19 research outputs found
Development of electrochemical devices for hydrocarbon sensing purposes in car exhaust gases
En la presente tesis doctoral se han desarrollado dispositivos electroquímicos de estado sólido para la detección selectiva de hidrocarburos en los gases de escape de coches. Diversos materiales fueron empleados para ello. También se llevó a cabo la activación catalítica del electrodo de trabajo para mejorar la reacción electroquímica del analito objetivo.
El etileno fue seleccionado como el analito objetivo para cuantificar la cantidad total de hidrocarburos ya que es uno de los hidrocarburos más abundantes en un gas de escape. Pero el dispositivo no solo debe proporcionar una respuesta selectiva al etileno, sino que también debe tener una baja sensibilidad cruzada a otros compuestos también abundantes en un gas de escape como monóxido de carbono, agua, dióxido de nitrógeno, etc. El dispositivo consiste en un sensor potenciométrico de estado sólido en el que óxido de zirconio estabilizado con 8% de óxido de itrio (8YSZ) es empleado como electrolito. Dos electrodos son impresos en la superficie de cada cara.
Primero, diversos óxidos fueron empleados como electrodo de trabajo utilizando a su vez platino como electrodo de referencia a 550ºC. Muchos de los materiales fueron descartados por su falta de selectividad al etileno, su alta sensibilidad cruzada al monóxido de carbono o por su respuesta no estable. Finalmente, Fe0.7Cr1.3O3 mezclado con 8YSZ fue seleccionado como el material más prometedor dada su buena selectividad al etileno con baja sensibilidad cruzada al monóxido de carbono. Esta configuración fue expuesta a agua como a fenantreno y metilnaftaleno. Esto produjo un aumento de la sensibilidad cruzada del dispositivo al monóxido de carbono, motivo por el que el sensor no sea adecuado para los objetivos de esta tesis. La estrategia adoptada consistió en actuar sobre el electrodo de referencia. El Platino, empleado habitualmente en la bibliografía como electrodo de referencia, fue cambiado por un conductor mixto iónico-electrónico activo al oxigeno: La0.8Sr0.2MnO3 mezclado con 8YSZ (LSM/8YSZ). Desgraciadamente, esto provocó un aumento de la sensibilidad cruzada al monóxido de carbono.
Diversas nanopartículas fueron añadidas en el electrodo de trabajo para mejorar la actividad catalítica y aumentar la reacción electroquímica al etileno. Níquel, titanio y aluminio (especialmente la combinación de los dos últimos con níquel) dieron la mejor respuesta: el sensor era selectivo al etileno con baja sensibilidad cruzada al monóxido de carbono, agua y fenantreno.
El efecto del espesor del electrolito en la respuesta del sensor también fue evaluado en un rango de 0.1 a 1.2 mm. Aunque no había una gran diferencia en la respuesta, la sensibilidad cruzada al monóxido de carbono era menor en el caso del dispositivo más fino. Otras alternativas al 8YSZ como electrolito también fueron evaluadas para trabajar a menores temperaturas (400 a 550ºC): oxido de cerio dopado con gadolinio (CGO) y óxido de zirconio estabilizado con un 10% de óxido de escandio (ScSZ). El dispositivo basado en ScSZ mostró un buen comportamiento a etileno a bajas temperaturas y en condiciones secas pero la adición de agua provocaba un aumento de la sensibilidad cruzada al monóxido de carbono. Una vez infiltrado el electrodo de trabajo con níquel, ambos dispositivos mostraron un buen comportamiento a bajas temperaturas en condiciones secas para concentraciones de etileno inferiores a 100 ppm, aunque la mejor respuesta fue obtenida a 550ºC. Ambos dispositivos mostraron una respuesta selectiva al etileno con baja sensibilidad cruzada al monóxido de carbono, agua y fenantreno.
Se estudió también el efecto de mezclar el electrodo de trabajo con un conductor iónico (8YSZ). Se mezcló La0.87Sr0.13CrO3 (LSC) con 8YSZ sin observarse un cambio en la respuesta comparado con el electrodo solo. Además la mejor configuración Fe0.7Cr1.3O3/8YSZ//8YSZ//LSM/8YSZ (infiltrado con níquel) fue expuesto a dioxide de nitrThe present thesis is focused on the development of solid-state electrochemical devices for the selective detection of hydrocarbons in car exhaust gases. For this purpose, several materials were tested as electrodes and electrolytes. Catalytic activation of the working electrode has also been taken into account to boost the electrochemical reaction of the target analyte.
