Lors de leur stockage ou de leur exposition, les objets du patrimoine sont soumis à des processus physico-chimiques d’altération liés à leur environnement et en particulier à l’action de polluants primaires (e.g. dioxyde de soufre, oxydes d’azote), secondaires (ozone) ou de composés organiques volatils (COVs). Il a été démontré que ces gaz/vapeurs se comportent comme des agents d’hydrolyse et d’oxydation. L’acide acétique fait partie des COVs ayant un impact considérable et reconnu dans la conservation des objets du patrimoine en particulier des films photographiques. En vue de lutter contre ses effets délétères, ce projet de thèse s’est focalisé sur la conception de nouveaux matériaux poreux hybrides multifonctionnels appelés « Metal-Organic Frameworks » (MOFs) pour la capture sélective de l’acide acétique en présence d’humidité (40% humidité relative) et à température ambiante. Les remarquables propriétés d’adsorption (sensibilité, sélectivité et capacité) et la grande versatilité des MOFs (balance hydrophile/hydrophobe, taille/forme des pores,…) ont été utilisés pour préconcentrer de façon sélective l’acide acétique en milieu humide. Les matériaux les plus performants ont ensuite été préparés sous forme de nanoparticules pour l’élaboration de films minces de qualité optique afin d’en étudier les propriétés d’adsorption et de co-adsorption (acide acétique/eau) par ellipsométrie. L’incorporation de nanoparticules métalliques plasmoniques a ensuite été effectuée afin de concevoir un capteur colorimétrique. L’objectif final de ce travail est de concevoir un nouveau type d’adsorbant caractérisé par une capacité et une sélectivité d’adsorption élevée et dont on pourrait aisément déterminer le niveau de saturation en acide acétique afin d’anticiper son remplacement et ainsi assurer la préservation des objets stockés et exposés dans les musées. / During their storage or their exhibition, the cultural heritage objects undergo physicochemical alteration processes related to their environment and in particular to the action of primary (e.g. sulfur dioxide, nitric oxides), secondary (ozone) pollutants or Volatile Organic Compounds (VOCs). It has been demonstrated that these gases/vapors are involved in hydrolysis and oxidation reactions. Among the most common VOCs encountered in museums, Acetic acid has a significant and recognized role in the deterioration of cultural heritage objects such as photographic films. In order to face this issue, this Ph.D. thesis focused on the design of new porous multifunctional hybrid materials denoted « Metal-Organic Frameworks » (MOFs) for the selective capture of acetic acid in the presence of moisture (40% relative humidity) and at room temperature. The remarkable adsorption properties (sensitivity, selectivity and capacity) and the great versatility of MOFs (hydrophicity/hydrophobicity balance, size/shape of pores,…) were used to preconcentrate selectively the acetic acid in humid conditions. The most performing materials were then prepared as nanoparticles and then used for the elaboration of high optical quality thin films in order to study the coadsorption (acetic acid/water) properties of MOFs by ellipsometry. The incorporation of plasmonic metal nanoparticles was then carried out in order to design a colorimetric sensor. The final objective is to devise a novel type of adsorbent that integrates a high VOC adsorption capacity and selectivity under humid conditions and an easy on-line monitoring of their saturation capacityin order to anticipate its replacement and therefore ensure the preservation of the stored and exhibited objects in museums.

