Sustainable waste recycling solution for the glass fibre reinforced polymer composite materials industry

In this paper the adequacy and the benefit of incorporating glass fibre reinforced polymer (GFRP) waste materials into polyester based mortars, as sand aggregates and filler replacements, are assessed. Different weight contents of mechanically recycled GFRP wastes with two particle size grades are included in the formulation of new materials. In all formulations, a polyester resin matrix was modified with a silane coupling agent in order to improve binder-aggregates interfaces. The added value of the recycling solution was assessed by means of both flexural and compressive strengths of GFRP admixed mortars with regard to those of the unmodified polymer mortars. Planning of experiments and data treatment were performed by means of full factorial design and through appropriate statistical tools based on analyses of variance (ANOVA). Results show that the partial replacement of sand aggregates by either type of GFRP recyclates improves the mechanical performance of resultant polymer mortars. In the case of trial formulations modified with the coarser waste mix, the best results are achieved with 8% waste weight content, while for fine waste based polymer mortars, 4% in weight of waste content leads to the higher increases on mechanical strengths. This study clearly identifies a promising waste management solution for GFRP waste materials by developing a cost-effective end-use application for the recyclates, thus contributing to a more sustainable fibre-reinforced polymer composites industry.

Selective recognition in potentiometric transduction of amoxicillin by molecularly imprinted materials

The indiscriminate use of antibiotics in food-producing animals has received increasing attention as a contributory factor in the international emergence of antibiotic-resistant bacteria (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004). Numerous analytical methods for quantifying antibacterial residues in edible animal products have been developed over years (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004; Botsoglou and Fletouris in Handbook of food analysis, residues and other food component analysis, Marcel Dekker, Ghent, 2004). Being Amoxicillin (AMOX) one of those critical veterinary drugs, efforts have been made to develop simple and expeditious methods for its control in food samples. In literature, only one AMOX-selective electrode has been reported so far. In that work, phosphotungstate:amoxycillinium ion exchanger was used as electroactive material (Shoukry et al. in Electroanalysis 6:914–917, 1994). Designing new materials based on molecularly imprinted polymers (MIPs) which are complementary to the size and charge of AMOX could lead to very selective interactions, thus enhancing the selectivity of the sensing unit. AMOX-selective electrodes used imprinted polymers as electroactive materials having AMOX as target molecule to design a biomimetic imprinted cavity. Poly(vinyl chloride), sensors of methacrylic acid displayed Nernstian slopes (60.7 mV/decade) and low detection limits (2.9 × 10−5 mol/L). The potentiometric responses were not affected by pH within 4–5 and showed good selectivity. The electrodes were applied successfully to the analysis of real samples.

Deteção eletroquímica da norfloxacina e trimetoprim em amostras de urina utilizando polímero molecularmente impresso modificado e grafeno

A norfloxacina e o trimetoprim são dois antibióticos antibacterianos usados para o tratamento de infeções urinárias, intestinais e respiratórias. A maioria dos fármacos exige uma dosagem que garanta os níveis de segurança e eficácia de atuação. A necessidade de dosear os medicamentos e os seus metabolitos é assim um controlo imperioso e em muitos casos regular no tratamento de um paciente. Neste trabalho desenvolveram-se dois sensores eletroquímicos para a deteção da norfloxacina (NFX) e do trimetoprim (TMP), usando como superfície de suporte o carbono vítreo. A busca de novos materiais que conferiram maior seletividade e sensibilidade aos sistemas de deteção e por outro lado apresentem menores riscos para o paciente quando usados em dispositivos que permitam uma análise point-of-care, é especialmente importante e pode ser uma parte crucial do processo de decisão clínica. Assim, os polímeros molecularmente impresos enquadram-se nesse perfil e o seu uso tem vindo a ser cada vez mais avaliado. A impressão molecular é uma tecnologia capaz de produzir polímeros que incorporam as moléculas do analito e que após remoção por solventes específicos, permitem dotá-los de locais específicos de reconhecimento estereoquímico. A seleção do pirrol como polímero molecularmente impresso (MIP) permitiu construir com sucesso os sensores para doseamento dos antibióticos. A fim de aumentar a sensibilidade do método incorporou-se grafeno na superfície do elétrodo. Este material tem vindo a ser largamente utilizado devido às suas propriedades: estrutura molecular, condutividade elétrica e aumento da superfície são algumas das características que mais despertam o interesse para a sua aplicação neste projeto. Os sensores desenvolvidos foram incorporados em sistemas eletroquímicos. Os métodos voltamétricos aplicados foram a voltametria cíclica, a voltametria de onda quadrada e ainda a impedância. As condições de análise foram otimizadas no que respeita à polimerização do pirrol (concentração do polímero, número de ciclos de eletropolimerização e respetivos potenciais aplicados, tempo de incubação, solvente de remoção do analito), ao pH da solução do fármaco, à gama de concentrações dos antibióticos e aos parâmetros voltamétricos dos métodos de análise. Para cada um dos antibióticos um elétrodo não-impresso foi também preparado, usando o procedimento de polimerização mas sem a presença da molécula do analito, e foi usado como controlo. O sensor desenvolvido para o trimetoprim foi usado no doseamento do fármaco em amostras de urina. As amostras foram analisadas sem qualquer diluição, apenas foram centrifugadas para remoção de proteínas e algum interferente. Os sensores construídos apresentaram comportamento linear na gama de concentrações entre 102 e 107 mol/L. Os resultados mostram boa precisão (desvios padrão inferiores a 11%) e os limites de deteção foram de 8,317 e 1,307 mol/L para a norfloxacina e o trimetoprim, respetivamente. Para validação do método foram ainda efetuados ensaios de recuperação tendo obtido valores superiores a 94%.

