Drying of porous building materials: hydraulic diffusivity and front propagation

One-dimensional drying of a porous building material is modelled as a nonlinear diffusion process. The most difficult case of strong surface drying when an internal drying front is created is treated in particular. Simple analytical formulae for the drying front and moisture profiles during second stage drying are obtained when the hydraulic diffusivity is known. The analysis demonstrates the origin of the constant drying front speed observed elsewhere experimentally. Application of the formulae is illustrated for an exponential diffusivity and applied to the drying of a fired clay brick.

Hydrothermal carbonization in the synthesis of sustainable porous carbon materials

Carbon materials are found versatile and applicable in wide range of applications. During the recent years research of carbon materials has focussed on the search of environmentally friendly, sustainable, renewable and low-cost starting material sources as well as simple cost-efficient synthesis techniques. As an alternative synthesis technique in the production of carbon materials hydrothermal carbonization (HTC) has shown a great potential. Depending on the application HTC can be performed as such or as a pretreatment technique. This technique allows synthesis of carbon materials i.e. hydrochars in closed vessel in the presence of water and self-generated pressure at relatively low temperatures (180-250 ˚C). As in many applications well developed porosity and heteroatom distribution are in a key role. Therefore in this study different techniques e.g. varying feedstock, templating and post-treatment in order to introduce these properties to the hydrochars structure were performed. Simple monosaccharides i.e. fructose or glucose and more complex compounds such as cellulose and sludge were performed as starting materials. Addition of secondary precursor e.g. thiophenecarboxaldehyde and ovalbumin was successfully exploited in order to alter heteroatom content. It was shown that well-developed porosity (SBET 550 m2/g) can be achieved via one-pot approach (i.e. exploitation of salt mixture) without conventionally used post-carbonization step. Nitrogen-enriched hydrochars indicated significant Pb(II) and Cr(VI) removal efficiency of 240 mg/g and 68 mg/g respectively. Sulphur addition into carbon network was not found to have enhancing effect on the adsorption of methylene blue or change acidity of the carbon material. However, these hydrochars were found to remove 99.9 % methylene blue and adsorption efficiency of these hydrochars remained over 90 % even after regeneration. In addition to water treatment application N-rich high temperature treated carbon materials were proven applicable as electrocatalyst and electrocatalyst support. Hydrothermal carbonization was shown to be workable technique for the production of carbon materials with variable physico-chemical properties and therefore hydrochars could be applied in several different applications e.g. as alternative low-cost adsorbent for pollutant removal from water.

Ceramic Materials Development for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC)

Solid oxide fuel cell (SOFC) is an electrochemical device that converts chemical energy into electric power with high efficiency. Traditional SOFC has its disadvantages, such as redox cycling instability and carbon deposition while using hydrocarbon fuels. It is because traditional SOFC uses Ni-cermet as anode. In order to solve these problems, ceramic anode is a good candidate to replace Ni. However, the conductivity of most ceramic anode materials are much lower than Ni metal, and it introduces high ohmic resistance. How to increase the conductivity is a hot topic in this research field. Based on our proposed mechanism, several types of ceramic materials have been developed. Vanadium doped perovskite, Sr1-x/2VxTi1-xO3 (SVT) and Sr0.2Na0.8Nb1-xVxO3 (SNNV), achieved the conductivity as high as 300 S*cm-1 in hydrogen, without any high temperature reduction. GDC electrolyte supported cell was fabricated with Sr0.2Na0.8Nb0.9V0.1O3 and the performance was measured in hydrogen and methane respectively. Due to vanadium’s intrinsic problems, the anode supported cell is not easy. Fe doped double perovskite Sr2CoMoO6 (SFCM) was also developed. By carefully doping Fe, the conductivity was improved over one magnitude, without any vigorous reducing conditions. SFCM anode supported cell was successfully fabricated with GDC as the electrolyte. By impregnating Ni-GDC nano particles into the anode, the cell can be operated at lower temperatures while having higher performance than the traditional Ni-cermet cells. Meanwhile, this SFCM anode supported SOFC has long term stability in the reformate containing methane. During the anode development, cathode improvement caused by a thin Co-GDC layer was observed. By adding this Co-GDC layer between the electrolyte and the cathode, the interfacial resistance decreases due to fast oxygen ion transport. This mechanism was confirmed via isotope exchange. This Co-GDC layer works with multiple kinds of cathodes and the modified cell’s performance is 3 times as the traditional Ni-GDC cell. With this new method, lowering the SOFC operation temperature is feasible.