Ethylene is one of the most abundant hydrocarbons in an exhaust gas and was selected as the target analyte to quantify the total amount of hydrocarbons. Not only the device has to be selective to ethylene but it must also have a low cross-sensitivity toward other pollutants abundant in an exhaust gas such as carbon monoxide, water, other hydrocarbons, nitrogen dioxide, etc. Thus, a solid-state potentiometric sensor was selected based on 8% Ytria-stabilized Zirconia (8YSZ) as electrolyte. Two electrodes were screen-printed on top of each face.
First, several metal oxides were tested as working electrode with platinum (Pt) as reference electrode at 550ºC. Most of the materials were discarded because of their lack of selectivity to ethylene, high cross-sensitivity toward carbon monoxide or problems regarding stability. Fe0.7Cr1.3O3 mixed with 8YSZ was finally selected as the most promising material because of its selective response to ethylene with relatively low cross-sensitivity toward carbon monoxide.
This sensor configuration was then exposed to water and phenanthrene and methylnaphthalene. This led to an increase of the cross-sensitivity of the device toward carbon monoxide making the device not suitable for the purposes of the present thesis. The approach to improve the sensor performance was to modify the reference electrode. Platinum, usually employed in literature as reference electrode, was exchanged for a mixed ionic-electronic conductor active to oxygen: La0.8Sr0.2MnO3 mixed with 8YSZ (LSM/8YSZ). Unfortunately, this increases the device activity toward carbon monoxide increasing its cross-sensitivity.
Several nanoparticles were added onto the working electrode to improve the catalytic activity and boost the electrochemical reaction of ethylene. Nickel, titanium and aluminum (the last two elements combined with nickel) provided the best performance: selectivity to ethylene with low cross-sensitivity toward carbon monoxide, water and phenanthrene.
The effect of the electrolyte thickness was also checked in the range from 0.1 to 1.2 mm. Although there was not a huge difference between them, the cross-sensitivity toward carbon monoxide was slightly lower for the thinnest sensor. Other alternatives to 8YSZ electrolyte were tested at lower working temperatures (400 to 550ºC) with the same electrodes materials: gadolinium-doped cerium oxide (CGO) and 10% scandia-stabilized Zirconia (ScSZ). ScsZ-based device showed a good performance in dry conditions but the addition of water decreased its suitability. Once improved the catalytic activity of the working electrode, both devices showed a good performance at lower temperature in dry conditions for ethylene concentration above 100 ppm but the best response was achieved at 550ºC. Both devices were selective to ethylene with low cross-sensitivity toward carbon monoxide, water and phenanthrene.
The effect of mixing the working electrode with an ionic conductor (8YSZ) was also tested by mixing La0.87Sr0.13CrO3 (LSC) with 8YSZ and no change in response was observed when compared to the bare electrode. Finally, the best sensor configuration Fe0.7Cr1.3O3/8YSZ//8YSZ//LSM/8YSZ (after infiltration with nickel) was exposed to nitrogen dioxide to check the cross-sensitivity. The response was still selective to ethylene even with the addition of nitrogen dioxide plus water.En la present tesi doctoral s'han desenvolupat dispositius electroquímics d'estat sòlid per a la detecció selectiva d' hidrocarburs als gasos d'escapament dels automòbils. Diversos materials van ser empleats per a tal fi. També es va dur a terme l'activació catalítica de l'elèctrode de treball per a millorar la reacció electroquímica al anàlit objectiu.
L' etilè va ser seleccionat com anàlit objectiu per a quantificar la quantitat total d' hidrocarburs, ja que és un dels hidrocarburs més abundants en un gas d'escapament. Però el dispositiu no ha de ser tan sols selectiu a l'etilè, sinó que també deu proporcionar una baixa sensibilitat creuada a altres elements força abundants en un gas d'escapament com són el monòxid de carboni, l'aigua, el diòxid de nitrogen, etc. Així, el dispositiu consisteix en un sensor potenciomètric d'estat sòlid en el que l'òxid de zirconi estabilitzat amb un 8% d'òxid d'itri (8YSZ) és empleat como a electròlit. Els elèctrodes van impresos a cadascuna de les superfícies del dispositiu.
