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Le présent travail s’intéresse à l’électro-dépôt et à la caractérisation des nanofilms Pt/Pd(hkl) ainsi que leurs propriétés en relation avec le stockage d’hydrogène. Les effets de taille nanométrique, de l’épaisseur et de l’orientation cristallographique du substrat ont été étudiés.En comparant les films Pd/Pt(111) et Pd/Pt(100), des caractéristiques distinctes ont été observées aussi bien pour les courbes d’électro-dépôt que durant les caractérisations électrochimiques et par AFM ex situ. Les dépôts Pd/Pt(100) ont montré la présence d’un dépôt en sous tension jusqu’à deux couches atomiques, ce qui est assez inhabituel. Les films plus épais montrent la présence de pyramides à base carrée alignées sur l’orientation (100) du substrat. Au contraire, seule la première couche de Pd/Pt(111) se dépose en sous-tension et le dépôt présente un caractère pseudomorphe jusqu’à 10 couches complètes.L’absorption d’hydrogène dans les nanofilms de Pd/Pt(100) a été étudiée avec une méthode « classique » dans une solution d’acide sulfurique. Nous avons développé une nouvelle méthode recourant à une électrode tournante à ménisque suspendu pour mesurer l’insertion d’hydrogène dans les films les plus minces de Pd/Pt(111), où l’insertion d’hydrogène et le dégagement de H2(g) ne sont pas bien séparés.Les isothermes d’insertion d’hydrogène présentent des points communs entre les deux systèmes, comme la réduction du taux maximal d’insertion (H/Pd)max comparé au Pd massif, valeur qui décroît avec la réduction d’épaisseur. La largeur de la région biphasique décroît aussi avec la réduction d’épaisseur de film et présent une pente. Cette pente a été attribuée à la présence de sites d’insertion non-équivalents résultant des contraintes induites par le substrat. Cependant, pour Pd/Pt(100), la pente est moins prononcée et la valeur de (H/Pd)max décroît plus rapidement avec l’épaisseur. Sa valeur pour Pd5ML/Pt(100) est à peine supérieure au taux d’insertion αmax du Pd massif. / The present work focuses on the electro-deposition and characterization of Pd/Pt(hkl) nanofilms and on their properties concerning hydrogen storage. The effects of the nanometric size, of the thickness and of the substrate’s orientation have been studied.Comparing Pd/Pt(111) and Pd/Pt(100) films, distinct features were observed either in the electrodeposition curve or in the electrochemical and ex situ AFM characterizations. Pd/Pt(100) deposits have shown the presence of an UPD process up to two layers, which is a quite uncommon phenomenon. Thicker films show the presence of square based pyramids, following the substrate’s (100) orientation. On the contrary, only the first layer is Under Potentially Deposited in Pd/Pt(111) films and the deposit presents a pseudomorphic character up to about 10 complete layers.Hydrogen absorption into the Pd/Pt(100) nanofilms was studied following a “classical” method in sulphuric acid medium. We have developed a new method using the hanging meniscus rotating disk electrode (HMRDE) to measure the hydrogen insertion into ultra-thin Pd/Pt(111) films, where H insertion and HER (Hydrogen Evolution Reaction) are not well separated. The hydrogen insertion isotherms present some common points between the two studied systems, like smaller value of the maximum hydrogen insertion rate (H/Pd)max compared to bulk Pd, value which decreases with the decrease of the thickness. The two-phase region width decreases with film thickness as well and presents a slope. Such slope has been attribtued to the presence of non-equivalent insertion sites due to substrate induced constraints. Nevertheless, for Pd/Pt(100) the slope is less pronounced and (H/Pd)max value decreases more rapidly with thickness. Its value in correspondence of Pd5ML/Pt(100) is only slightly higher than the αmax insertion rate of bulk Pd.

