Estudo da transição de fase da percolação através da entropia da informação

Various physical systems have dynamics that can be modeled by percolation processes. Percolation is used to study issues ranging from fluid diffusion through disordered media to fragmentation of a computer network caused by hacker attacks. A common feature of all of these systems is the presence of two non-coexistent regimes associated to certain properties of the system. For example: the disordered media can allow or not allow the flow of the fluid depending on its porosity. The change from one regime to another characterizes the percolation phase transition. The standard way of analyzing this transition uses the order parameter, a variable related to some characteristic of the system that exhibits zero value in one of the regimes and a nonzero value in the other. The proposal introduced in this thesis is that this phase transition can be investigated without the explicit use of the order parameter, but rather through the Shannon entropy. This entropy is a measure of the uncertainty degree in the information content of a probability distribution. The proposal is evaluated in the context of cluster formation in random graphs, and we apply the method to both classical percolation (Erd¨os- R´enyi) and explosive percolation. It is based in the computation of the entropy contained in the cluster size probability distribution and the results show that the transition critical point relates to the derivatives of the entropy. Furthermore, the difference between the smooth and abrupt aspects of the classical and explosive percolation transitions, respectively, is reinforced by the observation that the entropy has a maximum value in the classical transition critical point, while that correspondence does not occurs during the explosive percolation.

Geochemistry of sheeted dike complex minerals of ODP Hole 140-504B

Diabases were recovered during Legs 137 and 140 at Hole 504B from depths between 1621.5 and 2000.4 meters below seafloor in the lower sheeted dike complex. The samples contain multiple generations of millimetric to centimetric veins. The orientation of the measured veins suggests that two main vein sets exist: one characterized by shallow dipping and the other by random trend. Thermal contraction during rock cooling is considered the main mechanism responsible for fracture formation. Vein infill is related to the circulation of hydrothermal fluids near the spreading axis. Some veins are surrounded by millimeter-sized alteration halos due to fluid percolation from the fractures through the host rock. Vein-filling minerals are essentially amphibole, chlorite, and zeolites. Amphibole composition is controlled by the microstructural site of the rock. Actinolite is the main amphibole occurring in the veins and also in the groundmass away from the halos. In the alteration halos, amphibole shows composition of actinolitic hornblende and Mg-hornblende. Late-stage tension gashes and interstitial spaces in some amphibole-bearing veins are filled with zeolites, suggesting that the veins likely suffered multiple opening stages that record the cooling history of the circulating fluids. Evidence of deformation recorded by the recovered samples seems to be restricted to veins that clearly represent elements of weakness of the rock. On the basis of vein geometry and microstructure we infer structural interpretations for the formation mechanism and for deformation of veins.

(Tables 1-3) Geochemical composition of seepage water in soils obtained in Schleswig-Holstein, Germany

Under defined laboratory and field conditions, the investigation of percolating water through soil columns (podsol, lessive and peat) down to groundwater table shows that the main factors which control the chemical characteristics of the percolates are: precipitation, evaporation, infiltration rate, soil type, depth and dissolved organic substances. Evaporation and percolation velocity influences the Na+, SO4**2- and Cl- concentrations. Low percolation velocity leads also to longer percolation times and water logging in less permeable strata, which results in lower Eh-values and higher CO2-concentrations due to low gas exchange with the atmosphere. Ca2+ and Mg2+ carbonate concentration depends on soil type and depth. Metamorphism and decomposition of organic substances involve NO3 reduction and K+, Mg2+, SO4**2-, CO2, Fe2+,3+ transport. The analytical data were evaluated with multi variate statistical methods.