The synthesis of a scandium aluminium methylphosphonate ScAl₃(CH₃PO₃)₆ isostructural to the aluminium methylphosphonate AlMePO-α and with permanent microporosity is reported here for the first time. Structural characterisation of three lanthanide bisphosphonate structures (I,II,III) with the light lanthanides and N,N'-piperazine bis-(methylenephosphonic acid) and its 2-methyl and 2,5-dimethyl derivatives is described. The framework of structure type I shows considerable flexibility upon dehydration with a symmetry change from C2/c, a = 23.5864(2) Å, b = 12.1186(2) Å, c = 5.6613(2) Å, β = 93.040(2)˚) in the hydrated state to P2₁/n, a = 21.8361(12) Å, b = 9.3519(4) Å, c = 5.5629(3) Å, β = 96.560(4)˚ after dehydration. This cell volume reduces by 27% on dehydration and is accompanied by a change in the conformation of the piperazine ring from chair to boat configuration. The structures of type I (hydrated and dehydrated) were refined against synchrotron powder X-ray diffraction data. Despite the reversible hydration and flexibility, the structures possess no permanent porosity. Investigation of the solvothermal chemistry of scandium carboxylates identified routes to 7 framework structures 5 of which were previously unreported in the scandium system. Lower temperature solvothermal reactions using terephthalic acid (80 - 140°C using dimethylformamide and diethylformamide) yielded two scandium terephthalates, MIL-88B(Sc) and MIL-101(Sc), identified by laboratory X-ray powder diffraction. Whereas higher temperature (160 – 220°C), reactions gave MIL-53(Sc) and Sc₂BDC₃. Further study with the tri- and tetra-carboxylate linkers, trimesic acid, 3,3',5,5'-azobenzenetetracarboxylic acid and pyromellitic acid yielded MIL-100(Sc), Sc-ABTC and Sc₄PMA₃ respectively. Structural identification of MIL-100(Sc) and Sc-ABTC was performed by means of X-ray powder diffraction analysis and of Sc₄PMA₃ by single crystal X-ray diffraction. The structure of a small pore scandium terephthalate Sc₂BDC₃ was investigated as a function of temperature and of functionalization. In situ synchrotron X-ray diffraction data, collected on a Sc₂BDC₃ in vacuo, enabled a phase change from orthorhombic Fddd to monoclinic C2/c and the associated structural effects to be observed in detail. The orthorhombic structure displayed a negative thermal expansivity of 2.4 × 10⁻⁵ K⁻¹ over the temperature range 225 – 523 K which Rietveld analysis showed to be derived from carboxylate group rotation. Motion within the framework was studied by ²H wide-line and MAS NMR on deuterated Sc₂BDC₃ indicating π flips can occur in the phenyl rings above 298 K. The effects of functionalization on the Sc₂BDC₃ framework were investigated by reactions using the 2-amino- and 2-nitroterephthalic acid and gave evidence for a strong structural effect resulting from inclusion of the functional groups. The structure of Sc₂BDC₃ and the functionalised derivatives were solved using Rietveld analysis on synchrotron X-ray powder diffraction data. Sc₂(NH₂-BDC)₃ was solved using the orthorhombic Sc₂BDC₃ framework starting model and, over the temperature range studied, stayed orthorhombic Fddd. Sc₂(NO₂-BDC)₃, was shown to be monoclinic C2/c over the same temperature range, a result of the steric effects of the bulky –NO₂ group in a small pore framework. Partial ordering of the functional groups was observed in both Sc₂(NH₂-BDC)₃ and Sc₂(NO₂-BDC)₃. The strength of interaction for the Sc₂(NH₂-BDC)₃ with CO₂ was higher than that of the parent Sc₂BDC₃ due to the strong –NH₂•••CO₂ interaction. Despite the inclusion of a relatively large –NO₂ group along the walls of a channel ~4 Å in diameter the Sc₂(NO₂-BDC)₃ still showed permanent microporosity to CO₂ (2.6 mmol g⁻¹) suggesting that there must be some motion in the -NO₂ group to allow the CO₂ molecules to diffuse through the channels. The scandium analogue of the flexible terephthalate MIL-53, a competitive phase in the synthesis of Sc₂BDC₃, was prepared and characterised by Rietveld analysis on synchrotron X-ray powder diffraction data using a combination of literature structural models and models obtained from single crystal X-ray diffraction experiments. Experimental solid state ⁴⁵Sc, ¹³C and ¹H NMR data combined with NMR calculations on the structural models produced from diffraction analysis were used to identify the hydrated (MIL-53(Sc)-H₂O), calcined (MIL-53(Sc)-CAL) and high temperature (MIL-53(Sc)-HT) structures of MIL-53(Sc). Further to this the 2-nitroterephthalate derivative, MIL-53(Sc)-NO₂, was prepared and characterised using single crystal X-ray diffraction. The adsorptive properties of the parent terephthalate and the functionalised derivative were compared and in both cases showed a breathing behaviour, exemplified by steps in the adsorption isotherms. MIL-53(Sc)-CAL was found to possess a closed pore configuration in the dehydrated state, a previously unreported structural form for the MIL-53 series, and its presence can be observed in the low pressure region of the CO₂ adsorption isotherm as a non-porous plateau. The selectivity and separation properties of two MOFs, the nickel bisphosphonate, STA-12(Ni) and the scandium carboxylate, Sc₂BDC₃ were measured using breakthrough curves on mixtures of CH₄ and CO₂. The results showed both materials to be highly selective in the adsorption of CO₂ over CH₄. Column testing using a PLOT column of STA-12(Ni) and a packed column of Sc₂BDC₃ showed promising preliminary results with STA-12(Ni) displaying effective, baseline separation on low boiling point hydrocarbon mixtures (C1 – C4) while the smaller pore channels of Sc₂BDC₃ were effective in the size selective separation of higher boiling point branched and straight-chain hydrocarbons (C5 – C7).

