Le sol est un compartiment majeur de stockage du carbone (C) organique de l’écosystème terrestre. Il joue un rôle important dans la régulation du climat. Toute variation des flux de carbone entre l’atmosphère et l’écosystème terrestre pourrait avoir un impact important sur l’augmentation de CO2 dans l’atmosphère, mais aussi sur la diminution des teneurs en matière organique du sol et donc sur la fertilité des sols. Au Nord Cameroun, les sols sont exposés à de longues périodes sèches (5 à 6 mois par an) qui alternent avec une saison humide. La période de transition entre ces deux saisons, peut durer de mi-avril à fin juin et est caractérisée par des pluies très irrégulières. Ces cycles d’humectation-dessiccation pourraient selon la littérature accentuer la minéralisation du carbone organique du sol et le cycle des éléments nutritifs. L’objectif de cette étude est de quantifier l’impact des cycles humectation-dessiccation sur la minéralisation du carbone dans un contexte soudano-sahélien. Pour faire des mesures représentatives sur le terrain, il est nécessaire d’étudier la variation sur 24 heures de la respiration du sol après humectation suite à une période sèche. Cette mise au point méthodologique a montré que la respiration du sol présente une courbe quadratique au cours de la journée, devenant presque linéaire au cours de la nuit. La température et l’humidité du sol ont permis d’expliquer au moins 73% des variations sur 24 heures. Ces observations ont été utilisées pour proposer une méthode pour estimer la respiration moyenne diurne et nocturne après humectation des sols. La méthode proposée dans cette étude a l’avantage d’être basée sur un nombre réduit de mesures et est par conséquent plus facile à mettre en œuvre pour suivre la respiration du sol sur 24 heures après les premières pluies. Une première étude expérimentale de terrain a permis de montrer que la ré-humectation des sols et le mode de gestion des pailles ont augmenté la minéralisation du carbone de ces sols. En revanche, la fréquence des cycles humectation-dessiccation des sols sur une période de 50 jours n’a pas augmenté la minéralisation cumulée du carbone des sols. Au Nord Cameroun, la minéralisation rapide des pailles rend difficile l’augmentation des stocks de carbone du sol par conservation des pailles des cultures précédentes à la surface du sol. Dans une seconde expérimentation de laboratoire, en conditions contrôlées, les cycles humectation-dessiccation n’ont pas augmenté la minéralisation du carbone organique du sol et de l’azote (N) par rapport aux sols maintenus humides. Cependant, les émissions de CO2 ont augmenté avec l’addition de paille enrichie en carbone-13. Cette addition de la paille marquée a augmenté la minéralisation de la matière organique du sol (priming effect). La minéralisation de la paille a diminué avec les cycles humectation-dessiccation et la quantité de paille restante était de 102 µg Cg-1 sol sur les sols ré-humectés contre 48 µg Cg-1 sol sur les sols maintenus humides. L’absence de cette réponse de la minéralisation du carbone et d’azote du sol aux cycles humectation-dessiccation pourrait être liée à une baisse de l’activité microbienne durant les périodes de dessèchement et l’absence d’une augmentation soutenue des taux de minéralisation du carbone avec les cycles ultérieurs d’humectation-dessiccation. / Soil as a major storage component for terrestrial ecosystem’s organic carbon plays an important role in regulating climate and agricultural production. Any variation of carbon fluxes between the atmosphere and the terrestrial ecosystem can have a significant impact on the increase of carbon dioxide in the atmosphere but also the decrease in soil organic matter and thus accelarate soil fertility degradation. In northern Cameroon, the transition period between long dry periods with a wet season is characterized by very irregular rainfall that can last several weeks. These wetting-drying cycles can accentuate the mineralization of soil organic carbon and nutrient cycling. The objective of this study is to assess the impact of wet-dry cycles on carbon mineralization in a sudano-sahelian context. From methodological stand field measurements require to study the soil respiration variation over 24 hours after a wet period. This methodological test has shown that soil respiration has a quadratic curve during the day, becoming almost linear during the night. The temperature and soil moisture have explained together the variation over 24 hours (at least 73% ; p< 0.001). These observations have been used to propose a method for estimating the mean daytime and nighttime soil respiration after wetting the soil. Indeed the method proposed in this study has the advantage of being based on a small number of measurements and is, therefore, easier to implement to monitor 24-h soil respiration after the first rains following a long dry period. A first experiment has shown that the wetting of the soil and mulching increased soil carbon mineralization. However, wetting-drying cycles on soil did not increase the cumulative mineralization of soil carbon more than keeping the soil continuously moist. Indeed, in northern Cameroon, the rapid mineralization of crop residues makes it difficult to increase soil carbon stocks by mulching. In a second laboratory experiment, the wetting-drying cycles did not increase organic carbon and nitrogen mineralization from soils added with straw. However, carbon dioxide emissions increased on straw amended soils compared to soils without straw. This addition of the labeled straw increased mineralization of soil organic matter (priming effect). The mineralization of the straw also decreased with the wetting-drying cycles, thus the amount of straw remaining on soils was 102 µg C g-1 soil on re-wetted soils compared to 48 µg C g-1 soil for those with constant moisture. The lack of response for C and N mineralization during wetting-drying cycles may be linked to a decrease of microbial activity during dry periods and the lack of a steady increase in the carbon mineralization rate with subsequent wetting-drying cycles.