Nanoindentation Relaxation Study and Micromechanics of Cement-Based Materials

Ce travail évalue le comportement mécanique des matériaux cimentaires à différentes échelles de distance. Premièrement, les propriétés mécaniques du béton produit avec un bioplastifiant à base de microorganismes efficaces (EM) sont etudiées par nanoindentation statistique, et comparées aux propriétés mécaniques du béton produit avec un superplastifiant ordinaire (SP). Il est trouvé que l’ajout de bioplastifiant à base de produit EM améliore la résistance des C–S–H en augmentant la cohésion et la friction des nanograins solides. L’analyse statistique des résultats d’indentation suggère que le bioplastifiant à base de produit EM inhibe la précipitation des C–S–H avec une plus grande fraction volumique solide. Deuxièmement, un modèle multi-échelles à base micromécanique est dérivé pour le comportement poroélastique de la pâte de ciment au jeune age. L’approche proposée permet d’obtenir les propriétés poroélastiques requises pour la modélisation du comportoment mécanique partiellement saturé des pâtes de ciment viellissantes. Il est montré que ce modèle prédit le seuil de percolation et le module de Young non drainé de façon conforme aux données expérimentales. Un metamodèle stochastique est construit sur la base du chaos polynomial pour propager l’incertitude des paramètres du modèle à travers plusieurs échelles de distance. Une analyse de sensibilité est conduite par post-traitement du metamodèle pour des pâtes de ciment avec ratios d’eau sur ciment entre 0.35 et 0.70. Il est trouvé que l’incertitude sous-jacente des propriétés poroélastiques équivalentes est principalement due à l’énergie d’activation des aluminates de calcium au jeune age et, plus tard, au module élastique des silicates de calcium hydratés de basse densité.

Physical and chemical kinetics of structural build-up of cement suspensions

Abstract : The structural build-up of fresh cement-based materials has a great impact on their structural performance after casting. Accordingly, the mixture design should be tailored to adapt the kinetics of build-up given the application on hand. The rate of structural build-up of cement-based suspensions at rest is a complex phenomenon affected by both physical and chemical structuration processes. The structuration kinetics are strongly dependent on the mixture’s composition, testing parameters, as well as the shear history. Accurate measurements of build-up rely on the efficiency of the applied pre-shear regime to achieve an initial well-dispersed state as well as the applied stress during the liquid-solid transition. Studying the physical and chemical mechanisms of build-up of cement suspensions at rest can enhance the fundamental understanding of this phenomenon. This can, therefore, allow a better control of the rheological and time-dependent properties of cement-based materials. The research focused on the use of dynamic rheology in investigating the kinetics of structural build-up of fresh cement pastes. The research program was conducted in three different phases. The first phase was devoted to evaluating the dispersing efficiency of various disruptive shear techniques. The investigated shearing profiles included rotational, oscillatory, and combination of both. The initial and final states of suspension’s structure, before and after disruption, were determined by applying a small-amplitude oscillatory shear (SAOS). The difference between the viscoelastic values before and after disruption was used to express the degree of dispersion. An efficient technique to disperse concentrated cement suspensions was developed. The second phase aimed to establish a rheometric approach to dissociate and monitor the individual physical and chemical mechanisms of build-up of cement paste. In this regard, the non-destructive dynamic rheometry was used to investigate the evolutions of both storage modulus and phase angle of inert calcium carbonate and cement suspensions. Two independent build-up indices were proposed. The structural build-up of various cement suspensions made with different cement contents, silica fume replacement percentages, and high-range water reducer dosages was evaluated using the proposed indices. These indices were then compared to the well-known thixotropic index (Athix.). Furthermore, the proposed indices were correlated to the decay in lateral pressure determined for various cement pastes cast in a pressure column. The proposed pre-shearing protocol and build-up indices (phases 1 and 2) were then used to investigate the effect of mixture’s parameters on the kinetics of structural build-up in phase 3. The investigated mixture’s parameters included cement content and fineness, alkali sulfate content, and temperature of cement suspension. Zeta potential, calorimetric, spectrometric measurements were performed to explore the corresponding microstructural changes in cement suspensions, such as inter-particle cohesion, rate of Brownian flocculation, and nucleation rate. A model linking the build-up indices and the microstructural characteristics was developed to predict the build-up behaviour of cement-based suspensions The obtained results showed that oscillatory shear may have a greater effect on dispersing concentrated cement suspension than the rotational shear. Furthermore, the increase in induced shear strain was found to enhance the breakdown of suspension’s structure until a critical point, after which thickening effects dominate. An effective dispersing method is then proposed. This consists of applying a rotational shear around the transitional value between the linear and non-linear variations of the apparent viscosity with shear rate, followed by an oscillatory shear at the crossover shear strain and high angular frequency of 100 rad/s. Investigating the evolutions of viscoelastic properties of inert calcite-based and cement suspensions and allowed establishing two independent build-up indices. The first one (the percolation time) can represent the rest time needed to form the elastic network. On the other hand, the second one (rigidification rate) can describe the increase in stress-bearing capacity of formed network due to cement hydration. In addition, results showed that combining the percolation time and the rigidification rate can provide deeper insight into the structuration process of cement suspensions. Furthermore, these indices were found to be well-correlated to the decay in the lateral pressure of cement suspensions. The variations of proposed build-up indices with mixture’s parameters showed that the percolation time is most likely controlled by the frequency of Brownian collisions, distance between dispersed particles, and intensity of cohesion between cement particles. On the other hand, a higher rigidification rate can be secured by increasing the number of contact points per unit volume of paste, nucleation rate of cement hydrates, and intensity of inter-particle cohesion.

