant GFRP recyclates, with two different size gradings, were added to polyester based mortars as fine aggregate and filler replacements, at various load contents between 4% up to 12% in weight of total mass. Flexural and compressive loading capacities were evaluated and found better than those of unmodified polymer mortars. Obtained results highlight the high potential of recycled GFRP pultrusion waste materials as efficient and sustainable admixtures for concrete and mortar-polymer composites, constituting an emergent waste management solution.

Experimental study on polyester based concretes filled with glass fibre reinforced plastic recyclates – a contribution to composite materials sustainability

The development and applications of thermoset polymeric composites, namely fibre reinforced plastics (FRP), have shifted in the last decades more and more into the mass market [1]. Despite of all advantages associated to FRP based products, the increasing production and consume also lead to an increasing amount of FRP wastes, either end-of-lifecycle products, or scrap and by-products generated by the manufacturing process itself. Whereas thermoplastic FRPs can be easily recycled, by remelting and remoulding, recyclability of thermosetting FRPs constitutes a more difficult task due to cross-linked nature of resin matrix. To date, most of the thermoset based FRP waste is being incinerated or landfilled, leading to negative environmental impacts and supplementary added costs to FRP producers and suppliers. This actual framework is putting increasing pressure on the industry to address the options available for FRP waste management, being an important driver for applied research undertaken cost efficient recycling methods. [1-2]. In spite of this, research on recycling solutions for thermoset composites is still at an elementary stage. Thermal and/or chemical recycling processes, with partial fibre recovering, have been investigated mostly for carbon fibre reinforced plastics (CFRP) due to inherent value of carbon fibre reinforcement; whereas for glass fibre reinforced plastics (GFRP), mechanical recycling, by means of milling and grinding processes, has been considered a more viable recycling method [1-2]. Though, at the moment, few solutions in the reuse of mechanically-recycled GFRP composites into valueadded products are being explored. Aiming filling this gap, in this study, a new waste management solution for thermoset GFRP based products was assessed. The mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the potential added value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. The use of a cementless concrete as host material for GFRP recyclates, instead of a conventional Portland cement based concrete, presents an important asset in avoiding the eventual incompatibility problems arisen from alkalis silica reaction between glass fibres and cementious binder matrix. Additionally, due to hermetic nature of resin binder, polymer based concretes present greater ability for incorporating recycled waste products [3]. Under this scope, different GFRP waste admixed polymer mortar (PM) formulations were analyzed varying the size grading and content of GFRP powder and fibre mix waste. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacities of modified mortars with regard to waste-free polymer mortars.

GFRP waste reinforced polymer mortars: a new waste management solution for GFRP scrap material

To date, glass fibre reinforced polymer (GFRP) waste recycling is very limited and restricted by thermoset nature of binder matrix and lack of economically viable enduse applications for the recyclates. In this study, efforts were made in order to recycle grinded GFRP waste proceeding from pultrusion production scrap, into new and sustainable composite materials. For this purpose, GFRP waste recyclates, a mix of powdered and fibrous materials, were incorporated into polyester based mortars as fine aggregate and filler replacements, at different load contents (between 4% up to 12% of total mass) and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Test results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse in concrete-polymer composites.