Submitted by Maicon Juliano Schmidt (maicons) on 2015-04-09T19:46:05Z No. of bitstreams: 1 Rafaela Gava Padovan.pdf: 7081051 bytes, checksum: 9e1501c4f4ebed520c7882be21164038 (MD5) / Made available in DSpace on 2015-04-09T19:46:05Z (GMT). No. of bitstreams: 1 Rafaela Gava Padovan.pdf: 7081051 bytes, checksum: 9e1501c4f4ebed520c7882be21164038 (MD5) Previous issue date: 2013-09-05 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / FINEP - Financiadora de Estudos e Projetos / Os agregados reciclados de concreto, de um modo geral, apresentam elevada absorção de água, em função da sua maior porosidade. Esta absorção resulta em alterações no teor de água das misturas, e têm implicação direta sobre as propriedades microestruturais dos materiais à base de cimento, não sendo diferente com o agregado reciclado. Contudo, tais alterações ainda são pouco conhecidas nestes materiais. Esta pesquisa possui o objetivo de determinar a influência do processo de pré-molhagem do agregado no comportamento de concretos desenvolvidos através da incorporação de agregado graúdo reciclado de concreto (AGRC) em substituição ao agregado graúdo natural (AGN). O teor de substituição do AGRC em relação ao AGN utilizado foi de 50% em relação ao volume do concreto. Previamente à utilização do AGRC, foi realizada uma pré-molhagem do material com percentuais na ordem de 40, 60, 80 e 100% da água relativa à absorção total do resíduo. Foram adotadas relações água/cimento iniciais de 0,45; 0,55 e 0,65. O abatimento foi fixado em 100 ± 20 mm, realizando-se uma compensação de água da mistura no teor necessário para atingir este abatimento. Num segundo grupo, a menor quantidade de água utilizada na produção dos concretos sem aditivo foi adotada para a produção dos mesmos concretos, com percentuais de pré-molhagem de 40, 60 e 80%, utilizando-se aditivo superplastificante ao invés de água para que fosse atingido o abatimento fixado. Verificou-se a influência da pré-molhagem do AGRC sobre as propriedades do concreto fresco, através da determinação da consistência ao longo do tempo; e do concreto endurecido, através da resistência à compressão e absorção de água por capilaridade dos concretos, e a alteração de porosidade de amostras de argamassa extraídas dos concretos frescos após diferentes tempos de contato com o agregado reciclado. Os resultados obtidos indicam que a trabalhabilidade e a resistência a compressão dos concretos com AGRC são pouco influenciadas pelo teor de pré-molhagem, enquanto que a permeabilidade a água e o teor de vazios existente na argamassa da mistura sofrem influencia significativa: nos concretos com AGRC sem aditivo, há pequenas variações de permeabilidade e porosidade, sendo que o teor de pré-molhagem de 80% resulta em concretos menos porosos. Entretanto, nos concretos com AGRC e aditivo superplastificante, o menor teor de pré-molhagem testado (40%) se revela a melhor opção, pois a água de mistura é absorvida pelos poros vazios do agregado reciclado, o que diminui a porosidade da argamassa, e consequentemente a capilaridade do concreto. / Recycled aggregates have high water absorption properties due to its high porosity. It changes the water content of the mixtures, and has implications on the microstructural properties of cement-based materials as those who uses recycled aggregate; however, little is known about these materials. This research has the objective of determining the influence of aggregate pre-wetting in new concrete made with recycled coarse aggregate concrete (RCAC) replacing natural aggregate. The substitution ratio of natural coarse aggregate (NCA) in relation to RCAC was 50% relative to the volume of the concrete. Prior to employing RCAC, it was pre-wetted with pre-wetting levels of 40, 60, 80 and 100% of the total water absorption of the residue. Water to cement ratios were initially determined to be 0.45, 0.55 and 0.65. The slump was set at 100 ± 20 mm, performing a compensation on the water content of the mixture required to get this slump. In a second group, the smallest amount of water used in the concrete’s production without additive was set with saturation levels of 40, 60 and 80%, using a superplasticizer instead of water to achieve the required slump. The recycled concrete produced was found to influence the pre-wetting RCAC on the properties of fresh concrete, through determination of consistency over time, compressive strength and durability and water absorption by capillarity. Mortar samples were obtained from the extraction of recycled concrete. These samples were analyzed for porosity. The results indicate that the workability and the compressive strength of concretes with AGRC are little influenced by the amount of pre-wetting, while the water permeability and the void content of the mixture existing in the mortar suffer significant influence: in the concrete with no additive AGRC there are small variations in porosity and permeability, and in the amount of pre-wetting results in 80% less porous concrete. However, in concrete with AGRC and superplasticizer, the lowest level of pre-wetting tested (40%) proves the best option, because the mixing water is absorbed by the empty pores of recycled aggregate, which reduces the porosity of the mortar, and consequently the capillarity of hard concrete.

