Structure-transport relationships in disordered solids using integrated rate of gas sorption and mercury porosimetry

This work describes a new experimental approach that delivers novel information on structure-transport relationships in disordered porous pellets. Integrated rate of adsorption and mercury porosimetry experiments have been used to probe the relative importance of particular sub-sets of pores to mass transport rates within the network of two disordered porous solids. This was achieved by examining the relative rates of low pressure gas uptake into a network, both before, and after, a known set of pores was filled with frozen, entrapped mercury. For catalyst pellets, formed by tableting, it has been found that the compaction pressure affects the relative contribution to overall mass transport made by the subset of the largest pores. Computerised X-ray tomography (CXT) has been used to map the spatial distribution of entrapped mercury and revealed that the relative importance of the sub-sets of pores is related to their level of pervasiveness across the pellet, and whether they percolate to the centre of the pellet. It has been shown that a combination of integrated mercury porosimetry and gas sorption, together with CXT, can comprehensively reveal the impact of manufacturing process parameters on pellet structure and mass transport properties. Hence, the new method can be used in the design and optimisation of pellet manufacturing processes

Determination of pore network accessibility in hierarchical porous solids

This paper validates the hypothesis that the supposedly non-specific adsorbates nitrogen and argon wet heavy metals differently, and shows how this unexpected effect can be actively utilised to deliver information on pore inter-connectivity. To explore surface chemistry influences on differential adsorbate wetting, new findings for a mixed silica-alumina material were compared with data for pure silica and alumina materials. The new structural characterisation described can determine the distribution of the particular sub-set of meso-and micro-pores that connect directly to macropores that entrap mercury following porosimetry, as mapped by computerised X-ray tomography. Hence, it elucidates the spatial organization of the network and measures the improved accessibility to smaller pores provided by larger pores. It was shown that the silica-alumina pellets have a hierarchical pore-size arrangement, similar to the optimal blood vessel network architecture in animals. The network architecture derived from the new method has been independently validated using complementary gas sorption scanning curves, integrated mercury porosimetry, and NMR cryoporometry. It has also been shown that, rather than hindering interpretation of characterisation data, emergent effects for networks associated with these techniques can be marshalled to enable detailed assessment of the pore structures of complex, disordered solids

Determination of pore network accessibility in hierarchical porous solids

This paper validates the hypothesis that the supposedly non-specific adsorbates nitrogen and argon wet heavy metals differently, and shows how this unexpected effect can be actively utilised to deliver information on pore inter-connectivity. To explore surface chemistry influences on differential adsorbate wetting, new findings for a mixed silica-alumina material were compared with data for pure silica and alumina materials. The new structural characterisation described can determine the distribution of the particular sub-set of meso-and micro-pores that connect directly to macropores that entrap mercury following porosimetry, as mapped by computerised X-ray tomography. Hence, it elucidates the spatial organization of the network and measures the improved accessibility to smaller pores provided by larger pores. It was shown that the silica-alumina pellets have a hierarchical pore-size arrangement, similar to the optimal blood vessel network architecture in animals. The network architecture derived from the new method has been independently validated using complementary gas sorption scanning curves, integrated mercury porosimetry, and NMR cryoporometry. It has also been shown that, rather than hindering interpretation of characterisation data, emergent effects for networks associated with these techniques can be marshalled to enable detailed assessment of the pore structures of complex, disordered solids

Numerical porosimetry: Evaluation and comparison of yield stress fluids method, mercury intrusion porosimetry and pore network modelling approaches

Mercury Intrusion Porosimetry (MIP) is still today the reference porosimetry technique despite its environmental health and safety concerns. As a safe alternative, the Yield Stress fluids Method (YSM) consists in computing the Pore Size Distribution (PSD) of a given material from the pressure drop vs. flow rate measurements during injection of a yield stress fluid. However, the question arises whether the PSDs provided by YSM are representative of the actual pore dimensions. To answer this question, three numerical methods to obtain the PSD from digital images are proposed and compared in the present work. First, direct numerical simulations of YSM tests are performed in the considered media. Then, realistic PSDs are extracted from the images by using pore Network Modelling (NM). Furthermore, the obtained networks are also used to simulate MIP tests. The quantitative numerical results allow the evaluation of the relevance of YSM as an alternative to toxic MIP