Dans le but d’approfondir les connaissances fondamentales entre la structure des polymères associatifs intramoléculaires (polysavons) et leurs propriétés physico-chimiques en milieux aqueux, trois nouvelles familles de polymères amphiphiles cationiques ont été synthétisées par deux méthodes complémentaires permettant une grande variabilité de structure. Les polymères obtenus sont des poly(méth)acrylamides en peigne avec des groupes latéraux de type ammonium quaternaire portant une chaîne alkyle de taille variable. Une étude du comportement physico-chimique de ces polymères en solution, par viscosimétrie et spectroscopie de fluorescence avec deux sondes aux caractéristiques complémentaires, montre qu’ils présentent des propriétés de polysavons qui varient progressivement avec la structure des polymères amphiphiles étudiés, notamment la longueur de la chaîne alkyle latérale, la taille de l’espaceur entre les deux sites polaires amide et ammonium quaternaire et la masse molaire moyenne en nombre. En parallèle, la tensiométrie a montré que ces polyamphiphiles ont une très faible activité à l’interface eau/air confirmant la prédominance de l’effet hydrophobe, alors que les modèles moléculaires correspondants présentent d’excellentes propriétés tensio-actives. Des films de Langmuir ont ensuite été réalisés dans le cadre de la première étude de cette importance sur des polyamphiphiles cationiques. Dans ce domaine également, la grande variabilité de structure des polymères a permis des observations originales et de dégager de nouvelles relations entre la structure du polymère et les caractéristiques des isothermes de compression obtenues / In order to improve the fundamental knowledge of the relationships between the chemical structure of intramolecular associative polymers (polysoaps) and their physical chemical properties in aqueous media, three new families of cationic amphiphilic polymers were obtained by complementary methods offering great structure variability. The corresponding polymers were comb poly(meth)acrylamides with pendant ammonium groups with alkyl side chains of variable lengths. A first investigation of their physical chemical behaviour in aqueous solutions, by viscometry and fluorescence spectrometry with two complementary fluorescent probes, showed that they displayed polysoap properties which varied progressively with their chemical features, in particular the length of the alkyl side chain, the size of the spacer between the two polar amide and ammonium groups and the polymer molecular weight. Tensiometry confirmed the prevailing of the hydrophobic effect by showing that these polymers displayed a very weak activity at the water/air interface although the corresponding molecular models showed excellent tensio-active properties. Langmuir’s films were eventually obtained in the first study of this importance on cationic amphiphilic polymers. Here again, the great structural variability enabled original observations and new structure/properties relationships were obtained for the corresponding compression isotherms

Resumo: A banana é a fruta com maior produção mundial, sendo plantada em quase todos os continentes. Devido à grande oferta de banana no mercado, é notável a existência de problemas com a geração de resíduos causados por desperdícios (fruta sobremadura) e material celulósico gerado no cultivar. O presente trabalho tem como objetivo principal a aplicação do processo de secagem para resíduos do cultivar da banana nanica (Mussa spp. Haploide AAB ), visando seu possível aproveitamento na indústria. Resíduos de banana tipo nanica (casca, pedicelo, pedúnculo) e polpa foram caracterizados quimicamente, encontrando valores de cinza, umidade, matéria seca, proteína, lipídeos e carboidratos totais muito próximos à literatura. A relação entre o conteúdo de umidade e a atividade de água proporciona informações uteis para a armazenagem e processamento destes resíduos. Na pesquisa foram determinadas isotermas de desorção para casca, pedicelo e polpa de banana a seis temperaturas (20, 30, 40, 50, 60 e 70°C), na faixa de conteúdo de umidade entre 0,001-6,360 kg·kg -1 e atividades de água entre 0,02-0,907. O modelo teórico de GAB foi empregado para a modelagem das isotermas de desorção. Foi proposta a segunda derivada da solução analítica da equação de Clausius-Clapeyron para calcular o calor isostérico de sorção, a entropia diferencial e, a energia livre de Gibbs, através do modelo de GAB quando o efeito da temperatura em equilíbrio higroscópico é considerado. Experimentos de secagem para casca de banana foram realizados em um secador de leito fixo, a três diferentes velocidades de ar (2.5, 1.5 e 1.0 m·s -1 ), e quatro temperaturas (40, 50, 60 e 70°C). Os modelos de Peleg, Lewis, Henderson-Pabis e difusivo, foram empregados na modelagem das curvas de secagem. Na análise gráfica, encontrou-se que a velocidade de ar não influência no tempo final secagem... