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.

Estudo da susceptibilidade ao polimento dos agregados para camadas de desgaste de pavimentos rodoviários

Mestrado em Engenharia Geotécnica e Geoambiente

Dimensionamento de um secador em leito fluidizado para secagem de cereais

O objectivo desta tese é dimensionar um secador em leito fluidizado para secagem de cereais, nomeadamente, secagem de sementes de trigo. Inicialmente determinaram-se as condições de hidrodinâmica (velocidade de fluidização, TDH, condições mínimas de “slugging”, expansão do leito, dimensionamento do distribuidor e queda de pressão). Com as condições de hidrodinâmica definidas, foi possível estimar as dimensões físicas do secador. Neste ponto, foram realizados estudos relativamente à cinética da secagem e à própria secagem. Foi também estudado o transporte pneumático das sementes. Deste modo, determinaram-se as velocidades necessárias ao transporte pneumático e respectivas quedas de pressão. Por fim, foi realizada uma análise custos para que se soubesse o custo deste sistema de secagem. O estudo da secagem foi feito para uma temperatura de operação de 50ºC, tendo a ressalva que no limite se poderia trabalhar com 60ºC. A velocidade de operação é de 2,43 m/s, a altura do leito fixo é de 0,4 m, a qual sofre uma expansão durante a fluidização, assumindo o valor de 0,79 m. O valor do TDH obtido foi de 1,97 m, que somado à expansão do leito permite obter uma altura total da coluna de 2,76 m. A altura do leito fixo permite retirar o valor do diâmetro que é de 0,52 m. Verifica-se que a altura do leito expandido é inferior à altura mínima de “slugging” (1,20 m), no entanto, a velocidade de operação é superior à velocidade mínima de “slugging” (1,13 m/s). Como só uma das condições mínimas é cumprida, existe a possibilidade da ocorrência de “slugging”. Finalmente, foi necessário dimensionar o distribuidor, que com o diâmetro de orifício de 3 mm, valor inferior ao da partícula (3,48 mm), permite a distruibuição do fluido de secagem na coluna através dos seus 3061 orifícios. O inicio do estudo da secagem centrou-se na determinação do tempo de secagem. Além das duas temperaturas atrás referidas, foram igualmente consideradas duas humidades iniciais para os cereais (21,33% e 18,91%). Temperaturas superiores traduzem-se em tempos de secagem inferiores, paralelamente, teores de humidade inicial inferiores indicam tempos menores. Para a temperatura de 50ºC, os tempos de secagem assumiram os valores de 2,8 horas para a 21,33% de humidade e 2,7 horas para 18,91% de humidade. Foram também tidas em conta três alturas do ano para a captação do ar de secagem, Verão e Inverno representando os extremos, e a Meia- Estação. Para estes três casos, foi possível verificar que a humidade específica do ar não apresenta alterações significativas entre a entrada no secador e a corrente de saída do mesmo equipamento, do mesmo modo que a temperatura de saída pouco difere da de entrada. Este desvio de cerca de 1% para as humidades e para as temperaturas é explicado pela ausência de humidade externa nas sementes e na pouca quantidade de humidade interna. Desta forma, estes desvios de 1% permitem a utilização de uma razão de reciclagem na ordem dos 100% sem que o comportamento da secagem se altere significativamente. O uso de 100% de reciclagem permite uma poupança energética de cerca de 98% no Inverno e na Meia-Estação e de cerca de 93% no Verão. Caso não fosse realizada reciclagem, seria necessário fornecer à corrente de ar cerca de 18,81 kW para elevar a sua temperatura de 20ºC para 50ºC (Meia-Estação), cerca de 24,67 kW para elevar a sua temperatura de 10ºC para 50ºC (Inverno) e na ordem dos 8,90 kW para elevar a sua temperatura dos 35ºC para 50ºC (Verão). No caso do transporte pneumático, existem duas linhas, uma horizontal e uma vertical, logo foi necessário estimar o valor da velocidade das partículas para estes dois casos. Na linha vertical, a velocidade da partícula é cerca de 25,03 m/s e cerca de 35,95 m/s na linha horizontal. O menor valor para a linha vertical prende-se com o facto de nesta zona ter que se vencer a força gravítica. Em ambos os circuitos a velocidade do fluido é cerca de 47,17 m/s. No interior da coluna, a velocidade do fluido tem o valor de 10,90 m/s e a velocidade das partículas é de 1,04 m/s. A queda de pressão total no sistema é cerca de 2408 Pa. A análise de custos ao sistema de secagem indicou que este sistema irá acarretar um custo total (fabrico mais transporte) de cerca de 153035€. Este sistema necessita de electricidade para funcionar, e esta irá acarretar um custo anual de cerca de 7951,4€. Embora este sistema de secagem apresente a possibilidade de se realizar uma razão de reciclagem na ordem dos 100% e também seja possível adaptar o mesmo para diferentes tipos de cereais, e até outros tipos de materiais, desde que possam ser fluidizados, o seu custo impede que a realização deste investimento não seja atractiva, especialmente tendo em consideração que se trata de uma instalação à escala piloto com uma capacidade de 45 kgs.

