Evaluación de parámetros que influyen en el transporte de cloruros en hormigón parcialmente saturado

El deterioro del hormigón debido a la presencia del ion cloruro es causa frecuente de problemas en estructuras localizadas en ambiente marino y alta montaña. Su principal efecto consiste en la despasivación del acero de refuerzo embebido en el hormigón y su consecuente inicio de la corrosión del mismo. El ingreso del ion cloruro al interior del hormigón, está condicionado por una serie de parámetros de origen medioambiental e intrínsecos del hormigón. En función de estos parámetros el ingreso de cloruros en el hormigón puede deberse principalmente a los siguientes mecanismos: difusión y succión capilar. El estudio y evaluación de la resistencia del hormigón frente a cloruros, se ha desarrollado principalmente en condiciones saturadas del hormigón. Lo que ha significado que parámetros de importancia no sean considerados. Debido a esto, distintos procesos que suceden en estructuras reales no han sido identificados y estudiados correctamente. En este trabajo, se diseñó un programa de investigación para evaluar los parámetros que influyen en el transporte cloruros en hormigones no saturados. Para esto se diseñaron tres dosificaciones diferentes de hormigón. En la primera se empleó únicamente cemento portland, para el resto se utilizaron adiciones minerales (humo de sílice y escoria de alto horno). El empleo de adiciones se debió a que tienen un papel importante en la durabilidad de hormigones frente a cloruros. Los hormigones fueron dosificados con una relación agua/material cementício de 0,40 para el hormigón elaborado únicamente con cemento portland y 0,45 para las mezclas con adiciones. Para evaluar las propiedades de los hormigones en estado fresco y endurecido se realizaron ensayos vigentes en las normativas. Con los resultados obtenidos se determinaron parámetros de resistencia mecánica, microestructurales, resistencia al transporte de cloruros e higroscópicos. Una vez caracterizados los hormigones, se diseñó una propuesta experimental para estudiar los principales parámetros presentes en estructuras reales con presencia de cloruros. Tanto la concentración de cloruro como las condiciones ambientales se han variado teniendo como referencia las situaciones reales que podrían producirse en ambientes de alta montaña en la zona centro de España. La propuesta experimental consistió en tratar de evaluar la capacidad de los hormigones al transporte de iones en ambientes de alta montaña con presencia de sales fundentes. Para esto se establecieron 5 fases experimentales donde los principales parámetros ambientales y la presencia de iones agresivos sufrieron variaciones. Al término de cada fase se obtuvieron perfiles de penetración de cloruros en los hormigones y se evaluó la influencia de los parámetros presentes en cada fase. Los resultados experimentales se implementaron en un modelo numérico basado en la teoría de elementos finitos, desarrollado por el grupo de investigación del Departamento de Materiales de Construcción. Para esto fue necesario realizar la calibración y validación del modelo numérico para cada hormigón. El calibrado del modelo precisa de datos químicos y microestructurales de cada hormigón, tales como: capacidad de combinación de cloruros y propiedades difusivas e higroscópicas. Para la validación del modelo numérico se realizaron simulaciones de la propuesta experimental. Los resultados obtenidos se compararon con los valores experimentales. Con el objeto de poder estudiar en mayor profundidad la influencia del grado de saturación del hormigón durante la difusión de cloruros, se llevó a cabo una campaña experimental que consideró distintos grados de saturación en los hormigones. Para esto se establecieron en los hormigones cuatro grados de saturación distintos (50%, 60%, 80% y 100%, aproximadamente), posteriormente se expusieron a cloruro de sodio finamente molido. Una vez transcurrido el tiempo necesario se obtuvieron experimentalmente los perfiles de penetración de cloruros para cada grado de saturación y se calcularon los coeficientes de difusión. Los datos obtenidos durante la campaña experimental han demostrado la influencia positiva que ejercen las adiciones en las mezclas de hormigón. Sus principales ventajas son el refinamiento de la red porosa y el aumento en la capacidad de combinación de cloruros, además de mejorar sus propiedades mecánicas. La porosidad total en las mezclas no presentó grandes cambios, sin embargo, el cambio en la distribución del tamaño de poros es importante en las muestras con adiciones. En especial las fabricadas con humo de sílice. Los coeficientes de difusión y migración de cloruros para las mezclas con adiciones disminuyeron significativamente, igual que los valores de resistividad eléctrica. En los ensayos de penetración del agua bajo presión, fueron las muestras con adiciones las que mostraron las menores penetraciones. Los resultados obtenidos al final de la propuesta experimental permitieron estudiar los distintos parámetros involucrados. Se observó claramente que el proceso de difusión provoca el mayor transporte de cloruros hacia el interior del hormigón. Así mismo se comprobó que el lavado superficial y el secado de las probetas, trasladan cloruros hacia las zonas externas del hormigón. El primero debido a una baja concentración de cloruros externa, mientras que el secado provoca el movimiento de la solución de poro hacia las zonas de secado depositando cloruros en ellas. Las medidas higroscópicas permitieron determinar la existencia de dos zonas distintas en el interior del hormigón. La primera se localizó en el rango de 0-10mm, aproximadamente, en ésta se puso de manifiesto una mayor sensibilidad a los cambios experimentados en el exterior de las probetas. La segunda zona se localizó a una profundidad mayor de 10mm, aproximadamente. Se observó claramente una baja influencia de los cambios externos, siendo la difusión de cloruros el principal mecanismo de transporte presente en ella. En cuanto al estudio de la influencia del grado de saturación en la difusión de cloruros, se observó claramente una marcada diferencia entre los coeficientes de difusión de cloruro obtenidos. Para grados de saturación mayores del 80% el mecanismo de penetración de cloruros por difusión existe de forma significativa. Mientras que para valores inferiores los resultados revelaron que las vías de acceso disminuyen (poros conectado con agua) considerablemente limitando en un alto grado la penetración del agresivo. Para grados de saturación inferiores del 50% los valores del coeficiente de difusión son despreciables. The deterioration of concrete due to chloride ions is a frequent problem identified in structures located in marine and high-mountain environments. After entering the outer layer of the concrete, the chlorides tend to penetrate until they reach and then depassivate the steel bars. Subsequently, this induces the deterioration process of the reinforced concrete. This chloride penetration depends on the environmental conditions and intrinsic parameters of the concrete. Several transport mechanisms, such as diffusion, capillary suction and permeability can be present into the concrete. While recent research into the study and evaluation of concretes with chloride presence has been carried out in saturated concrete, it has not considered certain parameters that can modify this condition. Consequently, at the time of writing several processes that take place in real structures have not been identified and studied. In this work a research programme is designed to evaluate the parameters that influence chloride transport into non-saturated concrete. For this, three concrete mixes were designed by using high-early-strength Portland cement and mineral admixtures (silica fume and blast-slag furnace). The water-cement ratio was 0.40 for the concrete made solely with Portland cement and 0.45 for the concretes that used mineral admixtures as a cement replacement. A set of experimental tests were performed to evaluate the concrete properties both in fresh and hardened state. In addition, an experimental simulation was carried out under laboratory conditions in which the main objective was to assess resistance of concrete to chloride penetration under high-mountain conditions with the presence of de-icing salts. The environmental conditions and surface chloride concentration of the concrete used during the experimental simulation were chosen by considering conditions found in the high-mountain environment in central Spain. For the experimental simulation five phases were designed by varying the environmental parameters and concrete surface concentration. At the end of each phase a chloride profile was obtained with the aim of assessing the influence of the parameters on chloride transport. The experimental results were then used to calibrate and validate a numerical model based on finite element theory developed by the research team from the Construction Materials Department in a previous work. In order to carry out model calibration chemical and microstructural data for the concretes was required, such as binding capacity and the diffusive and hygroscopic properties. The experimental results were compared with the numerical simulations and provided a good fit. With the objective of studying the influence of the degree of concrete saturation on chloride diffusion, an experimental programme was designed. This entailed four saturation degrees (50%, 60%, 80% and 100%) being established in several concrete samples. The samples were then exposed to ground sodium chloride. Once the time required was achieved, the chloride profiles and diffusion coefficients were obtained for each saturation degree. The results obtained from the experimental program revealed a positive influence of the mineral admixtures on the concretes. Their effects were reflected in the pore-network refinement and the increase of chloride binding capacity, together with the improvement of the mechanical properties of the concretes. Total porosity did not reveal any notable change, though the pore-size distribution showed a significant degree of change in the concretes with mineral admixtures, specifically the samples prepared through use of silica fume. The chloride diffusion and migration coefficient, as well as the electrical resistivity values, decreased significantly in the concretes with admixtures. In the water penetration under pressure test, the concretes with admixtures presented the lowest penetration depth. The results obtained in the experimental simulation allowed study of the main parameters involved during the chloride penetration processes in non-saturated concretes in the presence of chlorides. According to the results, the diffusion process was the transport mechanism that transferred the greatest amount of chlorides into the concrete samples. In addition, a chloride movement toward external zones of the concrete, caused by the washing of concrete surface and the drying processes, was identified. The washing occurred when the concrete surface came into contact with a low-chloride concentration solution which initiated the outward movement of chloride diffusion. The drying processes corresponded to a movement of pore solution launched by water evaporation from the outer layer. Furthermore, hygroscopic measurements made in the concrete allowed two areas with distinct behavioural patterns to be identified. The first one, located in the range of approximately 0-10mm, showed a greater degree of influence regarding the changes of the external conditions. The second, situated at depths greater than 10mm, displayed a low influence of external conditions. The main process in this area was diffusion. Study of the influence of the degree of concrete saturation on chloride diffusion showed a clear difference among the chloride diffusion coefficients obtained. For degrees of concrete saturation higher than 80%, chloride penetration by diffusion tends to be significant. However, in the case of extent of saturation of lower than 80%, the results revealed that the access zone through which chlorides can penetrate decreased considerably. For degrees of concrete saturation lower than 50%, the chloride diffusion coefficients were negligible.