Este trabalho tem como objetivo caracterizar as mudanças microestruturais durante o recozimento isotérmico de um fio de ferro trefilado a frio e de pureza comercial com ênfase no crescimento de grão. Os recozimentos foram realizados no intervalo de 823-1173 K por diversos tempos. As informações estatísticas do tamanho de grão foram obtidas por meio do método dos interceptos lineares. O mapeamento das orientações foi obtido por meio de difração de elétrons retroespalhados (EBSD). O material apresenta uma microestrutura ferrítica e totalmente recristalizada a partir de 873 K. Foram encontrados indícios de crescimento normal de grão a partir de 1023 K, porém este crescimento não evoluiu consideravelmente ao longo do tempo de tratamento. Os resultados obtidos a partir do método dos interceptos lineares demonstram que a distribuição de tamanho de grão segue uma curva próxima à log-normal. Nas amostras recozidas a partir de 1123 K, verificou-se a ocorrência de crescimento anormal de grão. O crescimento anormal de alguns grãos inicia-se na região central do fio, estendendo-se até uma região próxima à superfície do fio. Algumas modificações na dimensão da amostra e na atmosfera de recozimento foram realizadas a fim de se estudar a interação destas variáveis no desenvolvimento dos grãos anormais. Foram identificados indícios morfológicos de que o mecanismo para ocorrência de crescimento anormal foi o molhamento de contornos no estado sólido (solid-state wetting) que depois foram confirmados pelas análises de micro e mesotexturas. A análise de microtextura também revela que o material apresenta duas componentes preferenciais, as fibras || DT e || DT, onde DT é a direção axial de trefilação. A primeira orientação é a mais intensa, sendo que seu fortalecimento parece ser impulsionado pelo crescimento anormal de grão. A segunda é menos intensa e parece estar relacionada com as orientações dos grãos oriundos da recristalização primária. Aspectos teóricos e analíticos sobre o crescimento de grão são apresentados e associados aos resultados experimentais e à literatura. / This Dissertation aims follow the microstructural changes occurring during isothermal annealing of commercially-pure cold-drawn iron wire, with emphasys on grain growth phenomena. The grain size data were obtained by means of the linear intercept method. The orientations scanning were done by means of electron backscatter diffraction patterns (EBSD). Isothermal annealing was performed within the temperature range 823 - 1173 K for several times. The material displays full recrystallization at temperatures above 873 K. Normal grain growth was observed above 1023 K, although this growth did not evolve through longer annealing times. The results of the linear intercept method show the grain size distribution has a log-normal shape. For samples annealed above 1123 K, abnormal grain growth occurs. The first signs of secondary recrystallization appear close to the center of the wire, growing towards the surface. Changes in the wire diameter and annealing atmosphere were performed to assess the effect of these variables on abnormal grain growth. Results point out that abnormal grain growth is driven by solid-state wetting. These morphological observations were also confirmed by micro and mesotexture analyses. The microtexture also shows the presence of two major fiber texture components || WD and || WD, were WD is the axial wire-drawn direction. The first one is the most intense and its strengthening seems to be related with abnormal grain growth. The second one is weaker and it seems to be most related with small primary recrystallized grains. Theoretical and analytical features about grain growth are presented and discussed in light of literature and experimental results.