Submitted by Rosangela Silva (rosangela.silva3@unioeste.br) on 2017-08-31T17:58:43Z No. of bitstreams: 2 Michael Feroldi.pdf: 1564105 bytes, checksum: b0057f88efcba9ac5541c4aa3b057f63 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-08-31T17:58:43Z (GMT). No. of bitstreams: 2 Michael Feroldi.pdf: 1564105 bytes, checksum: b0057f88efcba9ac5541c4aa3b057f63 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-03-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The transition from fossil sources of energy for renewables in the vehicular sector has been reality in recent years and in this sense the biogas and biomethane present significant potential for use in motor vehicles. Due to several technical issues inherent in methane storage are currently employed LNG (liquefied natural gas) and CNG (compressed natural gas) technologies, which spend high amounts of energy, cylinders and heavy duty equipment for safety reasons, which makes these more expensive technologies. On the other hand, in recent years the adsorption technology with porous materials (GNA) has been studied because it employs smaller amounts of energy and also cylinders built with lighter and cheap materials. In this sense, the present work aims to evaluate the performance of activated carbon in different granulometries (A=3-5 mm, B=2 mm and C= 1-1,5 mm) in storage of methane at 10 bar using factorial planning 2², evaluating also the input parameters of a storage system prototype (flow and temperature), built for the present work. The activated carbon samples in the three granulometries were characterized by N2 fisisorption technique for the determination of texture characteristics, Helium gas pycnometry for quantification of particle density and, scanning electron microscopy and infrared spectroscopy for observation of the morphological and indication of functional surface groups. Under the conditions employed in this study, it was observed the increased ability of adsorption of carbons with a decrease in temperature in all granulometries of carbon with the variation of the input flow to the coals A and B in the range evaluated. With the present study it was possible to triple the storage capacity filled cylinder (activated carbon A = V V-1 39.41) when compared with the empty cylinder (13.14 V V-1), and still submit desorption near 100% (60 ºC and 30 min), proving the efficacy of reuse of adsorbents in cyclic tests. / A transição das fontes fósseis de energia para as renováveis no setor veicular tem sido realidade nos últimos anos e, neste sentido o biogás e o biometano apresentam potencial expressivo para utilização em veículos automotores. Devido a diversas questões técnicas inerentes ao armazenamento do metano, atualmente são empregadas as tecnologias GNL (gás natural liquefeito) e GNC (gás natural comprimido), que despendem altas quantidades de energia, cilindros e equipamentos resistentes, por questões de segurança, o que torna estas tecnologias com custos elevados. Por outro lado, nos últimos anos a tecnologia de adsorção com materiais porosos (GNA) vem sendo estudada, pois emprega menores quantidades de energia e também cilindros construídos com materiais mais leves e baratos. Neste sentido, o presente trabalho tem por objetivo avaliar o desempenho de carvões ativados em três granulometrias (A=3-5 mm, B=2 mm e C= 1-1,5 mm) no armazenamento de metano a 10 bar, utilizando planejamento fatorial 2², avaliando também parâmetros de entrada de um sistema de armazenamento protótipo (vazão e temperatura), construído para condução do presente trabalho. As amostras de carvão ativado nas três granulometrias foram caracterizadas pelas técnicas de fisissorção de N2, para determinação das características texturais, picnometria de gás Hélio, para quantificação da densidade das partículas e, microscopia eletrônica de varredura e espectroscopia de infravermelho para observação da estrutura morfológica e indicação de grupos funcionais de superfície. Nas condições empregadas neste estudo, foi observado o aumento da capacidade de adsorção dos carvões com a diminuição da temperatura em todas as granulometrias do carvão e com a variação da vazão de entrada para os carvões A e B no intervalo avaliado. Com o presente estudo foi possível triplicar a capacidade de armazenamento do cilindro preenchido (carvão A = 39,41 V V-1) quando comparado com o cilindro vazio (13,14 V V-1) e, ainda, apresentarem dessorção próxima a 100% (60 ºC e 30 min), comprovando o reuso dos adsorventes em ensaios cíclicos.