Electrical and optical studies on carbon nanotube arrays

Single-walled carbon nanotubes (SWNTs) have been studied as a prominent class of high performance electronic materials for next generation electronics. Their geometry dependent electronic structure, ballistic transport and low power dissipation due to quasi one dimensional transport, and their capability of carrying high current densities are some of the main reasons for the optimistic expectations on SWNTs. However, device applications of individual SWNTs have been hindered by uncontrolled variations in characteristics and lack of scalable methods to integrate SWNTs into electronic devices. One relatively new direction in SWNT electronics, which avoids these issues, is using arrays of SWNTs, where the ensemble average may provide uniformity from device to device, and this new breed of electronic material can be integrated into electronic devices in a scalable fashion. This dissertation describes (1) methods for characterization of SWNT arrays, (2) how the electrical transport in these two-dimensional arrays depend on length scales and spatial anisotropy, (3) the interaction of aligned SWNTs with the underlying substrate, and (4) methods for scalable integration of SWNT arrays into electronic devices. The electrical characterization of SWNT arrays have been realized by polymer electrolyte-gated SWNT thin film transistors (TFTs). Polymer electrolyte-gating addresses many technical difficulties inherent to electrical characterization by gating through oxide-dielectrics. Having shown polymer electrolyte-gating can be successfully applied on SWNT arrays, we have studied the length scaling dependence of electrical transport in SWNT arrays. Ultrathin films formed by sub-monolayer surface coverage of SWNT arrays are very interesting systems in terms of the physics of two-dimensional electronic transport. We have observed that they behave qualitatively different than the classical conducting films, which obey the Ohm’s law. The resistance of an ultrathin film of SWNT arrays is indeed non-linear with the length of the film, across which the transport occurs. More interestingly, a transition between conducting and insulating states is observed at a critical surface coverage, which is called percolation limit. The surface coverage of conducting SWNTs can be manipulated by turning on and off the semiconductors in the SWNT array, leading to the operation principle of SWNT TFTs. The percolation limit depends also on the length and the spatial orientation of SWNTs. We have also observed that the percolation limit increases abruptly for aligned arrays of SWNTs, which are grown on single crystal quartz substrates. In this dissertation, we also compare our experimental results with a two-dimensional stick network model, which gives a good qualitative picture of the electrical transport in SWNT arrays in terms of surface coverage, length scaling, and spatial orientation, and briefly discuss the validity of this model. However, the electronic properties of SWNT arrays are not only determined by geometrical arguments. The contact resistances at the nanotube-nanotube and nanotube-electrode (bulk metal) interfaces, and interactions with the local chemical groups and the underlying substrates are among other issues related to the electronic transport in SWNT arrays. Different aspects of these factors have been studied in detail by many groups. In fact, I have also included a brief discussion about electron injection onto semiconducting SWNTs by polymer dopants. On the other hand, we have compared the substrate-SWNT interactions for isotropic (in two dimensions) arrays of SWNTs grown on Si/SiO2 substrates and horizontally (on substrate) aligned arrays of SWNTs grown on single crystal quartz substrates. The anisotropic interactions associated with the quartz lattice between quartz and SWNTs that allow near perfect horizontal alignment on substrate along a particular crystallographic direction is examined by Raman spectroscopy, and shown to lead to uniaxial compressive strain in as-grown SWNTs on single crystal quartz. This is the first experimental demonstration of the hard-to-achieve uniaxial compression of SWNTs. Temperature dependence of Raman G-band spectra along the length of individual nanotubes reveals that the compressive strain is non-uniform and can be larger than 1% locally at room temperature. Effects of device fabrication steps on the non-uniform strain are also examined and implications on electrical performance are discussed. Based on our findings, there are discussions about device performances and designs included in this dissertation. The channel length dependences of device mobilities and on/off ratios are included for SWNT TFTs. Time response of polymer-electrolyte gated SWNT TFTs has been measured to be ~300 Hz, and a proof-of-concept logic inverter has been fabricated by using polymer electrolyte gated SWNT TFTs for macroelectronic applications. Finally, I dedicated a chapter on scalable device designs based on aligned arrays of SWNTs, including a design for SWNT memory devices.

