Strength prediction and experimental validation of adhesive joints including polyethylene, carbon-epoxy and aluminium adherends

Polyolefins are especially difficult to bond due to their non-polar, non-porous and chemically inert surfaces. Acrylic adhesives used in industry are particularly suited to bond these materials, including many grades of polypropylene (PP) and polyethylene (PE), without special surface preparation. In this work, the tensile strength of single-lap PE and mixed joints bonded with an acrylic adhesive was investigated. The mixed joints included PE with aluminium (AL) or carbon fibre reinforced plastic (CFRP) substrates. The PE substrates were only cleaned with isopropanol, which assured cohesive failures. For the PE CFRP joints, three different surfaces preparations were employed for the CFRP substrates: cleaning with acetone, abrasion with 100 grit sand paper and peel-ply finishing. In the PE AL joints, the AL bonding surfaces were prepared by the following methods: cleaning with acetone, abrasion with 180 and 320 grit sand papers, grit blasting and chemical etching with chromic acid. After abrasion of the CFRP and AL substrates, the surfaces were always cleaned with acetone. The tensile strengths were compared with numerical results from ABAQUS® and a mixed mode (I+II) cohesive damage model. A good agreement was found between the experimental and numerical results, except for the PE AL joints, since the AL surface treatments were not found to be effective.

Diffusion characteristics of ethylene glycol in skeletal muscle

Part of the optical clearing study in biological tissues concerns the determination of the diffusion characteristics of water and optical clearing agents in the subject tissue. Such information is sufficient to characterize the time dependence of the optical clearing mechanisms—tissue dehydration and refractive index (RI) matching. We have used a simple method based on collimated optical transmittance measurements made from muscle samples under treatment with aqueous solutions containing different concentrations of ethylene glycol (EG), to determine the diffusion time values of water and EG in skeletal muscle. By representing the estimated mean diffusion time values from each treatment as a function of agent concentration in solution, we could identify the real diffusion times for water and agent. These values allowed for the calculation of the correspondent diffusion coefficients for those fluids. With these results, we have demonstrated that the dehydration mechanism is the one that dominates optical clearing in the first minute of treatment, while the RI matching takes over the optical clearing operations after that and remains for a longer time of treatment up to about 10 min, as we could see for EG and thin tissue samples of 0.5 mm.

Optical measurements of rat muscle samples under treatment with ethylene glycol and glucose

With the objective to study the variation of optical properties of rat muscle during optical clearing, we have performed a set of optical measurements from that kind of tissue. The measurements performed were total transmittance, collimated transmittance, specular reflectance and total reflectance. This set of measurements is sufficient to determine diffuse reflectance and absorbance of the sample, also necessary to estimate the optical properties. All the performed measurements and calculated quantities will be used later in inverse Monte Carlo (IMC) simulations to determine the evolution of the optical properties of muscle during treatments with ethylene glycol and glucose. The results obtained with the measurements already provide some information about the optical clearing treatments applied to the muscle and translate the mechanisms of turning the tissue more transparent and sequence of regimes of optical clearing.