Influência da temperatura e da energia de compactação nos parâmetros obtidos em ensaios no âmbito na marcação CE de misturas betuminosas

Em Portugal, grande parte da rede rodoviária é constituída por pavimentos flexíveis a quente, os quais têm vindo a ser alvo de um estudo exaustivo devido ao elevado aumento do tráfego registado nos últimos anos. Todos os estudos realizados em misturas betuminosas, após 1 de Março de 2008, utilizam as normativas da marcação CE, estabelecidas pela União Europeia no Âmbito da Directiva Comunitária nº 93/465/CEE e têm como objectivo garantir aos utentes que os materiais utilizados foram produzidos de forma controlada, de acordo com os requisitos definidos. Este trabalho teve como principal objectivo avaliar a influência da temperatura e da energia de compactação nas Misturas Betuminosas. Nesse intuito, estudaram‐se diferentes formulações das Misturas Betuminosas, nas quais se fez variar a temperatura e a energia de compactação. Neste trabalho apresentam‐se as formulações propostas, os ensaios realizados segundo a Marcação CE e a análise dos resultados obtidos. Executou‐se, também, o ensaio Marshall de forma a estudar e avaliar o desempenho da mistura. Pressupõe‐se que a variação da temperatura numa mistura betuminosa é bastante importante por ser responsável pelo comportamento dos betumes, o qual se reflecte na mistura originando variações no respectivo comportamento mecânico que serão tanto maiores quanto maior for a percentagem de betume da mesma. A energia de compactação tem como objectivo reduzir o índice de vazios da mistura através do rearranjo das partículas, originando desse modo uma diminuição da camada da mistura betuminosa, responsável pela melhoria do comportamento mecânico e funcional da camada.

Biomimetic norfloxacin sensors made of molecularly-imprinted materials for potentiometric transduction

A biomimetic sensor for norfloxacin is presented that is based on host-guest interactions and potentiometric transduction. The artificial host was imprinted into polymers made from methacrylic acid and/or 2-vinyl pyridine. The resulting particles were entrapped in a plasticized poly(vinyl chloride) (PVC) matrix. The sensors exhibit near-Nernstian response in steady state evaluations, and detection limits range from 0.40 to 1.0 μgmL−1, respectively, and are independent of pH values at between 2 and 6, and 8 and 11, respectively. Good selectivity was observed over several potential interferents. In flowing media, the sensors exhibit fast response, a sensitivity of 68.2 mV per decade, a linear range from 79 μM to 2.5 mM, a detection limit of 20 μgmL−1, and a stable baseline. The sensors were successfully applied to field monitoring of norfloxacin in fish samples, biological samples, and pharmaceutical products

