Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Sorption Behaviour of Selected Dairy Powder Mixtures: A Study of The Effects of Composition and Mixing Methods Abstract As water mediates physico-chemical reactions (i.e. Maillard reactions, phase changes of sugars and minerals, protein conformational changes), water-powder interactions during storage are critical for dairy powder stability. Therefore, the mechanisms of moisture adsorption from the environment and water distribution among components in the dry state need to be investigated, especially in mixed systems. In order to achieve this goal, the research reported in this thesis had two key objectives. The first was to examine the effect of the sorption properties and phase changes of individual components in relation to the sorption properties of the mixed system. This was achieved by adding three level concentrations of lactose and mineral rich dairy powder (10, 20 and 30%) to Milk Protein Concentrate containing 85% of protein (MPC-85). The second objective was to examine the effect of mixing methods on the sorption behaviour of mixed systems, by applying two different mixing methods, solution mixing and mechanical mixing (particulate mixing). In the solution mixing method, the components were mixed in the same water and then spray dried. In the mechanical mixing method, two individual powder components were physically mixed. For both mixed systems, the kinetics of moisture adsorption were determined at 4 different equilibrium relative humidity levels (22.5, 43.2, 65.4 and 84.3%) and the final equilibrium moisture contents were determined at 8 different equilibrium relative humidity levels (11.3, 22.5, 32.8, 43.2, 52.9, 65.4, 75.3 and 84.3%) at 25°C. The effect of lactose addition to the MPC powder tended to retard the moisture sorption of the mixtures. The increase of concentration level of the lactose that was introduced to the MPC system, through either solution or mechanical mixing, resulted in less moisture adsorption when compared to MPC itself (p-value<0.05). This effect tended to be greater with the increase in relative humidity. A similar effect was observed for MPC/mineral rich milk calcium powder (MC) mixtures. The application of different mixing methods modified the equilibrium moisture content of MPC/Lactose mixtures, even though both mixing methods resulted in similar monolayer moisture value. The monolayer moisture values calculated for both mixing methods were significantly lower than their theoretical values (p-value< 0.05). This suggested that a lactose-protein interaction might exist in both powders prepared by solution and mechanical mixing. Even though the interaction itself is hypothetical, the effect of interaction could be reflected by significant different adsorption rate (p-value < 0.05) of powders produced by different mixing method. A similar type of interaction might exist for the solution mixed MPC/MC system, even though different results were obtained for MPC/MC mixtures prepared by mechanical mixing. The addition of lactose to MPC tended to slow the rate of moisture adsorption. This deceleration might have been contributed to by a reduction of the protein hydration sites by the association of lactose molecules to these sites. In contrast to the MPC/lactose system, the addition of mineral rich MC powder to MPC did not significantly change the rate of adsorption (p-value<0.05). Different mixing methods were found to change the rate of moisture adsorption for the MPC/Lactose systems (p-value<0.05). Even though the mechanically mixed powder adsorbed faster than that of solution mixed powder and X-Ray measurement indicated lactose crystal formation, a drop of moisture during the sorption study was not observed. This suggests that water released during crystallisation might be adsorbed by protein. Meanwhile, the application of two different mixing methods did not modify adsorption rate of MPC/MC system, except for samples stored at RH 84.3%. At this environment, mechanically mixed MPC/MC powders were adsorbed more slowly than the solution mixed powder (p-value<0.05). It might reflect powder compaction or a collapse of the porous structure, leading to limited moisture transfer at the interface. Lactose proportions and different mixing methods influenced the glass-rubber transition temperature (Tg-r) of the MPC/Lactose mixtures. An increase in the proportion of lactose tended to depress Tg-r of the mixtures (p-value<0.05). The Tg-r of the mechanically mixed powder was lower than that of solution mixed powder, presumably on account of the Tg-r for mechanically mixed powder being dominated by phase separated sugar components. Meanwhile, the Tg-r of MPC/MC mixtures was not influenced by either MC proportion or mixing method, particularly for samples stored at below RH 65.4%. The XRD-pattern suggested that the crystal formed during storage of MPC/Lactose mixtures was α-lactose monohydrate. As confirmed by XRD, a drop in moisture for the mixture corresponded to the presence of a peak in the XRD pattern, except for mechanically mixed powder. In this type of powder, even though a peak was detected, a moisture drop was not observed. Within the sensitivity limits of XRD, a crystalline form was not observed for MPC/MC mixtures.

