Towards the development of poly (phenylene sulphide) based nanocomposites with enhanced mechanical, electrical and tribological properties

Novel poly(phenylene sulphide) (PPS) nanocomposites reinforced with an aminated derivative (PPS-NH2) covalently attached to acid-treated single-walled carbon nanotubes (SWCNTs) were prepared via simple melt-blending technique. Their morphology, viscoelastic behaviour, electrical conductivity, mechanical and tribological properties were investigated. Scanning electron microscopy revealed that the grafting process was effective in uniformly dispersing the SWCNTs within the matrix. The storage and loss moduli as a function of frequency increased with the SWCNT content, tending to a plateau in the low-frequency regime. The electrical conductivity of the nanocomposites was considerably enhanced in the range 0.1?0.5 wt% SWCNTs; electrical and rheological percolation thresholds occurred at similar nanotube concentrations. Mechanical tests demonstrated that with only 1.0 wt% SWCNTs the Young's modulus and tensile strength of the matrix improved by 51 and 37%, respectively, without decrement in toughness, ascribed to a very efficient load transfer. A moderate decrease in the friction coefficient and a 75% reduction in wear rate were found for the abovementioned nanotube loading, indicating that PPS-NH2-g-SWCNTs are good tribological additives for thermoplastic polymers. Based on the promising results obtained in this work, it is expected that these nanofillers will be used to develop high-performance thermoplastic/CNT nanocomposites for structural applications.

Effect of type of dietary carbohydrates on digestion, intestinal barrier and growth performance in 25-d weaned rabbits

