Dissolved organic contaminants that decrease the surface tension of water (surfactants) can have an effect on unsaturated flow through porous media due to the dependence of capillary pressure on surface tension. One and two-dimensional (1D, 2D) laboratory experiments and numerical simulations were conducted to study surfactant-induced unsaturated flow. The 1D experiments investigated differences in surfactant-induced flow as a function of contaminant mobility. The flow in a system contaminated with a high solubility, mobile surfactant, butanol, was much different than in a system contaminated with a sparingly soluble, relatively immobile surfactant, myristyl alcohol (MA). Because surface tension depression caused by MA was confined to the original source zone, the MA system was modeled using a standard unsaturated flow model (HYDRUS-1D) by assigning separate sets of hydraulic functions to the initially clean and source zones. To simulate the butanol system, HYDRUS-1D was modified to incorporate surfactant concentration-dependent changes to the moisture content-pressure head and unsaturated hydraulic conductivity functions. Following the 1D study, a two-dimensional flow cell (2.4 x 1.5 x 0.1 m) was used to investigate the infiltration of a surfactant contaminant plume from a point source on the soil surface, through the vadose zone, and toward a shallow aquifer. Above the top of the capillary fringe the advance of the surfactant solution caused a drainage front that radiated from the point source. Upon reaching the capillary fringe, the drainage front caused a localized depression of the capillary fringe and eventually a new capillary fringe height was established. Horizontal transport of surfactant in the depressed capillary fringe caused the propagation of a wedge-shaped drainage front in the downgradient direction. The numerical model HYDRUS-2D was modified to account for surfactant concentration-dependent effects on the unsaturated hydraulic functions and was successfully used to simulate the surfactant infiltration experiment. The extensive propagation of the drying front and the effect of vadose zone drainage on contaminant breakthrough time demonstrate the potential importance of considering surface tension effects on unsaturated flow and transport in systems containing surface-active organic contaminants or in systems where surfactants are used for remediation of the vadose zone or unconfined aquifers.

Selective laser sintering (SLS) is a commercial, powder-based manufacturing process that produces parts with complicated shape and geometry based on a computer solid model. One of the major drawbacks of SLSed inter-metallic and ceramic parts is their high porosity because of the use of binder system. High porosity results in poor mechanical, electrical and thermal properties of the preform and hence renders it unsuitable for various applications. This thesis attempts to infiltrate SLSed preforms by carrying out electrochemical deposition of metal ions inside the interconnected pore network. One of the major benefits of carrying out this novel process is low processing temperature as opposed to existing methods such as melt infiltration. Low temperature reduces both energy consumption and associated carbon-footprint and also minimizes undesirable structural changes. Both conductive and non-conductive preforms may be electrochemically infiltrated, and MMCs produced by this method have potential for use in structural applications. / text