Geometrical characterization of undisturbed soil samples using X-ray computed tomography image analysis. Effect of soil management on soil structure

El estudio de la estructura del suelo es de vital importancia en diferentes campos de la ciencia y la tecnología. La estructura del suelo controla procesos físicos y biológicos importantes en los sistemas suelo-planta-microorganismos. Estos procesos están dominados por la geometría de la estructura del suelo, y una caracterización cuantitativa de la heterogeneidad de la geometría del espacio poroso es beneficiosa para la predicción de propiedades físicas del suelo. La tecnología de la tomografía computerizada de rayos-X (CT) nos permite obtener imágenes digitales tridimensionales del interior de una muestra de suelo, proporcionando información de la geometría de los poros del suelo y permitiendo el estudio de los poros sin destruir las muestras. Las técnicas de la geometría fractal y de la morfología matemática se han propuesto como una poderosa herramienta para analizar y cuantificar características geométricas. Las dimensiones fractales del espacio poroso, de la interfaz poro-sólido y de la distribución de tamaños de poros son indicadores de la complejidad de la estructura del suelo. Los funcionales de Minkowski y las funciones morfológicas proporcionan medios para medir características geométricas fundamentales de los objetos geométricos tridimensionales. Esto es, volumen, superficie, curvatura media de la superficie y conectividad. Las características del suelo como la distribución de tamaños de poros, el volumen del espacio poroso o la superficie poro-solido pueden ser alteradas por diferentes practicas de manejo de suelo. En este trabajo analizamos imágenes tomográficas de muestras de suelo de dos zonas cercanas con practicas de manejo diferentes. Obtenemos un conjunto de medidas geométricas, para evaluar y cuantificar posibles diferencias que el laboreo pueda haber causado en el suelo. ABSTRACT The study of soil structure is of vital importance in different fields of science and technology. Soil structure controls important physical and biological processes in soil-plant-microbial systems. Those processes are dominated by the geometry of soil pore structure, and a quantitative characterization of the spatial heterogeneity of the pore space geometry is beneficial for prediction of soil physical properties. The technology of X-ray computed tomography (CT) allows us to obtain three-dimensional digital images of the inside of a soil sample providing information on soil pore geometry and enabling the study of the pores without disturbing the samples. Fractal geometry and mathematical morphological techniques have been proposed as powerful tools to analyze and quantify geometrical features. Fractal dimensions of pore space, pore-solid interface and pore size distribution are indicators of soil structure complexity. Minkowski functionals and morphological functions provide means to measure fundamental geometrical features of three-dimensional geometrical objects, that is, volume, boundary surface, mean boundary surface curvature, and connectivity. Soil features such as pore-size distribution, pore space volume or pore-solid surface can be altered by different soil management practices. In this work we analyze CT images of soil samples from two nearby areas with contrasting management practices. We performed a set of geometrical measures, some of them from mathematical morphology, to assess and quantify any possible difference that tillage may have caused on the soil.