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Banana is the most produced fruit in the world, being planted in every continent. Due to the large supply bananas in the market, the existence of problems with waste generation caused for overripe fruit and cellulosic material is noteworthy. The objective of this paper is the drying process implementation for banana waste, variety nanica (Mussa spp. Haploid AAB), for a possible application in the industry. Waste (peel, pedicel and peduncle) and pulp of banana nanica were characterized chemically, where values of ash, protein, fat, carbohydrates, and water were quantified, showing similar results with literature. The relationship between moisture content and water activity provides useful information for processing and storage of banana waste. The desorption isotherms of peel, pedicel and pulp of overripe bananas were determined at six different temperatures (20, 30, 40, 50, 60 and 70ºC) over wide ranges of moisture content (0,001-6,360 kg kg-1 d.b.) and water activity (0,02- 0,907). The theoretical model of GAB was used for modeling the desorption isotherms. An analytical solution of the Clausius-Clapeyron equation was proposed to compute the isosteric heat of sorption, the differential entropy, and the Gibbs' free energy, by means of the GAB model when the effect of temperature on hygroscopic equilibrium is considered. Drying kinetics for peel banana in convective hot air forced equipment were determined, at three air velocities (2.5, 1.5 and 1.0 m·s -1 ), and four temperatures (40, 50, 60 and 70 ° C). The models of Peleg, Lewis, Henderson-Pabis, and diffusive were used to the modeling of drying curves. In the graphical analysis, for all experiments, air velocity does not influence in the final time of drying, showed a decreasing rate period of drying. Finally, acid hydrolysis of dry peel banana was performed by using a central composite design experimental with three... (Complete abstract click electronic access below) / Orientador: Javier Telis Romero / Coorientador: Vanildo Luiz Del Bianchi / Co-oreintador: Henry Alexander Váquiro Herrera / Banca: Miriam Dupas Hubinger / Banca: José Francisco Lopes Filho / Mestre

L’objectif de cette thèse a consisté en la synthèse d’un polymère à empreinte moléculaire (MIP) permettant l’extraction du phosmet, un pesticide organophosphoré largement utilisé en oléiculture. La recherche du monomère fonctionnel (MF) disposant de la meilleure capacité à interagir de manière non-covalente avec le phosmet en présence du solvant porogène le plus approprié a été réalisée pour la toute première fois au moyen d’un capteur à acétylcholinestérase. Cette stratégie innovante a permis une meilleure compréhension des mécanismes cinétiques à l’œuvre lors de l’interaction MF-molécule cible. De par l’importance de son rôle dans la détermination de la structure d’un MIP, le choix d’un agent réticulant aux caractéristiques physico-chimiques adéquates a permis de sélectionner le meilleur MIP en s’appuyant sur l’étude des isothermes d’adsorption selon les modèles de Freundlich et Langmuir. La procédure d’extraction du phosmet selon la procédure MISPE (Molecularly Imprinted Solid Phase Extraction) a été effectuée par le biais d’une cartouche SPE dont la capacité a été évaluée à partir d’une solution standard. La validation du choix des réactifs de MIP sélectionnés a été confortée par la réalisation d’une expérience de réactivité croisée appliquée à une molécule analogue au phosmet. L’extraction du phosmet de l’huile d’olive a pu être effectuée avec succès selon un protocole d’extraction en flux inverse optimisé. Cette étude ouvre ainsi la voie à la recherche de nouvelles interactions MFs-molécules cibles au moyen de biocapteurs enzymatiques inhibant des composés toxiques tels que les herbicides, fongicides et autres pesticides. / The objective of this thesis has been the synthesis of a molecularly imprinted polymer (MIP) for the extraction of phosmet, an organophosphorus pesticide widely used in olive growing. The search for the functional monomer (FM) having the best ability to interact non-covalently with phosmet in the presence of the most suitable pore-forming solvent was carried out for the first time by means of an acetylcholinesterase sensor. This innovative strategy allowed us to better understand the kinetic mechanisms of FM-template interaction. Because of the importance of its role in determining the structure of a MIP, the selection of a crosslinking agent with adequate physicochemical characteristics made it possible to select the best MIP, whose adsorption isotherms were studied according to Freundlich and Langmuir models. Extraction of phosmet using a Molecularly Imprinted Solid Phase Extraction (MISPE) procedure was carried out via an SPE cartridge, whose capacity was evaluated from a standard solution. The choice of reagents and experimental conditions were validated by carrying out selectivity assays using another organophosphorus insecticide. Extraction of phosmet from olive oil was successfully carried out according to an optimized reverse flow extraction protocol. This work opens new opportunities for studying new FM-template interactions by means of enzymatic biosensors capable of detecting other inhibitors such as herbicides, fungicides and other pesticides.

