NANOPARTICLE REINFORCEMENT OF FERROUS ALLOYS: WETTABILITY AND MECHANICAL PROPERTIES

El refuerzo de matrices férricascon una fina dispersión de partículas nanométricas permite mejorar la dureza, resistencia mecánica e incluso permitiría mejorar la tenacidad del material al afinar el tamaño de grano.

Valoración del estado ecológico de la costa rocosa de Urdaibai (Bizkaia), mediante el estudio de fitobentos intermareal

Dentro de las medidas protectoras sobre la Reserva de la Biosfera de Urdaibai se encuentra el EDAR (Estación Depuradora de Aguas Residuales) de Lamiaran (Bermeo), que entrará en funcionamiento próximamente (otoño 2014). Para evaluar su impacto sobre el medio costero, el presente estudio realiza una primera valoración del estado ecológico de la costa abierta de la reserva mediante diversos parámetros del fitobentos intermareal. Se estableció una red de muestreo compuesta por dos localidades impactadas y cuatro control. En cada localidad se eligieron aleatoriamente dos estaciones y se muestrearon dos niveles en la zona intermareal inferior. Las localidades impactadas por aguas residuales reflejaban valores bajos de riqueza específica, cobertura, diversidad y cobertura de perennes junto a una mayor abundancia de especies estacionales de morfología simple. Sin embargo los análisis estadísticos no detectaron diferencias significativas entre ambos grupos de localidades (impactadas vs control) detectando únicamente diferencias significativas a nivel de estación, debido en gran medida al efecto de la dispersión de las unidades muestrales para los parámetros estudiados.

Avances en el modelado de la combustión de biomasa en spouted bed cónico

290 p.

Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

Charge and spin transport in graphene devices

170 p.

Umearen pisu sobera: esku-hartzea lehen mailako arretako pediatrian

200 p.

Effects of global change on the functioning of Mediterranean Rivers

138 p.

Measurement of polycyclic aromatic hydrocarbons in ambient air by fluorescence spectroscopic techniques

250 p. + anexos

Evaluación de un programa de fisioterapia respiratoria en pacientes sometidos a resección pulmonar

169 p.+ anexos

Efecto antitumoral de la terfenadina, antagonista del receptor H1 de la histamina, mediado por el complejo I mitocondrial

180 p.

Amniozentesiaren arriskuak eta teknika ez inbasiboak kromosomopatien detekziorako

SARRERA: Kromosomopatiei inguru gehiago ezagutzen doan heinean, hauek detektatzeko erabiltzen diren teknikak garatuz doaz. Detekzio teknikak bi taldeetan sailkatzen dira: teknika inbasiboak (amniozentesia, kordozentesia eta bellositate korionikoen azterketa) eta teknika ez inbasiboak (zelula edota azido nukleiko fetalen azterketa amaren odolean). HELBURUAK: Errebisio bibliografiko honen helburua amniozentesia eta froga ez inbasiboen deskribapena egitea da, baita hauen abantailak eta desabantailak deskribatzea. METODOLOGIA: Behin errebisio honen gaia zehaztuta egon zenean, bilaketa bibliografikoa egin zen Cochrane, PubMed eta beste datu baseetan. Ondoren, sartzeko eta baztertzeko irizpideak kontuan hartuta, artikuluen hautaketa egin zen. EMAITZAK: Amniozentesiaren teknikak hainbat arrisku dakar (abortua, amniorrea, lesioak fetuan, etab.) eta hauen portzentaiak altuak ez diren arren, haurdunaldian izan ahal dituzten ondorioak larriak dira. Bestalde, froga ez inbasiboen erabilpenen artean behin betiko diagnostikoa ezin da sartu hauen faltsu negatiboen tasa dela eta. Azkenik, erizaintzak rol garrantzitsua jokatzen du arlo honetan eta osasun langileek ezaguera eguneratuak izan beharko dituzte pazienteei informazio egokia emateko. ONDORIOAK: amniozentesiaren arrisku zerrenda luzea den arren, momentuz behin betiko diagnostikoa egiteko balio duen froga bakarra da (froga inbasiboekin batera) izan ere, froga ez inbasiboak momentuz ez daude prest behin betiko diagnostikoa egiteko.

Catéteres venosos centrales de larga duración y sus complicaciones. Reservorio venoso subcutáneo versus catéter central de inserción periférica : revisión bibliográfica.

Introducción: Los catéteres venosos centrales (CVC) de larga duración representan una alternativa para muchos pacientes receptores de tratamientos intravenosos prolongados y agresivos. Dentro de estos, es frecuente el uso de los reservorios venosos subcutáneos (RVS) y de los catéteres centrales de inserción periférica (PICC). En ambos, a pesar de sus numerosas ventajas, pueden surgir complicaciones que comprometan el funcionamiento del dispositivo y provocar la necesidad de retirarlo. Estas, además, pueden poner en peligro el bienestar e incluso la vida del paciente. Objetivos: Analizar las complicaciones asociadas a la implantación y uso de RVS y PICC. Metodología: Se realizó una búsqueda bibliográfica en las bases de datos: Scopus, ScienceDirect, Dialnet plus, ProQuest, OvidSP, SciELO, Cuiden y Elsevier. Resultados: Se seleccionaron seis estudios realizados sobre pacientes portadores de RVS y cinco sobre los PICC. En ellos se analizaron las complicaciones surgidas y los motivos de retirada de los dispositivos por complicaciones asociadas. Conclusiones: Los PICC presentan una morbilidad y una tasa de retirada por complicaciones mayor que los RVS. Las infecciones, obstrucciones y trombosis son las complicaciones con mayor prevalencia en ambos dispositivos junto con las extracciones accidentales en el caso de los PICC. Además, representan los motivos más habituales de retirada del CVC por alguna complicación. Las complicaciones pueden estar influenciadas por distintos factores, entre otros, los cuidados y mantenimiento que se realicen del dispositivo. Idioma: Español.