Polymer interaction with macroscopic carbon nanotube fibres and fabrication of nanostructured composites

El ensamblado de nanotubos de carbono (CNT) como una fibra macroscópica en la cual están orientados preferentemente paralelos entre sí y al eje de la fibra, ha dado como resultado un nuevo tipo de fibra de altas prestaciones derivadas de la explotación eficiente de las propiedades axiales de los CNTs, y que tiene un gran número de aplicaciones potenciales. Fibras continuas de CNTs se produjeron en el Instituto IMDEA Materiales mediante el proceso de hilado directo durante la reacción de síntesis por deposición química de vapores. Uno de los objetivos de esta tesis es el estudio de la estructura de estas fibras mediante técnicas del estado del arte de difracción de rayos X de sincrotrón y la elaboración de un modelo estructural de dicho material. Mediciones texturales de adsorción de gases, análisis de micrografías de electrones y dispersión de rayos X de ángulo alto y bajo (WAXS/SAXS) indican que el material tiene una estructura mesoporosa con una distribución de tamaño de poros ancha derivada del amplio rango de separaciones entre manojos de CNTs, así como una superficie específica de 170m2/g. Los valores de dimensión fractal obtenidos mediante SAXS y análisis Barrett-Joyner-Halenda (BJH) de mediciones texturales coinciden en 2.4 y 2.5, respectivamente, resaltando el carácter de red de la estructura de dichas fibras. La estructura mesoporosa y tipo hilo de las fibra de CNT es accesible a la infiltración de moléculas externas (líquidos o polímeros). En este trabajo se estudian los cambios en la estructura multiescala de las fibras de CNTs al interactuar con líquidos y polímeros. Los efectos de la densificación en la estructura de fibras secas de CNT son estudiados mediante WAXS/SAXS. El tratamiento de densificación junta los manojos de la fibra (los poros disminuyen de tamaño), resultando en un incremento de la densidad de la fibra. Sin embargo, los dominios estructurales correspondientes a la transferencia de esfuerzo mecánica y carga eléctrica en los nanotubos no son afectados durante este proceso de densificación; como consecuencia no se produce un efecto sustancial en las propiedades mecánicas y eléctricas. Mediciones de SAXS and fibra de CNT antes y después de infiltración de líquidos confirman la penetración de una gran cantidad de líquidos que llena los poros internos de la fibra pero no se intercalan entre capas de nanotubos adyacentes. La infiltración de cadenas poliméricas de bajo peso molecular tiende a expandir los manojos en la fibra e incrementar el ángulo de apertura de los poros. Los resultados de SAXS indican que la estructura interna de la fibra en términos de la organización de las capas de tubos y su orientación no es afectada cuando las muestras consisten en fibras infiltradas con polímeros de alto peso molecular. La cristalización de varios polímeros semicristalinos es acelerada por la presencia de fibras de CNTs alineados y produce el crecimiento de una capa transcristalina normal a la superficie de la fibra. Esto es observado directamente mediante microscopía óptica polarizada, y detectado mediante calorimetría DSC. Las lamelas en la capa transcristalina tienen orientación de la cadena polimérica paralela a la fibra y por lo tanto a los nanotubos, de acuerdo con los patrones de WAXS. Esta orientación preferencial se sugiere como parte de la fuerza impulsora en la nucleación. La nucleación del dominio cristalino polimérico en la superficie de los CNT no es epitaxial. Ocurre sin haber correspondencia entre las estructuras cristalinas del polímero y los nanotubos. Estas observaciones contribuyen a la compresión del fenómeno de nucleación en CNTs y otros nanocarbonos, y sientan las bases para el desarrollo de composites poliméricos de gran escala basados en fibra larga de CNTs alineados. ABSTRACT The assembly of carbon nanotubes into a macroscopic fibre material where they are preferentially aligned parallel to each other and to the fibre axis has resulted in a new class of high-performance fibres, which efficiently exploits the axial properties of the building blocks and has numerous applications. Long, continuous CNT fibres were produced in IMDEA Materials Institute by direct fibre spinning from a chemical vapour deposition reaction. These fibres have a complex hierarchical structure covering multiple length scales. One objective of this thesis is to reveal this structure by means of state-of-the-art techniques such as synchrotron X-ray diffraction, and to build a model to link the fibre structural elements. Texture and gas absorption measurements, using electron microscopy, wide angle and small angle X-ray scattering (WAXS/SAXS), and pore size distribution analysis by Barrett-Joyner-Halenda (BJH), indicate that the material has a mesoporous structure with a wide pore size distribution arising from the range of fibre bundle separation, and a high surface area _170m2/g. Fractal dimension values of 2.4_2.5 obtained from the SAXS and BJH measurements highlight the network structure of the fibre. Mesoporous and yarn-like structure of CNT fibres make them accessible to the infiltration of foreign molecules (liquid or polymer). This work studies multiscale structural changes when CNT fibres interact with liquids and polymers. The effects of densification on the structure of dry CNT fibres were measured by WAXS/SAXS. The densification treatment brings the fibre bundles closer (pores become smaller), leading to an increase in fibre density. However, structural domains made of the load and charge carrying nanotubes are not affected; consequently, it has no substantial effect on mechanical and electrical properties. SAXS measurements on the CNT fibres before and after liquid infiltration imply that most liquids are able to fill the internal pores but not to intercalate between nanotubes. Successful infiltration of low molecular weight polymer chains tends to expand the fibre bundles and increases the pore-opening angle. SAXS results indicate that the inner structure of the fibre, in terms of the nanotube layer arrangement and the fibre alignment, are not largely affected when infiltrated with polymers of relatively high molecular weight. The crystallisation of a variety of semicrystalline polymers is accelerated by the presence of aligned fibres of CNTs and results in the growth of a transcrystalline layer perpendicular to the fibre surface. This can be observed directly under polarised optical microscope, and detected by the exothermic peaks during differential scanning calorimetry. The discussion on the driving forces for the enhanced nucleation points out the preferential chain orientation of polymer lamella with the chain axis parallel to the fibre and thus to the nanotubes, which is confirmed by two-dimensional WAXS patterns. A non-epitaxial polymer crystal growth habit at the CNT-polymer interface is proposed, which is independent of lattice matching between the polymer and nanotubes. These findings contribute to the discussion on polymer nucleation on CNTs and other nanocarbons, and their implication for the development of large polymer composites based on long and aligned fibres of CNTs.