Il existe de nombreuses technologies de décontamination, néanmoins les spores et les biofilms bactériens demeurent une préoccupation majeure dans de nombreux domaines, tels que le secteur hospitalier, alimentaire et de la biodéfense car elles sont résistantes. Une mousse novatrice contenant un biocide (l’hypochlorite de sodium ou le peroxyde d’hydrogène) et un agent stabilisant (le Xanthane) a été étudiée pour répondre à ce besoin. Cette mousse a la capacité d’être mise en oeuvre de différentes façons sur le terrain par : pulvérisation au sol ; talochage et pulvérisation sur les murs ; remplissage de pièces entières (murs et sols). Le travail de thèse est d’évaluer les modes d’action biocide de ces mousses sur les spores et les biofilms. Afin d’étudier le mode d’action de ces mousses des protocoles expérimentaux ont été mis au point sur les spores et les biofilms suivant leurs futures mises en oeuvre (horizontale, verticale et remplissage) et suivant différents facteurs environnementaux pouvant influencer leur efficacité de décontamination (températures, salissures, matériaux, …). L’ensemble de ce travail de thèse a permis de distinguer l’intérêt de la mousse au Xanthane contenant NaOCl 5% par rapport à celle H2O2 12% pour répondre aux besoins spécifiques de la décontamination des agents de la menace biologique. Cette mousse permet une décontamination rapide de 7 logs de spores en 30 minutes pour chacune des trois voies de mise en oeuvre à 20°C. De plus, elle permet la destruction de biofilms contenant 107 de bactéries/cm² en 1 heure maximum sur un support horizontal et par remplissage. Cette mousse NaOCl est suffisamment mature pour pouvoir réaliser un futur transfert industriel. / Several decontamination technologies exist, however bacterial spores and biofilms remain a concern in a lot of fields, like hospital, alimentary and military. A new foam containing a biocide (sodium hypochlorite or hydrogen peroxide) and a stabilizing agent (Xanthan) has been studied to answer this problematic. This foam can be used in different ways on the field following contaminations: grounds’ spraying, walls’ covering and spraying, full pieces’ filling (walls and ground). The goal of this thesis is to evaluate the biocide efficiency of these foams on spores and biofilms. We optimized experimental protocols in order to study mechanisms of foams’ action on spores and biofilms based on theirs future applications (horizontal, vertical and filling) and depending on different environmental factors which may impact foam decontamination efficiencies (materials, temperatures, soil, …). This thesis work enabled to highlight the Xanthan foam containing 5% NaOCl from the one including 12% H2O2 in military sector. This foam allows a rapid decontamination, about 7 logs of spores in 30 minutes, for each of the three ways of use at 20°C. Moreover, the destruction of biofilms containing 107 logs of bacteria/cm² was achieved in 1 hour on a horizontal support by filling. This NaOCl foam is ready to be used for industrials.

A resiliência física de solos é proveniente de processos regenerativos que incluem ciclos de umedecimento e secamento, congelamento e descongelamento assim como as atividades biológicas. Este estudo testou a hipótese de que as propriedades físicas do solo,tais como a permeabilidade do solo ao ar, densidade do solo, porosidade de aeração e porosidade total são indicadores físicos eficientes para quantificar a resiliência de solos de diferentes texturas submetidos ao estresse mecânico (compactação) e após subseqüentes ciclos de umedecimento e secamento. O objetivo foi avaliar o comportamento e a resiliência do solo por meio de propriedades físicas de um Latossolo Vermelho. Foram retiradas 25 amostras indeformadas (0-0,05m) de dois solos: solo I com textura argilosa e solo II com textura franco argilo arenosa, realizando as determinações das propriedades físicas nos tratamentos: antes da compactação(A), depois da compactação (C0) e após ciclos de umedecimento e secamento (C1,C2,C3,C4). As propriedades densidade do solo e porosidade total não apresentaram recuperação da condição inicial após a compactação nos solos I e II, as propriedades conteúdo volumétrico de água e porosidade de aeração apresentaram recuperação parcial apenas no solo I, para o solo II também não apresentaram recuperação, e a permeabilidade do solo ao ar foi a propriedade que apresentou a melhor recuperação assim como foi a que apresentou maior resiliência. Em relação ao distinto comportamento dos dois solos, observou-se que o solo I foi mais resiliente que o solo II nas propriedades que apresentaram recuperação. / The soil physical resilience comes from regenerative processes which include cycles of wetting and drying, freezing and thawing as well as biological activities. This study tested the hypothesis that the physical properties of soil such as soil permeability, bulk density, aeration porosity and total porosity are efficient physical indicators to quantify the resilience of soils of different textures subjected to mechanical stress (compression) and after subsequent cycles of wetting and drying. The objective was to evaluate the behavior and soil resilience by means of physical properties of an Oxisol. Undisturbed samples were taken 25 (0-0.05 m) of two soils: clayey soil and soil with sandy clay loam texture, making determinations of physical properties in the treatments before compression (A), after compaction (C0) and after wetting and drying cycles (C1, C2, C3, C4). The bulk density properties and porosity did not recover the initial condition after compression in the soil I and II, the properties volumetric content of water and air-filled porosity showed only partial recovery in the soil I, II to the soil also showed no recovery and soil permeability to air was the property that showed the best recovery as well as showed the greatest resilience. Regarding the different behavior of the two soil, it was observed that the soil I was more resilient soil II in which showed recovery properties