Entwicklung selbstheilender Wärmedämmschichten

The presented work is dealing with the manufacturing of self-healing thermal barrier coatings by atmospheric plasma spraying that are applicable in high temperature processes with thermal loading. The turbine blades of gas turbines for example, experience thermal stresses that are induced into the thermal barrier coatings and can cause crack development. After a certain time these cracks grow and lead to a spallation of the coating. By this, the turbine blade would not be protected any more. With the integration of a self-healing process, the time between maintenances can be extended to save operational costs. The basic idea to realize such self-healing coatings is the integration of MoSi$_{2}$ as self-healing particles. The oxidation of MoSi$_{2}$ leads to the formation of SiO$_{2}$ that can infiltrate cracks and seals them. This can prevent the spallation of the coating. The presented work was performed within a project named SAMBA (self-healing thermal barrier coatings) that was funded by the European Union. The first step in the production of a self-healing thermal barrier coating was the integration of MoSi$_{2}$ particles into a coating. Yttria stabilized zirconia (YSZ) was used as coating matrix since this is the state of the art material. Due to a decomposition of the MoSi$_{2}$ when spraying it at conditions that are needed to produce coatings made out of YSZ, the manufacturing of a homogeneous mixed coating of YSZ and MoSi$_{2}$ from a powder mixture of both materials was not possible. This problem was solved by using a second injection point located at a distance from the plasma-torch-exit. Nevertheless the coatings made out of YSZ and pure MoSi$_{2}$ were not suitable to work as a self-healing thermal barrier coating due to the fact that the oxidation of MoSi$_{2}$ was not controlled. The volume expansion caused by the formation of SiO$_{2}$ induces stresses into the coating that lead to a failure and the spallation of the coating. The second step in the development was to encapsulate the MoSi$_{2}$ particles with Al$_{2}$O$_{3}$, as this encapsulation was supposed to work as a protection against a premature oxidation of the MoSi$_{2}$. As the spraying process leads to a deformation of the particles during deposition on the substrate, a pre-encapsulation of the powder would be destroyed. Because of this, the encapsulation has to be formed in-situ within the coating. Several coatings were produced using Al doped MoSi$_{2}$ to integrate it into the YSZ coatings. These coatings were heat treated and by this several requirements were determined that need to be fulfilled in order to enable the self-healing process. Coatings that have been produced using spraying parameters, that enable the fulfillment of these requirements, and these coatings resulted in an improvement of the lifetime of the coatings compared to standard YSZ coatings. Within the SAMBA project further analysis and investigations will be performed to be able to judge on the self-healing abilities of coatings produced by the procedures described in this work

Influenza della porosità sulle proprietà dei materiali. Un approccio fenomenologico basato sulla geometria frattale

In this thesis, the correlation between microstructure and properties of porous materials is analysed using Fractal Geometry. In particular, the effect of pore size distribution in fluid transport, thermal conductivity and some mechanical properties is studied. Materials used in cultural heritage, contemporary architecture and industrial engineering such as limestone, earth based materials, traditional ceramics, advanced ceramics (zirconia and alumina) and binder have been examined. The porosimetry experimental data has been acquired by mercury intrusion technique. In this research, a model based on fractal of Sierpinski carpet is used. By mixing fractal units with different dimension and configuration, it was possible to create a microstructure of material similar to experimental. Some fractal analytical procedures have been developed to predict thermal conductivity, sorptivity, water vapour permeability and elastic modulus. The data obtained by fractal model has been compared with experimental data. The results obtained are quite close to experimental ones and it has been revealed that this procedure is more effective than other model proposed in the recent literature