Caracterización del hormigón en relación a la difusión de gases y su correlación con el radón

Radon gas (Rn) is a natural radioactive gas present in some soils and able to penetrate buildings through the building envelope in contact with the soil. Radon can accumulate within buildings and consequently be inhaled by their occupants. Because it is a radioactive gas, its disintegration process produces alpha particles that, in contact with the lung epithelia, can produce alterations potentially giving rise to cancer. Many international organizations related to health protection, such as WHO, confirm this causality. One way to avoid the accumulation of radon in buildings is to use the building envelope as a radon barrier. The extent to which concrete provides such a barrier is described by its radon diffusion coefficient (DRn), a parameter closely related to porosity (ɛ) and tortuosity factor (τ). The measurement of the radon diffusion coefficient presents challenges, due to the absence of standard procedures, the requirement to establish adequate airtightness in testing apparatus (referred to here as the diffusion cell), and due to the fact that measurement has to be carried out in an environment certified for use of radon calibrated sources. In addition to this calibrated radon sources are costly. The measurement of the diffusion coefficient for non-radioactive gas is less complex, but nevertheless retains a degree of difficulty due to the need to provide reliably airtight apparatus for all tests. Other parameters that can characterize and describe the process of gas transport through concrete include the permeability coefficient (K) and the electrical resistivity (ρe), both of which can be measured relatively easily with standardized procedure. The use of these parameters would simplify the characterization of concrete behaviour as a radon barrier. Although earlier studies exist, describing correlation among these parameters, there is, as has been observed in the literature, little common ground between the various research efforts. For precisely this reason, prior to any attempt to measure radon diffusion, it was deemed necessary to carry out further research in this area, as a foundation to the current work, to explore potential relationships among the following parameters: porosity-tortuosity, oxygen diffusion coefficient, permeability coefficient and resistivity. Permeability coefficient measurement (m2) presents a more straightforward challenge than diffusion coefficient measurement. Some authors identify a relationship between both coefficients, including Gaber (1988), who proposes: k= a•Dn Equation 1 Where: a=A/(8ΠD020), A = sample cross-section, D020 = diffusion coefficient in air (m2/s). Other studies (Klink et al. 1999, Gaber and Schlattner 1997, Gräf and Grube et al. 1986), experimentally relate both coefficients of different types of concrete confirming that this relationship exists, as represented by the simplified expression: k≈Dn Equation 2 In each particular study a different value for n was established, varying from 1.3 to 2.5, but this requires determination of a value for n in a more general way because these proposed models cannot estimate diffusion coefficient. If diffusion coefficient has to be measured to be able to establish n, these relationships are not interesting. The measurement of electric resistivity is easier than diffusion coefficient measurement. Correlation between the parameters can be established via Einstein´s law that relates movement of electrical charges to media conductivity according to the expression: D_e=k/ρ Equation 3 Where: De = diffusion coefficient (cm2/s), K = constant, ρ = electric resistivity (Ω•cm). The tortuosity factor is used to represent the uneven geometry of concrete pores, which are described as being not straight, but tortuous. This factor was first introduced in the literature to relate global porosity with fluid transport in a porous media, and can be formulated in a number of different ways. For example, it can take the form of equation 4 (Mason y Malinauskas), which combines molecular and Knudsen diffusion using the tortuosity factor: D=ε^τ (3/2r √(πM/8RT+1/D_0 ))^(-1) Equation 4 Where: r = medium radius obtained from MIP (µm), M = gas molecular mass, R = ideal gases constant, T = temperature (K), D0 = coefficient diffusion in the air (m2/s). Few studies provide any insight as to how to obtain the tortuosity factor. The work of Andrade (2012) is exceptional in this sense, as it outlines how the tortuosity factor can be deduced from pore size distribution (from MIP) from the equation: ∅_th=∅_0•ε^(-τ). Equation 5 Where: Øth = threshold diameter (µm), Ø0 = minimum diameter (µm), ɛ = global porosity, τ = tortuosity factor. Alternatively, the following equation may be used to obtain the tortuosity factor: DO2=D0*ɛτ Equation 6 Where: DO2 = oxygen diffusion coefficient obtained experimentally (m2/s), DO20 = oxygen diffusion coefficient in the air (m2/s). This equation has been inferred from Archie´s law ρ_e=〖a•ρ〗_0•ɛ^(-m) and from the Einstein law mentioned above, using the values of oxygen diffusion coefficient obtained experimentally. The principal objective of the current study was to establish correlations between the different parameters that characterize gas transport through concrete. The achievement of this goal will facilitate the assessment of the useful life of concrete, as well as open the door to the pro-active planning for the use of concrete as a radon barrier. Two further objectives were formulated within the current study: 1.- To develop a method for measurement of gas coefficient diffusion in concrete. 2.- To model an analytic estimation of radon diffusion coefficient from parameters related to concrete porosity and tortuosity factor. In order to assess the possible correlations, parameters have been measured using the standardized procedures or purpose-built in the laboratory for the study of equations 1, 2 y 3. To measure the gas diffusion coefficient, a diffusion cell was designed and manufactured, with the design evolving over several cycles of research, leading ultimately to a unit that is reliably air tight. The analytic estimation of the radon diffusion coefficient DRn in concrete is based on concrete global porosity (ɛ), whose values may be experimentally obtained from a mercury intrusion porosimetry test (MIP), and from its tortuosity factor (τ), derived using the relations expressed in equations 5 y 6. The conclusions of the study are: Several models based on regressions, for concrete with a relative humidity of 50%, have been proposed to obtain the diffusion coefficient following the equations K=Dn, K=a*Dn y D=n/ρe. The final of these three relations is the one with the determination coefficient closest to a value of 1: D=(19,997*LNɛ+59,354)/ρe Equation 7 The values of the obtained oxygen diffusion coefficient adjust quite well to those experimentally measured. The proposed method for the measurement of the gas coefficient diffusion is considered to be adequate. The values obtained for the oxygen diffusion coefficient are within the range of those proposed by the literature (10-7 a 10-8 m2/s), and are consistent with the other studied parameters. Tortuosity factors obtained using pore distribution and the expression Ø=Ø0*ɛ-τ are inferior to those from resistivity ρ=ρ0*ɛ-τ. The closest relationship to it is the one with porosity of pore diameter 1 µm (τ=2,07), being 7,21% inferior. Tortuosity factors obtained from the expression DO2=D0*ɛτ are similar to those from resistivity: for global tortuosity τ=2,26 and for the rest of porosities τ=0,7. Estimated radon diffusion coefficients are within the range of those consulted in literature (10-8 a 10-10 m2/s).ABSTRACT El gas radón (Rn) es un gas natural radioactivo presente en algunos terrenos que puede penetrar en los edificios a través de los cerramientos en contacto con el mismo. En los espacios interiores se puede acumular y ser inhalado por las personas. Al ser un gas radioactivo, en