Análise e optimização global de uma linha de extrusão

Os objectivos principais deste estudo são a caracterização de uma das linhas de extrusão existentes na Cabelte, nomeadamente a linha de extrusão de referência EP5, composta por duas extrusoras. Pretende-se fazer a determinação de indicadores energéticos e de processo e a optimização do consumo energético, no que diz respeito à energia consumida e às perdas térmicas relativas a esta linha. Para fazer a monitorização da linha de extrusão EP5 foi colocado no quadro geral dessa linha um equipamento central de medida de forma a ser possível a sua monitorização. No entanto, para a extrusora auxiliar as medições foram efectuadas com uma pinça amperimétrica e um fasímetro. Foram também efectuados ensaios onde foi avaliada a quantidade de material transformada, para isso foi utilizado um equipamento de pesagem, doseador gravimétrico aplicado nas extrusoras. As medições de temperatura para os cálculos das perdas térmicas da extrusora principal e para a caracterização dos materiais plásticos, foram efectuadas utilizando um termómetro digital. Foram efectuados ensaios de débito às extrusoras auxiliar e principal e foi estudada a variação do factor de potência em função da rotação do fuso. Na perspectiva do utilizador final a optimização para a utilização racional de energia está na redução de encargos da factura de energia eléctrica. Essa factura não depende só da quantidade mas também do modo temporal como se utiliza essa energia, principalmente a energia eléctrica, bastante dependente do período em que é consumida. Uma metodologia diferente no planeamento da produção, contemplando o fabrico dos cabos com maior custo específico nas horas de menor custo energético, implicaria uma redução dos custos específicos de 18,7% para o horário de verão e de 20,4% para o horário de inverno. Os materiais de revestimento utilizados (PE e PVC), influenciam directamente os custos energéticos, uma vez que o polietileno (PE) apresenta sempre valores de entalpia superiores (0,317 kWh/kg e 0,281 kWh/kg)) e necessita de temperaturas de trabalho mais elevadas do que o policloreto de vinilo (PVC) (0,141 kWh/kg e 0,124 kWh/kg). O consumo específico tendencialmente diminui à medida que aumenta a rotação do fuso, até se atingir o valor de rotação óptimo, a partir do qual esta tendência se inverte. O cosφ para as duas extrusoras em estudo, aumenta sempre com o aumento de rotação do fuso. Este estudo permitiu avaliar as condições óptimas no processo de revestimento dos cabos, de forma a minimizarmos os consumos energéticos. A redução de toda a espécie de desperdícios (sobre consumos, desperdício em purgas) é uma prioridade de gestão que alia também a eficácia à eficiência, e constitui uma ferramenta fundamental para assegurar o futuro da empresa. O valor médio lido para o factor de potência (0,38) da linha EP5, valor extremamente baixo e que vem associado à energia reactiva, além do factor económico que lhe está inerente, condiciona futuras ampliações. A forma de se corrigir o factor de potência é instalando uma bateria de condensadores de 500 kVAr. Considerando o novo sistema tarifário aplicado à energia reactiva, vamos ter um ganho de 36167,4 Euro/ano e o período de retorno de investimento é de 0,37 ano (4,5 meses). Esta medida implica também uma redução anual na quantidade de CO2 emitida de 6,5%. A quantificação das perdas térmicas é importante, pois só desta forma se podem definir modos de actuação de forma a aumentar a eficiência energética. Se não existir conhecimento profundo dos processos e metodologias correctas, não podem existir soluções eficientes, logo é importante medir antes de avançar com qualquer medida de gestão.

Shear strength of adhesively bonded polyolefins with minimal surface preparation

Interest in polyethylene and polypropylene bonding has increased in the last years. However, adhesive joints with adherends which are of low surface energy and which are chemically inert present several difficulties. Generally, their high degree of chemical resistance to solvents and dissimilar solubility parameters limit the usefulness of solvent bonding as a viable assembly technique. One successful approach to adhesive bonding of these materials involves proper selection of surface pre-treatment prior to bonding. With the correct pre-treatment it is possible to glue these materials with one or more of several adhesives required by the applications involved. A second approach is the use of adhesives without surface pre-treatment, such as hot melts, high tack pressure-sensitive adhesives, solvent-based specialty adhesives and, more recently, structural acrylic adhesives as such 3M DP-8005® and Loctite 3030®. In this paper, the shear strengths of two acrylic adhesives were evaluated using the lap shear test method ASTM D3163 and the block shear test method ASTM D4501. Two different industrial polyolefins (polyethylene and polypropylene) were used for adherends. However, the focus of this study was to measure the shear strength of polyethylene joints with acrylic adhesives. The effect of abrasion was also studied. Some test specimens were manually abraded using 180 and 320 grade abrasive paper. An additional goal of this work was to examine the effect of temperature and moisture on mechanical strength of adhesive joints.

Acrylic adhesives in the polyolefins joining

The mechanical behaviour of single lap adhesive joints was characterized, using two commercial acrylic adhesives. For this purpose the surfaces were cleaned and abraded using fine grit abrasives. The effect of temperature and moisture in the mechanical strength was, also, evaluated. For this characterization, mechanical tests were carried out according procedure and geometry foreseen by ASTM D3163-01 [1] and ASTM D4501-01 [2] standards. The results show that it is possible to get good strengths without great surface preparation. The temperature and moisture effect observed don’t seem to be relevant for the mechanical behaviour.