Los objetivos globales de esta tesis han sido estudiar el efecto que los carbohidratos de la dieta ejercen sobre los rendimientos productivos, la barrera intestinal, y la digestión de animales destetados a 25 días de edad. Además se ha estudiado cuál es el mejor periodo para determinar la digestibilidad fecal tras el destete a esta edad. En el primer experimento se estudió el efecto de la fibra neutro detergente soluble (FNDS) sobre la barrera intestinal, digestión, microbiota intestinal y rendimientos productivos de gazapos en gazapos en la fase post-destete. Se diseñaron tres piensos isonutritivos en los que la única fuente de variación fueron los niveles de fibra soluble. A partir de una dieta control (AH) con 103 g/kg de materia seca de FNDS y alfalfa como fuente principal de fibra, se sustituyó la mitad de esta alfalfa por una mezcla de pulpa de remolacha y pulpa de manzana (75:25) en el pienso B-AP y por una mezcla de cascarilla y concentrado de proteína de soja (88:12) en el pienso OH, obteniéndose 131 y 79 g/kg de FNDS sobre materia seca, respectivamente. Los conejos se destetaron a 25 días y fueron alimentados con los piensos experimentales hasta los 35 días de edad, momento en el que se sacrificaron para la determinación de la digestibilidad ileal aparente (DIA) de la materia seca (MS), proteína bruta (PB) y almidón, la morfología de la mucosa, y actividad enzimática en el yeyuno, el tejido linfoide asociado a la mucosa, así como la microbiota intestinal. Para la determinación de la morfología de la mucosa se utilizaron adicionalmente 19 animales lactantes de 35 días de edad. Para el estudio de la tasa de mortalidad, se utilizaron 118 animales más por tratamiento que recibieron los piensos experimentales durante las dos semanas post-destete y posteriormente un pienso comercial hasta los 60 días de edad. Los animales recibieron durante todo el experimento medicación en el agua de bebida (100 ppm de apramicina sulfato y 120 ppm de tilosina tartrato). El nivel de fibra soluble mejoró los parámetros que se utilizaron para la caracterización del estado de la barrera intestinal. Los conejos alimentados con el mayor nivel de FNDS en el pienso presentaron una mayor longitud de los villi (P=0.001), un mayor ratio longitud villi/profundidad de las criptas (8.14; P=0.001), una mayor actividad disacaridásica (8671 μmol de glucosa/g de proteína; P=0.019), así como una mayor digestibilidad ileal (96.8%; P=0.002), observándose una reducción en el flujo ileal de almidón a medida que se incrementó el nivel de fibra soluble en el pienso (1,2 vs 0,5 g/d; P=0.001). Los animales lactantes a 35 días de edad presentaron un ratio longitud de villi/profundidad de las criptas menor que el observado en aquéllos alimentados con el pienso B-AP (6.70), pero superior al de los piensos AH y OH. Niveles inferiores de NDFS tendieron (P=0.074) a incrementar la respuesta inmune de tipo celular (linfocitos CD8+). El pienso también afectó a la producción de IL2 (CD25+; P=0.029; CD5+CD25+; P=0.057), pero sin llegar a establecerse una clara relación con el nivel de fibra soluble. La diversidad de la microbiota intestinal no se vio afectada por el pienso (P ≥ 0.38). Los animales alimentados con las piensos B-AP y AH presentaron una reducción en la frecuencia de detección de Clostridium perfringens tanto en íleon (P=0.062) como en ciego (4.3 vs. 17.6%, P =0.047), comparado con el pienso OH. Además la tasa de mortalidad (118 gazapos/pienso) disminuyó de 14.4% en el pienso OH a 5.1% en el pienso B-AP. Entre los 32 y los 35 días de edad se determinó la digestibilidad fecal aparente (14/pienso) de la materia seca (MS), energía bruta (EB), proteína bruta (PB), fibra neutro detergente (FND), fibra ácido detergente (FAD) y almidón. Este grupo, junto con otros nueve animales por tratamiento se utilizaron para determinar el peso del estómago y el ciego, la concentración cecal de ácidos grasos volátiles (AGV) y amoniaco (NH3), así como las tasas de similitud de la microbiota intestinal. Además se estudiaron los rendimientos productivos (35 animales/tratamiento) de los gazapos durante todo el período de cebo, consumiendo los piensos experimentales desde el destete hasta los 35 días y posteriormente un pienso comercial hasta los 60 días de edad. Niveles crecientes de FNDS mejoraron la digestibilidad fecal de la materia seca (MS) y energía (P<0.001). La inclusión FNDS aumentó de manera lineal el peso del contenido cecal (P=0.001) y el peso del aparato digestivo completo (P=0.008), y en los días previos al sacrificio disminuyó de manera lineal el consumo medio diario (P=0.040). Se observó además, una disminución lineal (P≤0.041) del pH del estómago. No se encontró relación entre el pH, la concentración y proporciones molares de AGV y el nivel de FNDS. El pienso pareció tener un efecto, incluso superior al de la madre, sobre la tasa de similitud de la microbiota, y los efectos fueron mayores a nivel cecal que ileal. La eficacia alimenticia aumentó de manera lineal en un 12% entre piensos extremos tras el destete (25- 39d) y en un 3% en el período global de cebo con niveles mayores de NDFS. El consumo medio diario durante la fase post-destete y durante todo el período de cebo, tendió a aumen tar (P≤0.079) con niveles mayores de FNDS, sin embargo no se apreció efecto sobre la ganancia media diaria (P≥0.15). En conclusión, el incremento del nivel de fibra soluble en el pienso parece resultar beneficioso para la salud del animal ya que mejora la integridad de la mucosa, y reduce la frecuencia de detección de potenciales patógenos como C. perfringens y Campylobacter spp. Conforme a estos resultados, debería tenerse en cuenta el contenido en fibra soluble en la formulación de piensos de conejos en la fase post-destete. El objetivo del segundo experimento fue determinar el efecto de la fuente de almidón sobre la digestión, la microbiota intestinal y los rendimientos productivos en conejos destetados con 25 días de edad. Se formularon tres piensos isonutritivos en los que se modificaron las principales fuentes de almidón: trigo crudo, trigo cocido y una combinación de trigo y arroz cocido. Dos grupos de 99 y 193 animales se destetaron con 25 días de edad. El primero de ellos se utilizó para la determinación de los parámetros productivos conforme al mismo protocolo seguido en el experimento anterior. El segundo de los grupos se utilizó para la determinación de la digestibilidad fecal de 32 a 35 d, la digestibilidad ileal aparente (DIA) a 35 d, la morfología de la mucosa intestinal, los parámetros de fermentación cecal; así como, la caracterización de la microbiota intestinal. Se utilizaron además dos grupos adicionales de animales 384 (medicados) y 177 (no medicados) para estudiar el efecto de la suplementación con antibióticos