This thesis presents a detailed experimental programme on understanding the mechanics of drilling in porous brittle solids. Gypsum was used as a model material for this experimental study, in which the mechanics of drilling was decoupled into equivalent problems of indentation and cutting. A comprehensive understanding of the mechanics of indentation and cutting was gained by performing experiments in 2-D conditions. A camera and microscope assembly was used to capture images at high temporal and spatial resolution to measure the in situ deformation. Particle image velocimetry (PIV) algorithm was used to measure the deformation parameters such as velocity, strain-rate, strain and volume change. In the last part of this research, drilling experiments were performed in 3-D conditions and an attempt was made for understanding the mechanics of drilling by relating the drilling experiment results to that of indentation and cutting. A series of wedge indentation experiments were performed under 2-D plane-strain conditions. Development of a parabolic zone of deformation, surrounding the indenter, was observed, wherein this size of the deformation zone and the strain accumulation in the deformation zone was a function of the geometry of the indenter. The maximum effective strain decreased and the overall strain field was more diffuse with increase in the wedge angle. Significant volume change was also observed in this deformation zone and the amount of volume change increased with increase in the porosity of the material. The zones of high volume change (compaction bands) were stacked in the form of layers oriented perpendicular to the direction of indentation. These compaction bands were more localized for the case of lower angles of wedge indenter. The extent of the compaction bands was also a function of porosity and spread over a larger area for the case of low porosity samples. A change in the material response was also observed with change in porosity and geometry of the indenter. The appearance of the crack was delayed with increase in porosity and reduction of wedge angle. The experimental results were also used to validate an analytical cavity expansion model. A better prediction of indentation pressure and the size of the deformation zone was possible after volume change corrections were incorporated into the cavity expansion formulation. A series of orthogonal cutting experiments were performed in 2-D plane-strain conditions. The e ect of tool geometry and the depth of cut on the mechanics of cutting was studied with the help of image based measurements and cutting force signatures. Different types of cutting mechanisms were observed for the case of positive and negative rake angle tool. A cyclic increase and decrease in the cutting force was observed in case of positive rake angle cutting tool. The decrease in the cutting force corresponded to the initiation of crack from the tip of the tool. The crack traversed towards the surface of the material and resulted in the removal of a material chip. With progress of cutting, the tool scratched the material surface, giving rise to the gradual increase in the cutting force as it again reached local maxima when the tool completely re-engaged with the material. For the case of negative rake angle, apart from cyclic increase and decrease of the cutting force, there was a development of a triangular dead zone at the tip of the cutting tool. The size of the dead zone varied cyclically with the progress of cutting. The length of crack, which resulted in the removal of the chip from the material, was found to be a function of the rake angle and the depth of cut. Drilling experiments were performed on gypsum samples in 3-D conditions. Two types of twist drills with different helix angles were used for this research work. Experiments were performed on the samples with two different porosities. Thrust force and torque signatures were recorded for five values of depth of cut per revolution. Since these experiments were performed in 3-D, image analysis was not performed. However, in order to ascertain a qualitative understanding of the drilling process, few experiments were performed on the edge of the material surface so that a cylindrical groove with semicircular cross section is made and the exposed surface of the material and the drill were imaged. The normalized thrust force and normalized torque were compared with indentation pressure and cutting force signatures and remarkable similarities between them was found. A transition from ductile to brittle type of response was observed with increase in the depth of cut per revolution, which was similar to what was observed in case of indentation. The magnitude of torque was found to be higher for high helix angle drills, which was counter to what was observed in cutting, which was due to the deposition of the material in helix for high helix angle drills, resulting in the reduction of the effective helix angle. An approximate estimate of the effective helix angle was made with the help of analytical solutions as well as from the qualitative analysis of the images.