Primer, diversos òxids es van emprar com a elèctrode de treball fent servir platí com elèctrode de referència a 550ºC. Molts dels materials van ser descartats per motiu de la seva manca de selectivitat al etilè, la seva alta sensibilitat creuada al monòxid de carboni o perquè la resposta no era estable. Finalment, el Fe0.7Cr1.3O3 mesclat amb 8YSZ va ser seleccionat com el material més prometedor atès a la selectivitat a l'etilè i la baixa sensibilitat creuada al monòxid de carboni. Aquesta configuració és doncs exposada tant a l'aigua com al fenantrè i al metilnaftalè. Això va produir un increment de la sensibilitat creuada al monòxid de carboni, fent que el dispositiu no resulti idoni per als objectius de la present tesi. Es va adoptar com a estratègia modificar l'elèctrode de referència. Platí, empleat sovintment com a elèctrode de referència a la bibliografia, va ser canviat per un conductor mixt iònic-electrònic actiu a l'oxigen: La0.8Sr0.2MnO3 mesclat amb 8YSZ (LSM/8YSZ). Malauradament, això va provocar l'augment de la sensibilitat creuada al monòxid de carboni.
Diverses nanopartícules van ser afegides al elèctrode de treball per tal de millorar la seva activitat catalítica i així augmentar la reacció electroquímica de l'etilè. Níquel, titani i alumini (especialment la combinació dels dos darrers amb níquel) van donar la millor resposta: el sensor era selectiu a l¿etilè amb una baixa sensibilitat creuada al monòxid de carboni, l'aigua i al fenantrè.
L'efecte del espessor del electròlit a la resposta del sensor també va ser avaluada en un rang de 0.1 a 1.2 mm. Malgrat que no hi ha una gran diferència en la resposta, la sensibilitat creuada al monòxid de carboni és menor en el cas del dispositiu més prim. Altres alternatives al 8YSZ com a electròlit van ser també avaluades per tal de treballar a temperatures menors (400 a 550ºC): òxid de ceri dopat amb gadolini (CGO) i òxid de zirconi estabilitzat amb un 10% d'òxid d'escandi (ScSZ).
El dispositiu basat en ScSZ va mostrar un bon comportament a l'etilè a baixes temperatures en condiciones seques, però la adició d'aigua provocava un augment de la sensibilitat creuada al monòxid de carboni. Una vegada que l'elèctrode de treball es infiltrat amb níquel, ambdós dispositius mostraren un bon comportament a baixes temperatures en condicions seques per a concentracions d'etilè menors de 100 ppm, encara que la millor resposta fou obtinguda a 550ºC. La resposta era selectiva a l'etilè amb una baixa sensibilitat creuada al monòxid de carboni, l'aigua i el fenantrè.