en el agua de bebida sobre la mortalidad. El procesado térmico del trigo mejoró ligeramente la digestibilidad ileal del almidón (P=0.020) pero no modificó el flujo final de almidón que alcanzó el ciego, observándose una mayor frecuencia de detección de Campylobacter spp. y Ruminococcus spp. en ciego (P≤0.023), pero sin cambios a nivel ileal. El procesado térmico del trigo no afectó tampoco a los parámetros productivos, la mortalidad, la digestibilidad ileal y fecal o la morfología de la mucosa. La sustitución parcial del trigo cocido por arroz cocido, penalizó la digestibilidad ileal del almidón (P=0.020) e incrementó el flujo ileal de este nutriente al ciego (P=0.007). Sin embargo no afectó a la mortalidad, pese a que se detectaron cambios en la microbiota tanto a nivel ileal como cecal, disminuyendo la frecuencia de detección de Campylobacter spp. (en íleon y ciego), Helicobacter spp. (en íleon) y Ruminococcus spp (en ciego) e incrementando Bacteroides spp. (en ciego) (P≤0.046). El empleo de arroz cocido en las piensos post-destete no tuvieron efectos sobre los parámetros productivos, la mortalidad, la digestibilidad ileal y fecal a excepción del almidón, o la morfología de la mucosa. La suplementación con antibiótico redujo la fre cuencia de detección de la mayoría de las bacterias estudiadas (P≤0.048), sobre todo para Campylobacter spp., Clostridium perfringens y Propionibacterium spp. (P≤0.048), observándose un efecto mayor a nivel ileal que cecal, lo que se asoció a la bajada significativa (P<0.001) de la mortalidad. En conclusión, los resultados de este experimento indican que la fuente de almidón afecta a la microbiota intestinal pero no influiye sobre la salud del animal. En relación al procesado, el uso de trigo cocido junto con arroz cocido no mejora los resultados obtenidos con trigo duro, si bienserían necesarios más experimentos que confirmaran este punto. El último de los experimentos se centró en un aspecto metodológico. Dado que, los conejos destetados presentan un patrón digestivo diferente al de un animal adulto resultado de su inmadurez digestiva, el objetivo buscado era tratar de determinar el mejor procedimiento para la determinación de la digestibilidad fecal en los gazapos en la fase post-destete. Para tal fin se utilizaron 15 animales/tratamiento de tres camadas diferentes que se destetaron con 25 días, suministrándoles un pienso comercial de crecimiento-cebo. Se registró el consumo medio diario y la excreción diaria de heces desde el día 25 hasta el día 40 de edad para la determinación de la digestibilidad de la MS. La camada afectó al consumo medio diario y la excreción de heces (P=0.013 y 0.014, respectivamente), observándose una tendencia (P=0.061) en la digestibilidad. La edad afectó (P<0.001) a todos estos factores, incrementándose de manera más evidente la excreción que la ingestión de materia seca en la primera semana de vida, para aumentar de forma paralela a partir de la segunda. La correlación entre el consumo medio diario fue mayor con la excreción de heces del mismo día que con la del día siguiente, por lo que se utilizó el primero para la determinación de la digestibilidad de la MS (MSd). La MSd disminuyó de manera lineal hasta los 32 días de edad (2.17±0.25 unidades porcentuales por día), mientras que permaneció constante desde los 32 a los 40 días (69.4±0.47%). Por otro lado, la desviación estándar de la MSd se redujo cuando se incrementó el período de recogida de 2 a 6 días en un 54%. Conforme a los resultados obtenidos, se puede concluir que no es aconsejable comenzar las pruebas de digestibilidad antes de los 32 días de edad y que el número de animales necesario para detectar diferencias significativas entre tratamientos dependerá del período de recogida de heces. ABSTRACT The global aim of this thesis has been to study the effect of dietary carbohydrates on growth, performance, digestion and intestinal barrier in 25-d weaned rabbits. In addition there has also been studied which is the best period to determine the fecal digestibility after weaning. The first experiment focused on the effect of Neutral Detergent Soluble Fibre (NDSF) on gut barrier function, digestion, intestinal microbiota and growth performance n rabbits in the post-weaning period. Three isonutritive diets which only varied in the levels of soluble fiber were formulated such as it described as follows: a control diet (AH) containing 103 g of neutral detergent soluble fiber, including alfalfa as main source of fiber, was replaced by a mixture of beet and apple pulp (75-25) in the B-AP diet and, by a mix of oat hulls and soybean protein concentrate (88:12) in the OH diet, resulting 131 and 79 g of NDFS/kg of dry matter, respectively. Rabbits, weaned at 25 days of age, were fed the experimental diets up to 35 days of age, moment in which they were slaughtered for apparent ileal digestibility (AID) of dry matter (DM), crude protein (CP) and starch, mucosa morphology, sucrose activity, characterization of lamina propria lymphocytes and intestinal microbiota. To assess mucosal morphology, 19 suckling 35-d-old rabbits were also used. For mortality study, besides these animals, 118 additional rabbits per treatment were fed the experimental diets for two weeks period and thereafter received a commercial diet until 60 days of age. Rabbits were water medicated during the whole experimental period (100 ppm de apramicine sulphate and 120 ppm of tylosine tartrate). Level of soluble fiber improved all the parameters used for the characterization of the intestinal barrier condition. Villous height of the jejunal mucosa increased with dietary soluble fiber (P=0.001). Villous height of jejunal mucosa increased with dietary soluble fiber (P = 0.001). Rabbits fed the highest level of soluble fiber (BA-P diet) showed the highest villous height/crypth depth ratio (8.14; P = 0.001), sucrase specific activity (8671 μmol glucose/ g protein; P = 0.019), and the greatest ileal starch digestibility (96.8%; P = 0.002). The opposite effects were observed in rabbits fed decreased levels of soluble fiber (AH and OH diets; 4.70, 5,848 μmol of glucose/g of protein, as average, respectively). The lowest ileal starch digestibility was detected for animal fed OH diet (93.2%). Suckling rabbits of the same age showed a lower villous height/crypt depth ratio (6.70) compared with the B-AP diet group, but this ration was higher that the AH or OH diet groups. Lower levels of soluble fiber tended (P = 0.074) to increase the cellular immune response (CD8+ lymphocytes). Diet affected IL-2 production (CD25+, P = 0.029; CD5+CD25+, P = 0.057), with no clear relationship between soluble fiber and IL-2. The intestinal microbiota biodiversity was not affected by diets (P ≥ 0.38). Animals fed B-AP and AH