Biodiesel production over lithium modified lime catalysts: activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca = 03 atomic ratio). The catalysts were calcined at 575 degrees C and 800 degrees C, for 5 h, to remove nitrate ions before reaction. The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)(2). The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO. In the tested condition (W-cat/W-oil = 5%; CH3OH/oil = 12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4 h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability. (C) 2013 Elsevier B.V. All rights reserved.

Real time fault injection using a modified debugging infrastructure

Dependability is a critical factor in computer systems, requiring high quality validation & verification procedures in the development stage. At the same time, digital devices are getting smaller and access to their internal signals and registers is increasingly complex, requiring innovative debugging methodologies. To address this issue, most recent microprocessors include an on-chip debug (OCD) infrastructure to facilitate common debugging operations. This paper proposes an enhanced OCD infrastructure with the objective of supporting the verification of fault-tolerant mechanisms through fault injection campaigns. This upgraded on-chip debug and fault injection (OCD-FI) infrastructure provides an efficient fault injection mechanism with improved capabilities and dynamic behavior. Preliminary results show that this solution provides flexibility in terms of fault triggering and allows high speed real-time fault injection in memory elements

Modified particle swarm optimization for day-ahead distributed energy resources scheduling including vehicle-to-grid

Mestrado em Engenharia Electrotécnica – Sistemas Eléctricos de Energia

A modified debugging infrastructure to assist real time fault injection campaigns

Fault injection is frequently used for the verification and validation of the fault tolerant features of microprocessors. This paper proposes the modification of a common on-chip debugging (OCD) infrastructure to add fault injection capabilities and improve performance. The proposed solution imposes a very low logic overhead and provides a flexible and efficient mechanism for the execution of fault injection campaigns, being applicable to different target system architectures.

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.

Optimization process of polyester polymer mortars modified with recycled GFRP waste aggregates – application of factorial experiment design-

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 polymer mortar aggregates, without significant loss of mechanical properties with regard to non-modified polymer mortars.

Design of experiments applied to the mix design process of polymer mortar materials modified with GFRP recyclates

In this work, the effect of incorporation of recycled glass fibre reinforced plastics (GFRP) waste materials, obtained by means of shredding and milling processes, on mechanical behavior of polyester polymer mortar (PM) materials was assessed. For this purpose, different contents of GFRP recyclates (between 4% up to 12% in mass), were incorporated into polyester PM materials as sand aggregates and filler replacements. The effect of silane coupling agent addition to resin binder was also evaluated. Applied waste material was proceeding from the shredding of the leftovers resultant from the cutting and assembly processes of GFRP pultrusion profiles. Currently, these leftovers, jointly with unfinished products and scrap resulting from pultrusion manufacturing process, are landfilled, with supplementary added costs. Thus, besides the evident environmental benefits, a viable and feasible solution for these wastes would also conduct to significant economic advantages. Design of experiments and data treatment were accomplish by means of full factorial design approach and analysis of variance ANOVA. Experimental results were promising toward the recyclability of GFRP waste materials as aggregates and reinforcement for PM materials, with significant improvements on mechanical properties with regard to non-modified formulations.

Modified Particle Swarm Optimization Applied to Integrated Demand Response and DG Resources Scheduling

The elastic behavior of the demand consumption jointly used with other available resources such as distributed generation (DG) can play a crucial role for the success of smart grids. The intensive use of Distributed Energy Resources (DER) and the technical and contractual constraints result in large-scale non linear optimization problems that require computational intelligence methods to be solved. This paper proposes a Particle Swarm Optimization (PSO) based methodology to support the minimization of the operation costs of a virtual power player that manages the resources in a distribution network and the network itself. Resources include the DER available in the considered time period and the energy that can be bought from external energy suppliers. Network constraints are considered. The proposed approach uses Gaussian mutation of the strategic parameters and contextual self-parameterization of the maximum and minimum particle velocities. The case study considers a real 937 bus distribution network, with 20310 consumers and 548 distributed generators. The obtained solutions are compared with a deterministic approach and with PSO without mutation and Evolutionary PSO, both using self-parameterization.