Optimisation de l'extraction, en réacteur "batch", de biomasse énergétique à l'aide d'émulsions ultrasoniques de solvants verts

L’industrie des biocarburants de deuxième génération utilise, entre autre, la biomasse lignocellulosique issue de résidus forestiers et agricoles et celle issue de cultures énergétiques. Le sorgho sucré [Sorghum bicolor (L.) Moench] fait partie de ces cultures énergétiques. L’intérêt croissant de l’industrie agroalimentaire et des biocarburants pour cette plante est dû à sa haute teneur en sucres (jusqu’à 60% en masse sèche). En plus de se développer rapidement (en 5-6 mois), le sorgho sucré a l’avantage de pouvoir croître sur des sols pauvres en nutriments et dans des conditions de faibles apports en eau, ce qui en fait une matière première intéressante pour l’industrie, notamment pour la production de bioéthanol. Le concept de bioraffinerie alliant la production de biocarburants à celle de bioénergies ou de bioproduits est de plus en plus étudié afin de valoriser la production des biocarburants. Dans le contexte d’une bioraffinerie exploitant la biomasse lignocellulosique, il est nécessaire de s’intéresser aux différents métabolites extractibles en plus des macromolécules permettant la fabrication de biocarburants et de biocommodités. Ceux-ci pouvant avoir une haute valeur ajoutée et intéresser l’industrie pharmaceutique ou cosmétique par exemple. Les techniques classiques pour extraire ces métabolites sont notamment l’extraction au Soxhlet et par macération ou percolation, qui sont longues et coûteuses en énergie. Ce projet s’intéresse donc à une méthode d’extraction des métabolites primaires et secondaires du sorgho sucré, moins coûteuse et plus courte, permettant de valoriser économiquement l’exploitation industrielle du de cette culture énergétique. Ce travail au sein de la CRIEC-B a porté spécifiquement sur l’utilisation d’une émulsion ultrasonique eau/carbonate de diméthyle permettant de diminuer les temps d’opération (passant à moins d’une heure au lieu de plusieurs heures) et les quantités de solvants mis en jeu dans le procédé d’extraction. Cette émulsion extractive permet ainsi de solubiliser à la fois les métabolites hydrophiles et ceux hydrophobes. De plus, l’impact environnemental est limité par l’utilisation de solvants respectueux de l’environnement (80 % d’eau et 20 % de carbonate de diméthyle). L’utilisation de deux systèmes d’extraction a été étudiée. L’un consiste en la recirculation de l’émulsion, en continu, au travers du lit de biomasse; le deuxième permet la mise en contact de la biomasse et des solvants avec la sonde à ultrasons, créant l’émulsion et favorisant la sonolyse de la biomasse. Ainsi, en réacteur « batch » avec recirculation de l’émulsion eau/DMC, à 370 mL.min[indice supérieur -1], au sein du lit de biomasse, l’extraction est de 37,91 % en 5 minutes, ce qui est supérieur à la méthode ASTM D1105-96 (34,01 % en 11h). De plus, en réacteur « batch – piston », où la biomasse est en contact direct avec les ultrasons et l’émulsion eau/DMC, les meilleurs rendements sont de 35,39 % en 17,5 minutes, avec 15 psig de pression et 70 % d’amplitude des ultrasons. Des tests effectués sur des particules de sorgho grossières ont donné des résultats similaires avec 30,23 % d’extraits en réacteur « batch » avec recirculation de l’émulsion (5 min, 370 mL.min[indice supérieur -1]) et 34,66 % avec le réacteur « batch-piston » (30 psig, 30 minutes, 95 % d’amplitude).