diets had a reduced cecal frequency of detection compatible with Campylobacter spp. (20.3 vs. 37.8, P = 0.074), and Clostridium perfringens (4.3 vs. 17.6%, P = 0.047), compared with the OH diet group. Moreover, the mortality rates decreased from 14.4 (OH diet) to 5.1% (B-AP diet) with the increased presence of soluble fiber in the diet. Between 32 and 35 days of age, faecal apparent digestibility of dry matter (DM), gross energy (GE), crude protein (CP), neutral detergent fiber (NDF), acid detergent fiber (ADF) and starch was determined (14/diet). This group, plus another nine rabbits/diet were used to determine weight of stomach and caecum and their contents, cecal fermentation traits and similarity rate (SR) of intestinal microbiota. Besides, growth performance parameters (35 rabbits/diet) were studied during the whole fattening period, in animals consuming the experimental feed after the weaning up to 35 days of age and later on a commercial diet up animals reached 60 days of age. Increasing levels of Neutral Detergent Soluble Fiber improved faecal dry matter and energy digestibility (P<0.001). NDSF inclusion improved linearly weight of the caecal content (P=0.001) and the total gastrointestinal tract (P=0.008), and in the previous days to slaughter a linear decrease of daily feed intake in diet with highest level of soluble fiber was also observed. Stomach pH decreased linearly with increasing levels of NDFS (P≤0.041). No relation between NDSF level on pH, concentration and molar proportion of VFA was found. Treatments appeared to influence the similarity rate of microbiota, even higher to mother effect. These effects were higher in ileum than in caecum. A linear positive effect of feed efficiency was observed, which increased around 12% in the two weeks post-weaning (25-39d) and 3% in the whole fattening period between extreme diets with highest levels of soluble fiber. Average daily feed intake during the two weeks after weaning and in the whole fattening period, tended (P≤0.079) to increase with highest levels of NDSF; although there were no effect on daily weight gain (≥0.15). In conclusion, an increase of soluble fiber in the feed seems to be beneficial for animal health, due to improve mucose integrity and reduce detection frequency of those poten tial pathogens like C. perfringens and Campylobacter spp. According to these results, level of soluble fiber should be taking care in feed rabbit formulation in the post-weaning period. The objective of the second experiment was to determine the effect of source of starch on digestion, intestinal microbiota and growth performance in twenty-five-day old weaned rabbits. To accomplish with this aim three iso-nutritive diets were formulated with different source of starch: raw wheat, boiled wheat and a combination of boiled wheat and boiled rice. Two groups of 99 and 193 rabbits were weaned at 25 days of age. The first group was used for growth performance determination following the same protocol than in previous experiment. The second group was used to determine faecal digestibility from 32 to 35 d, apparent ileal digestibility (AID) at 35 d, jejunal mucosa morphology, caecal fermentation traits and characterization of intestinal microbiota. For mortality, two additional groups of 384 (medicated) and 177 (not medicated) were used in order to study the effect of antibiotic water supply supplementation. Heat processing of starch slightly improved ileal digestibility of starch (P=0.020) but did not modify the flow of starch to the caecum. An increase in frequency of detection of Campylobacter spp. y Ruminococcus spp. was observed in the caecum (P≤0.023), with no changes at ileal level. Heat processing of wheat did not modify growth performance, mortality, ileal or faecal digestibility and mucosa morphology. Partial substitution of boiled wheat for boiled rice in the diet impaired ileal starch digestibility (P=0.020) and increased the ileal flow of this nutrient to the caecum (P=0.007). However, it did not affect mortality rate, although changes in the ileal and caecal intestinal microbiota were detected, decreasing the frequency of detection of Campylobacter spp. (both ileum and caecum), Helicobacter spp. (at ileum) and Ruminococcus spp (at caecum) and increasing the Bacteroides spp. (at caecum) (P≤0.046). The effect of boiled rice supplementation did not alter growth performance, mortality, ileal or faecal digestibility of other nutrients than starch, and mucosa morphology. Medication of rabbits reduced the ileal frequency of detection of most bacteria studied (P≤0.048), especially for Campylobacter spp., Clostridium perfringens y Propionibacterium spp. (P≤0.048), resulting the effect higher at ileal than caecal level and relating it with a strong reduction of mortality rate (P<0.001). In conclusion, the results of this experiment make think that the source of starch affects the intestinal microbiota but they do not seem to influence animal health. In relation to the effect of heat processed the use of cooked wheat or cooked rice it does not seem to im prove the results obtained with hard wheat, but there would be necessary more experiments that were confirming this point. The last experiment focused on a methodological aspect. Considering that, weaned rabbits have a different digestive pattern than older animals due to their digestive immaturity; the fixed objective was to determine the best procedure for faecal digestibility determination in young rabbits in the post-weaning period. Fifteen rabbits from 5 different litters were weaned at 25 days of age and fed with a commercial feed. Feed intake and faeces excretion were recorded daily from 25 to 40 days of age for dry matter digestibility (DMd) determination. Litter affected daily DM intake and excretion (P=0.013 y 0.014, respectively) and tended to affect DMd (P=0.061). Age affected all these factors (P<0.001), but ingestion increased slowly than dry matter excretion during the first week buth they evolved similarly in the second week. The correlation between daily feed intakes was higher with the faeces excretion of the day than with faeces excretion of the next day, and the first values were used to determine daily DMd. The DMd decreased linearly from weaning to 32 d of age (2.17±0.25 percentage units per day), whereas from 32 to 40 d remained constant (69.4±0.47%). On the other hand, average standard deviation of DMd decreased by 54% when the length of collection period increased from 2 to 6d. Consequently to the obtained results, it could be concluded that it would not be advisable to start digestibility trials before the 32 days of age and that the number of animals required to detect a significant difference among means would depend on the collection period.