Made available in DSpace on 2014-06-11T19:24:46Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-12-03Bitstream added on 2014-06-13T19:52:29Z : No. of bitstreams: 1 gorayeb_tcc_me_sjrp.pdf: 727819 bytes, checksum: c7b2371e2daddf295fbcad8a255c30b7 (MD5) / Este trabalho visa fornecer às autoridades sanitárias e ao setor industrial elementos que possam contribuir para a prevenção do perigo químico aflatoxina em amendoim (Arachis hypogaea L.) e seus derivados. O estudo foi realizado em três partes: A Parte A, compreendeu a elaboração dos planos APPCC (Análise dos Perigos e Pontos Críticos de Controle) no processamento das indústrias de beneficiamento de grãos de amendoim (Empresa A) e de fabricação de doces de amendoim (Empresa B), identificando as etapas do processo que apresentam pontos críticos de controle (PCC) para o perigo químico aflatoxina. Observou-se que nos dois processos não há nenhum método que consiga destruir, ou mesmo reduzir os teores, da micotoxina. Assim, restam manter rigorosos controles e monitoramentos em cada PCC quanto aos índices de aflatoxina e de umidade dos grãos como medidas preventivas para prevenir e reduzir a possibilidade de infestação dos grãos por fungos e conseqüente produção de aflatoxina. As etapas de recepção dos grãos, secagem, armazenamento e transporte são as que requerem maior atenção na cadeia de beneficiamento. Para a indústria de doces, as etapas mais críticas são as de recepção e armazenamento de grãos e de doces e o transporte. Na Parte B, foram obtidas as isotermas de sorção até o equilíbrio higroscópico de três variedades de amendoim (Runner IAC 886, Caiapó e Tatu Vermelho), para uma ampla faixa de umidade relativa e temperaturas controladas. Verificou-se que o equilíbrio higroscópico dos três amendoins é diretamente proporcional à umidade relativa do ar e decrescente com o aumento de temperatura, para uma mesma umidade relativa. A variedade Caiapó apresentou uma umidade de equilíbrio menor que as outras variedades, podendo-se dizer que a quantidade de lipídeos e carboidratos... / The purpose of this work is to provide technical information to the authorities and industries on aflatoxin production and prevention measures in peanuts (Arachis hypogaea L.) and its products. The work was divided in three parts: Part A: HACCP (Hazard Analysis and Control of Critical Points) plans elaboration in two industries, one of post-harvest treatment of peanuts (Industry A) and another of peanuts candy products (Industry B). Critical Control Points (CCP) for aflatoxin were indentified, and it was observed that no process measure is available to eliminate or even reduce the toxin. Thus, rigid monitoring and control on aflatoxin content must be carried on to avoid fungus infestation and hence toxin production. The process steps of raw peanuts reception, drying, storage and transportation are critical for Industry A. For Industry B, the most important steps are reception and storage of both raw peanuts and candies. Part B: sorption isotherms for three peanuts varieties (Runner IAC 886, Caiapó e Tatu vermelho) were obtained, for wide relative humidity (RH) and temperature (T) ranges. Hygroscopic equilibrium is directly proportional to RH and conversely proportional to T. Caiapó variety presented the lowest equilibrium moisture content (EMC), confirming that lipids and carbohydrates quantities area correlated to EMC. The Modified Halsey model was the best on representing the experimental sorption data. Part C: microbiological experiments were carried out to assess fungus growth and aflatoxin production in String bean and kernels of Runner IAC 886 peanuts. Two concentrations of Aspergilus flavus spores 104 e 106 spores/mL, were inoculated, two storage periods were used 15 and 30 days, three relative humidities were employed 75 %, 84 % and 90 %, and three temperature were applied 25, 30 and 35º C. Growth analysis was assessed by counting spores ...(Complete abstract click electronic access below)

A new modeling method for estimation of the longevity of infiltration system was suggested in this study. The model was one-dimensional, based on results from long-term infiltration sites in Sweden, taking some physical and chemical parameters as controlling factors. It defines the longevity of infiltration systems as the time during which the P solution in effulent is under national criteria (1 mg/L in this study), and it aims at providing the longevity for any given point of the infiltration system. The soil in the model was assumed to be totally homogenous and isotropic and water flow was assumed to be unsaturated flow and constant continuous inflow. The flow rate was calculated from the Swedish criteria for infiltration systems. The dominant process in the model would be the solute transport process; however, retardation controlled by sorption would play a more important role than advection and dispersion in determining the longevity in the model. By using the definition of longevity in this study, the longevity of the three soil columns at 1 m depth (Knivingaryd, Ringamåla and Luvehult) were 1703 days, 1674 days and 2575 days. The exhaustion time of the three soil columns under inflow of 5 mg/L were 2531 days, 2709 days and 3673 days. The calculated sorbed phosphorus quantity for soil from sites Kn, Lu and Ri when they reach estimated longevity were 0.177, 0.288 and 0.168 mg/g, while the maximum sorption of Kn, Lu and Ri were 0.182, 0.293 and 0.176 mg/g separately. From the result of sensitivity study of the model, the sorption capacity and flow velocity were most important to the longevity of the infiltration system. Lower flow velocity and higher P sorption capacity extend the longevity of an infiltration bed. Due to the sorption isotherm selected in this study and the assumption of instant equilibrium, the sorption rate of the soil column was quite linear, although the estimated longevity was much shorter than the real exhaustion time of the soil column. In fact the soil has almost reached its sorption maximum when the system reaches its longevity.