su proceso de desintegración emite partículas alfa que, al entrar en contacto con el epitelio pulmonar, pueden producir alteraciones del mismo causando cáncer. Muchos organismos internacionales relacionados con la protección de la salud, como es la OMS, confirman esta causalidad. Una de las formas de evitar que el radón penetre en los edificios es utilizando las propiedades de barrera frente al radón de su propia envolvente en contacto con el terreno. La principal característica del hormigón que confiere la propiedad de barrera frente al radón cuando conforma esta envolvente es su permeabilidad que se puede caracterizar mediante su coeficiente de difusión (DRn). El coeficiente de difusión de un gas en el hormigón es un parámetro que está muy relacionado con su porosidad (ɛ) y su tortuosidad (τ). La medida del coeficiente de difusión del radón resulta bastante complicada debido a que el procedimiento no está normalizado, a que es necesario asegurar una estanquidad a la celda de medida de la difusión y a que la medida tiene que ser realizada en un laboratorio cualificado para el uso de fuentes de radón calibradas, que además son muy caras. La medida del coeficiente de difusión de gases no radioactivos es menos compleja, pero sigue teniendo un alto grado de dificultad puesto que tampoco está normalizada, y se sigue teniendo el problema de lograr una estanqueidad adecuada de la celda de difusión. Otros parámetros que pueden caracterizar el proceso son el coeficiente de permeabilidad (K) y la resistividad eléctrica (ρe), que son más fáciles de determinar mediante ensayos que sí están normalizados. El uso de estos parámetros facilitaría la caracterización del hormigón como barrera frente al radón, pero aunque existen algunos estudios que proponen correlaciones entre estos parámetros, en general existe divergencias entre los investigadores, como se ha podido comprobar en la revisión bibliográfica realizada. Por ello, antes de tratar de medir la difusión del radón se ha considerado necesario realizar más estudios que puedan clarificar las posibles relaciones entre los parámetros: porosidad-tortuosidad, coeficiente de difusión del oxígeno, coeficiente de permeabilidad y resistividad. La medida del coeficiente de permeabilidad (m2) es más sencilla que el de difusión. Hay autores que relacionan el coeficiente de permeabilidad con el de difusión. Gaber (1988) propone la siguiente relación: k= a•Dn Ecuación 1 En donde: a=A/(8ΠD020), A = sección de la muestra, D020 = coeficiente de difusión en el aire (m2/s). Otros estudios (Klink et al. 1999, Gaber y Schlattner 1997, Gräf y Grube et al. 1986) relacionan de forma experimental los coeficientes de difusión de radón y de permeabilidad de distintos hormigones confirmando que existe una relación entre ambos parámetros, utilizando la expresión simplificada: k≈Dn Ecuación 2 En cada estudio concreto se han encontrado distintos valores para n que van desde 1,3 a 2,5 lo que lleva a la necesidad de determinar n porque no hay métodos que eviten la determinación del coeficiente de difusión. Si se mide la difusión ya deja de ser de interés la medida indirecta a través de la permeabilidad. La medida de la resistividad eléctrica es muchísimo más sencilla que la de la difusión. La relación entre ambos parámetros se puede establecer a través de una de las leyes de Einstein que relaciona el movimiento de cargas eléctricas con la conductividad del medio según la siguiente expresión: D_e=k/ρ_e Ecuación 3 En donde: De = coeficiente de difusión (cm2/s), K = constante, ρe = resistividad eléctrica (Ω•cm). El factor de tortuosidad es un factor de forma que representa la irregular geometría de los poros del hormigón, al no ser rectos sino tener una forma tortuosa. Este factor se introduce en la literatura para relacionar la porosidad total con el transporte de un fluido en un medio poroso y se puede formular de distintas formas. Por ejemplo se destaca la ecuación 4 (Mason y Malinauskas) que combina la difusión molecular y la de Knudsen utilizando el factor de tortuosidad: D=ε^τ (3/2r √(πM/8RT+1/D_0 ))^(-1) Ecuación 4 En donde: r = radio medio obtenido del MIP (µm), M = peso molecular del gas, R = constante de los gases ideales, T = temperatura (K), D0 = coeficiente de difusión de un gas en el aire (m2/s). No hay muchos estudios que proporcionen una forma de obtener este factor de tortuosidad. Destaca el estudio de Andrade (2012) en el que deduce el factor de tortuosidad de la distribución del tamaño de poros (curva de porosidad por intrusión de mercurio) a partir de la ecuación: ∅_th=∅_0•ε^(-τ) Ecuación 5 En donde: Øth = diámetro umbral (µm), Ø0 = diámetro mínimo (µm), ɛ = porosidad global, τ = factor de tortuosidad. Por otro lado, se podría utilizar también para obtener el factor de tortuosidad la relación: DO2=D0*-τ Ecuación 6 En donde: DO2 = coeficiente de difusión del oxígeno experimental (m2/s), DO20 = coeficiente de difusión del oxígeno en el aire (m2/s). Esta ecuación está inferida de la ley de Archie ρ_e=〖a•ρ〗_0•ɛ^(-m) y la de Einstein mencionada anteriormente, utilizando valores del coeficiente de difusión del oxígeno DO2 obtenidos experimentalmente. El objetivo fundamental de la tesis es encontrar correlaciones entre los distintos parámetros que caracterizan el transporte de gases a través del hormigón. La consecución de este objetivo facilitará la evaluación de la vida útil del hormigón así como otras posibilidades, como la evaluación del hormigón como elemento que pueda ser utilizado en la construcción de nuevos edificios como barrera frente al gas radón presente en el terreno. Se plantean también los siguientes objetivos parciales en la tesis: 1.- Elaborar una metodología para la medida del coeficiente de difusión de los gases en el hormigón. 2.- Plantear una estimación analítica del coeficiente de difusión del radón a partir de parámetros relacionados con su porosidad y su factor de tortuosidad. Para el estudio de las correlaciones posibles, se han medido los parámetros con los procedimientos normalizados o puestos a punto en el propio Instituto, y se han estudiado las reflejadas en las ecuaciones 1, 2 y 3. Para la medida del coeficiente de difusión de gases se ha fabricado una celda que ha exigido una gran variedad de detalles experimentales con el fin de hacerla estanca. Para la estimación analítica del coeficiente de difusión del radón DRn en el hormigón se ha partido de su porosidad global (ɛ), que se obtiene experimentalmente del ensayo de porosimetría por intrusión de mercurio (MIP), y de su factor de tortuosidad (τ), que se ha obtenido a partir de las relaciones reflejadas en las ecuaciones 5 y 6. Las principales conclusiones obtenidas son las siguientes: Se proponen modelos basados en regresiones, para un acondicionamiento con humedad relativa de 50%, para obtener el coeficiente de difusión del oxígeno según las relaciones: K=Dn, K=a*Dn y D=n/ρe. La propuesta para esta última relación es la que tiene un mejor ajuste con R2=0,999: D=(19,997*LNɛ+59,354)/ρe Ecuación 7 Los valores del coeficiente de difusión del oxígeno así estimados se ajustan a los obtenidos experimentalmente. Se considera adecuado el método propuesto de medida del coeficiente de difusión para gases. Los resultados obtenidos para el coeficiente de difusión del oxígeno se encuentran dentro del rango de los consultados en la literatura (10-7 a 10-8 m2/s) y son coherentes con el resto de parámetros estudiados. Los resultados de los factores de tortuosidad obtenidos de la relación Ø=Ø0*ɛ-τ son inferiores a la de la resistividad (ρ=ρ0*ɛ-τ). La relación que más se ajusta a ésta, siendo un 7,21% inferior, es la de la porosidad correspondiente al diámetro 1 µm con τ=2,07. Los resultados de los factores de tortuosidad obtenidos de la relación DO2=D0*ɛτ son similares a la de la resistividad: para la porosidad global τ=2,26 y para el resto de porosidades τ=0,7. Los coeficientes de difusión de radón estimados mediante estos factores de tortuosidad están dentro del rango de los consultados en la literatura (10-8 a 10-10 m2/s).