Calibración de una nariz electrónica tipo QCM y relación con las especificaciones para la calidad de la pera.

Las microbalanzas de cristal de cuarzo (QCM), son mecanismos piezoeléctricos, para transformarlos en sensores químicos es necesario recubrirlos con una capa de material capaz de capturar las moléculas del ambiente. Cuando una masa es adsorbida sobre la superficie del cristal, la frecuencia de oscilación cambia en proporción a la cantidad de masa (Di Natale et al. 1997). La respuesta de los sensores depende de numerosos factores que pueden ser difíciles de controlar, tales como la temperatura y la humedad del gas portador. Todos estos factores producen cambios en la selectividad de los sensores que afectan a la reproducibilidad de las medidas. A pesar de la existencia de numerosos estudios no existe ningún procedimiento establecido para la calibración de las QCM en relación con la sensibilidad necesaria en los sensores para el aseguramiento de la calidad en pera o en otras frutas.

Determinación de un modelo de geoide gravimétrico para Puerto Rico como sistema de referencia para las altitudes ortométricas

El geoide, definido como la superficie equipotencial que mejor se ajusta (en el sentido de los mínimos cuadrados) al nivel medio del mar en una determinada época, es la superficie que utilizamos como referencia para determinar las altitudes ortométricas. Si disponemos de una superficie equipotencial de referencia como dátum altimétrico preciso o geoide local, podemos entonces determinar las altitudes ortométricas de forma eficiente a partir de las altitudes elipsoidales proporcionadas por el Sistema Global de Navegación por Satélite (Global Navigation Satellite System, GNSS ). Como es sabido uno de los problemas no resueltos de la geodesia (quizás el más importante de los mismos en la actualidad) es la carencia de un dátum altimétrico global (Sjoberg, 2011) con las precisiones adecuadas. Al no existir un dátum altimétrico global que nos permita obtener los valores absolutos de la ondulación del geoide con la precisión requerida, es necesario emplear modelos geopotenciales como alternativa. Recientemente fue publicado el modelo EGM2008 en el que ha habido una notable mejoría de sus tres fuentes de datos, por lo que este modelo contiene coeficientes adicionales hasta el grado 2190 y orden 2159 y supone una sustancial mejora en la precisión (Pavlis et al., 2008). Cuando en una región determinada se dispone de valores de gravedad y Modelos Digitales del Terreno (MDT) de calidad, es posible obtener modelos de superficies geopotenciales más precisos y de mayor resolución que los modelos globales. Si bien es cierto que el Servicio Nacional Geodésico de los Estados Unidos de América (National Geodetic Survey, NGS) ha estado desarrollando modelos del geoide para la región de los Estados Unidos de América continentales y todos sus territorios desde la década de los noventa, también es cierto que las zonas de Puerto Rico y las Islas Vírgenes Estadounidenses han quedado un poco rezagadas al momento de poder aplicar y obtener resultados de mayor precisión con estos modelos regionales del geoide. En la actualidad, el modelo geopotencial regional vigente para la zona de Puerto Rico y las Islas Vírgenes Estadounidenses es el GEOID12A (Roman y Weston, 2012). Dada la necesidad y ante la incertidumbre de saber cuál sería el comportamiento de un modelo del geoide desarrollado única y exclusivamente con datos de gravedad locales, nos hemos dado a la tarea de desarrollar un modelo de geoide gravimétrico como sistema de referencia para las altitudes ortométricas. Para desarrollar un modelo del geoide gravimétrico en la isla de Puerto Rico, fue necesario implementar una metodología que nos permitiera analizar y validar los datos de gravedad terrestre existentes. Utilizando validación por altimetría con sistemas de información geográfica y validación matemática por colocación con el programa Gravsoft (Tscherning et al., 1994) en su modalidad en Python (Nielsen et al., 2012), fue posible validar 1673 datos de anomalías aire libre de un total de 1894 observaciones obtenidas de la base de datos del Bureau Gravimétrico Internacional (BGI). El aplicar estas metodologías nos permitió obtener una base de datos anomalías de la gravedad fiable la cual puede ser utilizada para una gran cantidad de aplicaciones en ciencia e ingeniería. Ante la poca densidad de datos de gravedad existentes, fue necesario emplear un método alternativo para densificar los valores de anomalías aire libre existentes. Empleando una metodología propuesta por Jekeli et al. (2009b) se procedió a determinar anomalías aire libre a partir de los datos de un MDT. Estas anomalías fueron ajustadas utilizando las anomalías aire libre validadas y tras aplicar un ajuste de mínimos cuadrados por zonas geográficas, fue posible obtener una malla de datos de anomalías aire libre uniforme a partir de un MDT. Tras realizar las correcciones topográficas, determinar el efecto indirecto de la topografía del terreno y la contribución del modelo geopotencial EGM2008, se obtuvo una malla de anomalías residuales. Estas anomalías residuales fueron utilizadas para determinar el geoide gravimétrico utilizando varias técnicas entre las que se encuentran la aproximación plana de la función de Stokes y las modificaciones al núcleo de Stokes, propuestas por Wong y Gore (1969), Vanicek y Kleusberg (1987) y Featherstone et al. (1998). Ya determinados los distintos modelos del geoide gravimétrico, fue necesario validar los mismos y para eso se utilizaron una serie de estaciones permanentes de la red de nivelación del Datum Vertical de Puerto Rico de 2002 (Puerto Rico Vertical Datum 2002, PRVD02 ), las cuales tenían publicados sus valores de altitud elipsoidal y elevación. Ante la ausencia de altitudes ortométricas en las estaciones permanentes de la red de nivelación, se utilizaron las elevaciones obtenidas a partir de nivelación de primer orden para determinar los valores de la ondulación del geoide geométrico (Roman et al., 2013). Tras establecer un total de 990 líneas base, se realizaron dos análisis para determinar la 'precisión' de los modelos del geoide. En el primer análisis, que consistió en analizar las diferencias entre los incrementos de la ondulación del geoide geométrico y los incrementos de la ondulación del geoide de los distintos modelos (modelos gravimétricos, EGM2008 y GEOID12A) en función de las distancias entre las estaciones de validación, se encontró que el modelo con la modificación del núcleo de Stokes propuesta por Wong y Gore presentó la mejor 'precisión' en un 91,1% de los tramos analizados. En un segundo análisis, en el que se consideraron las 990 líneas base, se determinaron las diferencias entre los incrementos de la ondulación del geoide geométrico y los incrementos de la ondulación del geoide de los distintos modelos (modelos gravimétricos, EGM2008 y GEOID12A), encontrando que el modelo que presenta la mayor 'precisión' también era el geoide con la modificación del núcleo de Stokes propuesta por Wong y Gore. En este análisis, el modelo del geoide gravimétrico de Wong y Gore presento una 'precisión' de 0,027 metros en comparación con la 'precisión' del modelo EGM2008 que fue de 0,031 metros mientras que la 'precisión' del modelo regional GEOID12A fue de 0,057 metros. Finalmente podemos decir que la metodología aquí presentada es una adecuada ya que fue posible obtener un modelo del geoide gravimétrico que presenta una mayor 'precisión' que los modelos geopotenciales disponibles, incluso superando la precisión del modelo geopotencial global EGM2008. ABSTRACT The geoid, defined as the equipotential surface that best fits (in the least squares sense) to the mean sea level at a particular time, is the surface used as a reference to determine the orthometric heights. If we have an equipotential reference surface or a precise local geoid, we can then determine the orthometric heights efficiently from the ellipsoidal heights, provided by the Global Navigation Satellite System (GNSS). One of the most common and important an unsolved problem in geodesy is the lack of a global altimetric datum (Sjoberg, 2011)) with the appropriate precision. In the absence of one which allows us to obtain the absolute values of the geoid undulation with the required precision, it is necessary to use alternative geopotential models. The EGM2008 was recently published, in which there has been a marked improvement of its three data sources, so this model contains additional coefficients of degree up to 2190 and order 2159, and there is a substantial improvement in accuracy (Pavlis et al., 2008). When a given region has gravity values and high quality digital terrain models (DTM), it is possible to obtain more accurate regional geopotential models, with a higher resolution and precision, than global geopotential models. It is true that the National Geodetic Survey of the United States of America (NGS) has been developing geoid models for the region of the continental United States of America and its territories from the nineties, but which is also true is that areas such as Puerto Rico and the U.S. Virgin Islands have lagged behind when to apply and get more accurate results with these regional geopotential models. Right now, the available geopotential model for Puerto Rico and the U.S. Virgin Islands is the GEOID12A (Roman y Weston, 2012). Given this need and given the uncertainty of knowing the behavior of a regional geoid model developed exclusively with data from local gravity, we have taken on the task of developing a gravimetric geoid model to use as a reference system for orthometric heights. To develop a gravimetric geoid model in the island of Puerto Rico, implementing a methodology that allows us to analyze and validate the existing terrestrial gravity data is a must. Using altimetry validation with GIS and mathematical validation by collocation with the Gravsoft suite programs (Tscherning et al., 1994) in its Python version (Nielsen et al., 2012), it was possible to validate 1673 observations with gravity anomalies values out of a total of 1894 observations obtained from the International Bureau Gravimetric (BGI ) database. Applying these methodologies allowed us to obtain a database of reliable gravity anomalies, which can be used for many applications in science and engineering. Given the low density of existing gravity data, it was necessary to employ an alternative method for densifying the existing gravity anomalies set. Employing the methodology proposed by Jekeli et al. (2009b) we proceeded to determine gravity anomaly data from a DTM. These anomalies were adjusted by using the validated free-air gravity anomalies and, after that, applying the best fit in the least-square sense by geographical area, it was possible to obtain a uniform grid of free-air anomalies obtained from a DTM. After applying the topographic corrections, determining the indirect effect of topography and the contribution of the global geopotential model EGM2008, a grid of residual anomalies was obtained. These residual anomalies were used to determine the gravimetric geoid by using various techniques, among which are the planar approximation of the Stokes function and the modifications of the Stokes kernel, proposed by Wong y Gore (1969), Vanicek y Kleusberg (1987) and Featherstone et al. (1998). After determining the different gravimetric geoid models, it was necessary to validate them by using a series of stations of the Puerto Rico Vertical Datum of 2002 (PRVD02) leveling network. These stations had published its values of ellipsoidal height and elevation, and in the absence of orthometric heights, we use the elevations obtained from first - order leveling to determine the geometric geoid undulation (Roman et al., 2013). After determine a total of 990 baselines, two analyzes were performed to determine the ' accuracy ' of the geoid models. The first analysis was to analyze the differences between the increments of the geometric geoid undulation with the increments of the geoid undulation of the different geoid models (gravimetric models, EGM2008 and GEOID12A) in function of the distance between the validation stations. Through this analysis, it was determined that the model with the modified Stokes kernel given by Wong and Gore had the best 'accuracy' in 91,1% for the analyzed baselines. In the second analysis, in which we considered the 990 baselines, we analyze the differences between the increments of the geometric geoid undulation with the increments of the geoid undulation of the different geoid models (gravimetric models, EGM2008 and GEOID12A) finding that the model with the highest 'accuracy' was also the model with modifying Stokes kernel given by Wong and Gore. In this analysis, the Wong and Gore gravimetric geoid model presented an 'accuracy' of 0,027 meters in comparison with the 'accuracy' of global geopotential model EGM2008, which gave us an 'accuracy' of 0,031 meters, while the 'accuracy ' of the GEOID12A regional model was 0,057 meters. Finally we can say that the methodology presented here is adequate as it was possible to obtain a gravimetric geoid model that has a greater 'accuracy' than the geopotential models available, even surpassing the accuracy of global geopotential model EGM2008.