Na atualidade estudos direcionados para a avaliação do risco químico e do impacto ambiental produzidos por compostos químicos de uso intensivo, como agrotóxicos, petroquímicos e fármacos, vêm ganhando importância por elucidarem as implicações ao meio ambiente e à saúde pública decorrentes deste uso pela sociedade moderna de forma a estabelecer parâmetros restritivos para suas aplicações, evitando-se danos posteriores. Este Estudo compreendeu as observações de sorção e de interação do antibiótico de uso animal e agrícola oxitetraciclina (OTC) com solos brasileiros e ácidos húmicos (AH) extraídos de solos, tendo-se como objetivos gerais comprovar a sorção aos solos e aos AH e verificar a influência da matéria orgânica (MO) e do pH sobre a sorção, definindo quais os mecanismos moleculares de interação envolvidos, cabendo destacar que as tetraciclinas são uma das principais classes de antibióticos utilizadas na pecuária brasileira, tanto para tratamento de enfermidades quanto como Antibióticos Promotores de Crescimento (APC), além de serem freqüentemente aplicados na agricultura para controle de fungos e bactérias. Utilizou-se a Cromatografia Líquida de Alta Eficiência (CLAE) para a coleta de dados quantitativos que permitiram a construção de isotermas de sorção solo-OTC em pH 4,8 e AH-OTC em três valores de pH (3,1, 4,8 e 8,3) para a comprovação da sorção e da influência do conteúdo de MO no primeiro caso, e na sorção aos AH, para o segundo caso. Os solos foram caracterizados conforme procedimento padrão da EMBRAPA, enquanto que os AH foram caracterizados segundo procedimentos recomendados pela literatura por meio das técnicas instrumentais de Análise Elementar, Absorção na Região do Infravermelho Médio, Ressonância Magnética Nuclear e Ressonância Paramagnética Eletrônica. Foram utilizadas as técnicas espectroscópicas de Absorção na Região do Infravermelho (Próximo e Médio) e Absorção e Fluorescência na Região do UV-Visível, para a avaliação dos possíveis mecanismos de interação envolvidos, como ligação de hidrogênio, interação hidrofóbica e transferência de elétrons. A isoterma de Freundlich apresentou-se como um modelo matemático adequado para a verificação da sorção solos-OTC e AH-OTC, a partir da aplicação de um método cromatográfico adequado, comprovando a sorção para os dois casos, bem como o efeito do conteúdo de MO dos solos e do pH do meio sobre a capacidade e a intensidade da sorção, a qual foi quantificada como de capacidade de sorção inferior em comparação a dados obtidos em clima temperado e de alta capacidade de sorção quando comparada à legislação ambiental brasileira. Foi observado que a OTC interagiu com os AH em uma larga faixa de valores de pH, indo de 3,1 a 8,3. Contudo, o meio no qual foi possível observar de uma forma mais acentuada a interação entre AH e OTC foi o meio básico (pH 8,2), sendo notado a existência de mecanismos de interação associados e dependentes do pH do meio, como: ligação de hidrogênio, interação hidrofóbica e transferência de prótons. / At present further studies on the risk assessment of chemical and environmental impact produced by chemical-intensive, such as pesticides, petrochemicals and pharmaceuticals, have gained importance for elucidating the implications for the environment and public health arising from this use by modern society to establish restrictive parameters for their applications, avoiding further damage. This Study comprised observations of sorption and interaction of antibiotic for animal and agriculture use oxytetracycline (OTC) with brazilian soils and humic acids (HA) extracted from soil, having as objectives to prove the general sorption to soils and the AH and the influence of organic matter (OM) and pH on the sorption, which define the molecular mechanisms of interaction involved, highlighting that tetracyclines are a major classes of antibiotics used in the brazilian cattle industry, both for treatment of diseases such as antibiotic growth promoters (AGP), and frequently also applied in agriculture to control fungi and bacteria. The High Performance Liquid Chromatography (HPLC) was used to collect quantitative data that allowed the construction of sorption isotherms soils-OTC in pH 4.8 and AH-OTC in three pH values (3.1, 4, 8 and 8.3) for proof of sorption and the influence of OM content in the first case, and sorption to AH, for the second case. The soils were characterized as standard procedure of EMBRAPA, while AH were characterized according to procedures recommended by the literature by means of instrumental techniques for Elemental Analysis, Absorption in the Region of the Middle Infrared, Nuclear Magnetic Resonance and Electron Paramagnetic Resonance. The Spectroscopic Absorption in the Infrared Region (Middle) and Fluorescence and Absorption in the Region and the UV-Visible were used for the evaluation of interaction mechanisms involved, such as hydrogen bonding, hydrophobic interactions and electron transfer. The Freundlich isotherm was presented as a mathematical model suitable for the verification of soils-OTC sorption and AH-OTC sorption from the application of a chromatographic method that is suitable, proving the sorption for the two cases as well as the effect of OM content of soils and the pH on the capacity and sorption intensity, which was quantified as the lower sorption capacity in comparison with data from temperate and high sorption capacity when compared to Brazilian environmental legislation. It was observed that the OTC interacted with the HA in a wide range of pH values, ranging from 3.1 to 8.3. However, the way in which it was possible to observe a more pronounced interaction between HA and OTC was the basic medium (pH 8.2), and noted the existence of mechanisms of interaction associated and dependent on pH, such as: link hydrogen, hydrophobic interaction and proton transfer.