MIP-graphene-modified glassy carbon electrode for the determination of trimethoprim

A novel sensitive electrochemical sensor was developed by electropolymerization of pyrrole(PY)and molecularly imprinted polymer (MIP)which was synthesized onto a glassy carbon electrode (GCE) in aqueous solution using cyclic voltammetry in the presence of Trimethoprim (TMP) as template molecules. Furthermore,a previous electrode modification was performed by deposition of a suspension of graphene on the electrode's surface. The performance of the imprinted and non-imprinted (NIP) films was evaluated by impedance spectroscopy (EIS) and cyclic voltammetry (CV) of a ferric solution. The molecularly imprinted film exhibited a high selectivity and sensitivity toward TMP. The sensor presented a linear range, between peak current intensity and logarithm of TMP concentration between 1.0x10-6 and 1.0x10-4 M. The results were accurate (with recoveries higher than 94%), precise (with standard deviations less than 5%) and the detection limit was 1.3x10-7 M. The new sensor is selective, simple to construct and easy to operate. The MIP sensor was successfully applied to quantify TMP in urinesamples.

Mechanical and thermal characterization of a structural polyurethane adhesive modified with thermally expandable particles

Thermally expandable particles (TEPs) are used in a wide variety of applications by industry mainly for weight reduction and appearance improvement for thermoplastics, inks, and coatings. In adhesive bonding, TEPs have been used for recycling purposes. However, TEPs might be used to modify structural adhesives for other new purposes, such as: to increase the joint strength by creating an adhesive functionally modified along the overlap of the joint by gradual heating and/or to heal the adhesive in case of damage. In this study, the behaviour of a structural polyurethane adhesive modified with TEPs was investigated as a preliminary study for further investigations on the potential of TEPs in adhesive joints. Tensile bulk tests were performed to get the tensile properties of the unmodified and TEPs-modified adhesive, while Double Cantilever Beam (DCB) test was performed in order to evaluate the resistance to mode I crack propagation of unmodified and TEPs-modified adhesive. In addition, in order to investigate the behaviour of the particles while encapsulated in adhesives, a thermal analysis was done. Scanning electron microscopy (SEM) was used to examine the fracture surface morphology of the specimens. The fracture toughness of the TEPs-modified adhesive was found to increase by addition of TEPs, while the adhesive tensile strength at yield decreased. The temperature where the particles show the maximum expansion varied with TEPs concentration, decreasing with increasing the TEPs content.

Modified Discrete PSO to Increase the Delivered Energy Probability in Distribution energy Systems

This paper proposes a PSO based approach to increase the probability of delivering power to any load point by identifying new investments in distribution energy systems. The statistical failure and repair data of distribution components is the main basis of the proposed methodology that uses a fuzzyprobabilistic modeling for the components outage parameters. The fuzzy membership functions of the outage parameters of each component are based on statistical records. A Modified Discrete PSO optimization model is developed in order to identify the adequate investments in distribution energy system components which allow increasing the probability of delivering power to any customer in the distribution system at the minimum possible cost for the system operator. To illustrate the application of the proposed methodology, the paper includes a case study that considers a 180 bus distribution network.

Application-Specific Modified Particle Swarm Optimization for energy resource scheduling considering vehicle-to-grid

This paper presents a modified Particle Swarm Optimization (PSO) methodology to solve the problem of energy resources management with high penetration of distributed generation and Electric Vehicles (EVs) with gridable capability (V2G). The objective of the day-ahead scheduling problem in this work is to minimize operation costs, namely energy costs, regarding the management of these resources in the smart grid context. The modifications applied to the PSO aimed to improve its adequacy to solve the mentioned problem. The proposed Application Specific Modified Particle Swarm Optimization (ASMPSO) includes an intelligent mechanism to adjust velocity limits during the search process, as well as self-parameterization of PSO parameters making it more user-independent. It presents better robustness and convergence characteristics compared with the tested PSO variants as well as better constraint handling. This enables its use for addressing real world large-scale problems in much shorter times than the deterministic methods, providing system operators with adequate decision support and achieving efficient resource scheduling, even when a significant number of alternative scenarios should be considered. The paper includes two realistic case studies with different penetration of gridable vehicles (1000 and 2000). The proposed methodology is about 2600 times faster than Mixed-Integer Non-Linear Programming (MINLP) reference technique, reducing the time required from 25 h to 36 s for the scenario with 2000 vehicles, with about one percent of difference in the objective function cost value.