LED bulbs technical specification and testing procedure for solar home systems

The definition of technical specifications and the corresponding laboratory procedures are necessary steps in order to assure the quality of the devices prior to be installed in Solar Home Systems (SHS). To clarify and unify criteria a European project supported the development of the Universal Technical Standard for Solar Home Systems (UTSfSHS). Its principles were to generate simple and affordable technical requirements to be optimized in order to facilitate the implementation of tests with basic and simple laboratory tools even on the same SHS electrification program countries. These requirements cover the main aspects of this type of installations and its lighting chapter was developed based on the most used technology at that time: fluorescent tubes and CFLs. However, with the consolidation of the new LED solid state lighting devices, particular attention is being given to this matter and new procedures are required. In this work we develop a complete set of technical specifications and test procedures that have been designed within the frame of the UTSfSHS, based on an intense review of the scientific and technical publications related to LED lighting and their practical application. They apply to lamp reliability, performance and safety under normal, extreme and abnormal operating conditions as a simple but complete quality meter tool for any LED bulb.

Present status of the Liquid Breeder Validation

One of the objectives of IFMIF (International Fusion Materials Irradiation Facility), as stated in its specifications, is the validation of breeder blanket concepts for DEMO design. The so-called Liquid Breeder Validation Module (LBVM) will be used in IFMIF to perform experiments under irradiation on functional materials related to liquid breeder concepts for future fusion reactors. This module, not considered in previous IFMIF design phases, is currently under design by CIEMAT in the framework of the IFMIF/EVEDA project. In this paper, the present status of the design of the LBVM is presented.