Nanohybrid materials as transducer surfaces for electrochemical sensing applications

A nanohybrid electrochemical transducer surface was developed using carbon and gold nanomaterials. The strategy relayed on casting multiwalled carbon nanotubes or carbon nanofibers onto a screen-printed carbon electrode surface, followed by in situ generation of gold nanoparticles by electrochemical deposition of ionic gold, in a reproducible manner. These transducers, so fabricated, were characterized using both electrochemical and microscopic techniques. Biofunctionality was evaluated using the streptavidin-biotin interaction system as the biological reaction model. These platforms allow to achieve low detection limits (in the order of pmoles), are reproducible and stable at least for a month after their preparation, being a perfect candidate to be used as transducer of different sensor devices.

Natural waste materials containing chitin as adsorbents for textile dyestuffs: batch and continuous studies

In this work three natural waste materials containing chitin were used as adsorbents for textile dyestuffs, namely the Anodonta (Anodonta cygnea) shell, the Sepia (Sepia officinalis) and the Squid (Loligo vulgaris) pens. The selected dyestuffs were the Cibacron green T3G-E (CI reactive green 12), and the Solophenyl green BLE 155% (CI direct green 26), both from CIBA, commonly used in cellulosic fibres dyeing, the most used fibres in the textile industry. Batch equilibrium studies showed that the materials’ adsorption capacities increase after a simple and inexpensive chemical treatment, which increases their porosity and chitin relative content. Kinetic studies suggested the existence of a high internal resistance in both systems. Fixed bed column experiments performed showed an improvement in adsorbents’ behaviour after chemical treatment. However, in the column experiments, the biodegradation was the main mechanism of dyestuff removal, allowing the materials’ bioregeneration. The adsorption was strongly reduced by the pore clogging effect of the biomass. The deproteinised Squid pen (grain size 0.500–1.41 mm) is the adsorbent with highest adsorption capacity (0.27 and 0.037 g/g, respectively, for the reactive and direct dyestuffs, at 20ºC), followed by the demineralised Sepia pen and Anodonta shell, behaving like pure chitin in all experiments, but showing inferior performances than the granular activated carbon tested in the column experiments.

Molecularly-imprinted materials for potentiometric transduction: application to the antibiotic enrofloxacin

Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mVΔlog([ENR]/M) varied within 48–63. The detection limits ranged from 0.28 to 1.01 µg mL 1. Sensors were independent from the pH of test solutions within 4–7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (47 mV/Dlog([ENR]/ M), wide linear range (1.0×10-5–1.0×10-3 M), low detection limit (0.9 µg mL-1), and a stable baseline for a 5×10-2 M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.

Selective recognition in potentiometric transduction of amoxicillin by molecularly imprinted materials

The indiscriminate use of antibiotics in foodproducing 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. AMOXselective 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.

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.

Luminol-doped nanostructured composite materials for chemiluminescent sensing of hydrogen peroxide

Silica based nanostructured composite materials doped with luminol and cobalt(II) ion were synthesized and characterized, resulting in a highly chemiluminescent material in the presence of hydrogen peroxide. A detection system with the CL light guided from the reaction tube to the photomultiplier tube using a one millimeter glass optical fiber was developed and assessed. A linear response was observed using a semi-logarithm calibration between 50–2000 µM hydrogen peroxide with 1 µM as the limit of detection.