Single-lap joints of similar and dissimilar adherends bonded with an acrylic adhesive

In this study, the tensile strength of single-lap joints (SLJs) between similar and dissimilar adherends bonded with an acrylic adhesive was evaluated experimentally and numerically. The adherend materials included polyethylene (PE), polypropylene (PP), carbon-epoxy (CFRP), and glass-polyester (GFRP) composites. The following adherend combinations were tested: PE/PE, PE/PP, PE/CFRP, PE/GFRP, PP/PP, CFRP/CFRP, and GFRP/GFRP. One of the objectives of this work was to assess the influence of the adherends stiffness on the strength of the joints since it significantly affects the peel stresses magnitude in the adhesive layer. The experimental results were also used to validate a new mixed-mode cohesive damage model developed to simulate the adhesive layer. Thus, the experimental results were compared with numerical simulations performed in ABAQUS®, including a developed mixed-mode (I+II) cohesive damage model, based on the indirect use of fracture mechanics and implemented within interface finite elements. The cohesive laws present a trapezoidal shape with an increasing stress plateau, to reproduce the behaviour of the ductile adhesive used. A good agreement was found between the experimental and numerical results.

Aplicação de métodos estocásticos na gestão de custos de construção de condutas de saneamento

O trabalho apresentado centra-se na determinação dos custos de construção de condutas de pequenos e médios diâmetros em Polietileno de Alta Densidade (PEAD) para saneamento básico, tendo como base a metodologia descrita no livro Custos de Construção e Exploração – Volume 9 da série Gestão de Sistemas de Saneamento Básico, de Lencastre et al. (1994). Esta metodologia descrita no livro já referenciado, nos procedimentos de gestão de obra, e para tal foram estimados custos unitários de diversos conjuntos de trabalhos. Conforme Lencastre et al (1994), “esses conjuntos são referentes a movimentos de terras, tubagens, acessórios e respetivos órgãos de manobra, pavimentações e estaleiro, estando englobado na parte do estaleiro trabalhos acessórios correspondentes à obra.” Os custos foram obtidos analisando vários orçamentos de obras de saneamento, resultantes de concursos públicos de empreitadas recentemente realizados. Com vista a tornar a utilização desta metodologia numa ferramenta eficaz, foram organizadas folhas de cálculo que possibilitam obter estimativas realistas dos custos de execução de determinada obra em fases anteriores ao desenvolvimento do projeto, designadamente numa fase de preparação do plano diretor de um sistema ou numa fase de elaboração de estudos de viabilidade económico-financeiros, isto é, mesmo antes de existir qualquer pré-dimensionamento dos elementos do sistema. Outra técnica implementada para avaliar os dados de entrada foi a “Análise Robusta de Dados”, Pestana (1992). Esta metodologia permitiu analisar os dados mais detalhadamente antes de se formularem hipóteses para desenvolverem a análise de risco. A ideia principal é o exame bastante flexível dos dados, frequentemente antes mesmo de os comparar a um modelo probabilístico. Assim, e para um largo conjunto de dados, esta técnica possibilitou analisar a disparidade dos valores encontrados para os diversos trabalhos referenciados anteriormente. Com os dados recolhidos, e após o seu tratamento, passou-se à aplicação de uma metodologia de Análise de Risco, através da Simulação de Monte Carlo. Esta análise de risco é feita com recurso a uma ferramenta informática da Palisade, o @Risk, disponível no Departamento de Engenharia Civil. Esta técnica de análise quantitativa de risco permite traduzir a incerteza dos dados de entrada, representada através de distribuições probabilísticas que o software disponibiliza. Assim, para por em prática esta metodologia, recorreu-se às folhas de cálculo que foram realizadas seguindo a abordagem proposta em Lencastre et al (1994). A elaboração e a análise dessas estimativas poderão conduzir à tomada de decisões sobre a viabilidade da ou das obras a realizar, nomeadamente no que diz respeito aos aspetos económicos, permitindo uma análise de decisão fundamentada quanto à realização dos investimentos.

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.