Evolución de las políticas de rehabilitación en Áreas de Rehabilitación Integrada en España (1978-2012)

El artículo estudia la evolución de las políticas de intervención en Áreas de Rehabilitación Integral (ARI) desarrolladas en España entre 1978 y 2012. Se analiza la aparición y consolidación del concepto en la política estatal de vivienda, desde el Real Decreto 3148/1978 hasta el Plan de Vivienda 2009-2012. Por otro lado se analiza la «integralidad» de las intervenciones en áreas urbanas, mediante el estudio de veinte casos representativos, entendiendo como integral aquella intervención que actúa en la ordenación urbana, el diseño urbano y el medioambiente local, la edificación y la dimensión socioeconómica. El trabajo procede de un estudio realizado para el Ministerio de Fomento mediante convenio suscrito con el Departamento de Urbanística y Ordenación del Territorio (ETSAM, UPM) para el Análisis de las políticas estatales y europeas en materia de regeneración urbana y rehabilitación de barrios.

Geographical structuring in the mtDNA of Italians.

Geographical patterns of mtDNA variation were studied in 12 Italian samples (1072 individuals) by two different spatial autocorrelation methods. Separate analyses of the frequencies of 12 restriction morphs show North-South clines, differences between Sardinia and the mainland populations, and the effects of isolation by distance. A recently developed autocorrelation statistic summarizing molecular similarity at all sites (AIDA; autocorrelation index for DNA analysis) confirms the presence of a clinical pattern; differences between random pairs of haplotypes tend to increase with their geographical distance. The partition of gene diversity, however, reveals that most variability occurs within populations, whereas differences between populations are minor (GST = 0.057). When the data from the 12 samples are pooled, two descriptors of genetic variability (number of polymorphic sites and average sequence difference between pairs of individuals) do not behave as expected under neutrality. The presence of clinal patterns, Tajima's tests, and a simulation experiment agree in suggesting that population sizes increased rapidly in Italy and Sicily but not necessarily so in Sardinia. The distribution of pairwise sequence differences in the Italian peninsula (excluding Sardinia) permits a tentative location of the demographic increase between 8000 and 20,500 years ago. These dates are consistent with archaeological estimates of two distinct expansion processes, occurring, respectively, in the Neolithic and after the last glacial maximum in the Paleolithic. Conversely, there is no genetic evidence that such processes have had a major impact on the Sardinian population.

Efeito da adição de fibras de cana-de-açúcar pré-tratadas na produção de metano advinda da biodigestão anaeróbia de gorduras do leite

A digestão anaeróbia é uma alternativa para o tratamento de resíduos com altas concentrações de matéria orgânica. Por meio dos processos anaeróbios é possível a produção de biogás, fonte de energia renovável e ambientalmente amigável. Elevadas concentrações de lipídios, todavia, apesar de representarem elevado potencial metanogênico, interferem negativamente nos sistemas de tratamento, podendo inibir a atividade microbiana e, consequentemente, a produção de metano. O presente projeto avaliou o efeito da adição de bagaço de cana-de-açúcar no processo de biodigestão anaeróbia de elevadas concentrações de gorduras advindas de efluentes de laticínio. Para tanto foi utilizado bagaço de cana-de-açúcar in natura e pré-tratadas pelos seguintes métodos: organossolve, hidrotérmico, explosão à vapor e ácido diluído. O uso desse material lignocelulósico teve o objetivo de controlar a inibição causada pelos produtos da hidrólise dos lipídios por meio de sua adsorção e, consequentemente, diminuição das concentrações de tais compostos no meio. Outra hipótese era que o bagaço de cana-de-açúcar pudessem agir como co-substrato no processo de biodigestão anaeróbia. Inicialmente realizaram-se ensaios de biodegradabilidade anaeróbia com concentrações crescentes de gordura, que resultaram em relação entre substrato e microrganismo 0,06, 0,1, 0,2, 0,4 e 0,6 g DQO/gSTV. O ensaio com concentração em que foi verificada a inibição severa (0,4 gDQO/gSTV) do processo foi repetido com adição das fibras tratadas e não tratadas. Aos dados de produção acumulada de metano ajustou-se modelo de Gompertz, e parâmetros cinéticos foram inferidos. O bagaço de cana-de-açúcar mostrou potencial como adsorvente de gordura, pois as produções metanogênicas foram superiores à condição inibida sem adição desse material. A adição de fibras pré-tratadas por método organossolve resultou nas maiores produções de metano.

Effect of the intercalated cation-exchanged on the properties of nanocomposites prepared by 2-aminobenzene sulfonic acid with aniline and montmorillonite

Polymer/montmorillonite nanocomposites were prepared. Intercalation of 2-aminobenzene sulfonic acid with aniline monomers into montmorillonite modified by cation was followed by subsequent oxidative polymerization of monomers in the interlayer spacing. The clay was prepared by cation exchange process between sodium cation in (M–Na) and copper cation (M–Cu). XRD analyses show the manifestation of a basal spacing (d-spacing) for M–Cu changes depending on the inorganic cation and the polymer intercalated in the M–Cu structure. TGA analyses reveal that polymer/M–Cu composites is less stable than M–Cu. The conductivity of the composites is found to be 103 times higher than that for M–Cu. The microscopic examinations including TEM picture of the nanocomposite demonstrated an entirely different and more compatible morphology. Remarkable differences in the properties of the polymers have also been observed by UV–Vis and FTIR, suggesting that the polymer produced with presence of aniline has a higher degree of branching. The electrochemical behavior of the polymers extracted from the nanocomposites has been studied by cyclic voltammetry which indicates the electroactive effect of nanocomposite gradually increased with aniline in the polymer chain.

High-Pressure Methane Storage in Porous Materials: Are Carbon Materials in the Pole Position?