Es va comprovar també l'efecte de mesclar l'elèctrode de treball amb un conductor iònic (8YSZ). Es va mesclar La0.87Sr0.13CrO3 (LSC) amb 8YSZ sense observa cap canví en la resposta comparada amb l'electrode sense 8YSZ. la millor configuració Fe0.7Cr1.3O3/8YSZ//8YSZ//LSM/8YSZ (infiltrado con níquel) fou exposadaToldra Reig, F. (2018). Development of electrochemical devices for hydrocarbon sensing purposes in car exhaust gases [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/110968TESI
Partial replacement of sodium in meat and fish products by using magnesium salts. A review
[EN] Sodium intake exceeds the nutritional recommendations in most industrialized countries becoming one concern for public health. This elimination or reduction is not simple due to its role in final food sensory, quality and safety. The aim of this work is to review the possibilities of magnesium ion, due to its healthy properties, to become a partial substitute of sodium in the production of fish and meat products, and a particular case for Spanish dry-cured ham and loin. Magnesium diffusion into different muscle based foods such as ham or loin, and its effect in the most important characteristics of the final product (microbiology, physico-chemical and sensory properties) has been analyzed. Results show that magnesium has more difficulty to penetrate inside the muscle and slightly modifies the water-holding capacity of proteins, their solubility and the enzymatic activity. Salty taste, bitterness and off-flavor are the most affected characteristics. However, these effects could be compensated by using longer post-salting periods and by employing masking agents. It is possible to reduce the sodium content in fish and meat products using magnesium as one of the ingredients, allowing to obtain new products with similar physicochemical characteristics and safety conditions.Grant AGL2007-65379-C02-01 & 02 and AGL2010-16305 from Ministry of Science and Innovation (Spain) and FEDER funds are acknowledged.Barat Baviera, JM.; Pérez-Esteve, É.; Aristoy, MC.; Toldra, F. (2013). Partial replacement of sodium in meat and fish products by using magnesium salts. A review. Plant and Soil. 368(1-2):179-188. https://doi.org/10.1007/s11104-012-1461-7S1791883681-2Albarracín W, Sánchez IC, Grau R, Barat JM (2011) Salt in food processing; usage and reduction: a review. Int J Food Sci Technol 46:1329–1336Aliño M, Grau R, Baigts D, Barat JM (2009a) Influence of sodium replacement on the salting kinetics of pork loin. J Food Eng 95:551–557Aliño M, Grau R, Toldrá F, Blesa E, Pagán MJ, Barat JM (2009b) Influence of sodium replacement on physicochemical properties of dry-cured loin. Meat Sci 83:423–430Aliño M, Grau R, Toldrá F, Barat JM (2010a) Physicochemical changes in dry-cured hams salted with potassium, calcium and magnesium chloride as a partial replacement for sodium chloride. Meat Sci 86:331–336Aliño M, Grau R, Toldrá F, Blesa E, Pagán MJ, Barat JM (2010b) Physicochemical properties and microbiology of dry-cured loins obtained by partial sodium replacement with potassium, calcium and magnesium. Meat Sci 85:580–588Aliño M, Grau R, Fuentes A, Barat JM (2010c) Characterisation of pile salting with sodium replaced mixtures of salts in dry-cured loin manufacture. J Food Eng 97:434–439Aliño M, Grau R, Fuentes A, Barat JM (2010d) Influence of low-sodium mixtures of salts on the post-salting stage of dry-cured ham process. 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Nanometric 3D Printing of Functional Materials by Atomic Layer Deposition
Atomic layer deposition (ALD) is a chemical vapour deposition (CVD) method that allows the layer-by-layer growth of functional materials by exposing a surface to different precursors in an alternative fashion. Thus, thanks to gas-solid reactions that are substrate-limited and self-terminating, precise control over thickness below the nanometer level can be achieved. While ALD was originally developed to deposit uniform coatings over large areas and on high-aspect-ratio features, in recent years the possibility to perform ALD in a selective fashion has gained much attention, in what is known as area-selective deposition (ASD). ASD is indeed a novel 3D printing approach allowing the deposition of functional materials (for example metals to oxides, nitrides or sulfides) with nanometric resolution in Z. The chapter will present an introduction to ALD, which will be followed by the description of the different approaches currently being developed for the ASD of functional materials (including initial approaches such as surface pre-patterning or activation, and newer concepts based on spatial CVD/ALD). The chapter will also include a brief overview of recent works involving the use of ALD to tune the properties of 3D printed parts
Uso combinado de VBA y Solver de Excel para la realización de ejercicios de optimización en ficheros Excel fácilmente evaluables
[EN] The present study is focused on the exploitation of the potential of VBA and