Zein da NIDCAP programaren eragina jaioberri goiztiarren neurogarapenean epe luzera? Atalez atal aztertua

Jaioberri goiztiarra, haurdunaldiko 37. astea baino lehen jaiotzen den haur heldugabea da. Jaioberri hauen biziraupen tasa azken hamarkadetako aurrerapen medikoei esker (inkubagailuak, farmakoak…) igo da baina bere heldugabetasunaren eraginez jaioberri hauen %23-60ak ezintasunak eta jarrera zein hezkuntza asaldurak pairatzen dituzte. 1970. urtean Heidelise Alsek NIDCAPa, (“Newborn Individualized Developmental Care and Assessment Program”) asmatu zuen, jaioberri bakoitzaren garapenean laguntzeko helburuarekin, beharrezko arreta berezia eta bakoitzarentzako zainketa planean oinarrituz. Helburua: NIDCAP metodoarekin kontaktuan egon ziren jaioberri goiztiarren eragina, epe luzera, nerbio sistemaren garapeneko atal motorea, atal kognitiboa eta neurosentsoriala aztertzean datza. Metodologia: Azterketa bibliografiko hau egiteko, beharrezko informazio bilaketa orokorra egin da helburua finkatzeko. Ondoren, Pubmed datu basean beharrezko irizpideak zehaztuta ikerlanak kritikoki irakurri, ebidentzian oinarrituz 11 hautatu eta landu ostean (guztira 946 jaioberri goiztiar aztertuz) garatu da. Emaitzak eta azterketa: Ikerlanen arabera NIDCAP metodoaren eraginetan egon diren 4, 9 eta 12 hilabeteko haurrek atal motorea garatuagoa duten datuak daude baina 18 eta 24 hilabeteko umeetan aldiz, ez dira ebidentziazko daturik aurkitu NIDCAParen efektu onuragarriei buruz, bere eraginaren efektua luzarora desagertuz. NIDCAP ereduaren erabilerak kognizio atalaren garapenean onurak ekartzen dituen datuak daude 9 hilabeteko haurretan (helburuak zuzentzeko gaitasunean eta arreta mantentzeko gaitasunean) eta 8 urteko haurretan ere (bat-bateko prozesamenduan) baina 12 eta 24 hilabeteko adinarekin, aldiz, ez dira eraginik hauteman. Garapeneko atal neurosentsorialean, ebidentziazko artikulu bakar baten arabera NIDCAParen erabilerak 8 urteko umeen ikusmen eta ahalmen espazialean laguntzen du. Ondorioa: NIDCAP metodoak jaioberri goiztiarretan daukan eragin gomendagarria dauka atal kognitiboan eta ikusmenean, baina oso eragin urria dauka metodo eraginkorra izateko.

Contributions to learning Bayesian network models from weakly supervised data: Application to Assisted Reproductive Technologies and Software Defect Classification

162 p.

Aireztapenen maiztasunaren neurketa bihotz biriketako berpiztean kapnografia erabiliz.

[EN]Hyperventilation, which is common both in-hospital and out-of-hospital cardiac arrest, decreases coronary and cerebral perfusion contributing to poorer survival rates in both animals and humans. Current resucitation guidelines recommend continuous monitoring of exhaled carbon dioxide (CO2) during cardiopulmonary resucitation (CPR) and emphasize good quality of CPR, including ventilations at 8-10 min1. Most of commercial monitors/de- brilators incorporate methods to compute the respiratory rate based on capnography since it shows uctuations caused by ventilations. Chest compressions may induce artifacts in this signal making the calculation of the respiratory rate di cult. Nevertheless, the accuracy of these methods during CPR has not been documented yet. The aim of this project is to analyze whether the capnogram is reliable to compute ventilation rate during CPR. A total of 91 episodes, 63 out-of-hospital cardiac arrest episodes ( rst database) and 28 in-hospital cardiac arrest episodes (second database) were used to develop an algorithm to detect ventilations in the capnogram, and the nal aim is to provide an accurate ventilation rate for feedback purposes during CPR. Two graphic user interfaces were developed to make the analysis easier and another two were adapted to carry out this project. The use of this interfaces facilitates the managment of the databases and the calculation of the algorithm accuracy. In the rst database, as gold standard every ventilation was marked by visual inspection of both the impedance, which shows uctuations with every ventilation, and the capnography signal. In the second database, volume of the respiratory ow signal was used as gold standard to mark ventilation instants since it is not a ected by chest compressions. The capnogram was preprocessed to remove high frequency noise, and the rst di erence was computed to de ne the onset of inspiration and expiration. Then, morphological features were extracted and a decission algorithm built based on the extracted features to detect ventilation instants. Finally, ventilation rate was calculated using the detected instants of ventilation. According to the results obtained in this project, the capnogram can be reliably used to give feedback ventilation rate, and therefore, on hyperventilation in a resucitation scenario.