Chemical reaction network of flavylium ions in heterogeneous media

Dissertação apresentada para a obtenção do Grau de Doutor em Química, especialidade em Química-Física, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Formative assessment and motivation in higher education: a successful approach in mechanical engineer thermodynamics

Between 2000/01 and 2006/07, the approval rate of a Thermodynamics course in a Mechanical Engineer graduation was 25%. However, a careful analysis of the results showed that 41% of the students chosen not to attend or dropped out, missing the final examination. Thus, a continuous assessment methodology was developed, whose purpose was to reduce drop out, motivating students to attend this course, believing that what was observed was due, not to the incapacity to pass, but to the anticipation of the inevitability of failure by the students. If, on one hand, motivation is defined as a broad construct pertaining to the conditions and processes that account for the arousal, direction, magnitude, and maintenance of effort, on the other hand, assessment is one of the most powerful tools to change the will that students have to learn, motivating them to learn in a quicker and permanent way. Some of the practices that were implemented, included: promoting learning goal orientation rather than performance goal orientation; cultivating intrinsic interest in the subject and put less emphasis on grades but make grading criteria explicit; emphasizing teaching approaches that encourage collaboration among students and cater for a range of teaching styles; explaining the reasons for, and the implications of, tests; providing feedback to students about their performance in a form that is non-egoinvolving and non-judgemental and helping students to interpret it; broadening the range of information used in assessing the attainment of individual students. The continuous assessment methodology developed was applied in 2007/08 and 2008/09, having found an increase in the approval from 25% to 55% (30%), accompanied by a decrease of the drop out from 41% to 23,5% (17,5%). Flunking with a numerical grade lowered from 34,4% to 22,0% (12,4%). The perception by the students of the continuous assessment relevance was evaluated with a questionnaire. 70% of the students that failed the course respond that, nevertheless, didn’t repent having done the continuous assessment.

An SEM investigation of the pozzolanic activity of a waste catalyst oil refinery

The most active phase of the fluid catalytic cracking (FCC) catalyst, used in oil refinery, is zeolite-Y which is an aluminosilicate with a high internal and external surface area responsible for its high reactivity. Waste FCC catalyst is potentially able to be reused in cement-based materials - as an additive - undergoing a pozzolanic reaction with calcium hydroxide (Ca(OH)2) formed during cement hydration [1-3]. This reaction produces additional strength-providing reaction products i.e., calcium silicate hydrate (C-S-H) and hydrous calcium aluminates (C-A-H) which exact chemical formula and structure are still unknown. Partial replacement of cement by waste FCC catalyst has two key advantages: (1) lowering of cement production with the associated pollution reduction as this industry represents one of the largest sources of man-made CO2 emissions, and (2) improving the mechanical properties and durability of cement-based materials. Despite these advantages, there is a lack of fundamental knowledge on pozzolanic reaction mechanisms as well as spatial distribution of porosity and solid phases interactions at the microstructural level and consequently their relationship with macroscopical engineering properties of catalyst/cement blends. Within this scope, backscattered electron (BSE) images acquired in a scanning electron microscope (SEM) equipped with Energy-Dispersive Spectroscopy (EDS) and by X-ray diffraction were used to investigate chemical composition of hydration products and to analyse spatial information of the microstructure of waste FCC catalyst blended cement mortars. For this purpose mortars with different levels of cement substitution by waste catalyst as well as with different hydration ages, were prepared. The waste FCC catalyst used is produced by the Portuguese refinery company Petrogal S.A.

Probabilistic models for mechanical properties of prestressing strands

This study focus on the probabilistic modelling of mechanical properties of prestressing strands based on data collected from tensile tests carried out in Laboratório Nacional de Engenharia Civil (LNEC), Portugal, for certification purposes, and covers a period of about 9 years of production. The strands studied were produced by six manufacturers from four countries, namely Portugal, Spain, Italy and Thailand. Variability of the most important mechanical properties is examined and the results are compared with the recommendations of the Probabilistic Model Code, as well as the Eurocodes and earlier studies. The obtained results show a very low variability which, of course, benefits structural safety. Based on those results, probabilistic models for the most important mechanical properties of prestressing strands are proposed.