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.

Synthesis of molecular biomimetics

Biomimetics has paved the way toward new materials and technologies inspired in Nature. Biomolecules and their supramolecular organization have today a leading role in biomimetics, benefiting from the recent advances in nanotechnology. The production of biomimetic materials may be however a difficult task, because Nature does it very well. The use of several building blocks assembled in bottom-up arrangement is without doubt at the core of this process. Such building blocks include different molecules or molecular arrangements, of synthetic or natural origin, such as amino acids, lipids, carbohydrates, nucleic acids, carbon allotropes, dendrimers, or organosilanes, among others. The most common approaches to produce synthetic biomimetic materials are reported herein, with special emphasis to building blocks and their supramolecular arrangement.

Estudo da corrosão provocada pelo cloro e procura de materiais alternativos

Muitas instalações municipais são alvo de manutenção permanente, devido ao uso de produtos químicos que provocam a corrosão e degradação dos mais diversos materiais. Esta degradação acarreta custos elevados para os municípios e privação de uso de algumas instalações devido a manutenção curativa ou preventiva. Um estudo adequado do efeito dos produtos utilizados, poderia conduzir à utilização de materiais mais nobres, que aumentasse significativamente o tempo de vida dos produtos mais atacados pela degradação por corrosão, através de estudos que permitissem avaliar a relação custo-benefício e, caso esta fosse favorável, proceder à substituição de determinados componentes em materiais relativamente fracos, por outros com uma maior capacidade para resistir aos ataques produzidos pelo meio em que estão inseridos. Este estudo foi efectuado com vista a estudar a degradação de determinados materiais expostos essencialmente à acção do Cloro em instalações municipais, permitindo assim seleccionar novos materiais que permitissem uma vida útil dos componentes mais alargada, estudando convenientemente a relação custo-benefício. Foi possível observar que a introdução de alguns materiais mais nobres, poderá reduzir drasticamente as operações de manutenção, diminuindo os custos e reduzindo também o tempo de indisponibilidade dos equipamentos municipais.

An integrated recycling approach for GFRP pultrusion wastes: recycling and reuse assessment into new composite materials using Fuzzy Boolean Nets

In this study, efforts were made in order to put forward an integrated recycling approach for the thermoset based glass fibre reinforced polymer (GPRP) rejects derived from the pultrusion manufacturing industry. Both the recycling process and the development of a new cost-effective end-use application for the recyclates were considered. For this purpose, i) among the several available recycling techniques for thermoset based composite materials, the most suitable one for the envisaged application was selected (mechanical recycling); and ii) an experimental work was carried out in order to assess the added-value of the obtained recyclates as aggregates and reinforcement replacements into concrete-polymer composite materials. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified concrete-polymer composites with regard to unmodified materials. In the mix design process of the new GFRP waste based composite material, the recyclate content and size grade, and the effect of the incorporation of an adhesion promoter were considered as material factors and systematically tested between reasonable ranges. The optimization process of the modified formulations was supported by the Fuzzy Boolean Nets methodology, which allowed finding the best balance between material parameters that maximizes both flexural and compressive strengths of final composite. Comparing to related end-use applications of GFRP wastes in cementitious based concrete materials, the proposed solution overcome some of the problems found, namely the possible incompatibilities arisen from alkalis-silica reaction and the decrease in the mechanical properties due to high water-cement ratio required to achieve the desirable workability. Obtained results were very promising towards a global cost-effective waste management solution for GFRP industrial wastes and end-of-life products that will lead to a more sustainable composite materials industry.