Os materiais reativos orgânicos, como turfas e compostos, apresentam um considerável potencial efetivo de utilização na remediação de áreas contaminadas por metais potencialmente tóxicos, haja vista sua elevada capacidade de adsorção, comumente associada a altos teores de matéria orgânica. O emprego do composto orgânico se torna vantajoso por ser uma possibilidade de destinação final correta dos resíduos sólidos urbanos compostáveis, conforme as políticas públicas, podendo agregar valor econômico e ambiental ao resíduo. Nessa perspectiva, na seleção dos materiais reativos mais viáveis para serem empregados na retenção de metais é imprescindível sua caracterização (geológica e geotécnica) e o estudo de sua real capacidade adsortiva, através de ensaios de adsorção. Assim, o objetivo desta pesquisa foi a caracterização geológica e geotécnica de uma turfa (proveniente da bacia hidrográfica do rio Mogi Guaçu, município de Cravinhos) e de quatro compostos (compostos total, indiano, estático e alambrado, advindos de composteiras localizadas na Universidade de São Paulo - São Carlos), bem como ensaios de adsorção (equilíbrio em lote) com chumbo (Pb), zinco (Zn) e cádmio (Cd). Para tanto foram realizados os seguintes ensaios de caracterização: granulometria, massa específica dos sólidos, densidade, teor de umidade, parâmetros físico-químicos (potencial hidrogeniônico (pH), &Delta;pH, potencial de oxi-redução (Eh) e condutividade elétrica (CE), ponto de efeito salino nulo (PESN), matéria orgânica (MO), teor de cinzas (Cz), capacidade de troca catiônica (CTC), capacidade de retenção de água (CRA), composição elementar (C, H e N), carbono orgânico, Difratometria de Raios-X (DRX), Fluorescência de Raios-X (FRX), Microscopia Eletrônica de Varredura/Espectroscopia de Energia Dispersiva por Raios-X (MEV/EDS) e Análise Térmica Diferencial (ATD). A partir do conhecimento minucioso dos parâmetros físicos e químicos dos materiais foi possível proceder o ensaio de equilíbrio em lote com soluções monoelementares de Pb, Zn e Cd com oito concentrações distintas e inferiores a 220 mg L-1 e razão material reativo/solução de 1/50 (conforme definido em etapa preliminar). Quanto aos resultados de caracterização, turfa e compostos apresentaram características promissoras para a adsorção. A turfa revelou um pH moderadamente ácido (5,1), um &Delta;pH negativo (-1,0) atestando para a presença majoritária de cargas negativas na superfície das partículas, o que foi confirmado pelo PESN (3,6) < pH (5,1), um considerável teor de MO (520,43 mg kg-1) e uma CTC elevada (91,00 cmolc kg-1). Já os compostos exibiram valores de pH ligeiramente ácidos a ligeiramente básicos (6,4 a 7,7), &Delta;pH negativo (-0,4 a -1,0), MO promissora (193,92 a 418,70 mg kg-1) e CTC variável (29,00 a 75,00 cmolc kg-1). Em termos gerais, os compostos total e indiano apresentaram características mais favoráveis para a retenção metálica o que foi confirmado por etapa preliminar do ensaio de adsorção. Como o composto indiano sobressaiu levemente na imobilização de Cd e Zn e por ele apresentar maior controle no processo de compostagem ele foi o escolhido para a realização do ensaio de equilíbrio em lote com variadas concentrações de Pb, Zn e Cd, assim como a turfa. Os resultados finais de adsorção atestaram que a turfa e o composto indiano apresentaram a mesma ordem de afinidade metálica: Pb > Cd > Zn, sendo que o composto revelou uma tendência superior de adsorção. A turfa revelou uma porcentagem de remoção metálica (A%) superior a 90% para concentrações de Pb de até 137 mg L-1, enquanto o composto adsorveu mais de 98% do Pb em todas as concentrações estudadas (26 a 214 mg L-1), não atingindo o estado de saturação. Dessa forma, turfa e compostos, caracterizados por um baixo custo e uma significativa disponibilidade, podem ser enquadrados