Research progress on reuse of fluid catalytic cracking waste from oil refinery in cement-based materials

Present paper present the main results obtained in the scope of an ongoing project which aims to contribute to the valorization of a waste generated by the Portuguese oil company in construction materials. This waste is an aluminosilicate with high pozzolanic reactivity. Several different technological applications had already been tested with success both in terms of properties and compliance with the corresponding standards specifications. Namely, this project results already demonstrated that this waste can be used in traditional concrete, self-compacted concrete, mortars (renders, masonry mortar, concrete repair mortars), cement main constituent as well as alkali activated binders.

One-step in situ synthesis of polyamide microcapsules with inorganic payload and their transformation into responsive thermoplastic composite materials

Well-dispersed loads of finely powdered metals, metal oxides, several carbon allotropes or nanoclays are incorporated into highly porous polyamide 6 microcapsules in controllable amounts via an original one-step in situ fabrication technique. It is based on activated anionic polymerization (AAP) of ε-caprolactam in a hydrocarbon solvent performed in the presence of the respective micro- or nanosized loads. The forming microcapsules with typical diameters of 25-50 µm entrap up to 40 wt% of load. Their melt processing produces hybrid thermoplastic composites. Mechanical, electric conductivity and magnetic response measurements show that transforming of in situ loaded microcapsules into composites by melt processing (MP) is a facile and rapid method to fabricate materials with high mechanical resistance and electro-magnetic characteristics sufficient for many industrial applications. This novel concept requires low polymerization temperatures, no functionalization or compatibilization of the loads and it is easy to scale up at industrial production levels.

Cost-efficient one-part alkali-activated mortars with low global warming potential for floor heating systems applications

Increasing building energy efficiency is one the most cost-effective ways to reduce emissions. The use of thermal insulation materials mitigates heat loss in buildings, therefore minimising heat energy needs. In recent years, several papers were published on the subject of foam alkali-activated cements with enhanced thermal conductivity. However, on those papers cost analysis was strangely avoided. This paper presents experimental results on one-part alkali-activated cements. It also includes global warming potential assessment and cost analysis. Foam one-part alkali-activated cements cost simulations considering two carbon dioxide social costs scenarios are also included. The results show that one-part alkali-activated cements mixtures based on 26%OPC + 58.3%FA + 8%CS + 7.7%CH and 3.5% hydrogen peroxide constitute a promising cost-efficient (67 euro/m3), thermal insulation solution for floor heating systems. This mixture presents a low global warming potential of 443 KgCO2eq/m3. The results confirm that in both carbon dioxide social cost scenarios the mixture 26 OPC + 58.3 FA + 8 CS + 7.7 CH with 3.5% hydrogen peroxide foaming agent is still the most cost efficient.

Carbon materials as new generation of new electron shuttles for the anaerobic degradation of environmental xenobiotics

Tese de Doutoramento em Engenharia Química e Biológica

Effect of different carbon materials as electron shuttles in the anaerobic biotransformation of nitroanilines

Aromatic amines resulted from azo dyes biotransformation under anaerobic conditions are generally recalcitrant to further anaerobic degradation. The catalytic effect of carbon materials (CM) on the reduction of azo dyes is known and has been confirmed in this work by increasing 3-fold the biological reduction rate of Mordant Yellow 1 (MY1). The resulting m-nitroaniline (m-NoA) was further degraded to m-phenylenediamine (m-Phe) only in the presence of CM. The use of CM to degraded anaerobically aromatic amines resulted from azo dye reduction was never reported before. In the sequence, we studied the effect of different CM on the bioreduction of o-, m- and p-NoA. Three microporous activated carbons with different surface chemistry, original (AC0), chemical oxidized with HNO3 (ACHNO3) and thermal treated (ACH2), and three mesoporous carbons, xerogels (CXA and CXB) and nanotubes (CNT) were assessed. In the absence of CM, NoA were only partially reduced to the corresponding Phe, whereas in the presence of CM, more than 90% was converted to the corresponding Phe. ACH2 and AC0 were the best electron shuttles, increasing the rates up to 8-fold. In 24h, the biological treatment of NoA and MY1 with AC0, decreased up to 88% the toxicity towards a methanogenic consortium, as compared to the non-treated solutions. This article is protected by copyright. All rights reserved

Estimation of surface area and pore volume of activated carbons by methylene blue and iodine numbers

Data of methylene blue number and iodine number of activated carbons samples were calibrated against the respective surface area, micropore volume and total pore volume using multiple regression. The models obtained from the calibrations were used in predicting these physical properties of a test group of activated carbon samples produced from several raw materials. In all cases, the predicted values were in good agreement with the expected values. The method allows extracting more information from the methylene blue and iodine adsorption studies than normally obtained with this type of material.