Use of Sludge as Ceramic Materials

Nowadays, with increase amounts of sludge derived from the treatment of domestic sewage put pressure into research on systems for the adequate use of these materials. The aim of the present work is to study the use of sludge ash, from sintering and calcinated process, as a raw material for the ceramic industry. Using the sewage sludge ashes as ceramic raw material there will be no contamination of soil and underground water. Metals and toxic compounds like Al, Fe, Ba, Cr, Cu, Mn and Zn oxides were analyzed and characterized by X-ray fluorescence (XRF), scanning electron microscopy (SEM) and plasma emission spectroscopy (ICP-OES). The leached material was chemically analyzed where the integration of oxides into the ceramic matrix of sludge ash was observed. Residual decomposition was analyzed by TG, DTG and DTA curves.

Biomorphous SiC ceramics prepared from cork oak as precursor

Porous ceramic materials of SiC were synthesized from carbon matrices obtained via pyrolysis of natural cork as precursor. We propose a method for the fabrication of complex-shaped porous ceramic hardware consisting of separate parts prepared from natural cork. It is demonstrated that the thickness of the carbon-matrix walls can be increased through their impregnation with Bakelite phenolic glue solution followed by pyrolysis. This decreases the material's porosity and can be used as a way to modify its mechanical and thermal characteristics. Both the carbon matrices (resulted from the pyrolysis step) and the resultant SiC ceramics are shown to be pseudomorphous to the structure of initial cork. Depending on the synthesis temperature, 3C-SiC, 6H-SiC, or a mixture of these polytypes, could be obtained. By varying the mass ratio of initial carbon and silicon components, stoichiometric SiC or SiC:C:Si, SiC:C, and SiC:Si ceramics could be produced. The structure, as well as chemical and phase composition of the prepared materials were studied by means of Raman spectroscopy and scanning electron microscopy.

Porous materials for thermal management under extreme conditions

A brief analysis is presented of how heat transfer takes place in porous materials of various types. The emphasis is on materials able to withstand extremes of temperature, gas pressure, irradiation, etc., i.e. metals and ceramics, rather than polymers. A primary aim is commonly to maximize either the thermal resistance (i.e. provide insulation) or the rate of thermal equilibration between the material and a fluid passing through it (i.e. to facilitate heat exchange). The main structural characteristics concern porosity (void content), anisotropy, pore connectivity and scale. The effect of scale is complex, since the permeability decreases as the structure is refined, but the interfacial area for fluid-solid heat exchange is, thereby, raised. The durability of the pore structure may also be an issue, with a possible disadvantage of finer scale structures being poor microstructural stability under service conditions. Finally, good mechanical properties may be required, since the development of thermal gradients, high fluid fluxes, etc. can generate substantial levels of stress. There are, thus, some complex interplays between service conditions, pore architecture/scale, fluid permeation characteristics, convective heat flow, thermal conduction and radiative heat transfer. Such interplays are illustrated with reference to three examples: (i) a thermal barrier coating in a gas turbine engine; (ii) a Space Shuttle tile; and (iii) a Stirling engine heat exchanger. Highly porous, permeable materials are often made by bonding fibres together into a network structure and much of the analysis presented here is oriented towards such materials. © 2005 The Royal Society.