Graphene-based biomimetic materials targeting urine metabolite as potential cancer biomarker: Application over different conductive materials for potentiometric transduction

This work presents a novel surface Smart Polymer Antibody Material (SPAM) for Carnitine (CRT, a potential biomarker of ovarian cancer), tested for the first time as ionophore in potentiometric electrodes of unconventional configuration. The SPAM material consisted of a 3D polymeric network created by surface imprinting on graphene layers. The polymer was obtained by radical polymerization of (vinylbenzyl) trimethylammonium chloride and 4-styrenesulfonic acid (signaling the binding sites), and vinyl pivalate and ethylene glycol dimethacrylate (surroundings). Non-imprinted material (NIM) was prepared as control, by excluding the template from the procedure. These materials were then used to produce several plasticized PVC membranes, testing the relevance of including the SPAM as ionophore, and the need for a charged lipophilic additive. The membranes were casted over solid conductive supports of graphite or ITO/FTO. The effect of pH upon the potentiometric response was evaluated for different pHs (2-9) with different buffer compositions. Overall, the best performance was achieved for membranes with SPAM ionophore, having a cationic lipophilic additive and tested in HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) buffer, pH 5.1. Better slopes were achieved when the membrane was casted on conductive glass (-57.4 mV/decade), while the best detection limits were obtained for graphite-based conductive supports (3.6 × 10−5mol/L). Good selectivity was observed against BSA, ascorbic acid, glucose, creatinine and urea, tested for concentrations up to their normal physiologic levels in urine. The application of the devices to the analysis of spiked samples showed recoveries ranging from 91% (± 6.8%) to 118% (± 11.2%). Overall, the combination of the SPAM sensory material with a suitable selective membrane composition and electrode design has lead to a promising tool for point-of-care applications.

New modified electrochemical conductive paper support for BSA detection

Chemical sensors and biosensors are widely used to detect various kinds of protein target biomolecules. Molecularly Imprinted Polymers (MIPs) have raised great interest in this area, because these act as antibody-like recognition materials, with high affinity to the template molecule. Compared to natural antibodies, these are also of lower cost and higher stability. There are different types of supports used to carry MIP materials, mostly of these made of gold, favourably assembled on a Screen Printed Electrode (SPE) strategy. For this work a new kind of support for the sensing layer was developed: conductive paper. This support was made by modifying first cellulose paper with paraffin wax (to make it waterproof), and casting a carbon-ink on it afterwards, to turn it conductive. The SPAM approach previously reported in1 was employed herein to assemble to MIP sensing material on the conductive paper. The selected charged monomers were (vinylbenzyl) trimethlammonium chloride (positive charge) or vinylbenzoic acid (negative charge), used to generate binding positions with single-type charge (positive or negative). The non-specific binding area of the MIP layer was assembled by chronoamperometry-assisted polymerization (at 1 V, for 60, 120 or 180 seconds) of vinylbenzoate, cross-linked with ethylene glycol vinyl ether. The BSA biomolecules lying within the polymeric matrix were removed by Proteinase K action. All preparation stages of the MIP assembly were followed by FTIR, Raman spectroscopy and, electrochemical analysis. In general, the best results were obtained for longer polymerization times and positively charged binding sites (which was consistent with a negatively-charged protein under physiological pH, as BSA). Linear responses against BSA concentration ranged from 0.005 to 100 mg/mL, in PBS buffer standard solutions. The sensor was further calibrated in standard solutions that were prepared in synthetic or real urine, and the analytical response became more sensitive and stable. Compared to the literature, the detection capability of the developed device is better than most of the reported electrodes. Overall, the simplicity, low cost and good analytical performance of the BSA SPE device, prepared with positively charged binding positions, seems a suitable approach for practical application in clinical context. Further studies with real samples are required, as well as gathering with electronic-supporting devices to allow on-site readings.

Detection of cardiac biomarker proteins using a disposable based on a molecularly imprinted polymer grafted onto graphite