A dynamic knowledge-based decision support system to handle solids separation problems in activated sludge systems: development and validation

El sistema de fangs activats és el tractament biològic més àmpliament utilitzat arreu del món per la depuració d'aigües residuals. El seu funcionament depèn de la correcta operació tant del reactor biològic com del decantador secundari. Quan la fase de sedimentació no es realitza correctament, la biomassa no decantada s'escapa amb l'efluent causant un impacte sobre el medi receptor. Els problemes de separació de sòlids, són actualment una de les principals causes d'ineficiència en l'operació dels sistemes de fangs activats arreu del món. Inclouen: bulking filamentós, bulking viscós, escumes biològiques, creixement dispers, flòcul pin-point i desnitrificació incontrolada. L'origen dels problemes de separació generalment es troba en un desequilibri entre les principals comunitats de microorganismes implicades en la sedimentació de la biomassa: els bacteris formadors de flòcul i els bacteris filamentosos. Degut a aquest origen microbiològic, la seva identificació i control no és una tasca fàcil pels caps de planta. Els Sistemes de Suport a la Presa de Decisions basats en el coneixement (KBDSS) són un grup d'eines informàtiques caracteritzades per la seva capacitat de representar coneixement heurístic i tractar grans quantitats de dades. L'objectiu de la present tesi és el desenvolupament i validació d'un KBDSS específicament dissenyat per donar suport als caps de planta en el control dels problemes de separació de sòlids d'orígen microbiològic en els sistemes de fangs activats. Per aconseguir aquest objectiu principal, el KBDSS ha de presentar les següents característiques: (1) la implementació del sistema ha de ser viable i realista per garantir el seu correcte funcionament; (2) el raonament del sistema ha de ser dinàmic i evolutiu per adaptar-se a les necessitats del domini al qual es vol aplicar i (3) el raonament del sistema ha de ser intel·ligent. En primer lloc, a fi de garantir la viabilitat del sistema, s'ha realitzat un estudi a petita escala (Catalunya) que ha permès determinar tant les variables més utilitzades per a la diagnosi i monitorització dels problemes i els mètodes de control més viables, com la detecció de les principals limitacions que el sistema hauria de resoldre. Els resultats d'anteriors aplicacions han demostrat que la principal limitació en el desenvolupament de KBDSSs és l'estructura de la base de coneixement (KB), on es representa tot el coneixement adquirit sobre el domini, juntament amb els processos de raonament a seguir. En el nostre cas, tenint en compte la dinàmica del domini, aquestes limitacions es podrien veure incrementades si aquest disseny no fos òptim. En aquest sentit, s'ha proposat el Domino Model com a eina per dissenyar conceptualment el sistema. Finalment, segons el darrer objectiu referent al seguiment d'un raonament intel·ligent, l'ús d'un Sistema Expert (basat en coneixement expert) i l'ús d'un Sistema de Raonament Basat en Casos (basat en l'experiència) han estat integrats com els principals sistemes intel·ligents encarregats de dur a terme el raonament del KBDSS. Als capítols 5 i 6 respectivament, es presenten el desenvolupament del Sistema Expert dinàmic (ES) i del Sistema de Raonament Basat en Casos temporal, anomenat Sistema de Raonament Basat en Episodis (EBRS). A continuació, al capítol 7, es presenten detalls de la implementació del sistema global (KBDSS) en l'entorn G2. Seguidament, al capítol 8, es mostren els resultats obtinguts durant els 11 mesos de validació del sistema, on aspectes com la precisió, capacitat i utilitat del sistema han estat validats tant experimentalment (prèviament a la implementació) com a partir de la seva implementació real a l'EDAR de Girona. Finalment, al capítol 9 s'enumeren les principals conclusions derivades de la present tesi.