Man-tailored biomimetic sensor of molecularly imprinted materials for the potentiometric measurement of oxytetracycline

A novel biomimetic sensor for the potentiometric transduction of oxytetracycline is presented. The artificial host was imprinted in methacrylic acid and/or acrylamide based polymers. Different amounts of molecularly imprinted and non-imprinted polymers were dispersed in different plasticizing solvents and entrapped in a poly(vinyl chloride) matrix. Only molecularly imprinted based sensors allowed a potentiometric transduction, suggesting the existence of host–guest interactions. These sensors exhibited a near-Nernstian response in steady state evaluations; slopes and detection limits ranged 42–63 mV/decade and 2.5–31.3 µg/mL, respectively. Sensors were independent from the pH of test solutions within 2–5. Good selectivity was observed towards glycine, ciprofloxacin, creatinine, acid nalidixic, sulfadiazine, cysteine, hydroxylamine and lactose. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (65 mV/decade), wide linear range (5.0×10−5 to 1.0×10−2 mol/L), low detection limit (19.8 µg/mL), and a stable baseline for a 5×10−3M citrate buffer (pH 2.5) carrier. The sensors were successfully applied to the analysis of drugs and urine. This work confirms the possibility of using molecularly imprinted polymers as ionophores for organic ion recognition in potentiometric transduction.

Bisphenol A migration from plastic materials: direct insight of ecotoxicity in Daphnia magna

Bisphenol A (BPA) is an endocrine disrupting chemical (EDC) whose migration from food packaging is recognized worldwide. However, the real overall food contamination and related consequences are yet largely unknown. Among humans, children’s exposure to BPA has been emphasized because of the immaturity of their biological systems. The main aim of this study was to assess the reproductive impact of BPA leached from commercially available plastic containers used or related to child nutrition, performing ecotoxicological tests using the biomonitoring species Daphnia magna. Acute and chronic tests, as well as single and multigenerational tests were done. Migration of BPA from several baby bottles and other plastic containers evaluated by GC-MS indicated that a broader range of foodstuff may be contaminated when packed in plastics. Ecotoxicological test results performed using defined concentrations of BPA were in agreement with literature, although a precocious maturity of daphnids was detected at 3.0 mg/L. Curiously, an increased reproductive output (neonates per female) was observed when daphnids were bred in the polycarbonate (PC) containers (145.1±4.3 % to 264.7±3.8 %), both in single as in multigenerational tests, in comparison with the negative control group (100.3±1.6 %). A strong correlated dose-dependent ecotoxicological effect was observed, providing evidence that BPA leached from plastic food packaging materials act as functional estrogen in vivo at very low concentrations. In contrast, neonate production by daphnids cultured in polypropylene and non-PC bottles was slightly but not significantly enhanced (92.5±2.0 % to 118.8±1.8 %). Multigenerational tests also revealed magnification of the adverse effects, not only on fecundity but also on mortality, which represents a worrying trend for organisms that are chronically exposed to xenoestrogens for many generations. Two plausible explanations for the observed results could be given: a non-monotonic dose–response relationship or a mixture toxicity effect.

Low-loss austempered ductile iron gears: experimental evaluation comparing materials and lubricants

An experimental study to evaluate the power dissipation of gears was performed. Three low-loss gear models were manufactured using standard 20° pressure angle tools. Austempered ductile iron (ADI) and 20MnCr5 carburized steel gears were tested in an FZG gear test machine using mineral, ester and polyalphaolephine (PAO)-based oils. The results compare power dissipation, the influence of different tooth flank geometries, materials and lubricants. This work concludes that conventional power-transmission gears can be replaced by these improved and more efficient low–loss models, which can be produced using common tools and that steel gears can be successfully replaced by austempered ductile iron gears.

Mechanical behaviour analysis of polyester polymer mortars modified with recycled GFRP waste materials

In this study the effect of incorporation of recycled glass-fibre reinforced polymer (GFRP) waste materials, obtained by means of milling processes, on mechanical behaviour of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste powder and fibres, with distinct size gradings, were incorporated into polyester based mortars as sand aggregates and filler replacements. Flexural and compressive loading capacities were evaluated and found better than unmodified polymer mortars. GFRP modified polyester based mortars also show a less brittle behaviour, with retention of some loading capacity after peak load. Obtained results highlight the high potential of recycled GFRP waste materials as efficient and sustainable reinforcement and admixture for polymer concrete and mortars composites, constituting an emergent waste management solution.