Descending pain modulation in a Kaolin-induced hydrocephalus rat model

Pain transmission at the spinal cord is modulated by descending actions that arise from supraspinal areas which collectively form the endogenous pain control system. Two key areas involved of the endogenous pain control system have a circunventricular location, namely the periaqueductal grey (PAG) and the locus coeruleus (LC). The PAG plays a crucial role in descending pain modulation as it conveys the input from higher brain centers to the spinal cord. As to the LC, it is involved in descending pain inhibition by direct noradrenergic projections to the spinal cord. In the context of neurological defects, several diseases may affect the structure and function of the brain. Hydrocephalus is a congenital or acquired disease characterized by an enlargement of the ventricles which leads to a distortion of the adjacent tissues, including the PAG and LC. Usually, patients suffering from hydrocephalus present dysfunctions in learning and memory and also motor deficits. It remains to be evaluated if lesions of the periventricular brain areas involved in pain control during hydrocephalus may affect descending pain control and, herein, affect pain responses. The studies included in the present thesis used an experimental model of hydrocephalus (the rat injected in the cisterna magna with kaolin) to study descending modulation of pain, focusing on the two circumventricular regions referred above (the PAG and the LC). In order to evaluate the effects of kaolin injection into the cisterna magna, we measured the degree of ventricular dilatation in sections encompassing the PAG by standard cytoarquitectonic stanings (thionin staining). For the LC, immunodetection of the noradrenaline-synthetizing enzyme tyrosine hydroxylase (TH) was performed, due to the noradrenergic nature of the LC neurons. In general, rats with kaolin-induced hydrocephalus presented a higher dilatation of the 4th ventricle, along with a tendency to a higher area of the PAG. Due to the validated role of detection the c-fos protooncogene as a marker of neuronal activation, we also studied neuronal activation in the several subnuclei which compose the PAG, namely the dorsomedial, dorsolateral, lateral and ventrolateral (VLPAG) parts. A decrease in the numbers of neurons immunoreactive for Fos protein (the product of activation of the c-fos protooncogene) was detected in rats injected with kaolin, whereas the remaining PAG subnuclei did not present changes in Fos-immunoreactive nuclei. Increases in the levels of TH in the LC, namely at the rostral parts of the nucleus, were detected in hydrocephalic animals. The following pain-related parameters were measured, namely 1) pain behavioural responses in a validated pain inflammatory test (the formalin test) and 2) the nociceptive activation of spinal cord neurons. A decrease in behavioral responses was detected in rats with kaolin-induced hydrocephalus was detected, namely in the second phase of the test (inflammatory phase). This is the phase of the formalin test in which the motor behaviour is less important, which is important since a semi-quantitative analysis of the motor performance of rats injected with kaolin indicates that these animals may present some motor impairments. Collectively, the results of the behavioral studies indicate that rats with kaolin-induced hydrocephalus exhibit hypoalgesia. A decrease in Fos expression was detected at the superficial dorsal layers of the spinal cord in rats with kaolin-induced hydrocephalus, further indicating that hydrocephalus decreases nociceptive responses. It remains to be ascertained if this is due to alterations in the PAG and LC in the rats with kaolin-induced hydrocephalus, which may affect descending pain modulation. It remains to be evaluated what are the mechanisms underlying the increased pain inhibition at the spinal dorsal horn in the hydrocephalus rats. Regarding the VLPAG, the decrease in neuronal activity may impair descending modulation. Since the LC has higher levels of TH in rats with kaolininduced hydrocephalus, which also appears to increase the noradrenergic innervation in the spinal dorsal horn, it is possible that an increase in the release of noradrenaline at the spinal cord accounts for pain inhibition. Our studies also determine the need to study in detail patients with hydrocephalus namely in what concerns their thresholds to pain and to perform imaging studies focused on the structure and function of pain control areas in the brain.

Chitosan/AuNPs Modified Graphene Electrochemical Sensor for Label-Free Human Chorionic Gonadotropin Detection

A new immunosensor is presented for human chorionic gonadotropin (hCG), made by electrodepositing chitosan/gold-nanoparticles over graphene screen-printed electrode (SPE). The antibody was covalently bound to CS via its Fc-terminal. The assembly was controlled by electrochemical Impedance Spectroscopy (EIS) and followed by Fourier Transformed Infrared (FTIR). The hCG-immunosensor displayed linear response against the logarithm-hCG concentration for 0.1–25 ng/mL with limit of detection of 0.016 ng/mL. High selectivity was observed in blank urine and successful detection of hCG was also achieved in spiked samples of real urine from pregnant woman. The immunosensor showed good detection capability, simplicity of fabrication, low-cost, high sensitivity and selectivity.

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.