Made available in DSpace on 2014-12-17T15:42:26Z (GMT). No. of bitstreams: 1 WaldeniceAM.pdf: 1082421 bytes, checksum: bd7f6b4a35f59108d7807a3a68e163a3 (MD5) Previous issue date: 2007-03-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Textile activity results in ef&#64258;uents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-&#64257;rst-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well &#64257;tted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good &#64257;ts, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process / A atividade t?xtil resulta em e&#64258;uentes com uma variedade de corantes. Dentre os v?rios processos para a remo??o de corantes destes e&#64258;uentes, o de sor??o constitui um dos m?todos mais efetivos, sendo a quitosana um sorvente alternativo bastante promissor para este &#64257;m. A sor??o do corante alaranjado de metila em part?culas de quitosana reticulada foi avaliada atrav?s de estudos de equil?brio e cin?tica de sor??o em diferentes pHs. Al?m da an?lise com o modelo de pseudo-ordem normalmente adotado na literatura (por exemplo, pseudo-primeira-ordem e pseudo-segunda-ordem), um novo modelo envolvendo uma cin?tica de pseudo-n-ordem foi usada, sendo ndeterminado via regress?o n?o-linear, usando o m?todo de Levenberg-Marquardt. Medidas de potencial zeta indicaram intera??es eletrost?ticas importantes no processo de sor??o. Com rela??o aos estudos de equil?brio, os dados foram bem representados pela isoterma h?brida Langmuir-Freundlich, e a energia livre de Gibbs de sor??o como uma fun??o da massa de corante por ?rea de part?cula mostrou que este processo torna-se mais homog?neo ? medida que o pH da fase cont?nua diminui. Considerando a cin?tica de sor??o, apesar do modelo de pseudo-n-ordem descrever bem os dados experimentais, a equa??o cin?tica envolvendo difus?o-adsor??o foi mais consistente em termos de descri??o f?sico-qu?mica do processo de sor??o

Les systèmes à base de biopolymères à faible teneur en humidité sont couramment rencontrés dans les aliments. Bien entendu, il est primordial de comprendre les bases physiques de leur qualité: texture, performances dans le temps ou en fonction de leur composition. Le vieillissement physique des systèmes composites rend les changements survenant dans le stockage des produits comestibles difficiles à prévoir. Les objectifs de ce travail étaient d'évaluer l'incidence de la présence de saccharose et de la teneur en eau de fabrication sur les propriétés physico-chimiques du produit fini. La stabilité physique de ces matériaux a été contrôlée grâce à une étude à différentes échelles moléculaires. Ensuite, les relations entre les données multi-échelles ont été examinées. L'effet du saccharose (0 à 20%) et de l'eau d'alimentation (10 et 15%) sur les mélanges d'extrusion a été étudié à l'aide d'un extrudeur double vis conduit dans les mêmes conditions. Les propriétés physiques et microstructurales des produits extrudés expansés ont été examinées sous diverses conditions d'humidité relative. La réduction des teneurs en sucre et en eau d’alimentation a fait augmenter la pression et l’énergie mécanique spécifique, ce qui a réduit la dégradation de l’amidon et augmenté la viscosité dans l’extrudeur en particulier à la teneur en eau la plus élevée. L'augmentation de la pression dans l’extrudeur a entraîné une expansion plus importante des extrudés. Par contre, la technique d'imagerie neutronique montré que le saccharose réduisait la taille des pores, et donc augmentait la densité apparente et ce qui était particulièrement évident en utilisant. Cette technique a été appliquée pour la première fois sur des produits extrudés. Les images de tomographie 2D ont indiqué des différences structurelles internes entre les extrudés à différentes teneurs en saccharose et stockés à humidité relative différente. Toutefois, l'analyse d'images 3D a montré que l'impact de ces facteurs sur la distribution de la taille des pores et le taux de porosité n'était pas significatif. En fin d'extrusion, les échantillons étaient à l'état amorphe à la suite de la gélatinisation de l'amidon et de la fonte du sucre. Leursrs propriétés thermiques ont été analysées par analyse enthalpique différentielle (AED) et les températures e transition vitreuse ont été étudiées. Les thermogrammess d’AED ont été minutieusement étudiés via une déconvolution de la dérivée première de la variation d’enthalpie. Cette approche a mis en évidence que les systèmes composites étudiés présentaient des phases multiples avec des transitions vitreuses distinctes. Ces dernières sont associées à une phase riche en polymère (amidon principalement) et / ou à une phase riche en plastifiant (sucre) dont le comportement dépendait de la teneur en eau de l'échantillon. Les isothermes de sorption ont montré qu’aux faibles Aw et pour une valeur donnée, a la teneur en eau des