Polymer-based piezoelectric and triboelectric generators form the basis of well-known energy harvesting methods that are capable of transforming ambient vibrational energy into electrical energy via electrical polarization changes in a material and contact electrification, respectively. However, the low energy conversion efficiency and limited thermal stability of polymeric materials hinder practical application. While nanostructured polymers and polymer-based nanocomposites have been widely studied to overcome these limitations, the performance improvement has not been satisfactory due to limitations pertaining to long-standing problems associated with polymeric materials; such as low crystallinity of nanostructured polymers, and in the case of nanocomposites, poor dispersion and distribution of nanoparticles in the polymer matrix. In this thesis, novel functional polymeric nanomaterials, for stable and physically robust energy harvesting applications, are proposed by developing advanced nanofabrication methods. The focus is on ferroelectric polymeric nanomaterials, as this class of materials is particularly well-suited for both piezoelectric and triboelectric energy harvesting. The thesis is broadly divided into two parts. The first part focuses on Nylon-11 nanowires grown by a template-wetting method. Nylon-11 was chosen due to its reasonably good ferroelectric properties and high thermal stability, relative to more commonly studied ferroelectric polymers such as polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE)). However, limitations in thin-film fabrication of Nylon-11 have led to poor control over crystallinity, and thus investigation of this material for practical applications had been mostly discontinued, and its energy harvesting potential never fully realised. The work in this thesis shows that these problems can be overcome by adopting nanoporous template-wetting as a versatile tool to grow Nylon-11 nanowires with controlled crystallinity. Since the template-grown Nylon-11 nanowires exhibit a polarisation without any additional electrical poling process by exploiting the nanoconfinement effect, they have been directly incorporated into nano-piezoelectric generators, exhibiting high temperature stability and excellent fatigue performance. To further enhance the energy harvesting capability of Nylon-11 nanowires, a gas -flow assisted nano-template (GANT) infiltration method has been developed, whereby rapid crystallisation induced by gas-flow leads to the formation of the ferroelectric δʹ-phase. The well-defined crystallisation conditions resulting from the GANT method not only lead to self-polarization but also increases average crystallinity from 29 % to 38 %. δʹ-phase Nylon-11 nanowires introduced into a prototype triboelectric generator are shown to give rise to a six-fold increase in output power density as observed relative to the δʹ-phase film-based device. Interestingly, based on the accumulated understanding of the template-wetting method, Nylon-11, and energy harvesting devices, it was found that thermodynamically stable α-phase Nylon-11 nanowires are most suitable for triboelectric energy generators, but not piezoelectric generators. Notably, definitive dipole alignment of α-phase nanowires is shown to have been achieved for the first time via a novel thermally assisted nano-template infiltration (TANI) method, resulting in exceptionally strong and thermally stable spontaneous polarization, as confirmed by molecular structure simulations. The output power density of a triboelectric generator based on α-phase nanowires is shown to be enhanced by 328 % compared to a δʹ-phase nanowire-based device under the same mechanical excitation. The second part of the thesis presents recent progress on polymer-based multi-layered nanocomposites for energy harvesting applications. To solve the existing issues related to poor dispersion and distribution of nanoparticles in the polymer matrix, a dual aerosol-jet printing method has been developed and applied. As a result, outstanding dispersion and distribution. Furthermore, this method allows precise control of the various physical properties of interest, including the dielectric permittivity. The resulting nanocomposite contributes to an overall enhancement of the device capacitance, which also leads to high-performance triboelectric generators. This thesis therefore presents advances in novel functional polymeric nanomaterials for energy harvesting applications, with improved performance and thermal stability. It further offers insight regarding the long-standing issues in the field of Nylon-11, template-wetting, and polymer-based nanocomposites.