Asymptotic scattering and duality in the one-dimensional three-state quantum Potts model on a lattice

We determine numerically the single-particle and the two-particle spectrum of the three-state quantum Potts model on a lattice by using the density matrix renormalization group method, and extract information on the asymptotic (small momentum) S-matrix of the quasiparticles. The low energy part of the finite size spectrum can be understood in terms of a simple effective model introduced in a previous work, and is consistent with an asymptotic S-matrix of an exchange form below a momentum scale p*. This scale appears to vanish faster than the Compton scale, mc, as one approaches the critical point, suggesting that a dangerously irrelevant operator may be responsible for the behaviour observed on the lattice.

Superconducting Transition-Edge Sensor Physics

Despite record-setting performance demonstrated by superconducting Transition Edge Sensors (TESs) and growing utilization of the technology, a theoretical model of the physics governing TES devices superconducting phase transition has proven elusive. Earlier attempts to describe TESs assumed them to be uniform superconductors. Sadleir et al. 2010 shows that TESs are weak links and that the superconducting order parameter strength has significant spatial variation. Measurements are presented of the temperature T and magnetic field B dependence of the critical current Ic measured over 7 orders of magnitude on square Mo/Au bilayers ranging in length from 8 to 290 microns. We find our measurements have a natural explanation in terms of a spatially varying order parameter that is enhanced in proximity to the higher transition temperature superconducting leads (the longitudinal proximity effect) and suppressed in proximity to the added normal metal structures (the lateral inverse proximity effect). These in-plane proximity effects and scaling relations are observed over unprecedentedly long lengths (in excess of 1000 times the mean free path) and explained in terms of a Ginzburg-Landau model. Our low temperature Ic(B) measurements are found to agree with a general derivation of a superconducting strip with an edge or geometric barrier to vortex entry and we also derive two conditions that lead to Ic rectification. At high temperatures the Ic(B) exhibits distinct Josephson effect behavior over long length scales and following functional dependences not previously reported. We also investigate how film stress changes the transition, explain some transition features in terms of a nonequilibrium superconductivity effect, and show that our measurements of the resistive transition are not consistent with a percolating resistor network model.

Nanofiltration membranes modified with aromatic polyamide dendrimers active layers

This thesis describes the modification of the commercial TFC-S nanofiltration membrane with shape-persistent dendritic architectures. Amphiphilic aromatic polyamide dendrimers (G1-G3) are synthesized via a divergent approach and used for membrane modification by direct percolation. The permeate samples collected from the percolation experiments are analyzed by UV-Vis spectroscopy to instantly monitor the influence of dendrimer generations on percolation behaviors and new active layer formation. The membrane structures are further characterized by Rutherford backscattering spectrometry (RBS) and atomic force microscopy (AFM) techniques, suggesting a low-level accumulation of dendrimers inside the TFC-S NF membranes and subsequent formation of an additional aramide dendrimer active layer. Thus, all the modified TFC-S membranes have a double active layer structure. A PES-PVA film is used as a control membrane showing that structural compatibility between the dendrimer and supports plays an important role in the membrane modification process. The performance of modified TFC-S membrane is evaluated on the basis of rejection abilities of a variety of water contaminants having a range of sizes and chemistry. As the water flux is inversely proportional to the thickness of the active layer, we optimize the amount of dendrimers deposited for specific contaminants to improve the solute rejection while maintaining high water flux.