Dynamic failure in ductile porous materials

In this paper, a mathematical model of dynamic fracture in porous ductile materials under intense dynamic general loading is developed. The mathematical model includes the influence of inertial effects and material rate sensitivity, as well as the contribution of surface energy of a void and material work-hardening. In addition, the condition of the void compaction is considered as well. The threshold stresses for the void growth and compaction are obtained. A simple criterion for ductile fracture which is associated with material distention and plastic deformation is adopted. As an application of the theoretical model, the processes of two-dimensional spallation in LY12 aluminum alloy are successfully simulated by means of two-dimensional finite-difference Lagrangian code.

Development of selected electro-active polymer-ceramic nanocomposites as pyroelectric thermal/infrared detector materials

The present work emphasises on the synthesis and characterization of electro-active polymer-ceramic nanocomposites which can be used for pyroelectric thermal/infrared detection applications. Two sets of samples belong to polymer-microcrystalline composites have also been investigated in the work. The polymers used in the work have been commercially available ones, but the nanoceramics have been synthesized following simple chemical routes and aqueous organic gel routes. After characterizing the nanoceramics for their structure by powder XRD, they have been dispersed in liquid polymer and sonicated for uniform dispersion. The viscous mixture so formed was cast in the form of films for experimentation. Samples with volume fraction of the ceramic phase varied from 0 to 0.25 have been prepared. Solution growth was followed to prepare microcrystalline samples for the polymer-microcrystalline composites. The physical properties that determine the pyroelectric sensitivity of a material are dielectric constant, dielectric loss, pyroelectric coefficient, thermal conductivity and specific heat capacity. These parameters have been determined for all the samples and compositions reported in this work.The pyroelectric figures of merit for all the samples were determined. The pyroelectric figures of merit that determine the pyroelectric sensitivity of a material are current sensitivity, voltage responsivity and detectivity. All these have been determined for each set of samples and reported in the thesis. In order to assess the flexibility and mouldability of the composites we have measured the Shore hardness of each of the composites by indentation technique and compared with the pyroelectric figures of merit. Some important factors considered during the material fabrication stages were maximum flexibility and maximum figures of merit for pyroelectric thermal/IR detection applications. In order to achieve these goals, all the samples are synthesized as composites of polymers and nano/microcrystalline particles and are prepared in the form of freestanding films. The selected polymer matrices and particle inclusions possess good pyroelectric coefficients, low thermal and dielectric properties, so that good pyroelectric figures of merit could be achieved. The salient features of the work include the particle size of the selected ceramic materials. Since they are in nanometer size it was possible to achieve high flexibility and moldability with high figures of merit for even low volume fractions of inclusions of the prepared nanocrystalline composites. In the case of microcrystalline TGS and DTGS, their composites in PU matrix protect them from fragility and humidity susceptibility and made them for environmental friendly applications.

Characterization of ceramic powders used in the inCeram systems to fixed dental Prosthesis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Caracterización de la cerámica para su empleo como material de enfriamiento evaporativo en la envolvente de los edificios = Ceramic characterization towards its application as evaporative cooling material in building envelopes