This is a brief summary of the Fourteenth International Bologna Conference on Magnetic Resonance in Porous Media (MRPM14).

<p>The rapid growth of fields such as metamaterials, composites, architected materials, porous solids, and micro/nano materials, along with the continuing advancements in design and fabrication procedures have led to the synthesis of complex structures having intricate material distributions and non-trivial geometries. These materials find important applications including biomedical implants and devices, aerospace and naval structures, and micro/nano-electromechanical devices. Theoretical and experimental evidences have shown that these structures exhibit size-dependent (or, nonlocal) effects. This implies that the response of a point within the solid is affected by a collection of points; ultimately a manifestation of the multiscale deformation process. Broadly speaking, at a continuum level, the mathematical description of these multiscale phenomena leads to integral constitutive models, that account for the long-range interactions via nonlocal kernels. </p> <p><br></p> <p>Despite receiving considerable attention, the existing class of approaches to nonlocal elasticity are predominantly phenomenological in nature, following from their definition of the material parameters of the nonlocal kernel based on 'representative volume element' (RVE)-based statistical homogenization of the heterogeneous microstructure. The size of the RVE required for practical simulation, does not achieve a full-resolution of the intricate heterogeneous microstructure, and also implicitly enforces the use of symmetric nonlocal kernels to achieve thermodynamic consistency and mathematically well-posedness. The latter restriction directly limits the application of existing approaches only to the linear deformation analysis of either periodic or isotropic nonlocal structures. Additionally, the lack of a consistent characterization of the nonlocal effects, often results in inconsistent (also labeled as 'paradoxical') predictions depending on the nature of the external loading. In order to address these fundamental theoretical gaps, this dissertation develops a fractional-order kinematic approach to nonlocal elasticity by leveraging cutting-edge mathematical operators derived from the field of fractional calculus.</p> <p><br></p> <p>In contrast to the class of existing class of approaches that adopt an integral stress-strain constitutive relation derived from the equilibrium of the RVE, the fractional-order approach is predicated on a differ-integral (fractional-order) strain-displacement relation. The latter relation is derived from a fractional-order deformation-gradient mapping between deformed and undeformed configurations, and this approach naturally localizes and captures the effect of nonlocality at the root of the deformation phenomena. The most remarkable consequence of this reformulation consists in its ability to achieve thermodynamic and mathematical consistency, irrespective of the nature of the nonlocal kernel. The convex and positive-definite nature of the formulation enabled the use of variational principles to formulate well-posed governing equations, the incorporation of nonlinear effects, and enabled the development of accurate finite element simulation methods. The aforementioned features, when combined with a variable-order extension of the fractional-order continuum theory, enabled the physically consistent application of the nonlocal formulation to general continua exhibiting asymmetric interactions; ultimately a manifestation of material heterogeneity. Indeed, a rigorous theoretical analysis was conducted to demonstrate the natural ability of the variable-order in capturing the role of microstructure in the deformation of heterogeneous porous solids. These advantages allowed the application of the fractional-order kinematic approach to accurately and efficiently model the response of porous beams and plates, with random microstructural descriptions. Results derived from multiphysical loading conditions, as well as nonlinear deformation regimes, are used to demonstrate the causal relation between the kinematics-based fractional-order characterization of nonlocal effects and the natural role of microstructure in determining the macroscopic response of heterogeneous solids. The potential implications of the developed formalism on scientific discovery of material laws are examined in-depth, and different areas for further research are identified.</p>