Natural gas storage on porous materials (ANG) is a promising alternative to conventional on-board compressed (CNG) or liquefied natural gas (LNG). To date, Metal–organic framework (MOF) materials have apparently been the only system published in the literature that is able to reach the new Department of Energy (DOE) value of 263 cm3 (STP: 273.15 K, 1 atm)/cm3; however, this value was obtained by using the ideal single-crystal density to calculate the volumetric capacity. Here, we prove experimentally, and for the first time, that properly designed activated carbon materials can really achieve the new DOE value while avoiding the additional drawback usually associated with MOF materials (i.e., the low mechanical stability under pressure (conforming), which is required for any practical application).

Use of Eutectic Mixtures for Preparation of Monolithic Carbons with CO2-Adsorption and Gas-Separation Capabilities

With global warming becoming one of the main problems our society is facing nowadays, there is an urgent demand to develop materials suitable for CO2 storage as well as for gas separation. Within this context, hierarchical porous structures are of great interest for in-flow applications because of the desirable combination of an extensive internal reactive surface along narrow nanopores with facile molecular transport through broad “highways” leading to and from these pores. Deep eutectic solvents (DESs) have been recently used in the synthesis of carbon monoliths exhibiting a bicontinuous porous structure composed of continuous macroporous channels and a continuous carbon network that contains a certain microporosity and provides considerable surface area. In this work, we have prepared two DESs for the preparation of two hierarchical carbon monoliths with different compositions (e.g., either nitrogen-doped or not) and structure. It is worth noting that DESs played a capital role in the synthesis of hierarchical carbon monoliths not only promoting the spinodal decomposition that governs the formation of the bicontinuous porous structure but also providing the precursors required to tailor the composition and the molecular sieve structure of the resulting carbons. We have studied the performance of these two carbons for CO2, N2, and CH4 adsorption in both monolithic and powdered form. We have also studied the selective adsorption of CO2 versus CH4 in equilibrium and dynamic conditions. We found that these materials combined a high CO2-sorption capacity besides an excellent CO2/N2 and CO2/CH4 selectivity and, interestingly, this performance was preserved when processed in both monolithic and powdered form.

Very high methane uptake on activated carbons prepared from mesophase pitch: A compromise between microporosity and bulk density

Two petroleum residues were pyrolyzed under two different conditions to obtain pitches with low or high mesophase content. The effect of the KOH: precursor ratio and the activation temperature on the packing density and porous texture of the carbons have been studied and optimized. Activated carbons combining high micropore volume (>1 cm3/g) and high packing density (0.7 g/cm3) have been successfully prepared. Regarding excess methane adsorption capacities, the best results (160 cm3 (STP)/cm3 at 25 °C and 3.5 MPa) were obtained using the pitch with the higher content of the more organized mesophase, activated at relatively low temperature (700 °C), with a medium KOH: precursor ratio (3:1). Some of the activated carbons exhibit enhanced adsorption capacity at high pressure, giving values as high as 175 cm3 (STP)/cm3 at 25 °C and 5 MPa and 200 cm3 (STP)/cm3 at 25 °C and 10 MPa (the same amount as in an empty cylinder but at half of the pressure), indicating a contribution of large micropores and narrow mesopores to adsorption at high pressure. The density of methane in pores between 1 and 2.5 nm at pressure up to 10 MPa was estimated to understand their contribution to the total adsorption capacity.

Spectroscopic, calorimetric, and catalytic evidences of hydrophobicity on Ti-MCM-41 silylated materials for olefin epoxidations

Hydrophobic Ti-MCM-41 samples prepared by post-synthesis silylation treatment demonstrate to be highly active and selective catalysts in olefins epoxidation by using organic hydroperoxides as oxidizing agents in liquid phase reaction systems. Epoxide yields show important enhancements with increased silylation degrees of the Ti-mesoporous samples. Catalytic studies are combined and correlated with spectroscopic techniques (e.g. XRD, XANES, UV-Visible, 29Si MAS-NMR) and calorimetric measurements to better understand the changes in the surface chemistry of Ti-MCM-41 samples due to the post-synthesis silylation treatment and to ascertain the role of these trimethylsilyl groups incorporated in olefin epoxidation. In such manner, the effect of the organic moieties on solids, and both water and glycol molecules contents on the catalytic activity and selectivity are analyzed in detail. Results show that the hydrophobicity level of the samples is responsible for the decrease in water adsorption and, consequently, the negligible formation of the non-desired glycol during the catalytic process. Thus, catalyst deactivation by glycol poisoning of Ti active sites is greatly diminished, this increasing catalyst stability and leading to practically quantitative production of the corresponding epoxide. The extended use of these hydrophobic Ti-MCM-41 catalysts together with organic hydroperoxides for the highly efficient and selective epoxidation of natural terpenes is also exemplified.

Paving the way for methane hydrate formation on metal–organic frameworks (MOFs)

The presence of a highly tunable porous structure and surface chemistry makes metal–organic framework (MOF) materials excellent candidates for artificial methane hydrate formation under mild temperature and pressure conditions (2 °C and 3–5 MPa). Experimental results using MOFs with a different pore structure and chemical nature (MIL-100 (Fe) and ZIF-8) clearly show that the water–framework interactions play a crucial role in defining the extent and nature of the gas hydrates formed. Whereas the hydrophobic MOF promotes methane hydrate formation with a high yield, the hydrophilic one does not. The formation of these methane hydrates on MOFs has been identified for the first time using inelastic neutron scattering (INS) and synchrotron X-ray powder diffraction (SXRPD). The results described in this work pave the way towards the design of new MOF structures able to promote artificial methane hydrate formation upon request (confined or non-confined) and under milder conditions than in nature.