extrudés diminuait avec l’augmentation des teneurs en saccharose et que l'effet inverse était observé aux aw élevées. L’étude de la cinétique apparente de lala diffusion de l'eau a mis en évidence deux sites de sorption différents. Le premier est caractérisé par une cinétique quasi constante qui pourrait correspondre à un phénomène d'adsorption à la surface. Le second site présente d’abord un ralentissement initial de la cinétique de sorption, tandis qu’une forte augmentation est constatée lorsque la teneur en eau était plus élevée. Ce comportement peut être lié à un effondrement de la structure. Une étude par RMN à cyclage de champ rapide à basse fréquence a montré que les temps de relaxation dépendaient de la teneur en saccharose et en eau. Une carte de stabilité a été tracée pour modéliser les évolutions rhéologiques des matrices avec la teneur en eau en lien avec les transitions de phases des matériaux (...). / Low-moisture biopolymer-based systems are commonly encountered in food. Obviously, understanding the physical basis of their quality: e.g texture, or performance over time or as a function of their composition is of primary importance. The objectives of this work were to evaluate how the presence of sucrose and water content affects physico-chemical properties. The physical stability of these materials were monitored through an insight at different molecular scales. Then the relations between the multi-scale studies were investigated. The effect of sucrose (0–20%) and feed water (10 and 15%) on extrusion blends was studied using a twin screw extruder under the same processing settings. The physical and microstructural properties of extruded products were examined at various RH. Reducing both sugar levels and feed water increased die pressure and specific mechanical energy, as a consequence, it reduced starch degradation and increased in viscosity. The effect was more pronounced with increasing feed water content. The increased die pressure resulted in higher expansion of the porous extrudates. Sucrose was shown to increase the bulk density and reduce the pore size, this was particularly evident by using neutron imaging technique. This technique was applied for the first time in extrudate. 2D tomography images indicated internal structural differences between extrudates containing different sucrose content and stored at low and high % RH, while 3D image analysis showed impact of these factors on pore size distribution and % porosity were not significant. The extruded samples were in the amorphous state as a result of starch gelatinization and sugar melting. Their thermal properties were analyzed with DSC and their Tg were studied. The DSC thermograms were thoroughly studied through a Gaussian deconvolution of the first derivative of their heat low. This approach evidenced a multiple phase behavior with different glass transitions in composite systems. They were associated with either a polymer-rich phase and/or a plasticizer-rich phase which behavior depended on the sample water content. Physical aging accompanied with an increase in rigidity at low aw, resulted in an increased bulk density and more pronounced with increasing sucrose content. Sorption isotherms showed the water content of extrudates decreased when product contains high sucrose at low aw range and the inverse effect was observed at high aw. Apparent kinetics of water diffusion showed two different sorption sites, the first kinetics was almost constant and could be adsorption phenomena at the surface. The second one reflected first an initial slowing in dynamics whereas a sharp increase was found at higher water content. Addition of sucrose or water decreased both Tgs in extrudates. Young's modulus showed water acts as anti-plasticizer at low aw, while it shows a plasticizing effect at high aw. A stability map can explain the brittle-ductile transition occurred below Tg. Fast field cycling NMR study at low frequency highlighted that T1 depended on sucrose and water content. T1 and T2 measured using Low field NMR decrease as a function of water content, while the impact pf sucrose were not significant. T2 showing a minimum probably indicating the exchange of protons of water and macromolecules in composite system. The impact of sucrose content was not significant for T1 and for T2 at low water content. FFC NMR showed T1 results consistent with the LF NMR measurement.In conclusion, physicochemical studies of the influence of water and sucrose content on glassy materials showed that the material properties can be investigated at different levels from the macro- to the microscopic scale and these results clearly presented the need for complementary techniques to probe the dynamics in the glassy state of heterogeneous food systems that could be facilitated to manage the stability during storage of this type of dry products.