Contribution to structural parameters computation: volume models and methods

Bio-CAD and in-silico experimentation are getting a growing interest in biomedical applications where scientific data coming from real samples are used to compute structural parameters that allow to evaluate physical properties. Non-invasive imaging acquisition technologies such as CT, mCT or MRI, plus the constant growth of computer capabilities, allow the acquisition, processing and visualization of scientific data with increasing degree of complexity. Structural parameters computation is based on the existence of two phases (or spaces) in the sample: the solid, which may correspond to the bone or material, and the empty or porous phase and, therefore, they are represented as binary volumes. The most common representation model for these datasets is the voxel model, which is the natural extension to 3D of 2D bitmaps. In this thesis, the Extreme Vertices Model (EVM) and a new proposed model, the Compact Union of Disjoint Boxes (CUDB), are used to represent binary volumes in a much more compact way. EVM stores only a sorted subset of vertices of the object¿s boundary whereas CUDB keeps a compact list of boxes. In this thesis, methods to compute the next structural parameters are proposed: pore-size distribution, connectivity, orientation, sphericity and roundness. The pore-size distribution helps to interpret the characteristics of porous samples by allowing users to observe most common pore diameter ranges as peaks in a graph. Connectivity is a topological property related to the genus of the solid space, measures the level of interconnectivity among elements, and is an indicator of the biomechanical characteristics of bone or other materials. The orientation of a shape can be defined by rotation angles around a set of orthogonal axes. Sphericity is a measure of how spherical is a particle, whereas roundness is the measure of the sharpness of a particle's edges and corners. The study of these parameters requires dealing with real samples scanned at high resolution, which usually generate huge datasets that require a lot of memory and large processing time to analyze them. For this reason, a new method to simplify binary volumes in a progressive and lossless way is presented. This method generates a level-of-detail sequence of objects, where each object is a bounding volume of the previous objects. Besides being used as support in the structural parameter computation, this method can be practical for task such as progressive transmission, collision detection and volume of interest computation. As part of multidisciplinary research, two practical applications have been developed to compute structural parameters of real samples. A software for automatic detection of characteristic viscosity points of basalt rocks and glasses samples, and another to compute sphericity and roundness of complex forms in a silica dataset.El Bio-Diseño Asistido por Computadora (Bio-CAD), y la experimentacion in-silico est an teniendo un creciente interes en aplicaciones biomedicas, en donde se utilizan datos cientificos provenientes de muestras reales para calcular par ametros estructurales que permiten evaluar propiedades físicas. Las tecnologías de adquisicion de imagen no invasivas como la TC, TC o IRM, y el crecimiento constante de las prestaciones de las computadoras, permiten la adquisicion, procesamiento y visualizacion de datos científicos con creciente grado de complejidad. El calculo de parametros estructurales esta basado en la existencia de dos fases (o espacios) en la muestra: la solida, que puede corresponder al hueso o material, y la fase porosa o vacía, por tanto, tales muestras son representadas como volumenes binarios. El modelo de representacion mas comun para estos conjuntos de datos es el modelo de voxeles, el cual es una extension natural a 3D de los mapas de bits 2D. En esta tesis se utilizan el modelo Extreme Verrtices Model (EVM) y un nuevo modelo propuesto, the Compact Union of Disjoint Boxes (CUDB), para representar los volumenes binarios en una forma mucho mas compacta. El modelo EVM almacena solo un subconjunto ordenado de vertices de la frontera del objeto mientras que el modelo CUDB mantiene una lista compacta de cajas. En esta tesis se proponen metodos para calcular los siguientes parametros estructurales: distribucion del tamaño de los poros, conectividad, orientacion, esfericidad y redondez. La distribucion del tamaño de los poros ayuda a interpretar las características de las muestras porosas permitiendo a los usuarios observar los rangos de diametro mas comunes de los poros mediante picos en un grafica. La conectividad es una propiedad topologica relacionada con el genero del espacio solido, mide el nivel de interconectividad entre los elementos, y es un indicador de las características biomecanicas del hueso o de otros materiales. La orientacion de un objeto puede ser definida por medio de angulos de rotacion alrededor de un conjunto de ejes ortogonales. La esfericidad es una medida de que tan esferica es una partícula, mientras que la redondez es la medida de la nitidez de sus aristas y esquinas. En el estudio de estos parametros se trabaja con muestras reales escaneadas a alta resolucion que suelen generar conjuntos de datos enormes, los cuales requieren una gran cantidad de memoria y mucho tiempo de procesamiento para ser analizados. Por esta razon, se presenta un nuevo metodo para simpli car vol umenes binarios de una manera progresiva y sin perdidas. Este metodo genera una secuencia de niveles de detalle de los objetos, en donde cada objeto es un volumen englobante de los objetos previos. Ademas de ser utilizado como apoyo en el calculo de parametros estructurales, este metodo puede ser de utilizado en otras tareas como transmision progresiva, deteccion de colisiones y calculo de volumen de interes. Como parte de una investigacion multidisciplinaria, se han desarrollado dos aplicaciones practicas para calcular parametros estructurales de muestras reales. Un software para la deteccion automatica de puntos de viscosidad característicos en muestras de rocas de basalto y vidrios, y una aplicacion para calcular la esfericidad y redondez de formas complejas en un conjunto de datos de sílice

Applications of x-ray computed microtomography to material science: devices and prespectives