Ce travail de thèse met en évidence deux phénomènes microscopiques dissipatifs au voisinage de la ligne de contact dans les phénomènes de capillarité et d'adhésion. L'étude s'appuie sur des expériences dynamiques et des modélisations théoriques. La mesure expérimentale de quantités macroscopiques et la théorie hydrodynamique permettent d'extraire les informations dynamiques localisées au voisinage la ligne de contact. Les différents phénomènes dissipatifs localisés au voisinage de la ligne de contact ont pour origines les propriétés des substrats sur lesquels se déplace la ligne de contact. Pour une surface rigide hétérogène, nous avons développé un modèle rhéologique de la ligne de contact fondé sur l'hydrodynamique, permettant d'établir théoriquement l'évolution temporelle de la ligne de contact et de ses déformations. Une décomposition modale fondée sur la réduction de l'énergie par la théorie du chemin de réaction fournit une prédiction quantitative de la dynamique thermiquement activée de la ligne de contact, en accord avec l'expérience réalisée. Pour un substrat déformable, à partir de l'analyse de deux expériences différentes de mouillage dynamique et de l'estimation de la dissipation dans le substrat, fondée sur sa viscoélasticité, nous avons développé une compréhension générale du comportement dynamique d'une ligne de contact sur un substrat viscoélastique. Pour finir, ce modèle de dissipation viscoélastique est appliqué au cas de l'adhésion réversible, où expérimentalement nous mesurons la dynamique de pelage et de recollement sur un substrat viscoélastique. Cette extension à l'adhésion permet de relier les phénomènes interfaciaux en une compréhension générale / This thesis reveals two dissipative microscopic phenomena close to the contact line in the fields of capillarity and adhesion. The study is based on dynamic experiments and theoretical predictions. Experimental measurement of macroscopic quantities and the hydrodynamic theory give access to dynamic information located close to the contact line. The different dissipative phenomena, located close to the contact line, originate from the properties of the substrates on which the contact line moves. For a heterogeneous rigid surface, we have developed a rheological model of the contact line based on hydrodynamics, in order to theoretically establish the temporal evolution of the contact line and its deformations. A modal decomposition based on the reduction of the energy by the reaction path theory allows a quantitative prediction of the thermally activated dynamics of the contact line, in agreements with the experiment carried out. For a deformable substrate, based on the analysis of two different experiments of wetting dynamics and on the estimation of the dissipation in the substrate founded on its viscoelasticity, a general understanding of the dynamical behavior of contact lines on viscoelastic substrates is achieve. Finally, this viscoelastic model is applied to the case of weak adhesion, where experimentally we measured the peeling dynamics from a viscoelastic substrate. This extension to adhesion bridge the gap between different interfacial phenomena into a general understanding

Due to their ability to confer enhanced surface properties without compromising the properties of the substrate, coatings have become ubiquitous in heavy industrial applications for corrosion, wear, and thermal protection, among others. Kinetic Metallization (KM), a solid-state impact consolidation and coating process, is well-suited for depositing industrial coatings due to its versatility, low substrate heat input, and low cost. The ability of KM coatings to adhere to the substrate is determined by the quality of the interface. The purpose of this study is to develop a model to predict the interfacial quality of KM coatings using known coating and substrate properties. Of the various contributions to adhesion of KM coatings, research suggests that the thermodynamic Work of Adhesion (WAD) is the most fundamental. It is useful to define interfacial quality in terms of the critical strain energy release rate (GC) at which coating delamination occurs. Studies show that GC for a given interface is related to WAD. This study attempts to develop a theoretical model for calculating WAD and understand the relationship between GC and WAD. For a bimetallic interface between two transition metals, WAD can be theoretically calculated using known electronic and physical properties of each metal: the molar volume, V, the surface energy, γ, and the enthalpy of alloy formation, ΔHinterface; ΔHinterface is a function of the molar volume, V, the work function, φ, and the electron density at the boundary of the Wigner-Seitz cell, nWS.WAD for Ni-Cu and Ni-Ti interfaces were 3.51 J/m2 and 4.55 J/m2, respectively. A modified Four-point bend testing technique was used to experimentally measure GC for Ni-Cu and Ni-Ti specimens produced by KM. These tests yielded mean G­C values of 50.92 J/m2 and 132.68 J/m2 for Ni-Cu and Ni-Ti specimens, respectively. Plastic deformation and surface roughness are likely the main reasons for the large discrepancy between GC and WAD. At the 95% confidence level, the mean GC of the Ni-Ti interface is significantly higher than that of the Ni-Cu interface. Further testing is recommended to better understand the relationship between WAD and GC.