De nos jours, l’utilisation de liants à faible teneur en clinker est de plus en plus courante. Or la cinétique de réaction des additions minérales utilisées est plus lente que celle du clinker. Si les conditions de cure ne sont pas adaptées, le matériau aura une structure poreuse plus importante, ce qui le rendra plus sensible à la pénétration des agents agressifs extérieurs comme le CO2 ou les Cl-. La carbonatation du béton est l’un des principaux phénomènes pouvant diminuer la durée de vie d’une structure en béton armé. En effet, elle entraine une diminution du pH de la solution interstitielle qui a pour conséquence une dépassivation des armatures, puis la corrosion de ces dernières si les conditions s’y prêtent.L’objectif de cette thèse est d’étudier l’impact de la carbonatation au jeune âge sur des liants à faible teneur en clinker. Pour cela l’étude se compose de deux aspects : le premier est l’étude de l’impact de l’hydratation et de la carbonatation sur les propriétés de transport et les isothermes de sorption hydrique, et le second est l’étude de l’impact du couplage hydratation-séchage-carbonatation sur la microstructure et la structure poreuse. Pour le premier aspect, les propriétés de transport étudiées sont la diffusion de l’O2, la diffusion de la vapeur d’eau, la perméabilité à l’eau liquide qui sont des données d’entrée dans les modèles de carbonatation ainsi que la perméabilité aux gaz qui est un indicateur de durabilité. Pour le second aspect, l’impact du couplage est mesuré par ATG et DRX pour déterminer l’assemblage de phases, de plus de la porosimétrie par intrusion de Mercure et des pesées hydrostatiques sont effectuées pour détecter le changement de la structure poreuse. Les matériaux étudiés sont des pâtes de ciment et des bétons avec un rapport eau/ liant de 0,57 avec l’un des trois liants suivants : CEM I, CEM I +30% de cendres volantes et CEM I +60% de laitiers.Pour le premier aspect, les résultats montrent que pour les pâtes de CEM I le temps de cure a un faible impact sur les isothermes de sorption de vapeur d’eau s’il est compris entre 3 jours et 6 mois. Alors que, pour les pâtes de CEM I + 60% de laitier, l’augmentation du temps de cure accroit significativement la teneur en eau (pour HR=65%, tcure=3 jours et pour tcure=6 mois ) dû à une augmentation de la teneur en C-S-H. D’autre part, la carbonatation entraine une diminution de la teneur en eau de l’échantillon, ainsi que l’amplitude de l’hystérésis. De plus, le gel a une porosité plus grossière. Par ailleurs, la carbonatation entraine une augmentation de la perméabilité aux gaz des matériaux. Pour le second aspect, les résultats montrent que l’utilisation d’additions minérales diminue la résistance à la carbonatation du matériau et que cette résistance augmente avec le temps de cure si l’échantillon contient des additions. La carbonatation de la portlandite, des C-S-H et des aluminates est concomitante. De plus, pour les matériaux aux laitiers, les résultats montrent qu’ils sont plus sensibles à la carbonatation des C-S-H et des aluminates que les CEM I. En effet quand le rapport variation molaire de CaCO3 sur variation molaire de Portlandite est calculé, il vaut 1.8 pour le CEM I et environ 3.5 pour les matériaux aux laitiers. Enfin, la carbonatation entraine une diminution du degré de saturation de l’échantillon. En effet, le degré de saturation à la surface de l’échantillon passe de 50% à 35% après carbonatation pour les échantillons de CEM I et de 50% à 5% pour les échantillons de CEM I + 60% de laitiers. Cette diminution peut s’expliquer par la diminution de la surface spécifique qui est divisée par 2 après carbonatation due à la décalcification des C-S-H. Même si la carbonatation entraine une diminution de porosité cette dernière est trop faible dans ce cas pour contrer cet effet / Nowaday, low clinker content binders are used more and more often. But the kinetics reactions of the supplementary cementitious materials (SCM) are slower than this one of clinker. If the curing conditions are not adapted, material will have a bigger pore structure and becomes more sensitive to the ingress of aggressive species from the environment like the CO2 or Cl-. Carbonation is one of main phenomena which can lead to decrease the life time of reinforced concrete structure. Indeed, it leads to a decrease of pore solution pH which leads to the depassivation of rebar. Then these rebars can be corroded if the conditions are appropriate.The aim of this thesis is to study the impact of carbonation at early age for binder with a low clinker content. This study was composed of two aspects: the first one is focus on the impact of hydration and carbonation on the transport properties and the water vapour sorption isotherms (WVSI), and the second one is focus on the impact of coupling hydration – drying-carbonation on the microstructure and the pore structure. For the first aspect, the studied transport properties was O2 diffusivity, water vapour diffusivity, water liquid permeability which are inputs for carbonation modelling and the intrinsic gas permeability which is a durability