Πολλοί μικροοργανισμοί έχουν την ικανότητα να σχηματίζουν βιοφίλμ στη διεπιφάνεια μεταξύ ενός υδατικού διαλύματος και ενός άλλου ρευστού, στερεού ή πορώδους υλικού. Η ανάπτυξη βιοφίλμ σε πορώδη υλικά έχει σημαντικό ρόλο σε πληθώρα διεργασιών, όπως η βιοαποδόμηση ρύπων στο έδαφος και η βιολογικά ενισχυμένη απόληψη πετρελαίου από ταμιευτήρες. Στην παρούσα εργασία μελετώνται τα φαινόμενα μεταφοράς και η δυναμική συμπεριφορά της ανάπτυξης μικροβιακών βιοφίλμ κατά τη βιοαποδόμηση οργανικών ενώσεων σε πορώδη υλικά. Οι κύριοι στόχοι και τα αποτελέσματα της διατριβής εντάσσονται σε τρεις άξονες. Ο πρώτος άξονας περιλαμβάνει τη διεξαγωγή πειραμάτων ανάπτυξης βιοφίλμ σε γυάλινα δοκίμια πορώδους μέσου για την αποσαφήνιση των μηχανισμών φραξίματος στην κλίμακα των πόρων και την συσχέτιση πορώδους-διαπερατότητας στην κλίμακα του πορώδους μέσου. Ο δεύτερος άξονας περιλαμβάνει την ανάπτυξη μιας μεθοδολογίας για τη μαθηματική περιγραφή: α) της διεργασίας μεταφοράς μάζας δια μοριακής διαχύσεως, και β) της διεργασίας μεταφοράς ορμής κατά τη ροή του εξωκυτταρικού υδατικού διαλύματος, σε κυτταρικά βιολογικά υλικά (βιοφίλμ, μικροβιακά συσσωματώματα, ιστοί). Η μεθοδολογία συνδυάζει τη μέθοδο χωρικής στάθμισης δια συνάρτησης βάρους για την ανάπτυξη των διεπουσών εξισώσεων, με μοντέλα μοναδιαίων κελιών για τον υπολογισμό των συντελεστών που υπεισέρχονται στις διέπουσες εξισώσεις. Ο τρίτος άξονας περιλαμβάνει την ανάπτυξη ενός νέου, ιεραρχικού, υβριδικού εξομοιωτή της δυναμικής συμπεριφοράς μικροβιακών βιοφίλμ σε πορώδη υλικά. Ο εξομοιωτής προβλέπει: α) τη δομική και βιολογική ετερογένεια στην κλίμακα του βιοφίλμ, β) τη μορφή και το ρυθμό ανάπτυξης του βιοφίλμ μέσα στους πόρους ρεαλιστικών πορωδών δομών, και γ) τη συζυγή μεταβολή του πεδίου ροής και της χωρικής κατανομής των συγκεντρώσεων διαλελυμένων χημικών ειδών. / Numerous bacteria are able to form biofilms at the interface between an aqueous solution and another fluid, solid or porous material. Biofilm growth in porous media is of key importance in a variety of processes, such as the biodegradation of pollutants in soil and biologically enhanced oil recovery from subsurface reservoirs. In the present work, the transport phenomena and the dynamics of biofilm growth during the biodegradation of organic pollutants in porous media are studied. The main goals and results of the dissertation are developed along the following axes. The first axis involves the conduction of experiments of biofilm growth in glass models of porous media for the elucidation of the clogging mechanism on the pore scale and the permeability-porosity correlation on the scale of the porous medium. The second axis involves the development of a methodology for the mathematical description of: (a) the diffusive mass transfer process, and, (b) the momentum transfer during the flow of the extra-cellular aqueous solution in cellular biological media (biofilms, microbial flocs, tissues). The methodology combines the spatial averaging method via a weight function for the formulation of the governing equations, with unit cell models for the calculation of the coefficients that enter the governing equations. The third axis involves the development of a novel, hierarchical, hybrid simulator of the dynamic behavior of microbial biofilms in porous materials. The simulator predicts: (a) the structural and biological heterogeneity on the biofilm scale, (b) the pattern and rate of growth rate of biofilms in the pores of realistic porous structures, and (c) the conjugate alteration of the flow field and the spatial distribution of the concentration of solutes.

The aim of the PhD thesis has been the development of two multi-physics models based on common theoretical basis, but applied to two very different areas: i) the study of the behavior of concrete at early age, essentially for the prevention of early cracking and related issues- ii) the analysis of physical, chemical and biological processes that govern growth and development of cancer. The development of a numerical tool to model concrete at early age is of great importance for the design of durable and sustainable structures. The model has been implemented on the finite element code CAST3M (developed by CEA), also it was validated and nowadays allows multiple applications: study of stresses and cracking phenomena in young concrete, thermal and hygral gradients, autogenous and drying shrinkage, inhibition of hydration caused by drying, creep, stress redistribution, study repairs, etc.. In the fight against cancer, it is clear that the advance of medical strategies based on numerical analysis have a critical scientific interest and can have a great social impact. The equations which govern the thermo-hydro-chemo-mechanical behavior of concrete at early age have may formal analogies with those used to model tumor growth. Hence, these equations have been readapted and a novel mathematical model for tumor growth has been developed. The model was implemented in Cast3M and the first numerical results have been encouraging since very close to the experimental data present in the literature.

This work is dedicated to present and validate a new and generalized macroscopic nonlocal theory of sound propagation in rigid-framed porous media saturated with a viscothermal fluid. This theory allows to go beyond the limits of the classical local theory and within the limits of linear theory, to take not only temporal dispersion, but also spatial dispersion into account. In the framework of the new approach, a homogenization procedure is proposed to upscale the dynamics of sound propagation from Navier-Stokes-Fourier scale to the volume-average scale, through solving two independent microscopic action-response problems. Contrary to the classical method of homogenization, there is no length-constraint to be considered alongside of the development of the new method, thus, there is no frequency limit for the medium effective properties to be valid. In absence of solid matrix, this procedure leads to Kirchhoff-Langevin's dispersion equation for sound propagation in viscothermal fluids. The new theory and upscaling procedure are validated in three cases corresponding to three different periodic microgeometries of the porous structure. Employing a semi-analytical method in the simple case of cylindrical circular tubes filled with a viscothermal fluid, it is found that the wavenumbers and impedances predicted by nonlocal theory match with those of the long-known Kirchhoff's exact solution, while the results by local theory (Zwikker and Kosten's) yield only the wavenumber of the least attenuated mode, in addition, with a small discrepancy compared to Kirchhoff's. In the case where the porous medium is made of a 2D square network of cylindrical solid inclusions, the frequency-dependent phase velocities of the least attenuated mode are computed based on the local and nonlocal approaches, by using direct Finite Element numerical simulations. The phase velocity of the least attenuated Bloch wave computed through a completely different quasi-exact multiple scattering method taking into account the viscothermal effects, shows a remarkable agreement with those obtained by the nonlocal theory in a wide frequency range. When the microgeometry is in the form of daisy chained Helmholtz resonators, using the upscaling procedure in nonlocal theory and a plane wave modelling lead to two effective density and bulk modulus functions in Fourier space. In the framework of the new upscaling procedure, Zwikker and Kosten's equations governing the pressure and velocity fields' dynamics averaged over the crosssections of the different parts of Helmholtz resonators, are employed in order to coarse-grain them to the scale of a periodic cell containing one resonator. The least attenuated wavenumber of the medium is obtained through a dispersion equation established via nonlocal theory, while an analytical modelling is performed, independently, to obtain the least attenuated Bloch mode propagating in the medium, in a frequency range where the resonance phenomena can be observed. The results corresponding to these two different methods show that not only the Bloch wave modelling, but also, especially, the modelling based on the new theory can describe the resonance phenomena originating from the spatial dispersion effects present in the macroscopic dynamics of the matarial.