El presente trabajo de investigación determina las características de la cerámica que más eficientemente se comporta a evaporación y a enfriamiento. Con el objeto de ser empleado como material integrado en la envolvente de los edificios para reducir su carga de refrigeración. La cerámica es un buen material para ser empleado para la refrigeración por evaporación. Es un sólido poroso inerte que, tras ser sometido a cocción a temperaturas por encima de los 900ºC, resulta uno de los materiales que mejor se comportan como contenedor de agua en su red capilar para, posteriormente, ir liberándola por evaporación al mismo tiempo que se enfría su superficie. La metodología general de investigación, se divide en tres etapas: Búsqueda y análisis del estado de la técnica y de la investigación. Estudio teórico de la eficacia del enfriamiento evaporativo como estrategia de enfriamiento pasivo en la arquitectura. Etapa experimental, desarrollada en tres fases: una primera de definición de los parámetros determinantes del Enfriamiento Evaporativo en piezas cerámicas, una segunda de selección cerámica y diseño de ensayos experimentales y una tercera de caracterización de la cerámica bajo criterios de evaporación y de enfriamiento. El recorrido por el estado de la cuestión ha identificado las aplicaciones tecnológicas y las investigaciones científicas que emplean el Enfriamiento Evaporativo con piezas cerámicas como técnica de enfriamiento. Como resultado se ha obtenido una tabla de clasificación de sistemas de enfriamiento evaporativo y se ha constatado que el conjunto de las aplicaciones están centradas en el diseño de piezas o sistemas pero que, sin embargo, no existe una definición de las características de la cerámica para su empleo como material de enfriamiento por evaporación. El estudio teórico de la eficacia del empleo del enfriamiento evaporativo como estrategia de enfriamiento pasivo en la arquitectura se ha realizado mediante cálculos de porcentaje de ampliación de horas en confort con empleo de técnicas de enfriamiento evaporativo directo e indirecto (EED y EEI). Como resultado se obtienen unos mapas para el ámbito español de potencial de aplicación del EED y EEI. Los resultados permiten afirmar que mediante EE se puede llegar a confort en prácticamente la totalidad de las horas de los días más cálidos del año en muchas localidades. La metodología experimental se ha desarrollado en tres fases. En la fase inicial, se han definido los parámetros determinantes del enfriamiento evaporativo en un medio cerámico mediante ensayos experimentales de capacidad de evaporación y de caracterización. Se realizaron un total de 12 ensayos. Se determinó que el material cerámico tiene una gran influencia en la capacidad de evaporación y enfriamiento en las piezas cerámicas, apoyando la hipótesis inicial y la necesidad de caracterizar el material. La primera fase empírica se centró en la selección cerámica y el diseño de los ensayos experimentales de comportamiento hídrico. Se seleccionaron muestras de 5 tipos de cerámica. Se realizaron 4 tipos de ensayos de caracterización y 6 tipos de ensayos experimentales de comportamiento hídrico (total 123 muestras ensayadas). Los resultados obtenidos son de dos tipos, por un lado, se determinó cuál es el tipo de cerámica que más eficientemente se comporta a EE y, por otro, se rediseñaron los ensayos de la última fase experimental. Para la segunda fase experimental se seleccionaron cerámicas de fabricación manual abarcando el mayor número de localidades del ámbito español. Se realizaron ensayos de caracterización de 7 tipos y ensayos de comportamiento hídrico de 5 tipos (total 197 muestras ensayadas). Los resultados de caracterización han permitido aportar unos rangos de las características de la cerámica que más eficientemente se comporta en los ensayos de comportamiento hídrico. Al final de la investigación se ha caracterizado el material cerámico aportando características acerca de su porosidad, capacidad de absorción, color, rugosidad y mineralogía. Así como datos de referencia de su comportamiento hídrico. Además se ha desarrollado una metodología de ensayo específica que permite evaluar la capacidad de enfriamiento eficiente de una pieza cerámica. ABSTRACT The purpose of this research is to determine the characteristics of ceramic materials having the most efficient performance in terms of evaporation and cooling, so that they can be integrated in building envelopes to reduce cooling loads. Ceramics are suitable materials for cooling through passive evaporation. After being fired at temperatures over 900 °C (1,652 °F), the capillary network of this inert porous medium turns to be excellent to retain water, which is progressively liberated by evaporation while the material surface gets colder. Research methodology has involved the following steps: Search and analysis on the state of the art in technology and research. Theoretical study on the efficiency of evaporation as passive cooling strategies in buildings. Experimental stage developed in three phases, namely: definition of parameters determining evaporative cooling in ceramic elements; ceramic selection and design of experimental tests; characterization of ceramic materials under evaporation and cooling criteria. Search and analysis on the state of the art in this field have been useful to identify technology applications and scientific research where ceramics are employed for evaporative cooling. The resulting table shows that applications are wholly focused on the design of pieces and systems. Nonetheless, there is lack of definition of material characteristics in this scope. The theoretical study on efficiency of the passive strategy applied to buildings has been realized by calculation of the percentage increase in comfort hours through direct/indirect evaporative cooling techniques (DEC/IEC). The mapping of their potential application in Spain clearly shows that comfort conditions can be reached in almost all the hours of the hottest days in many towns. In the initial phase of the experimental stage, parameters determining evaporative cooling in ceramic media have been defined. For this purpose, characterization tests and evaporation and cooling rates experiments have been carried out; the number of samples tested amounted to 12. It has been concluded that material characteristics have great influence on these rates, which supports the initial hypothesis and the need for their characterization. The first empirical phase has focused on ceramic selection and design of water behaviour experimental methods. The samples covered five different kinds of ceramic materials. Four different characterization tests and six different water behaviour experiments were carried out; the number of samples tested amounted to 123. The experimental testing procedures served to determine the most efficient types of ceramic materials in terms of evaporative cooling efficiency and, at the same time, made it necessary to change the original designed experimental test for the last phase. In the second phase, a number of varied hand-made ceramic tiles have been selected. Seven different characterization tests and five different water behaviour tests were carried out; the number of samples amounted to 197. The results of characterization served to establish a range of features in ceramic materials according to their efficiency in water behaviour experiments. Finally, ceramic materials have been characterized according to porosity, water absorption, colour, surface roughness and mineralogy. Also, reference data regarding water behaviour have been included. Moreover, an innovative and specific experimental test to evaluate cooling efficiency of ceramic tiles has been developed.