factor. For the second aspect, the coupling impact was measured by TGA and DRX to determine the phase assemblage; moreover Mercury intrusion porosimetry (MIP) and hydrostatic weigh were carried out to measure the change in the pore structure. The studied materials were cement pastes and concretes with water to binder ratio of 0.57 with one of the following binders: CEM I, CEM I +30% PFA and CEM I + 60% GGBS.For the first part, results show that a curing time between 3 days and 6 months has a low impact on the WVSI for the CEM I paste. Whereas, in the CEM I +60% GGBS paste, when the curing time increases, the water content increases (for a RH=65%, tcuring=3 days and for tcuring=6 months ), this is due to the increase of the C-S-H content. Moreover, carbonation leads to decrease the water content and the hysteresis becomes flat. Additionally, carbonation leads to increase the intrinsic gas permeability. For the second part, the results show that the use of SCM decreases the carbonation resistance and this resistance increases with the curing time. Carbonation of Portlandite, C-S-H and aluminates occurs in the same time. Moreover, the CEM I +60% GGBS paste are more sensitive to the carbonation of C-S-H and aluminates than the CEM I paste. Indeed, the molar variation of CaCO3 to the molar variation of Portlandite ratio has a value around 3.5 for the CEM I +60% GGBS and 1.8 for the CEM I. Finally, carbonation leads to decrease the water saturation degree at the surface of sample. Indeed, the degree of saturation at the surface of the sample increases from 50% to 35% after carbonation for the CEM I paste and from 50% to 5% for the CEm I +60% GGBS paste. This decrease can be explained by the decrease of the BET specific surface which is divided by 2 after carbonation. It is due to the decalcification of C-S-H. Although carbonation leads to a decrease of porosity, this one is too small in this case to counter this effect

Le présent travail a pour objectif de comprendre l’influence des paramètres géométriques des éco-matériaux d’enveloppe, tels que le béton de chanvre, sur les mécanismes de transferts couplés de chaleur, d'air et d’humidité afin de prédire le comportement du bâtiment dans le but de le piloter et de l’améliorer dans sa durabilité. Pour cela, une approche multi-échelle est mise en place. Elle consiste à maîtriser les phénomènes physiques dominants et leurs interactions à l’échelle microscopique. S’ensuit, une modélisation à double échelle, microscopique–macroscopique, des transferts couplés de chaleur, d’air et d’humidité qui prend en compte les propriétés intrinsèques et la topologie microstructurale du matériau moyennant le recours à la tomographie rayon X conjuguée à la corrélation d’images 2D et 3D. Pour cela, une campagne de caractérisation fine des propriétés physiques et hygrothermiques du béton de chanvre confectionné au laboratoire a été réalisée. Elle s’est focalisée sur l’étude de l’impact du vieillissement, l’état thermique et hydrique du matériau sur ses propriétés intrinsèques. Les résultats montrent une excellente capacité d'isolation thermique et de régulation naturelle d’humidité du béton de chanvre. Puis, une caractérisation microscopique par différentes techniques d’imagerie a été effectuée. Les reconstructions 3D du matériau réel scanné au tomographe aux rayons X à différentes résolutions montrent que le béton de chanvre possède plusieurs échelles de porosité, allant de la microporosité au sein du liant et des chènevottes à la macroporosité inter-particulaire. Le comportement hygro-morphique sous sollicitations hydriques a été ensuite étudié. Les résultats de la corrélation d’image numérique 2D et de la tomographie aux rayons X couplés à la corrélation d’images volumiques, montrent la nature du comportement du béton de chanvre soumis à des hygrométries différentes. En effet, la chènevotte subit des déformations plus importantes que le liant, causant ainsi des modifications de la microstructure du matériau. Sur le volet de la modélisation, moyennant la technique d’homogénéisation périodique un modèle des transferts couplés de chaleur, d’air et d’humidité dans les matériaux poreux de construction a été développé. Les tenseurs de diffusion et de conductivité thermique homogénéisés ont été calculés numériquement. Ensuite, une confrontation entre les résultats du calcul des coefficients de diffusion macroscopique et ceux expérimentaux obtenus au LaSIE a été réalisée. Elle met en évidence la qualité de la prédiction. De plus, la conductivité thermique de la phase solide a été ainsi déduite. Les résultats obtenus dans le cadre de ce travail de thèse ont mis en exergue l’influence de l’état hydrique et thermique du béton de chanvre sur ces propriétés intrinsèques, et sa microstructure très hétérogène. Ils ont révélé aussi les limites des approches phénoménologiques basées sur l’établissement des bilans de masse, de quantité de mouvement et d’énergie. / The aim of this work is to understand the influence of the geometric parameters of envelope eco-materials, such as hemp concrete, on the mechanisms of coupled heat, air and