A numerical model based on fundamental engineering principles was developed and validated to establish a relationship between process parameters and the final properties of woodbased composite boards. The model simulates the mat formation, then compresses the reconstituted mat to its final thickness in a virtual press. The number of interacting variables during the hot-compression process is prohibitively large to assess a wide variety of data by experimental means. Therefore, the main advantage of the model based approach that the effect of the hot-compression parameters on the final properties of wood-based composite boards can be monitored without extensive experimentation. The mat formation part of the model is based on the Monte Carlo simulation technique to reproduce the spatial structure of the mat. The dimensions and the density of each flake are considered as random variables in the model, which follow certain probability density distributions. The parameters of these distributions are derived from data collected on industrial flakes by using an image analysis technique. The model can simulate the structure of a threelayer oriented strandboard (OSB) mat as well as the structure of random fiber networks. A grid is superimposed on the simulated mat and the number of flakes, the thickness, and the density of the mat at each grid point are computed. Additionally, the model predicts the change in several void volume fractions within the mat and the contact area between the flakes during consolidation. The void volume fractions are directly related to the physical properties of the mat, such as thermal conductivity, diffusivity, and permeability, and the contact area is an indicator of the effectively bonded area within the mat. The heat and mass transfer part of the model predicts the change of air content, moisture content, and temperature at designated mesh points in the cross section of the mat during the hotcompression. The water content is subdivided into vapor and bound water components. The free water component is not considered in the model due to the low (typically 6-7 %) initial moisture content of the flakes. The gas phase (air and vapor) moves by bulk flow and diffusion, while the bound water only moves by diffusion across the mat. The heat flow occurs by conduction and convection. The spatial derivatives of the resulting coupled partial differential equations are discretized by finite differences. The resulting ordinary differential equation in time is solved by a differential-algebraic system solver (DDASSL). The internal environment within the mat can be predicted among different initial and boundary conditions by this part of the hot-compression model. In the next phase of the research, the viscoelastic (time, temperature, and moisture dependent) response of the flakes was modeled using the time-temperature-moisture superposition principle of polymers. A master curve was created from data available in the literature, which describes the changing relaxation modulus of the flakes as a function of moisture and temperature at different locations in the mat. Then the flake mat was compressed in a virtual press. The stress-strain response is highly nonlinear due to the cellular structure of the mat. Hooke's Law was modified with a nonlinear strain function to account for the behavior of the flake mat in transverse compression. This part of the model gives insight into the vertical density profile formation through the thickness of the mat. Laboratory boards were produced to validate the model. A split-plot experimental design, with three different initial mat moisture contents (5, 8.5, 12 %), three final densities (609, 641, 673 kg êm3 or 38, 40, 42 lb ê ft3), two press platen temperatures (150, 200 °C), and three different press closing times (40, 60, 80 s) was applied to investigate the effect of production parameters on the internal mat conditions and the formation of the vertical density profile. The temperature and gas pressure at six locations in the mat, and the resultant density profiles of the laboratory boards, were measured. Adequate agreement was found between the model predicted and the experimentally measured temperature, pressure, and vertical density profiles. The complete model uses pressing parameters (press platen temperature, press schedule) and mat properties (flake dimensions and orientation, density distribution, initial moisture content and temperature) to predict the resulting internal conditions and vertical density profile formation within the compressed board. The density profile is related to all the relevant mechanical properties (bending strength, modulus of elasticity, internal bond strength) of the final board. The model can assist in the optimization of the parameters for hot-pressing woodbased composites and improve the performance of the final panel. / Ph. D.

Alterations of fluid phase transitions in porous materials are conventionally employed for the characterization of mesoporous solids. In the first approximation, this may be based on the application of the Kelvin equation for gas–liquid and the Gibbs–Thomson equation for solid–liquid phase equilibria for obtaining pore size distributions. Herein, we provide a comparative analysis of different phase coexistences measured in mesoporous silica solids with different pore sizes and morphology. Instead of comparing the resulting pore size distributions, we rather compare the transitions directly by using a common coordinate for varying the experiment’s thermodynamic parameters based on the two equations mentioned. Both phase transitions in these coordinates produce comparable results for mesoporous solids of relatively large pore sizes. In contrast, marked differences are found for materials with smaller pore sizes. This illuminates the fact that, with reducing confinement sizes, thermodynamic fluctuations become increasingly important and different for different equilibria considered. In addition, we show that in the coordinate used for analysis, mercury intrusion matches perfectly with desorption and freezing transitions.