A low-cost disposable was developed for rapid detection of the protein biomarker myoglobin (Myo) as a model analyte. A screen printed electrode was modified with a molecularly imprinted material grafted on a graphite support and incorporated in a matrix composed of poly(vinyl chloride) and the plasticizer o-nitrophenyloctyl ether. The protein-imprinted material (PIM) was produced by growing a reticulated polymer around a protein template. This is followed by radical polymerization of 4-styrenesulfonic acid, 2-aminoethyl methacrylate hydrochloride, and ethylene glycol dimethacrylate. The polymeric layer was then covalently bound to the graphitic support, and Myo was added during the imprinting stage to act as a template. Non-imprinted control materials (CM) were also prepared by omitting the Myo template. Morphological and structural analysis of PIM and CM by FTIR, Raman, and SEM/EDC microscopies confirmed the modification of the graphite support. The analytical performance of the SPE was assessed by square wave voltammetry. The average limit of detection is 0.79 μg of Myo per mL, and the slope is −0.193 ± 0.006 μA per decade. The SPE-CM cannot detect such low levels of Myo but gives a linear response at above 7.2 μg · mL−1, with a slope of −0.719 ± 0.02 μA per decade. Interference studies with hemoglobin, bovine serum albumin, creatinine, and sodium chloride demonstrated good selectivity for Myo. The method was successfully applied to the determination of Myo urine and is conceived to be a promising tool for screening Myo in point-of-care patients with ischemia.

Biomimetic Sensor Potentiometric System for Doxycycline Antibiotic Using a Molecularly Imprinted Polymer as an Artificial Recognition Element

Molecular imprinting is a useful technique for the preparation of functional materials with molecular recognition properties. A Biomimetic Sensor Potentiometric System was developed for assessment of doxycycline (DOX) antibiotic. The molecularly imprinted polymer (MIP) was synthesized by using doxycycline as a template molecule, methacrylic acid (MAA) and/or acrylamide (AA) as a functional monomer and ethylene glycol dimethacrylat (EGDMA) as a cross-linking agent. The sensing elements were fabricated by the inclusion of DOX imprinted polymers in polyvinyl chloride (PVC) matrix. The sensors showed a high selectivity and a sensitive response to the template in aqueous system. Electrochemical evaluation of these sensors under static (batch) mode of operation reveals near-Nernstian response. MIP/MAA membrane sensor was incorporated in flow-through cells and used as detectors for flow injection analysis (FIA) of DOX. The method has the requisite accuracy, sensitivity and precision to assay DOX in tablets and biological fluids.

A novel antibody-like material for breast cancer antigen CA15-3, used to track breast cancer by potentiometric transduction

This work presents the development of a low cost sensor device for the diagnosis of breast cancer in point-of-care, made with new synthetic biomimetic materials inside plasticized poly(vinyl chloride), PVC, membranes, for subsequent potentiometric detection. This concept was applied to target a conventional biomarker in breast cancer: Breast Cancer Antigen (CA15-3). The new biomimetic material was obtained by molecularly-imprinted technology. In this, a plastic antibody was obtained by polymerizing around the biomarker that acted as an obstacle to the growth of the polymeric matrix. The imprinted polymer was specifically synthetized by electropolymerization on an FTO conductive glass, by using cyclic voltammetry, including 40 cycles within -0.2 and 1.0 V. The reaction used for the polymerization included monomer (pyrrol, 5.0×10-3 mol/L) and protein (CA15-3, 100U/mL), all prepared in phosphate buffer saline (PBS), with a pH of 7.2 and 1% of ethylene glycol. The biomarker was removed from the imprinted sites by proteolytic action of proteinase K. The biomimetic material was employed in the construction of potentiometric sensors and tested with regard to its affinity and selectivity for binding CA15-3, by checking the analytical performance of the obtained electrodes. For this purpose, the biomimetic material was dispersed in plasticized PVC membranes, including or not a lipophilic ionic additive, and applied on a solid conductive support of graphite. The analytical behaviour was evaluated in buffer and in synthetic serum, with regard to linear range, limit of detection, repeatability, and reproducibility. This antibody-like material was tested in synthetic serum, and good results were obtained. The best devices were able to detect 5 times less CA15-3 than that required in clinical use. Selectivity assays were also performed, showing that the various serum components did not interfere with this biomarker. Overall, the potentiometric-based methods showed several advantages compared to other methods reported in the literature. The analytical process was simple, providing fast responses for a reduced amount of analyte, with low cost and feasible miniaturization. It also allowed the detection of a wide range of concentrations, diminishing the required efforts in previous sample pre-treating stages.

Carnitine tailored Sensors on Surface Molecular Imprinting based on Graphene layers

III Jornadas de Electroquímica e Inovação (Electroquímica e Nanomateriais), na Universidade de Trás-os-Montes e Alto Douro, Vila Real, 16 a 17 de Setembro de 2013