No description available.

Periodic mesoporous material is a class of solids that possess periodically ordered pores with sizes of 2–50 nm. After a brief introduction to the synthesis, structure, property and function of periodic mesoporous materials in general in Chapter 1, a specific type of periodic mesoporous material, periodic mesoporous organosilica (PMO), is examined in detail in Chapter 2. Chapter 3 and Chapter 4 focus on the application of periodic mesoporous organosilica as low-dielectric-constant (low-k) insulating materials on semiconductor microprocessors. Specifically, Chapter 3 introduces a vapor-phase delivery technique, vacuum-assisted aerosol deposition, for the synthesis of PMO thin films; Chapter 4 studies one property crucial for the application of low-k PMO in detail—hydrophobicity. The focus of Chapter 5 turns to a novel sandwich-structured nanocomposite made of periodic mesoporous silica and graphene oxide. In Chapter 6, progress towards the synthesis of periodic mesoporous quartz is summarized. A conclusion and an outlook are given in Chapter 7.

Periodic mesoporous material is a class of solids that possess periodically ordered pores with sizes of 2–50 nm. After a brief introduction to the synthesis, structure, property and function of periodic mesoporous materials in general in Chapter 1, a specific type of periodic mesoporous material, periodic mesoporous organosilica (PMO), is examined in detail in Chapter 2. Chapter 3 and Chapter 4 focus on the application of periodic mesoporous organosilica as low-dielectric-constant (low-k) insulating materials on semiconductor microprocessors. Specifically, Chapter 3 introduces a vapor-phase delivery technique, vacuum-assisted aerosol deposition, for the synthesis of PMO thin films; Chapter 4 studies one property crucial for the application of low-k PMO in detail—hydrophobicity. The focus of Chapter 5 turns to a novel sandwich-structured nanocomposite made of periodic mesoporous silica and graphene oxide. In Chapter 6, progress towards the synthesis of periodic mesoporous quartz is summarized. A conclusion and an outlook are given in Chapter 7.

Two of the hottest areas in porous materials research in the last decade have been in energy storage, mainly hydrogen and methane, and in carbon capture and sequestration (CCS). Although these topics are intricately linked in terms of our future energy landscape, the specific materials needed to solve these problems must have significantly different properties. High pressure gas storage is most often linked with high surface areas and pore volumes, while carbon capture sorbents require high sorption enthalpies to achieve the needed selectivity. The latter typically involves separating CO2 from mixed gas streams of mostly nitrogen via a temperature swing adsorption (TSA) process. Much of the excitement has arisen because of the potential of metal-organic frameworks (MOFs) and porous polymer networks (PPNs). Both classes of materials have extremely high surface areas (upwards of 4000 m2/g) and can be modified to have specific physical properties, thus enabling high performance materials for targeted applications. This dissertation focuses on the synthesis and characterization of these novel materials for both applications by tuning framework topologies, composition, and surface properties. Specifically, two routes to synthesize a single molecule trap (SMT) highlight the flexibility of MOF design and ability to tune a framework to interact with specifically one guest molecule; computational and experimental evidence of the binding mechanism are shown as well. Furthermore, eight PPNs are synthesized and characterized for post-combustion carbon capture and direct air capture applications. In addition a high-throughput model, grounded in thermodynamics, to calculate the energy penalty associated with the carbon capture step is presented in order to evaluate all materials for TSA applications provide a comparison to the state of the art capture technologies. This includes results of working capacity and energy calculations to determine parasitic loads (per ton of CO2 captured) from readily available experimental data of any material (adsorption isotherms and heat capacities) using a few simple equations. Through various systematic investigations, trends are analyzed to form structure property relationships that will aid future material development.

The ascent of liquids with low dielectric constant on straight cylinders are obtained.