Solver tools of Excel during the execution of a computer practice lesson within
the subject of “Analysis and simulation of processes” corresponding to the
bachelor’s degree of Chemical Engineering. VBA was used to design an Excel
spreadsheet that integrates the following items: the assignment of different
series of experimental data to the students, the guided and structured execution
of three exercises, and the automated evaluation of the practice questions by
the professor. The integrated and structured design of the lesson has
advantages for both the students and the professors, since it simplifies the
execution and evaluation of the report, while it also allows an effective use of
time for the development of the students’ competencies. The use of VBA and
the working environment of Excel provides more flexibility and freedom to the
professor for designing practice lectures or tests than other available
platforms, in which the professor needs to adapt the structure of the exercise
to pre-established forms. The development of the practice lecture in a compact
Excel file facilitated the obtention of good qualifications by the students[ES] El presente trabajo se centra en explotar el potencial de las herramientas VBA y Solver de Excel para la realización de un problema de optimización en una práctica de informática de la asignatura “Análisis y simulación de procesos” del grado de Ingeniería Química. Mediante el uso de macros y VBA se ha diseñado un problema en hojas de cálculo de Excel en las cuales se integran: la asignación de diferentes series de datos experimentales a los alumnos, la realización de forma guiada y estructurada de tres ejercicios, y la evaluación automatizada de las prácticas por parte del profesor. El diseño integrado y estructurado de la práctica tiene ventajas tanto para el alumnado como para el profesorado, puesto que facilita la realización y calificación de la práctica y permite una utilización efectiva del tiempo para el desarrollo de competencias en los alumnos. El uso de VBA y del entorno de trabajo de Excel permite al profesor tener mayor flexibilidad y libertad para el diseño de prácticas o de exámenes que las que permiten otras plataformas existentes en las que el profesor tiene que adaptarse a las formas preestablecidas. El desarrollo de la práctica en un archivo compacto de Excel facilitó la obtención de buenas puntuaciones por parte de los alumnos.Santafé Moros, MA.; Gozálvez Zafrilla, JM.; Toldra Reig, F.; Catalán Martínez, D.; Martí Calatayud, MC. (2019). Uso combinado de VBA y Solver de Excel para la realización de ejercicios de optimización en ficheros Excel fácilmente evaluables. En IN-RED 2019. V Congreso de Innovación Educativa y Docencia en Red. Editorial Universitat Politècnica de València. 1178-1191. https://doi.org/10.4995/INRED2019.2019.10482OCS1178119
Desarrollo y aplicación del software DISEVAP_edu como apoyo al aprendizaje del diseño y análisis de procesos de evaporación de múltiples efectos
[EN] Evaporation is an important process operation taught in the subject
“Extension on Separation Operations” of the Master in Chemical Engineering
of the UPV. Main teaching objectives concerning to this operation are to
deepen in the design and operation of the multi-effect evaporation systems. To
cover successfully these objectives and to help in the development of
transversal competences, the ASEI team has developed the DISEVAP software
that allows you to evaluate the evaporation configurations faster and to study
the effect of the most influential factors on the process performance. In the
present article, the organizational changes within the subject that have been
used in a reflection on how to improve the use of software to develop the skills
related to reasoning are detailed. Likewise, the methodology for obtaining
information on the level of competence acquired by the student is detailed,
which has allowed comparing teaching results obtained using the program
with those of previous years. The results indicate that the methodology based
on the use of the program has achieved an improvement in teaching. However,
it is still necessary to make certain readjustments to develop its maximum
potential in coming years.