Influência do tamanho da amostra na determinação da curva de retenção da água no solo

A curva de retenção da água no solo é um dos principais instrumentos para avaliar a qualidade física dos solos e possibilitar seu manejo adequado. Por meio da Teoria da Capilaridade vários equipamentos foram desenvolvidos para determinar a intensidade com que a água está retida ao solo, porém, pouco se tem dado atenção para verificar se os pressupostos para o real funcionamento da teoria estão sendo atendidos. Um aspecto refere-se ao tamanho da amostra utilizada para determinar a curva de retenção, de modo que haja continuidade dos feixes capilares na amostra e placa porosa. Desta forma, este trabalho propõe avaliar diferentes tamanhos de amostra indeformada para a determinação da curva de retenção. Para isso, coletaram-se amostras em anéis volumétricos cilíndricos de três tamanhos (altura) diferentes (T1 - 0,075 m; T2 - 0,05 m; T3 - 0,025 m;) e mesmo diâmetro interno (0,07 m), dos horizontes diagnósticos de um Latossolo e um Nitossolo em áreas experimentais da Escola Superior de Agricultura Luiz de Queiroz (Esalq/USP), Piracicaba - SP. Realizou-se a caracterização física destes solos, por meio da análise granulométrica, densidade do solo, densidade de partículas, porosidade total e teor de carbono orgânico. As curvas foram determinadas para cada tamanho de amostra, utilizando-se o Funil de Haines, para as tensões 0,5, 1, 4, 6 e 10 kPa, e a Câmara de Pressão de Richards para 33, 100 e 500 kPa. As curvas de retenção foram ajustadas pelo modelo utilizado por van Genuchten. Estimadas as curvas, avaliou-se a distribuição de poros do solo das amostras, determinando-se a curva de frequência acumulada de poros em função do logaritmo do raio e, depois pela diferenciação das equações de ajuste das curvas de retenção, a curva diferencial de frequência acumulada de poros. Os resultados mostram que o Latossolo, por ter textura arenosa no horizonte estudado, não apresentou diferença significativa nas curvas de retenção para os tamanhos das amostras estudadas. Verificou-se pouca modificação na distribuição dos poros deste solo, que possui teor elevado das frações areia fina e muito fina, e desenvolveram papel importante para a retenção de água. O Nitossolo, por sua vez, apresentou diferença significativa da curva obtida pela amostra de menor tamanho (T3), havendo maior retenção de água com a diminuição do tamanho da amostra. Devido a sua textura muito argilosa, o arranjo estrutural deste solo foi diferenciado ao se utilizar as amostras maiores, com provável interrupção e descontinuidade dos feixes capilares. Consequentemente, houve também alteração na distribuição dos poros, com redução dos mesoporos e aumento dos microporos. Desta forma, pode-se concluir que o tamanho da amostra influenciou a curva de retenção da água devido à complexidade estrutural do solo, que provavelmente é diferente nas amostras maiores por causa da continuidade dos feixes capilares, principalmente no Nitossolo. Em outras palavras, quanto menor o tamanho da amostra há menor diferenciação no arranjo de poros, ou seja, maior proximidade da real condição do solo e, assim, uma interpretação da retenção de água \"mais correta\" por meio da Teoria da Capilaridade.