como potenciais materiais reativos orgânicos para a imobilização de cátions metálicos, principalmente Pb2+ e Cd2+. / Organic reactive materials, such as peat and compounds, have a considerable potential for use in the remediation of contaminated areas by potentially toxic metals, due to their high adsorption capacity, commonly associated with high organic matter content. The use of organic compound becomes advantageous because it is a possibility of final destination for the compostable municipal solid waste, according to the public policies, being able to add economic and environmental value to the waste. In this perspective, the selection of the most viable reactive materials to be used in the retention of metals is needful, its characterization (geological and geotechnical) and the study of its real adsorptive capacity through adsorption tests are essential. Thus, the objective of this research was to characterize the geological and geotechnical characteristics of a peat (from Mogi Guaçu\'s basin in the city Cravinhos) and four compounds (total, indian, static and wired, from composters located at the University of São Paulo), besides batch tests with lead (Pb), zinc (Zn) and cadmium (Cd). To achieve the objectives, the following tests were done: particle size analysis, solids specific mass\' determination, density, moisture content, physico-chemical parameters (potential hydrogenion - pH, &Delta;pH, oxy-reduction potential - Eh and electrical conductivity - EC), point of zero salt effect (PZSE), organic matter (OM), ash content, cation exchange capacity (CEC), water retention capacity (WRC), elemental composition (C, H and N), organic carbon, X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), Scanning Electron Microscopy/X-Ray Dispersive Energy Spectroscopy (SEM/DES) and Differential Thermal Analysis (DTA). From the detailed knowledge of the physical and chemical parameters of the materials was possible to perform the batch equilibrium test with monoelemental solutions of Pb, Zn and Cd with different concentrations below 220 mg L-1 and reactive material/solution ratio of 1/50 (as defined in the preliminary stage). Regarding the characterization results, peat and compounds presented promising characteristics for adsorption. The peat showed moderately acidic pH (5.1), negative &Delta;pH (-1.0) attesting to a majority presence of negative charges on the surface of the particles, which was confirmed by the PZSE (3.6) < pH (5.1), a considerably high OM content (520.43 mg kg-1) and a high CEC (91.00 cmolc kg-1). The compounds exhibited from slightly acidic to slightly basic pH values (6.4 to 7.7), negative &Delta;pH (-0.4 to -1.0), promising OM (193.92 to 418.70 mg kg-1) and variable CEC (29.00 to 75.00 cmolc kg-1). In general, terms, the total and indian compounds presented more favorable characteristics for metal retention, what was confirmed by the preliminary step of the adsorption test. As the Indian compound had a small enhancement on the immobilization of Cd and Zn and due, it showed greater control in the composition process, it was chosen for a batch equilibrium test with varying concentrations of Pb, Zn and Cd, as well as a peat. The final adsorption results showed that the peat and the indian compound had the same order of metal affinity: Pb > Cd > Zn, whereby the compound showed a higher adsorption tendency. The peat showed a metal removal percentage (A%) higher than 90% for Pb concentrations up to 137 mg L-1, while the compound adsorbed more than 98% at all concentrations studied (26 to 214 mg L-1) not reaching the saturation state. Thus, peat and organic compounds, characterized by a low cost and a significant availability, can be classified as potential organic low-cost reactive materials for metal cations immobilization, mainly Pb2+ and Cd2+.