[ES] La evaporación es una importante operación de proceso enseñada en la asignatura “Ampliación de Operaciones de Separación” del Máster Universitario de Ingeniería Química de la UPV. Los principales objetivos docentes de Máster concernientes a esta operación son profundizar en el diseño y funcionamiento de sistemas de múltiples efectos. Para poder cubrir estos objetivos docentes satisfactoriamente y ayudar en el desarrollo de competencias transversales, el equipo ASEI ha desarrollado el software DISEVAP, el cual permite evaluar con rapidez diferentes configuraciones de evaporación y estudiar el efecto de los factores más influyentes sobre las prestaciones del proceso. En el presente artículo se detallan los cambios organizativos dentro de la asignatura que han sido necesarios haciendo una reflexión sobre cuál es la mejor forma de aprovechar el software para desarrollar competencias relacionadas con el razonamiento. Asimismo, se detalla la metodología de obtención de información sobre el nivel de competencia adquirido por el alumno, la cual ha permitido comparar resultados docentes obtenidos utilizando el programa con los de años previos. Los resultados indican que la metodología basada en el uso del programa ha logrado una mejora de la docencia, si bien, son necesarios ciertos reajustes para desarrollar su máximo potencial en años venideros.Gozálvez Zafrilla, JM.; Santafé Moros, MA.; Catalán Martínez, D.; Toldra Reig, F.; Martí Calatayud, MC. (2019). Desarrollo y aplicación del software DISEVAP_edu como apoyo al aprendizaje del diseño y análisis de procesos de evaporación de múltiples efectos. En IN-RED 2019. V Congreso de Innovación Educativa y Docencia en Red. Editorial Universitat Politècnica de València. 1165-1177. https://doi.org/10.4995/INRED2019.2019.10481OCS1165117
Diseño de dispositivos multisensores para detección de HCs y/o CO
[EN] The present project is based on the development of solid electrolite based multisensors that permit detection of one or various compounds. Several materials are studied in order to detect HCs and/or CO. Multisensor devices will be designed with the most promising studied materiales.[ES] Se basa en el desarrollo de dispositivos que permitan alojar múltiples sensores de electrolito sólido para la detección de uno o varios compuestos. Se estudiaran diversos materiales que puedan detectar HCs y/o CO. Se diseñará un dispositivo multisensor con los materiales más prometedores de los estudiados.Toldra Reig, F. (2014). Diseño de dispositivos multisensores para detección de HCs y/o CO. http://hdl.handle.net/10251/59648Archivo delegad
Development of Potentiometric Sensors for C2H4 Detection
Gas exhaust emissions in vehicles are increasingly restrictive in EU and USA. Diesel engines are particularly affected by limitation in hydrocarbons and NOx concentrations. This work presents a screening of working electrode materials to develop a potentiometric sensor, with the most promising material to detect being C2H4 at 550 °C. The device consists of a dense 8YSZ (8 mol% Y2O3 stabilized ZrO2) disk as oxide-ion conducting electrolyte, whereas platinum is screen-printed in the back face as reference electrode. As working electrode, several materials such as Fe0.7Cr1.3O3, ZnCr2O4, Fe2NiO4, La0.8Sr0.2CrO3−δ (LSC), La0.8Sr0.2MnO3 (LSM), and NiO+5%wt Au were tested to detect C2H4. Sensor voltage was measured for several concentrations of C2H4 and CO as these are two of the major oxidizable compounds in a diesel exhaust gas. Fe0.7Cr1.3O3 was selected as the most promising material because of its response to C2H4 and CO. Not only is the response to the individual analytes important, but the C2H4 cross-sensitivity toward CO is also important. Fe0.7Cr1.3O3 showed a good performance to C2H4, with low cross-sensitivity to CO. In addition, when 0.16 ppm of phenanthrene is added, the sensor still has a slightly better response to C2H4 than to CO. Nevertheless, the sensor exposure to high concentrations (>85 ppm) of polycyclic aromatic hydrocarbons led to signal saturation. On the other hand, the operation in wet conditions induces lower sensor sensitivity to C2H4 and higher cross-sensitivity toward CO increase, i.e., the sensor response becomes similar for C2H4 and CO
Royal Jelly: Chemistry, Storage and Bioactivities
Royal jelly (RJ) has been known for centuries, but in the last 5-6 decades its systematic production and consumption has increased. RJ is secreted by the hypopharyngeal and mandibular glands of worker honeybees (Apis mellifera). This thick and milky substance contains water, proteins, carbohydrates, lipids, minerals, vitamins and such bio-active compounds as acetylcholine, peptides, the hormones testosterone, progesterone, prolactin, estradiol, (hydroxydecanoic acid) (HAD), adenosine monophosphate (AMP)-N1Oxide, polyphenols, flavonoids and adenosine. Because of its bioactive compounds, RJ can be considered as a functional and nutraceutical food. The main goal of this review is to summarize and update its physicochemical properties, bio-active ingredients, storage stability and shelf life. The functional properties are antioxidative activity, insulin-like action, improvement against diabetes, liver protection, antitumoral action, neurotrophic action, antibiotic effect, anti-inflammatory action and wound healing, hypotensive effect and blood regulatory actions, anti-aging effect and skin protection, effects on the reproductive system and fertility and also fortifying, tonic action and immunomodulating and anti-alergic activity. RJ may cause allergic reactions, asthma and even fatal anaphylaxis in some humans. Therefore, RJ should be orally ingested as nutreaceutical agent or food-ingredient only after an allergy test