Nuclear magnetic resonance (NMR) provides a variety of tools for the structural characterization of porous solids. In this paper, we discuss a relatively novel approach called NMR cryodiffusometry, which is based on a simultaneous assessment of both the phase state of intraporous liquids at low temperatures, using NMR cryoporometry, and their transport properties, using NMR diffusometry. Choosing two model porous materials with ordered and disordered pore structures as the host systems, we discuss the methodological and fundamental aspects of the method. Thus, with the use of an intentionally micro-structured mesoporous silicon, we demonstrate how its structural features give rise to specific patterns in the effective molecular diffusivities measured upon progressive melting of a frozen liquid in the mesopores. We then present the results of a detailed study of the transport properties of the same liquid during both melting and freezing processes in Vycor porous glass, a material with a random pore structure. 1

Les matériaux nanocomposites poreux organisés présentent de nombreuses propriétés dans le domaine de l’adsorption. Cette étude est portée sur la synthèse de matériaux poreux de grande aire spécifique fonctionnalisés par des nanoparticules métalliques en visant des applications dans le domaine de l’adsorption: en phase liquide et en phase gazeuse.La première application concerne la détection en phase liquide de molécules à de faibles concentrations. Des nanocomposites composés d’une matrice poreuse de silice dans laquelle sont insérées des nanoparticules de métaux nobles (i.e. Ag@SiO2 et Au@SiO2) sont étudiés comme substrats SERS en couplant thermodynamique et spectroscopie Raman. Ce couplage de l’étude de la réponse Raman et de l’étude thermodynamique de l’adsorption a conduit à une meilleure compréhension de l’influence des particules sur le seuil de détection de la molécule. L’influence de plusieurs paramètres sur la réponse Raman de la molécule sonde et sur ses propriétés d’adsorption a aussi été étudiée (la taille des particules, la nature chimique du métal, etc.).La seconde application concerne le stockage d’hydrogène. Des nanocomposites composés de matrices poreuses de silice ou de carbone dans lesquelles sont incorporées des nanoparticules d’un métal de transition (i.e. Ni@SiO2 et Ni@Carbone) sont étudiés comme matériaux de stockage en couplant manométrie et microcalorimétrie d’adsorption. La mise en place d’une méthode de réduction adaptée a constitué une étape importante de ce travail. Ce couplage d’études thermodynamiques de l’adsorption a permis de déterminer les propriétés d’adsorption de l’hydrogène à basse température et basses pressions de ces matériaux. / Nanocomposite organized porous materials present many properties in particular in the field of adsorption. This study was based on the synthesis of porous materials of high specific surface area functionalized with metal nanoparticles focusing in particular on two applications in the field of adsorption: one in the liquid phase and the other one in the gas phase.The first application is the detection of molecules in the liquid phase at low concentrations. Nanocomposites composed of a porous silica matrix in which are inserted noble metal nanoparticles (i.e. Ag@SiO2 and Au@SiO2) are studied as SERS (Surface Enhanced Raman Scattering) substrates by coupling thermodynamics and Raman spectroscopy. The coupling of the Raman response study and the thermodynamics of adsorption study leads to a better understanding of the influence of the particles on the molecule detection threshold. The influence of various parameters on the Raman response of the probe molecule and its adsorption properties were also studied (the particle size, the chemical nature of the metal, etc.)The second application relates to the storage of hydrogen since Nanocomposites composed of porous silica or carbon matrices in which are incorporated transition metal nanoparticles (i.e. Ni@SiO2 and Ni@Carbon) were studied as storage materials by coupling the adsorption manometry and microcalorimetry. The establishment of a suitable reduction method was an important step in this work. This coupling of thermodynamic studies of the adsorption was used to determine the adsorption properties of hydrogen at low temperature and low pressures of these materials.