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.

New end-use application for GFRP recyclates as reinforcement for concrete-polymer materials’

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: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. 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. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one-factor-at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as aggregates and filler replacements for polymer mortar, with significant gain of mechanical properties with regard to non-modified polymer mortars.

Backside-surface imprinting as a new strategy to generate specific plastic antibody materials

A backside protein-surface imprinting process is presented herein as a novel way to generate specific synthetic antibody materials. The template is covalently bonded to a carboxylated-PVC supporting film previously cast on gold, let to interact with charged monomers and surrounded next by another thick polymer. This polymer is then covalently attached to a transducing element and the backside of this structure (supporting film plus template) is removed as a regular “tape”. The new sensing layer is exposed after the full template removal, showing a high density of re-binding positions, as evidenced by SEM. To ensure that the templates have been efficiently removed, this re-binding layer was cleaned further with a proteolytic enzyme and solution washout. The final material was named MAPS, as in the back-side reading of SPAM, because it acts as a back-side imprinting of this recent approach. It was able to generate, for the first time, a specific response to a complex biomolecule from a synthetic material. Non-imprinted materials (NIMs) were also produced as blank and were used as a control of the imprinting process. All chemical modifications were followed by electrochemical techniques. This was done on a supporting film and transducing element of both MAPS and NIM. Only the MAPS-based device responded to oxLDL and the sensing layer was insensitive to other serum proteins, such as myoglobin and haemoglobin. Linear behaviour between log(C, μg mL−1) versus charged tranfer resistance (RCT, Ω) was observed by electrochemical impedance spectroscopy (EIS). Calibrations made in Fetal Calf Serum (FCS) were linear from 2.5 to 12.5 μg mL−1 (RCT = 946.12 × log C + 1590.7) with an R-squared of 0.9966. Overall, these were promising results towards the design of materials acting close to the natural antibodies and applied to practical use of clinical interest.

New sensing materials of molecularly-imprinted polymers for the selective recognition of Chlortetracycline

As a result of the stressful conditions in aquaculture facilities there is a high risk of bacterial infections among cultured fish. Chlortetracycline (CTC) is one of the antimicrobials used to solve this problem. It is a broad spectrum antibacterial active against a wide range of Gram-positive and Gram-negative bacteria. Numerous analytical methods for screening, identifying, and quantifying CTC in animal products have been developed over the years. An alternative and advantageous method should rely on expeditious and efficient procedures providing highly specific and sensitive measurements in food samples. Ion-selective electrodes (ISEs) could meet these criteria. The only ISE reported in literature for this purpose used traditional electro-active materials. A selectivity enhancement could however be achieved after improving the analyte recognition by molecularly imprinted polymers (MIPs). Several MIP particles were synthesized and used as electro-active materials. ISEs based in methacrylic acid monomers showed the best analytical performance according to slope (62.5 and 68.6 mV/decade) and detection limit (4.1 × 10−5 and 5.5 × 10−5 mol L−1). The electrodes displayed good selectivity. The ISEs are not affected by pH changes ranging from 2.5 to 13. The sensors were successfully applied to the analysis of serum, urine and fish samples.

Experiments on new polymer based mortars filled with FRP waste recyclates - a quantitative analysis

Glass fibre-reinforced plastics (GFRP) have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. 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, 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, were incorporated into polyester based mortars as fine aggregate and filler replacements at different load contents and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behaviour over unmodified polyester based mortars, thus indicating the feasibility of the waste reuse in polymer mortars and concrete. © 2011, Advanced Engineering Solutions.

Eco-efficiency approaches towards a sustainable composite materials manufacturing industry’

In this study the potential eco-efficiency performance of a pultrusion manufacturing company was assessed. Indicators values and eco-efficiency ratios were estimated taking into account the implementation of new proceedings and procedures in the production process of glass fibre reinforced polymers (GFRP) pultrusion profiles. Two different approaches were foreseen: 1)Adoption of a new heating system for pultrusion die in the manufacturing process, more effective and with minor heat losses; and 2) Recycling approach, with partial waste reuse of scrap material derived from manufacturing, cutting and assembly processes of GFRP profiles. 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.

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.