Relevance of porosity and surface chemistry of superactivated carbons in capacitors

We show, through some examples, that chemical activation by alkaline hydroxides permits the preparation of activated carbons with tailored pore volume, pore size distribution, pore structure and surface chemistry, which are useful for their application as electrodes in supercapacitors. Examples are presented discussing the importance of each of these properties on the double layer capacitance, on the kinetics of the electric double-layer charge-discharge process and on the pseudo-capacitative contribution from the surface functional groups or the addition of a conducting polymer.

Assessment of CO2 adsorption capacity on activated carbons by a combination of batch and dynamic tests

In this work, batch and dynamic adsorption tests are coupled for an accurate evaluation of CO2 adsorption performance for three different activated carbons obtained from olives stones by chemical activation followed by physical activation with CO2 at varying times, i.e. 20, 40 and 60 h. Kinetic and thermodynamic CO2 adsorption tests from simulated flue-gas at different temperature and CO2 pressure are carried out both in batch (a manometric equipment operating with pure CO2) and dynamic (a lab-scale fixed-bed column operating with CO2/N2 mixture) conditions. The textural characterization of the activated carbon samples shows a direct dependence of both micropore and ultramicropore volume on the activation time, hence AC60 has the higher contribution. The adsorption tests conducted at 273 and 293 K showed that, when CO2 pressure is lower than 0.3 bar, the lower the activation time the higher CO2 adsorption capacity and a ranking ωeq(AC20)>ωeq(AC40)>ωeq(AC60) can be exactly defined when T= 293 K. This result can be likely ascribed to a narrower pore size distribution of the AC20 sample, whose smaller pores are more effective for CO2 capture at higher temperature and lower CO2 pressure, the latter representing operating conditions of major interest for decarbonation of a flue-gas effluent. Moreover, the experimental results obtained from dynamic tests confirm the results derived from the batch tests in terms of CO2 adsorption capacity. It is important to highlight that the adsorption of N2 on the synthesized AC samples can be considered negligible. Finally, the importance of a proper analysis of characterization data and adsorption experimental results is highlighted for a correct assessment of CO2 removal performances of activated carbons at different CO2 pressure and operating temperature.

Sorbent design for CO2 capture under different flue gas conditions

CO2 capture by solid sorbents is a physisorption process in which the gas molecules are adsorbed in a different porosity range, depending on the temperature and pressure of the capture conditions. Accordingly, CO2 capture capacities can be enhanced if the sorbent has a proper porosity development and a suitable pore size distribution. Thus, the main objective of this work is to maximize the CO2 capture capacity at ambient temperature, elucidating which is the most suitable porosity that the adsorbent has to have as a function of the emission source conditions. In order to do so, different activated carbons have been selected and their CO2 capture capacities have been measured. The obtained results show that for low CO2 pressures (e.g., conditions similar to post-combustion processes) the sorbent should have the maximum possible volume of micropores smaller than 0.7 nm. However, the sorbent requires the maximum possible total micropore volume when the capture is performed at high pressures (e.g., conditions similar to oxy-combustion or pre-combustion processes). Finally, this study also analyzes the important influence that the sorbent density has on the CO2 capture capacity, since the adsorbent will be confined in a bed with a restricted volume.

Novel silica membrane material for molecular sieve applications

Development of new silica membranes properties, e.g., molecular sieving properties, has been increasingly gaining importance in the last few years. A novel unsupported silica membrane, referred to as hydrophobic metal-doped silica, was developed by cobalt-doping within the organic templated silica matrix. The novel material was prepared by the acid-catalyzed hydrolysis and condensation process of tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES), which is the precursor for methyl ligand covalently bounded to the silica matrix. The synthesis and surface properties of the novel unsupported silica membrane as well as the unsupported blank silica and modified silica membranes were revealed by surface and microstructural techniques, such as water contact angle measurement, FTIR, X-ray, Solid-state 29Si MAS NMR, TGA and N2 and CO2 adsorption measurements. The results showed that the thermal stability of the organic templated silica matrix was enhanced by cobalt-doping process. A hydrophobic microporous silica membrane material with high thermal stability up to ∼560 °C in oxidizing atmosphere and a narrow pore size distribution centered at 1.1 nm was obtained. Therefore, a novel precursor material for molecular sieve silica membranes applications has been achieved and developed.