Development, implementation and evaluation of an activated sludge supervisory system for the Granollers WWTP

La present tesi pretén recollir l'experiència viscuda en desenvolupar un sistema supervisor intel·ligent per a la millora de la gestió de plantes depuradores d'aigües residuals., implementar-lo en planta real (EDAR Granollers) i avaluar-ne el funcionament dia a dia amb situacions típiques de la planta. Aquest sistema supervisor combina i integra eines de control clàssic de les plantes depuradores (controlador automàtic del nivell d'oxigen dissolt al reactor biològic, ús de models descriptius del procés...) amb l'aplicació d'eines del camp de la intel·ligència artificial (sistemes basats en el coneixement, concretament sistemes experts i sistemes basats en casos, i xarxes neuronals). Aquest document s'estructura en 9 capítols diferents. Hi ha una primera part introductòria on es fa una revisió de l'estat actual del control de les EDARs i s'explica el perquè de la complexitat de la gestió d'aquests processos (capítol 1). Aquest capítol introductori juntament amb el capítol 2, on es pretén explicar els antecedents d'aquesta tesi, serveixen per establir els objectius d'aquest treball (capítol 3). A continuació, el capítol 4 descriu les peculiaritats i especificitats de la planta que s'ha escollit per implementar el sistema supervisor. Els capítols 5 i 6 del present document exposen el treball fet per a desenvolupar el sistema basat en regles o sistema expert (capítol 6) i el sistema basat en casos (capítol 7). El capítol 8 descriu la integració d'aquestes dues eines de raonament en una arquitectura multi nivell distribuïda. Finalment, hi ha una darrer capítol que correspon a la avaluació (verificació i validació), en primer lloc, de cadascuna de les eines per separat i, posteriorment, del sistema global en front de situacions reals que es donin a la depuradora

Peroxydisulfate in MCM-48 silicas: powerful and clean materials for the removal of toxic gases

Sodium persulfate introduced into ordered MCM-48 silicas is described. The resulting materials are compared with existing activated carbon-based systems and MCM-48 containing transition metals such as Cu(II) and Cr(VI) for the decomposition of hydrogen cyanide and cyanogen. MCM-48 materials containing sodium persulfate alone improve on the protection offered by benchmark activated carbon systems and MCM-48 materials containing Cu(II) and Cr(VI), without the health risks associated with these metal ions.

Statins and selective inhibition of Rho kinase protect small conductance calcium-activated potassium channel function (KCa2.3) in cerebral arteries

Background: In rat middle cerebral and mesenteric arteries the KCa2.3 component of endothelium-dependent hyperpolarization (EDH) is lost following stimulation of thromboxane (TP) receptors, an effect that may contribute to the endothelial dysfunction associated with cardiovascular disease. In cerebral arteries, KCa2.3 loss is associated with NO synthase inhibition, but is restored if TP receptors are blocked. The Rho/Rho kinase pathway is central for TP signalling and statins indirectly inhibit this pathway. The possibility that Rho kinase inhibition and statins sustain KCa2.3 hyperpolarization was investigated in rat middle cerebral arteries (MCA). Methods: MCAs were mounted in a wire myograph. The PAR2 agonist, SLIGRL was used to stimulate EDH responses, assessed by simultaneous measurement of smooth muscle membrane potential and tension. TP expression was assessed with rt-PCR and immunofluorescence. Results: Immunofluorescence detected TP in the endothelial cell layer of MCA. Vasoconstriction to the TP agonist, U46619 was reduced by Rho kinase inhibition. TP receptor stimulation lead to loss of KCa2.3 mediated hyperpolarization, an effect that was reversed by Rho kinase inhibitors or simvastatin. KCa2.3 activity was lost in L-NAME-treated arteries, but was restored by Rho kinase inhibition or statin treatment. The restorative effect of simvastatin was blocked after incubation with geranylgeranyl-pyrophosphate to circumvent loss of isoprenylation. Conclusions: Rho/Rho kinase signalling following TP stimulation and L-NAME regulates endothelial cell KCa2.3 function. The ability of statins to prevent isoprenylation and perhaps inhibit of Rho restores/protects the input of KCa2.3 to EDH in the MCA, and represents a beneficial pleiotropic effect of statin treatment.