moisture transfers, in order to predict behavior of the building to control and improving it in its durability. For this a multi-scale approach is implemented. It consists of mastering the dominant physical phenomena and their interactions on the microscopic scale. Followed by a dual-scale modeling, microscopic-macroscopic, of coupled heat, air and moisture transfers that takes into account the intrinsic properties and microstructural topology of the material using X-ray tomography combined with the correlation of 2D and 3D images. A characterization campaign of physical and hydrothermal properties of the hemp concrete manufactured in the laboratory was carried. It focused on studying the impact of aging, thermal and hydric state of the material on these intrinsic properties. The results show an excellent thermal insulation and natural moisture regulation capacity of hemp concrete. Then, a microscopic characterization by different imaging techniques was performed. The 3D reconstructions of the real material scanned with X-ray tomography at different resolutions show that hemp concrete has several scales of porosity, ranging from micro-porosity within the binder and hemp shiv to the inter-particle macro-porosity. The hydromorphic behavior under hydric solicitations was studied. The results of the 2D digital image correlation and X-ray tomography coupled with the volumetric image correlation show the nature of the behavior of hemp concrete subjected to different relative humidities. In fact, the hemp shiv undergoes greater deformations than the binder, thus causing changes in the microstructure of the material. On the modeling part, a model of coupled heat, air and moisture transfer in porous building materials was developed using the periodic homogenization technique. The homogenized tensors of diffusion and thermal conductivity were determined numerically. Then, a confrontation between the results of the calculation of the macroscopic diffusion coefficients and the experimental results obtained at the LaSIE was carried out. It highlights the quality of the prediction. In addition, the thermal conductivity of the solid phase was thus deduced. The results obtained in the framework of this PhD thesis have highlighted the influence of the hydric and thermal state of the hemp concrete on these intrinsic properties and its very heterogeneous microstructure. They also revealed the limitations of phenomenological approaches based on the establishment of the balances of mass, amount of motion and energy

Made available in DSpace on 2014-06-11T19:24:45Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-21Bitstream added on 2014-06-13T20:12:59Z : No. of bitstreams: 1 villavelez_ha_me_sjrp.pdf: 807308 bytes, checksum: 262020576b600a66d35be63d82b014a7 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / 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... / 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)

Cette étude a fait l'objet de deux parties. L'une porte sur l'effet de différents types d'activation (chimique, thermique, mécanique) de kaolins (géo-matériaux riches en kaolinite) sur leurs propriétés de décoloration vis-à-vis de l'huile de riz. L'autre traite de l'effet de la taille et de la morphologie de kaolinites de synthèse sur leurs propriétés d'adsorption.Cette étude a montré que lorsque le kaolin était chauffé à plus de 100°C avant de subir une activation acide en milieu sulfurique, citrique ou oxalique, la capacité de décoloration vis-à-vis de l'huile de riz était fortement réduite. Cet effet a été directement mis en relation avec la destruction partielle ou totale de la structure de la kaolinite, associée à une forte lixiviation de l'aluminium de l'échantillon et à la précipitation de silice amorphe. Il s'est donc avéré que la préservation des sites aluminols présents sur les surfaces externes des particules de kaolinites semblait être un critère primordial à conserver en vue d'obtenir de bonne capacité de décoloration. Dans ce contexte, les meilleures capacités de décoloration (82% environ) ont été obtenues en utilisant conjointement un traitement thermique modéré (<100°C), un broyage mécanique de l'échantillon avant l'étape d'activation acide, une concentration en acide de l'ordre de 0.3 à 0.5 mol/L et un rapport (argile)/(solution acide) de l'ordre de 1/50. Notons que les plus fortes valeurs de surfaces spécifiques n'ont pas forcément été associées aux échantillons présentant les meilleures capacités de décoloration en raison de la présence de silice amorphe et de la non-préservation des sites aluminols de la kaolinite ; sites responsables de l'adsorption des pigments de molécules de chlorophylle-a.Par ailleurs, aucune étude à notre connaissance ne reliait directement les morphologies de particules de phyllosilicates à leurs propriétés d'adsorption vis-à-vis de deux cations inorganiques. Dans le cas des kaolinites naturelles, une charge permanente souvent significative et attribuable à des impuretés minéralogiques empêche toute tentative de relier directement la forme des particules à un coefficient de sélectivité entre deux