Le domaine des nanotechnologies représente la thématique de recherche la plus importante de ce début de 21ème siècle. L’enjeu, bien que apparemment simple est de taille : réaliser des objets ou des structures fonctionnelles, les plus petits possibles et ce de manière reproductible, i.e. en maîtrisant leur taille, leur position. S’inscrivant dans cette problématique, ce travail de thèse porte sur le développement d’une technique originale d’assemblage dirigé de nanostructures à partir de particules d’or et d’argent sous forme de nanofils, nanocristaux, nanoanneaux et nanodisques sur des substrats rigides. Cette technique s’appuie sur une méthode purement chimique reconnue et basée sur la réduction colloïdale in situ de sels métalliques sur une surface. L’organisation bi ou tridimensionnelle de ces nanoparticules métalliques est, de plus, induite par une préstructuration du substrat réalisée par le dépôt d’un film mince de copolymères diblocs. En effet, l’auto-assemblage de films minces de copolymère permet de réaliser, par micro-séparation de phase à la paroi, un réseau bidimensionnel hexagonal de cylindres verticaux. La suppression d’une des phases du système permet de générer alors un film organique nanoporeux organisé sur le substrat qui va servir de masque et permettre d’assembler des nanoparticules métalliques lors d’une seconde étape. L’initiation du dépôt de nanoparticules métalliques dans les pores du masque a été réalisée sous ultravide en épitaxie par jets moléculaires ou par voie colloïdale en solution. La croissance finale (complète) des cristaux métalliques d’argent a été poursuivie enfin par voie colloïdale en solution. Les propriétés spectroscopiques, de mouillage et électrochimiques des structures nanoparticulaires étudiées dans ce travail ont été directement corrélées aux morphologies cristallines de surface. Une des perspectives de ce travail préliminaire est el développement d’une plateforme MEMS générique pour la détection de traces de plusieurs types de molécules (volatiles et réfractaires) par voie électrochimique. / Nanotechnology became one of the most important research field of the 21st century. Though seemingly simple, the challenge is huge: achieving the formation of the smallest objects or functional structures (in a reproducible manner) and being able to control acurately their sizes and positions, as well. Answering these demands, this thesis deals with the development of a novel technique focusing on the directed growth and assembly of metallic nanostructures onto rigid substrates. First, the combination of phase separation of a block copolymer leading to the formation of nanopores, and gold nanocolloids synthesis confined in the nanoholes, has allowed the facile fabrication of hexagonally arranged gold nanoparticles onto silicon wafer. Then, the in situ reduction of colloidal silver salts has lead to the selective growth of metallic crystals onto the rigid prepatterned substrate. The control of both the physical parameters of the patterning and the chemical synthesis ones has induced the formation of various microstructures metallic morphologies ranging from nanowires, nanocrystals, nanorings and nanodisks. Spectroscopic properties, wetting and electrochemical these nanoparticles structures were finally investigated and directly correlated with crystal surface morphologies. One of the perspectives of this preliminary work is the development of a MEMS generic platform allowing the electrochemical detection of trace of molecules (volatile or refractory).

Aggregate breakdown is an important process controlling the availability of fine soil material necessary for structural sealing of soil surfaces under rainfall. It may be caused by slaking resulting from rapid soil wetting and by physical dispersion resulting from direct and indirect energetic raindrop impacts. Relationships have been proposed by others predicting steady infiltration rate and saturated hydraulic conductivity from final aggregate size following high energy rainfall on initially dry, uncovered soil surfaces. Under these extreme conditions, both rapid wetting and energetic raindrop impact result in maximum aggregate breakdown and surface sealing. Knowledge of the relative importance of these two agents under less severe conditions and knowledge of how increased aggregate stability due to conservative soil management may ameliorate them should improve prediction and management of aggregate breakdown and surface sealing. ¶ This study has isolated and quantified effects of rapid soil wetting and energetic raindrop impact on aggregate breakdown and surface sealing. Simulated rainfall was applied to re-packed soils from differing tillage treatments on light textured soils from near Cowra and Condobolin in New South Wales, Australia. Aggregate breakdown was assessed using aggregate size distribution, determined by wet sieving and summarised by a range of statistics. The degree of breakdown was assessed after 66 mm of simulated rainfall whilst the rate of change in aggregate size distribution was assessed by sampling after 5, 10, 15, 30 and 60 mm. The degree of surface sealing was assessed using final surface hydraulic conductivity after 66 mm rainfall calculated from inferred infiltration and measured sub-seal soil water potential. The rate of surface sealing was assessed prior to ponding using cumulative rainfall volume at ponding and throughout the post-ponding phase by decline in surface hydraulic conductivity as a function of cumulative rainfall kinetic energy. Two levels of raindrop kinetic energy flux and three wetting treatments were used to isolate effects of these agents of aggregate breakdown and surface sealing. ¶ Significant surface aggregate breakdown was observed when either rapid soil wetting or highly energetic raindrop impact were allowed to occur. The majority of the data suggest a negative interaction between the two agents. When soil was initially dry rapid soil wetting was the dominant agent causing rapid aggregate breakdown, generally within the first 5 mm of rainfall. When rapid soil wetting was prevented by tension pre-wetting, energetic raindrop impact was the dominant agent and was able to cause aggregate breakdown of an almost equivalent degree. This breakdown occurred over a period lasting for up to 30 mm of rainfall. In contrast, the rate and degree of surface sealing were influenced primarily by raindrop kinetic