Yield functions for porous materials with cubic symmetry using different definitions of yield

Plastic yield criteria for porous ductile materials are explored numerically using the finite-element technique. The cases of spherical voids arranged in simple cubic, body-centred cubic and face-centred cubic arrays are investigated with void volume fractions ranging from 2 % through to the percolation limit (over 90 %). Arbitrary triaxial macroscopic stress states and two definitions of yield are explored. The numerical data demonstrates that the yield criteria depend linearly on the determinant of the macroscopic stress tensor for the case of simple-cubic and body-centred cubic arrays - in contrast to the famous Gurson-Tvergaard-Needleman (GTN) formula - while there is no such dependence for face-centred cubic arrays within the accuracy of the finite-element discretisation. The data are well fit by a simple extension of the GTN formula which is valid for all void volume fractions, with yield-function convexity constraining the form of the extension in terms of parameters in the original formula. Simple cubic structures are more resistant to shear, while body-centred and face-centred structures are more resistant to hydrostatic pressure. The two yield surfaces corresponding to the two definitions of yield are not related by a simple scaling.

Formation of nanostructured porous Cu-Au surfaces : the influence of cationic sites on (electro)-catalysis

The fabrication of nanostructured bimetallic materials through electrochemical routes offers the ability to control the composition and shape of the final material that can then be effectively applied as (electro)-catalysts. In this work a clean and transitory hydrogen bubble templating method is employed to generate porous Cu–Au materials with a highly anisotropic nanostructured interior. Significantly, the co-electrodeposition of copper and gold promotes the formation of a mixed bimetallic oxide surface which does not occur at the individually electrodeposited materials. Interestingly, the surface is dominated by Au(I) oxide species incorporated within a Cu2O matrix which is extremely effective for the industrially important (electro)-catalytic reduction of 4-nitrophenol. It is proposed that an aurophilic type of interaction takes place between both oxidized gold and copper species which stabilizes the surface against further oxidation and facilitates the binding of 4-nitrophenol to the surface and increases the rate of reaction. An added benefit is that very low gold loadings are required typically less than 2 wt% for a significant enhancement in performance to be observed. Therefore the ability to create a partially oxidized Cu–Au surface through a facile electrochemical route that uses a clean template consisting of only hydrogen bubbles should be of benefit for many more important reactions.