cations pour des sites latéraux donnés. Des kaolinites ont donc été synthétisées par voie hydrothermale en considérant différentes conditions physico-chimiques, afin d'obtenir des morphologies variées (hexagones plus ou moins anisotropes). Pour ces échantillons synthétiques pour lesquels aucune impureté minéralogique et charge permanente n'a été détectée, des isothermes expérimentales d'adsorption entre Na+ et H+ ont été mesurées. Ces cations ont été choisis étant donné leur présence ubiquiste dans les eaux naturelles et leur fort pouvoir compétiteur par rapport aux cations traces métalliques. Grâce aux surfaces spécifiques des sites latéraux et des densités de site issues de la cristallographie des différentes faces présentes dans nos échantillons ((010), (110), (1-10)), un coefficient de sélectivité entre Na+ et H+ sur l'ensemble des sites latéraux d'une morphologie donnée a pu être estimé à l'aide d'un modèle de complexation de surface. Les résultats ont montré que le coefficient de sélectivité Na+/H+ dépendait très fortement de la morphologie de la particule, et que par conséquent les propriétés d'adsorption des kaolinites ne pouvaient pas être obtenues avec précision sans une connaissance fine de la morphologie des particules. / The dissertation consists of two main parts; the first part is devoted to the effect of physical/thermal and chemical activation of kaolin on bleaching of rice bran oil. In this study, samples were prepared from natural Ranong kaolin. This study focused on the effects of both thermal treatment (from 100 to 900°C) and chemical activation (sulfuric acid, hydrochloric acid, citric acid and oxalic acid using different acid concentrations or different clay/acid ratio) on the capacity of kaolins to bleach rice bran oil. When kaolin was treated with high temperature (>100°C) prior to reflux and with a high acid concentration during reflux, the kaolinite structure was partially or completely destroyed associated to a dramatic leaching of alumina, and amorphous silica dominated the samples. The measured maximum bleaching capacity obtained was not consistent with the highest specific surface area and pore volume; rather, it depended on the alumina contents in the samples. Thus, the partial preservation of the kaolinite structure is crucial to obtain an appropriate bleaching capacity of kaolin. This is directly related to the preservation of the aluminol sites present at the kaolinite surface. XRF analysis showed that the alumina contents of 28-34% were values to reach in order to obtain optimum bleaching capacities of kaolin, independently of the different acid used. Finally, optimum bleaching of ~83%, ~82% and ~81% were achieved by grinding the kaolin prior to reflux with low acid concentration of hydrochloric acid (0.5 M), sulfuric acid (0.3 M) and citric acid (0.5 M), respectively with clay/acid ratio of 1:50.The second part of the thesis aims to elucidate the influence of morphology of kaolinites on their sorption properties. For that, Na+/H+ sorption isotherms in water saturated conditions of synthetic kaolinites and natural well crystallized kaolinite, called KGa--1b commercialized by the Clay Mineral Society, were performed and interpreted. Kaolinites used in this study were hydrothermally synthesized from partially crystallized kaolinite as a function of different final pH (pHF) ranging from 0.8 to 8.3. Results obtained for KGa--1b were compared with data obtained in literature for this mineral, in order to fully validate this approach. This study found that cation exchange capacity, due to both isomorphic substitutions in the crystals (permanent charge), and silanol and aluminol edge sites were highly variable. Typically, CEC at pH=9 varied from ~0.8 cmolc/kg for well crystallized kaolinite (pHF 0.8) to ~33 cmolc/kg for disordered lath-shaped kaolinite (pHF 8.3). Na+/H+ sorption isotherms were obtained for all synthetic kaolinites as a function of pH ranging from pH 3 to 11. Results showed that sorption of Na+ increases dramatically with pH. Typically for all kaolinite samples except for the one synthesized at pHF=8.3, Na+ sorption is rigorously equal to zero when pH<7, indicating no permanent charge in the samples (in contrast to natural KGa--1b kaolinite), and increases when pH>7 due to sorption on edge sites. The amount of dissolved silica measured during Na+/H+ isotherm is higher for experiments performed with kaolinites synthesized in basic conditions (for pHF 7.4 and pHF 8.3) than for kaolinites synthesized in acid conditions (for pHF 0.8 and pHF 3.3). These latter results lead to conclude that sorption site density can be considered constant when pH is between 4 and 10, independently of the morphologies of particles. In this context, a thermodynamic modeling procedure using a complexation model was applied to interpret the data obtained with hexagonal- and lath-shaped particles. During this procedure, selectivity coefficient between Na+ and H+ cations were obtained considering the total edge site densities calculated from lateral specific surfaces estimated for synthetic kaolinites and crystallography data.