2006/2007The three-dimensional visualization of the inner microstructural features of objects and materials is an aspect of relevant interest for a wide range of scientific and industrial applications. X-ray computed microtomography (μ-CT) is a powerful non-destructive technique capable to satisfy these needs. Once the complete reconstruction of the sample is available, a quantitative characterisation of the microstructure is essential. Through digital image processing tools, image analysis software or custom developed algorithms, it is possible to obtain an exhaustive geometrical, morphological and topological description of the features inside the volume, or to extract other particular parameters of interest (e.g. porosity, voids distribution, cell size distribution, average struts length, connectivity between the cells, tortuosity). This thesis was carried out at the third-generation Elettra Synchrotron Radiation Facility (Trieste, Italy), where a hard X-ray imaging beamline is available. The experience developed at this beamline has leaded scientists to design a complementary state-of-the-art μ-CT facility based on a micro-focus X-ray source, working both in absorption and phase contrast mode. In this dissertation a detailed description of this facility is given together with a rigorous characterization of the imaging system capabilities, in terms of the actual achievable spatial resolution, in order to optimize the working parameters for the different experiments. The main artefacts that concur to the degradation of the quality of the reconstructed images have been considered (e.g. beam hardening effects, ring artefacts, uncertainness associated with the cone-beam geometry): procedures are presented in order to eliminate, or at least to reduce, the causes of these artefacts. The aspects related to the digital image processing of the reconstructed data are intensively developed in this study: appropriated methodologies have been elaborated capable to deal with the different three-dimensional data of complex porous media, providing a correlation between the microstructure and the macroscopic behaviour of the observed materials. Three representative examples obtained with the described methods are used to demonstrate the application of μ-CT, combined with the developed image processing tools, to material science: the geometrical and morphological characterisation of polyurethane foams employed in the automotive industry due their vibro-acoustic properties; a new approach to characterize the resonance spruce wood microstructure in order to study its acoustical behaviour; finally, the possibility of revealing defects in hybrid-friction stir welded aluminium joints, guiding the optimization of the process parameters.La visualizzazione tridimensionale della struttura interna di oggetti e materiali costituisce un aspetto di notevole interesse per una ampia gamma di applicazioni scientifiche ed industriali. La microtomografia computerizzata a raggi X (μ-CT) rappresenta una potente tecnica di indagine adeguata a soddisfare tali richieste. Una volta completata la ricostruzione del campione in esame, è essenziale poter fornire una caratterizzazione quantitativa della microstruttura evidenziata. Attraverso gli strumenti messi a disposizione dalle moderne tecniche di analisi di immagine, per mezzo di software dedicati o algoritmi personalizzati, è possibile ottenere una descrizione esaustiva della geometria, morfologia e topologia degli elementi microstrutturali presenti, che consenta l’estrazione dei parametri di interesse per la particolare applicazione (porosità, distribuzione dei vuoti, dimensione degli elementi, lunghezze caratteristiche, grado di interconnessione, tortuosità etc.). Il presente lavoro di tesi è stato svolto presso il laboratorio di luce sincrotrone di terza generazione Elettra (Trieste, Italia), dove è disponibile una linea sperimentale dedicata all’imaging con raggi X duri. L’esperienza acquisita da parte dei ricercatori di questa linea ha consentito poi la progettazione di una stazione per μ-CT complementare, allo stato dell’arte e basata su una sorgente di radiazione a microfuoco, capace di operare con modalità di raccolta delle immagini sia in assorbimento sia in contrasto di fase. In questa tesi viene fornita una dettagliata descrizione della stazione, accompagnata da una rigorosa caratterizzazione del sistema impiegato per l’acquisizione e la ricostruzione delle immagini, in termini di risoluzione spaziale raggiungibile, così da consentire l’ottimizzazione dei parametri critici di lavoro nelle differenti condizioni sperimentali. Vengono poi presi in considerazione i principali artefatti che contribuiscono al deterioramento della qualità delle immagini ottenute (come il beam hardening, gli artefatti ad anello, gli artefatti legati all’incertezza geometrica associata al fascio conico etc.): vengono quindi proposti dei metodi per l’eliminazione, o almeno la riduzione, delle cause che li determinano. Nella tesi inoltre sono sviluppati in maniera approfondita gli aspetti connessi al trattamento dei dati digitali raccolti: sono state infatti elaborate delle metodologie appropriate, capaci di trattare i diversi tipi di dato provenienti dall’analisi di mezzi porosi, determinanti per la comprensione della correlazione tra la microstruttura del materiale ed il suo comportamento macroscopico. Infine, vengono proposti tre esempi rappresentativi per dimostrare l’efficacia dell’applicazione della μ-CT, in combinazione con gli strumenti di analisi di immagine messi a punto, alla scienza dei materiali: la caratterizzazione geometrica e morfologica di schiume di poliuretano impiegate nell’industria automobilistica come isolante vibro-acustico; un nuovo approccio rivolto alla caratterizzazione della struttura del legno di risonanza al fine di studiarne il comportamento acustico; la possibilità di mettere in luce i difetti in giunti di saldatura di leghe d’alluminio realizzati con la tecnica ibrida friction stir welding/TIG in maniera da ottimizzare i parametri di processo.XX Ciclo197