Modifications of surface materials and their effects on cleanability as studied by radiochemical methods

Modifications of surface materials and their effects on cleanability have important impacts in many fields of activity. In this study the primary aim was to develop radiochemical methods suitable for evaluating cleanability in material research for different environments. Another aim was to investigate the effects of surface modifications on cleanabilitity and surface properties of plastics, ceramics, concrete materials and also their coatings in conditions simulating their typical environments. Several new 51Cr and 14C labelled soils were developed for testing situations. The new radiochemical methods developed were suitable for examining different surface materials and different soil types, providing quantitative information about the amount of soil on surfaces. They also take into account soil soaked into surfaces. The supporting methods colorimetric determination and ATP bioluminescence provided semi-quantitative results. The results from the radiochemical and supporting methods partly correlated with each other. From a material research point of view numerous new materials were evaluated. These included both laboratory-made model materials and commercial products. Increasing the amount of plasticizer decreased the cleanability of poly(vinyl chloride) (PVC) materials. Microstructured surfaces of plastics improved the cleanability of PVC from particle soils, whereas for oil soil microstructuring reduced the cleanability. In the case of glazed ceramic materials, coatings affected the cleanability. The roughness of surfaces correlated with cleanability from particle soils and the cleanability from oil soil correlated with the contact angles. Organic particle soil was removed more efficiently from TiO2-coated ceramic surfaces after UV-radiation than without UV treatment, whereas no effect was observed on the cleanability of oil soil. Coatings improved the cleanability of concrete flooring materials intended for use in animal houses.

Mesoporous silica- and silicon-based materials as carriers for poorly water soluble drugs

New chemical entities with unfavorable water solubility properties are continuously emerging in drug discovery. Without pharmaceutical manipulations inefficient concentrations of these drugs in the systemic circulation are probable. Typically, in order to be absorbed from the gastrointestinal tract, the drug has to be dissolved. Several methods have been developed to improve the dissolution of poorly soluble drugs. In this study, the applicability of different types of mesoporous (pore diameters between 2 and 50 nm) silicon- and silica-based materials as pharmaceutical carriers for poorly water soluble drugs was evaluated. Thermally oxidized and carbonized mesoporous silicon materials, ordered mesoporous silicas MCM-41 and SBA-15, and non-treated mesoporous silicon and silica gel were assessed in the experiments. The characteristic properties of these materials are the narrow pore diameters and the large surface areas up to over 900 m²/g. Loading of poorly water soluble drugs into these pores restricts their crystallization, and thus, improves drug dissolution from the materials as compared to the bulk drug molecules. In addition, the wide surface area provides possibilities for interactions between the loaded substance and the carrier particle, allowing the stabilization of the system. Ibuprofen, indomethacin and furosemide were selected as poorly soluble model drugs in this study. Their solubilities are strongly pH-dependent and the poorest (< 100 µg/ml) at low pH values. The pharmaceutical performance of the studied materials was evaluated by several methods. In this work, drug loading was performed successfully using rotavapor and fluid bed equipment in a larger scale and in a more efficient manner than with the commonly used immersion methods. It was shown that several carrier particle properties, in particular the pore diameter, affect the loading efficiency (typically ~25-40 w-%) and the release rate of the drug from the mesoporous carriers. A wide pore diameter provided easier loading and faster release of the drug. The ordering and length of the pores also affected the efficiency of the drug diffusion. However, these properties can also compensate the effects of each other. The surface treatment of porous silicon was important in stabilizing the system, as the non-treated mesoporous silicon was easily oxidized at room temperature. Different surface chemical treatments changed the hydrophilicity of the porous silicon materials and also the potential interactions between the loaded drug and the particle, which further affected the drug release properties. In all of the studies, it was demonstrated that loading into mesoporous silicon and silica materials improved the dissolution of the poorly soluble drugs as compared to the corresponding bulk compounds (e.g. after 30 min ~2-7 times more drug was dissolved depending on the materials). The release profile of the loaded substances remained similar also after 3 months of storage at 30°C/56% RH. The thermally carbonized mesoporous silicon did not compromise the Caco-2 monolayer integrity in the permeation studies and improved drug permeability was observed. The loaded mesoporous silica materials were also successfully compressed into tablets without compromising their characteristic structural and drug releasing properties. The results of this research indicated that mesoporous silicon/silica-based materials are promising materials to improve the dissolution of poorly water soluble drugs. Their feasibility in pharmaceutical laboratory scale processes was also confirmed in this thesis.