Bond Strength of Dental Adhesive Systems Irradiated with Ionizing Radiation

Purpose: The aim of the present paper was to determine the effect of different types of ionizing radiation on the bond strength of three different dentin adhesive systems. Materials and Methods: One hundred twenty specimens of 60 human teeth (protocol number: 032/2007) sectioned mesiodistally were divided into 3 groups according to the adhesives systems used: SB (Adper Single Bond Plus), CB (Clearfil SE Bond) and AP (Adper Prompt Self-Etch). The adhesives were applied on dentin and photo-activated using LED (Lec 1000, MMoptics, 1000 mW/cm(2)). Customized elastomer molds (0.5 mm thickness) with three orifices of 1.2 mm diameter were placed onto the bonding areas and filled with composite resin (Filtek Z-250), which was photo-activated for 20 s. Each group was subdivided into 4 Subgroups for application of the different types of ionizing radiation: ultraviolet radiation (UV), diagnostic x-ray radiation (DX), therapeutic x-ray radiation (TX) and without irradiation (control group, CG). Microshear tests were carried out (Instron, model 4411), and afterwards the modes of failure were evaluated by optical and scanning electron microscope and classified using 5 scores: adhesive failure, mixed failures with 3 significance levels, and cohesive failure. The results of the shear bond strength test were submitted to ANOVA with Tukey`s test and Dunnett`s test, and the data from the failure pattern evaluation were analyzed with the Mann Whitney test (p = 0.05). Results: No change in bond strength of CB and AP was observed after application of the different radiation types, only SB showed increase in bond strength after UV (p = 0.0267) irradiation. The UV also changed the failure patterns of SB (p = 0.0001). Conclusion: The radio-induced changes did not cause degradation of the restorations, which means that they can be exposed to these types of ionizing radiation without weakening the bond strength.

Comparison of SERS performances of Co and Ni ultrathin films over silver to electrochemically activated Co and Ni electrodes

In this work, the surface-enhanced Raman scattering (SERS) spectra of pyridine (py) on thin films of Co and Ni electrodeposited on an Ag electrode activated by oxidation-reduction cycles (ORC) are presented. The SERS spectra from the thin films were compared to those of py on activated bare transition metal electrodes. It was verified that the SERS spectra of py on 3 monolayers (ML)-thick films of Ni and Co presented only bands assignable to the py adsorbed on transition metal surfaces. It was also observed that even for 50 ML-thick transition metal films, the py SERS intensity was ca. 40% of the intensity from the 3 ML-thick films. The relative intensities of the SERS bands depended on the thickness of the films, and for films thicker than 7 ML for Co and 9 ML for Ni they were very similar to those of the bare transition metal electrodes. The transition metal thin films over Ag activated electrodes presented SERS intensities 3 orders of magnitude higher than the ones from bare transition metal electrodes. These films are more suitable to study the adsorption of low Raman cross-section molecules than are ORC-activated transition metal electrodes.

The Effect of Residence Time on the Tensile Properties of Superelastic and Thermal Activated Ni-Ti Orthodontic Wires

Since the 1980s, different devices based on superelastic alloys have been developed to fulfill orthodontic applications. Particularly in the last decades several researches have been carried out to evaluate the mechanical behavior of Ni-Ti alloys, including their tensile, torsion and fatigue properties. However, studies regarding the dependence of elastic properties on residence time of Ni-Ti wires in the oral cavity are scarce. Such approach is essential since metallic alloys are submitted to mechanical stresses during orthodontic treatment as well as pH and temperature fluctuations. The goal of the present contribution is to provide elastic stress-strain results to guide the orthodontic choice between martensitic thermal activated and austenitic superelastic Ni-Ti alloys. From the point of view of an orthodontist, the selection of appropriate materials and the correct maintenance of the orthodontic apparatus are essential needs during clinical treatment. The present work evaluated the elastic behavior of Ni-Ti alloy wires with diameters varying from 0.014 to 0.020 inches, submitted to hysteresis tensile tests with 8% strain. Tensile tests were performed after periods of use of 1, 2 and 3 months in the oral cavity of patients submitted to orthodontic treatment. The results from the hysteresis tests allowed to exam the strain range covered by isostress lines upon loading and unloading, as well as the residual strain after unloading for both superelastic and thermal activated Ni-Ti wires. Superelastic Ni-Ti wires exhibited higher load isostress values compared to thermal activated wires. It was found that such differences in the load isostress values can increase with increasing residence time.