0 comportamento higroscópico do suco de laranja liofilizado, e aditivado com malto-dextrinas e lactose, e de misturas mecânicas do suco liofilizado com os aditivos secos, foi estudado através da cinética e das isotermas de sorção de água, em diferentes temperaturas. Avaliou-se as características espectrais no visível e ultravioleta, e o teor de vitamina C, de amostras de suco de laranja liofilizado expostas a diferentes umidades relativas e temperaturas. Estudou-se a influência do valor de pH e natureza do tampão sobre a retenção do limoneno emulsionado em soluções de lactose, liofilizadas. A liofilização praticamente não alterou o teor de vitamina C e as características espectrais do suco de laranja, mas aumentou o valor monomolecular da malto-dextrina (dextrose equivalente de 9 a 12%). A lactose liofilizada apresentou-se no estado amorfo. Os teores de umidade de equilíbrio das misturas aditivadas liofilizadas, foram menores que os das misturas mecânicas. Os aditivos reduziram a sorção de umidade em função do tempo. A retenção do limoneno foi influenciada pela sua concentração inicial, sendo que ocorreu a major perda, durante a liofilização na major concentração utilizada. / The higroscopic behavior of freeze-dried orange juice, with added maltodextrins and lactose and mechanical mixtures with this additives was studied through the kinetics and isoterms of water sorption in different temperatures. It was evaluated the spectral characteristics, in the visible and ultraviolet range, and the vitamin C content from samples of freeze-dried orange juice exposed at different relative humidities and temperatures. It was studied the influence of pH and buffer composition, on the limonene retention of freeze-dried emulsions. The spectral characteristics and vitamin C content showed no alterations after liofilization the maltodextrin (9-12 % dextrose equivalent monomolecular value increased. Freezedried lactose was amorphous. The equilibrium humidity content of the samples with additives were reduced when compared with mechanical mixtures. The additives also reduced the rate of water sorption. The limonene retention during freeze-drying was influenced by the initial concentration of the emulsion. The greater concentration studied showed the lower retention value.

Le caractère fortement hydrophile des isolants thermiques bio-sourcés, a montré que les modèles classiques de transfert thermique ne sont pas suffisamment adaptés pour leur caractérisation thermique. Ce travail de thèse vise à répondre à cette problématique par des approches expérimentale et théorique des transferts couplés chaleur-humidité. Dans l’approche expérimentale, un isolant thermique en feutre de fibres de lin (FFL) a été développé puis caractérisé, dans différents états hygrométriques, au moyen d’un dispositif Plan Chaud asymétrique. Des isothermes d’adsorption de l’humidité corrélés aux modèles théoriques GAB, GDW et Park permettent une caractérisation hydrique de cet isolant. Dans l’approche théorique, un modèle physique, de transfert couplé chaleur-humidité au sein de l’isolant FFL humide, est proposé. Il est résolu numériquement, en configuration 3D transitoire, par la méthode de éléments finis sous COMSOL Multiphysics et par la méthode des différences finies, en configuration 1D transitoire, sous MATLAB. La méthode de Levenberg-Marquardt couplée avec le modèle direct 1D transitoire et les températures mesurées a permis d’estimer la conductivité thermique apparente de l'échantillon étudié avec une erreur relative inférieure à 6% par rapport aux mesures expérimentales, validant ainsi les modèles théoriques. / The conventional heat transfer models are not sufficiently suitable for thermal characterization of bio-sourced thermal insulating materials due to their strongly hydrophilic nature. The proposed work in this PhD thesis aims to answer this problem with experimental and theoretical approaches of coupled heat-moisture transfers. In the experimental approach, a thermal insulating material based on Flax Fiber Felt (FFF) is developed and then characterized at different hygrometric conditions with an asymmetric hot plate device. The humidity diffusion characterization of the samples is done using the GAB, GDW and Park theoretical moisture adsorption isotherm models. In the theoretical approach, a physical model of heat and mass transfer is proposed. It is solved numerically, in transient 3D configuration, by the finite element method under COMSOL Multiphysics and, in transient 1D configuration, by the finite difference method under MATLAB. The Levenberg-Marquardt method coupled with the 1D transient direct model and the measured temperatures made it possible to estimate the apparent thermal conductivity of the studied sample with a relative error of less than 6% compared to the experimental measurements, thus validating the theoretical models.