energy with highly energetic impact leading to significant surface sealing, irrespective of soil wetting. For the soils studied, it was concluded that structural sealing of surface soil, could be significantly reduced by protecting the soil surface from energetic raindrop impact but that prevention of surface aggregate breakdown required amelioration of both processes. ¶ In addition to the negative interaction referred to above, a positive interaction was observed whereby energetic raindrop impact occurring concurrently with rapid soil wetting caused a greater degree of aggregate breakdown and a greater degree of surface sealing than energetic raindrop impact occurring subsequent to rapid soil wetting. The effect on surface sealing may be explained by the effect of lower sub-seal water potential that necessarily results from initially dry soil condition required for concurrent rapid wetting. However, the effect on aggregate breakdown remains unexplained. ¶ Notwithstanding the above, permeability was reduced under high kinetic energy rainfall even when soil wetting was reduced to very slow rates by tension pre-wetting. Likewise, surface sealing did occur under low kinetic energy rainfall for the least stable soil following rapid soil wetting. It was concluded that threshold soil wetting rates and threshold rainfall energy levels, proposed by others, are either not applicable to these soils or are negligible. ¶ The rate and degree of aggregate breakdown was also dependent on the soil with the Cowra soil being more stable than the Condobolin soil. Greater aggregate stability brought about by conservative tillage treatments at both soil locations retarded and reduced surface sealing. Unvalidated simulation modelling was used to illustrate possible effects for the soil water balance. In contrast to the conclusions of Loch (1994b), that were based on soils throughout eastern Queensland, the soil water balance simulations predicted that the residual benefits in ameliorating surface sealing resulting from improved aggregate stability could significantly reduce point runoff under the lower intensity winter rainfalls experienced in southern New South Wales. ¶ Limited testing with Condobolin soil following tension pre-wetting showed that rainfall intensity, varying over the range from 16.5 to 66 mm h-1, had little effect on the decline in surface hydraulic conductivity as a function of cumulative rainfall kinetic energy. This contrasts with greater seal permeability under higher rainfall intensities observed by Romkens et al. (1985) and others. It is proposed that an alternative explanation exists for the observations of Romkens et al. based on reduction in seal permeability due to lower sub-seal water potential under lower intensity rainfall. ¶ Post-ponding reduction in K[subscript sat] under high kinetic energy rainfall exhibited exponential decline as a function of cumulative raindrop kinetic energy as proposed by Moore (1981b). However, inferred rates of decline prior to ponding were more rapid than measured post-ponding rates suggesting that infiltration models using only a single exponential rate of surface K[subscript sat] decline based on post-ponding measurements may be in error. Potential for error is greatest at early times for loose soil that is highly susceptible to sealing. ¶ Pre-ponding decline in surface aggregation was also relatively more rapid than post-ponding decline. This discrepancy was evident irrespective of soil pre-wetting. From this it was concluded that the more rapid initial aggregate breakdown and surface sealing was due, at least in part, to processes other than aggregate slaking due to rapid soil wetting. An explanation has been proposed as follows. Raindrops initially fall on aggregates that have not been subjected to rainfall and therefore each drop has the capacity to cause greater aggregate breakdown than subsequent raindrops that fall on aggregates or soil fragments that have been strong enough to survive preceding rainfall impacts. Such a mechanism could provide an alternative explanation of the findings of Baumhardt et al. (1991) who found that less cumulative raindrop kinetic energy was necessary to achieve a given reduction in surface conductance when the cumulative energy was supplied through lower energy drops. ¶ Relationships predicting rates of surface sealing using aggregate breakdown under rainfall and aggregate stability were evaluated. Post-ponding infiltration rate and surface K[subscript sat] were related to aggregate size by exponential functions. The proportion of surface aggregates less than 0.125 mm in diameter provided slightly more consistent relationships. Parameters of fitted relationships differed among wetting pre-treatments suggesting that the influence of sub-seal water potential on surface K[subscript sat] must be considered whenever such relationships are developed or applied. Aggregate stability determined by wet sieving was related to rainfall volume required for ponding, final K[subscript sat] and final aggregate size but only for initially dry soil suggesting that such relationships may be unique to the rainfall, soils and flow conditions used to develop them. ¶ This study has established the relative importance of rapid soil wetting and energetic raindrop impact in both aggregate breakdown and surface sealing over a range of antecedent soil water and rainfall conditions. It has quantified the effectiveness of culturally induced aggregate stability in ameliorating effects of these two important agents and illustrated the potentially significant consequences for the soil water balance. It has quantified temporal patterns of surface sealing and aggregate breakdown and proposed an alternative mechanism explaining more rapid aggregate breakdown during the initial stages of rainfall. It has identified possible explanations for effects of rainfall intensity on surface sealing observed in other studies. It has also partially evaluated a mechanism proposed to explain important effects of subseal water potential on seal permeability found in this and other studies. These significant findings have been used with the findings of other studies to amend the conceptual model proposed by Le Bissonnias (1990). The amended model gives a more complete description of the relationships between parameters and processes determining aggregate breakdown and structural surface sealing under rainfall.