The effect of superplasticizers on the mechanical performance of concrete made with fine recycled concrete aggregates

It is considered that using crushed recycled concrete as aggregate for concrete production is a viable alternative to dumping and would help to conserve abiotic resources. This use has fundamentally been based on the coarse fraction because the fine fraction is likely to degrade the performance of the resulting concrete. This paper presents results from a research work undertaken at Institut Superior Tecnico (IST), Lisbon, Portugal, in which the effects of incorporating two types of superplasticizer on the mechanical performance of concrete containing fine recycled aggregate were evaluated. The purpose was to see if the addition of superplasticizer would offset the detrimental effects associated with the use of fine recycled concrete aggregate. The experimental programme is described and the results of tests for splitting tensile strength, modulus of elasticity and abrasion resistance are presented. The relative performance of concrete made with recycled aggregate was found to decrease. However, the same concrete with admixtures in general exhibited a better mechanical performance than the reference mixes without admixtures or with a less active superplasticizer. Therefore, it is argued that the mechanical performance of concrete made with fine recycled concrete aggregates can be as good as that of conventional concrete, if superplasticizers are used to reduce the water-cement ratio of the former concrete.

Mechanical properties of stent-graft materials

An aneurysm is a localized blood-filled dilatation of an artery whose consequences can be deadly. One of its current treatments is endovascular aneurysm repair, a minimally invasive procedure in which an endoprosthesis, called a stent-graft, is placed transluminally to prevent wall rupture. Early stent-grafts were custom designed for the patient through the assembling of off-the-shelf components by the operating surgeon. However, nowadays, stent-grafts have become a commercial product. The existing endoprostheses differ in several aspects, such as shape design and materials, but they have in common a metallic scaffold with a polymeric covering membrane. This article aims to gather relevant information for those who wish to understand the principles of stent-grafts and even to develop new devices. Hence, a stent-graft classification based on different characteristics is presented and the desired features for an ideal device are pointed out. Additionally, the materials currently in use to fabricate this type of endoprosthesis are reviewed and new materials are suggested.

Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study

Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

Study of thermochemical treatments of cork in the 150-400ºC range using colour analysis and Ftir spectroscopy

A study of chemical transformations of cork during heat treatments was made using colour variation and FTIR analysis. The cork enriched fractions from Quercus cerris bark were subjected to isothermal heating in the temperature range 150–400 ◦C and treatment time from 5 to 90 min. Mass loss ranged from 3% (90 min at 150 ◦C) to 71% (60 min at 350 ◦C). FTIR showed that hemicelluloses were thermally degraded first while suberin remained as the most heat resistant component. The change of CIE-Lab parameters was rapid for low intensity treatments where no significant mass loss occurred (at 150 ◦C L* decreased from the initial 51.5 to 37.3 after 20 min). The decrease in all colour parameters continued with temperature until they remained substantially constant with over 40% mass loss. Modelling of the thermally induced mass loss could be made using colour analysis. This is applicable to monitoring the production of heat expanded insulation agglomerates.

Mechanical behavior and localized failure modes in a porous basalt from the Azores

Basaltic rocks are the main component of the oceanic upper crust, thus of potential interest for water and geothermal resources, storage of CO2 and volcanic edifice stability. In this work, we investigated experimentally the mechanical behavior and the failure modes of a porous basalt, with an initial connected porosity of 18%. Results were acquired under triaxial compression experiments at confining pressure in the range of 25-200 MPa on water saturated samples. In addition, a purely hydrostatic test was also performed to reach the pore collapse critical pressure P*. During hydrostatic loading, our results show that the permeability is highly pressure dependent, which suggests that the permeability is mainly controlled by pre-existing cracks. When the sample is deformed at pressure higher than the pore collapse pressure P*, some very small dilatancy develops due to microcracking, and an increase in permeability is observed. Under triaxial loading, two modes of deformation can be highlighted. At low confining pressure (Pc < 50 MPa), the samples are brittle and shear localization occurs. For confining pressure > 50 MPa, the stress-strain curves are characterized by strain hardening and volumetric compaction. Stress drops are also observed, suggesting that compaction may be localized. The presence of compaction bands is confirmed by our microstructure analysis. In addition, the mechanical data allows us to plot the full yield surface for this porous basalt, which follows an elliptic cap as previously observed in high porosity sandstones and limestones.