Textural Characterization of Micro- and Mesoporous Carbons Using Combined Gas Adsorption and n-Nonane Preadsorption

Porous carbon and carbide materials with different structures were characterized using adsorption of nitrogen at 77.4 K before and after preadsorption of n-nonane. The selective blocking of the microporosity with n-nonane shows that ordered mesoporous silicon carbide material (OM-SiC) is almost exclusively mesoporous whereas the ordered mesoporous carbon CMK-3 contains a significant amount of micropores (25%). The insertion of micropores into OM-SiC using selective extraction of silicon by hot chlorine gas leads to the formation of ordered mesoporous carbide-derived carbon (OM-CDC) with a hierarchical pore structure and significantly higher micropore volume as compared to CMK-3, whereas a CDC material from a nonporous precursor is exclusively microporous. Volumes of narrow micropores, calculated by adsorption of carbon dioxide at 273 K, are in linear correlation with the volumes blocked by n-nonane. Argon adsorption measurements at 87.3 K allow for precise and reliable calculation of the pore size distribution of the materials using density functional theory (DFT) methods.

Characterization of Carbon Molecular Sieve Membranes Supported on Ceramic Tubes

Carbon molecular sieve membranes have been analyzed in supported and unsupported configurations in this experimental study. The membranes were used to adsorb CO2, N2 and CH4, and their adsorption data were analyzed to establish differences in rate and capacity of adsorption between the two types of samples (supported and unsupported). Experimental results show an important effect of the support, which can be considered as an additional parameter to tailor pore size on these carbon membranes. Immersion calorimetry values were measured by immersing the membranes into liquids of different molecular dimensions (dichloromethane, benzene, n-hexane, 2,2-dimethylbutane). Similarities were found between adsorption and calorimetric analysis. The pore volume of the samples analyzed ranged from 0.016 to 0.263 cm3/g. The effect of the pyrolysis temperature, either 550 or 700 °C, under N2 atmosphere was also analyzed. Quantification of the pore-size distribution of the support was done by liquid-liquid displacement porosimetry. The composite membrane was used for CO2/CH4 separation before and after pore plugging was done. The ideal selectivity factors value (4.47) was over the Knudsen theoretical factor (0.60) for membrane pyrolyzed at 600 °C, which indicates the potential application of these membranes for the separation of low-molecular weight gases.

Comparison Between Dcrit Considering the Abrupt Variation and Inflexion in the Concrete Mercury Intrusion Porosimetry Curve

Mercury intrusion porosimetry (MIP) has been widely used to evaluate the quality of concrete through the pore size distribution parameters. Two of these parameters are the critical pore diameter (Dcrit) and the percentage of the most interconnected net of pores compared to the total volume of pores. Some researchers consider Dcrit as the diameter obtained from the inflexion point of the cumulative mercury intrusion curve while others consider Dcrit as the diameter obtained from the point of abrupt variation in the same curve. This study aims to analyze two groups of concretes of varying w/c ratios, one cast with pozzolanic cement and another with high initial strength cement, in order to determine which of these diameters feature a better correlation with the quality parameters of the concretes. The concrete quality parameters used for the evaluations were (1) the w/c ratios and (2) chloride diffusion coefficients measured at approximately 90 days. MIP cumulative distributions of the same concretes were also measured at about 90 days, and Dcrit values were determined (1) from the point of abrupt variation and alternatively, (2) from the inflexion point of each of these plots. It was found that Dcrit values measured from the point of abrupt variation were useful indicators of the quality of the concrete, but the Dcrit values based on the inflexion points were not. Hence, it is recommended that Dcrit and the percentage of the most interconnected volume of pores should be obtained considering the point of abrupt variation of the cumulative curve of pore size distribution.

Structural and mechanical properties of nanostructured granular alumina catalysts

Granular gamma-Al2O3 support and 8 wt % CuO/gamma-Al2O3 catalyst were synthesized by a sol-gel granulation method. The pore structure, crush strength, hardness, and elasticity of these sol-gel-derived catalysts were studied and compared with similar commercial catalysts prepared by non-sol-gel methods. Alumina and CuO-coated alumina granular particles prepared by different methods have different macro- and microstructure. The sol-gel-derived granular gamma-alumina and CuO-coated gamma-alumina granular particles have a structure defined by compact packing of uniform, nanosized gamma-alumina crystallites. They are characterized by a more uniform pore size distribution and larger surface area as compared to similar commercial samples with a structure defined by packing of aggregates consisting of nonuniform gamma-alumina crystallites. Because of the differences in the macro- and microstructure, the sol-gel-derived granular samples offer higher crush strength and greater hardness than the commercial samples.

The comparative characterization of structural heterogeneity of mesoporous activated carbon fibers (ACFs)

The comparative analysis of the most widely used methods of mesoporosity characterization of two activated carbon fibers is presented. Not only the older methods are used, i.e. Barrett, Joyner and Halenda (BJH), Dubinin (the so-called first variant-D-1ST and the so-called second variant-D-2ND), Dollimore and Heal (DH), and Pierce (P) but the recently developed ones, i.e. the method of Nguyen and Do (ND) and that developed by Do (Do) are also applied. Additionally, the method of the characterization of fractality is put to use (fractal analog of FHH isotherm). The results are compared and discussed. (C) 2002 Elsevier Science B.V. All fights reserved.

Refined method of potential enhancement in the equilibria characterization of activated carbon. Comparison with GCMC and DFT

In this paper, we present a technique for equilibria characterization of activated carbon having slit-shaped pores. This method was first developed by Do (Do, D. D. A new method for the characterisation of micro-mesoporous materials. Presented at the International Symposium on New Trends in Colloid and Interface Science, September 24-26, 1998 Chiba, Japan) and applied by his group and other groups for characterization of pore size distribution (PSD) as well as adsorption equilibria determination of a wide range of hydrocarbons. It is refined in this paper and compared with the grand canonical Monte Carlo (GCMG) simulation and density functional theory (DFT). The refined theory results in a good agreement between the pore filling pressure versus pore width and those obtained by GCMG and DFT. Furthermore, our local isotherms are qualitatively in good agreement with those obtained by the GCMC simulations. The main advantage of this method is that it is about 4 orders of magnitude faster than the GCMC simulations, making it suitable for optimization studies and design purposes. Finally, we apply our method and the GCMG in the derivation of the PSD of a commercial activated carbon. It was found that the PSD derived from our method is comparable to that derived from the GCMG simulations.