EACS: Effective Avoidance Combination Strategy

International audience

Phase transitions in gene networks evolved under different selection rules

Mathematical models of gene regulation are a powerful tool for understanding the complex features of genetic control. While various modeling efforts have been successful at explaining gene expression dynamics, much less is known about how evolution shapes the structure of these networks. An important feature of gene regulatory networks is their stability in response to environmental perturbations. Regulatory systems are thought to have evolved to exist near the transition between stability and instability, in order to have the required stability to environmental fluctuations while also being able to achieve a wide variety of functions (corresponding to different dynamical patterns). We study a simplified model of gene network evolution in which links are added via different selection rules. These growth models are inspired by recent work on `explosive' percolation which shows that when network links are added through competitive rather than random processes, the connectivity phase transition can be significantly delayed, and when it is reached, it appears to be first order (discontinuous, e.g., going from no failure at all to large expected failure) instead of second order (continuous, e.g., going from no failure at all to very small expected failure). We find that by modifying the traditional framework for networks grown via competitive link addition to capture how gene networks evolve to avoid damage propagation, we also see significant delays in the transition that depend on the selection rules, but the transitions always appear continuous rather than `explosive'.

Irrigacao por sulco com e sem utilizacao da agua de escoamento superficial.

Compararam-se dois sistemas de irrigacao por sulcos. Um deles constou da aplicacao de vazoes constantes, atraves de sifoes, para valores de R iguais a 0,26; 1 e 2. O outro constou de reutilizacao da agua escoada para valores de R iguaia a 0,5, 1 e 2. Observaram-se decrescimos nas perdas por percolacao, enquanto as eficiencias de aplicaca oe de distribuicao aumentaram, o mesmo acontecendo com as perdas por escoamento em ambos os sistemas de irrigacao, quando o valor de R aumentou. A eficiencia de irrigacao cresceu com o valor de R, quando se reutilizou a agua de escoamento, ocorrendo o inverso quando nao se reutilizou esta agua. Foram feitas determinacoes quanto a flutuacao da vazao de escoamento disponivel durante a irrigacao de cinco setores consecutivos, visando o dimensionamento de sistemas de irrigacao com reutilizacao desta agua.

Mensuração de perdas de sedimentos por escoamento superficial em encostas, com uso de parcelas de erosão, em diferentes usos e coberturas do solo no Bioma Cerrado : Bacia Hidrográfica do Ribeirão do Gama/DF

Dissertação (mestrado)—Universidade de Brasília, Instituto de Ciências Humanas, Departamento de Geografia, 2015.

Efecto antiinflamatorio de extractos metanólicos de plantas de Azuay y Loja (Ecuador) a través del modelo de peces cebra

Los peces cebra son utilizados como modelo biológico para screening primario de extractos de plantas con potencial bioactividad, aprovechando sus similitudes: genética, fisiológica y respuesta farmacológica con los mamíferos. En el estudio se empleó este modelo para valorar la actividad antiinflamatoria de 36 extractos metanólicos de plantas medicinales utilizadas en las provincias de Azuay y Loja (Ecuador). Parte del material vegetal fue recolectado con el aporte de una hierbatera de etnia Saraguro. Los extractos fueron preparados por percolación y su toxicidad fue evaluada en peces cebra en concentraciones variables de 400 a 3,125 μg/ml, determinándose la máxima concentración tolerada para cada uno de ´estos. La actividad antiinflamatoria se evaluó a través del ensayo de migración leucocitaria inducida por lipopolisacárido de Sallmonella typhi. Los extractos de: Cestrum aff. peruvianum, Galinsoga parviflora, Galium sp., Oenothera tetraptera, Peperomia aff. galioides , Passiflora ampullaceae y Ambrosia arborescens, correspondientes al 18,92% de los analizados, mostraron un potencial antiinflamatorio comparable con indometacina y dexametasona; siendo el extracto metanólico de Cestrum aff. peruvianum el más relevante a 50 g/ml. El análisis fitoquímico básico de los extractos se realizó por cromatografía de capa fina, evidenciándose la presencia de saponinas y terpenoidoes como compuestos principales en la mayoría de los extractos.