Adhesion and wear behaviour of NCD coatings on Si3N4 by micro-abrasion tests

Nanocrystalline diamond (NCD) coatings offer an excellent alternative for tribological applications, preserving most of the intrinsic mechanical properties of polycrystalline CVD diamond and adding to it an extreme surface smoothness. Silicon nitride (Si3N4) ceramics are reported to guarantee high adhesion levels to CVD microcrystalline diamond coatings, but the NCD adhesion to Si3N4 is not yet well established. Micro-abrasion tests are appropriate for evaluating the abrasive wear resistance of a given surface, but they also provide information on thin film/substrate interfacial resistance, i.e., film adhesion. In this study, a comparison is made between the behaviour of NCD films deposited by hot-filament chemical vapour deposition (HFCVD) and microwave plasma assisted chemical vapour deposition (MPCVD) techniques. Silicon nitride (Si3N4) ceramic discs were selected as substrates. The NCD depositions by HFCVD and MPCVD were carried out using H2–CH4 and H2–CH4–N2 gas mixtures, respectively. An adequate set of growth parameters was chosen for each CVD technique, resulting in NCD films having a final thickness of 5 m. A micro-abrasion tribometer was used, with 3 m diamond grit as the abrasive slurry element. Experiments were carried out at a constant rotational speed (80 r.p.m.) and by varying the applied load in the range of 0.25–0.75 N. The wear rate for MPCVD NCD (3.7±0.8 × 10−5 m3N−1m−1) is compatible with those reported for microcrystalline CVD diamond. The HFCVD films displayed poorer adhesion to the Si3N4 ceramic substrates than the MPCVD ones. However, the HFCVD films show better wear resistance as a result of their higher crystallinity according to the UV Raman data, despite evidencing premature adhesion failure.

Hexachlorophene as a topically applied chemical for prophylaxis against Schistosoma mansoni infections in mice

Treatment of mouse tail skins with hexachlorophene (1.25% w/v) in absolute methanol or 70% isopropanol suppressed Schistosoma mansoni infections by more than 95% even when the application was performed up to three days prior to exposure to cercarial suspensions by tail immersion. Treatment with concentrations of 0.313% or higher one day prior to exposure provided at least 98% protection when the treated surface was not subjected to water washes of greater duration than 1/2 hour. Tail immersion application of 1.25% hexachlorophene one day prior to exposure still provided 87-92% protection after 3 hours water wash. Wipe application of 1.25% hexachlorophene three days prior to exposure still provided 93% protection following 3 hours water wash. High cercarial recoveries from exposure tubes at the end of exposure periods indicated high antipenetrant activity for hexachlorophene. Sufficient hexachlorophene leached from treated tail skins into the surrounding water to affect subsequently added cercariae so that they were no longer infective to untreated mice.

Incorporating sustainability into a chemical company’s modus operandi

The intent of this dissertation is to review relevant existing management systems and chemical industry initiatives to identify synergies, overlaps and gaps with Sustainability best practices, to map the barriers to the incorporation of Sustainability and formulate recommendations to facilitate execution of Sustainability practices within existing management systems. A chemical industry Sustainability survey was conducted through APEQ, the Portuguese association of chemical companies, which constitutes the first baseline on the topic for this national industry association. The commonly used international standards and the Responsible Care® (RC) initiative were cross-referenced against the United Nations Global Compact Assessment Tool. Guidance on how to incorporate Sustainability into a company‘s modus operandi was collapsed into Sustainability Playbooks. The survey revealed that 73% of the APEQ member companies that participated in the survey have a Sustainability Plan. Both large and small/medium APEQ member companies see the market not willing to pay extra for ‗greener‘ products as one of the main barriers. APEQ large enterprise see complexity of implementation and low return on investment as the other most significant barriers while small/medium enterprise respond that the difficulty to predict customer sustainability needs is the other most significant barrier. Amongst many other insights from this survey reported to APEQ, Life Cycle Assessment practices were found to have a low level of implementation and were also considered of low importance, thus identifying a very important opportunity in Sustainability practices to be addressed by APEQ. Two hundred and seventy three assessment points from United Nations Global Compact Assessment Tool plus five additional items were cross-referenced with international standard requirements. With the authorization of the intellectual property owners, the United Nations Global Compact Assessment Tool was modified to introduce actionable recommendations for each gap identified by management standard. This tool was automated to output specific recommendations for 63 possible combinations after simply selecting from a list of commonly used management standards and the RC initiative. Finally this modified tool was introduced into Playbooks for Incorporation of Sustainability at two levels: a ―Get Started Playbook‖ for beginners or small/medium size enterprise and an ―Advanced Playbook‖ as a second advancement stage or for large enterprise.

Pontes pedonais em madeira lamelada colada:caracterização, dimensionamento, patologia e conservação

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

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.