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.

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.

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 2014-12-17T14:07:17Z (GMT). No. of bitstreams: 1 LauraXL_DISSERT.pdf: 3047950 bytes, checksum: 570af1df35d3161d6677ac6ec832e390 (MD5) Previous issue date: 2013-12-16 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Recent studies are investigating a new class of inorganic materials which arise as a promising option for high performance applications in the field of photoluminescence. Highlight for rare earth (TR +3 ) doped, which have a high luminous efficiency, long decay time and being able to emit radiation in the visible range, specific to each element. In this study, we synthesized ZrO2: Tb +3 , Eu +3 , Tm +3 nanoparticles complex polymerization method (CPM). We investigated the influences caused by the heat treatment temperature and the content of dopants in zirconia photoluminescent behavior. The particles were calcined at temperature of 400, 500 and 600 ? C for two hours and ranged in concentration of dopants 1, 2, 4 and 8 mol% TR +3 . The samples were characterized by thermal analysis, X-ray diffraction, photoluminescence of measurements and uv-visible of spectroscopies. The results of X-ray diffraction confirmed the formation of the tetragonal and cubic phases in accordance with the content of dopants. The photoluminescence spectra show emission in the region corresponding simultaneous to blue (450 nm), green (550 nm) and red (615 nm). According to the results, ZrO2 particles co-doped with rare earth ions is a promising material white emission with a potential application in the field of photoluminescence / Estudos recentes investigam uma nova classe de materiais inorg?nicos que surgem como uma op??o promissora em aplica??es de alto desempenho no campo da fotoluminesc?ncia. Destaque para f?sforos dopados com ?ons de terras raras (TR +3 ), que possuem uma alta efici?ncia luminosa, um longo tempo de decaimento e por serem capazes de emitir radia??es na faixa do vis?vel, espec?ficas de cada elemento. Neste trabalho, foram sintetizadas nanopart?culas de ZrO2:Tb +3 , Eu +3 , Tm +3 pelo m?todo de polimeriza??o dos complexos (MPC). Foram investigadas as influ?ncias causadas pela temperatura de tratamento t?rmico e pelo teor dos dopantes no comportamento fotoluminescente da zirc?nia. As part?culas foram calcinadas nas temperaturas de 400, 500 e 600?C durante duas horas e a concentra??o dos dopantes variou em 1, 2, 4 e 8% mol TR +3 . As amostras foram caracterizadas por an?lises t?rmicas (TG/ DSC), difra??o de raios X (DRX), medidas de fotoluminesc?ncia (FL) e espectroscopia na regi?o do UV-Vis?vel (UV-vis). Os resultados de difra??o de raios X confirmaram a forma??o das fases tetragonal e c?bica de acordo com o teor de dopantes. Os espectros de fotoluminesc?ncia apresentam emiss?es simult?neas correspondentes na regi?o do azul (450 nm), do verde (550 nm) e do vermelho (615 nm). De acordo com os resultados obtidos, as part?culas de ZrO2 codopadas com ?ons de terras raras apresentam-se como um material promissor para emiss?o no branco com um potencial de aplica??o no campo da fotoluminesc?ncia

O escopo desta dissertação é o desenvolvimento de um método para detectar os modelos da matriz dinâmica que estejam degradando o desempenho de controladores preditivos baseados em modelos. O método proposto se baseia na análise de correlação cruzada entre o erro nominal do controlador em malha fechada e a uma estimativa da contribuição de cada canal para o cálculo da saída, filtrada pela função de sensibilidade do controlador. Esse método pode ser empregado na auditoria de controladores com variáveis controladas em setpoints e/ou com variáveis que operem entre faixas, como é usual de se encontrar na indústria. Esta dissertação apresenta os resultados da aplicação bem sucedida do método no sistema de quatro tanques (JOHANSSON, 2000), para o qual três cenários foram avaliados. No primeiro cenário, o método localizou corretamente discrepâncias de ganho e de dinâmica de modelos de um controlador preditivo baseado em modelos (Model-based Predictive Controller, ou controlador MPC). No segundo, o método foi utilizado para avaliar a influência de uma variável externa para melhorar o desempenho de um controlador afetado por distúrbios não medidos. No terceiro cenário, o método localizou canais com modelos nulos que deveriam ser incluídos na matriz de controle de um controlador MPC de estrutura descentralizada. Os resultados deste estudo de caso foram comparados com aqueles obtidos pelo método proposto por BADWE, GUDI e PATWARDHAN (2009), constatando-se que o método proposto é mais robusto que o método usado na comparação, não demandando ajustes de parâmetros por parte do usuário para fornecer bons resultados. A dissertação inclui também um estudo de caso da aplicação industrial do método na auditoria de desempenho de um controlador preditivo linear de estrutura descentralizada, com doze variáveis controladas, oito manipuladas e quatro distúrbios não medidos, aplicado a um sistema de fracionamento de propeno e propano em uma indústria petroquímica. A auditoria permitiu reduzir o escopo de revisão do controlador a dezenove canais da matriz, sendo que quatorze destes correspondiam a canais com modelos nulos que deveriam ser incluídos na matriz. A eficácia do método foi comprovada repetindo-se a avaliação da qualidade de modelo para todas as variáveis controladas. / The scope of this dissertation is the development of a method to detect the models of the dynamic matrix that are affecting the performance of model-based predictive controllers. The proposed method is based on the cross correlation analysis between the nominal controller error and an estimate of the contribution of each channel to the controller output, filtered by the controller nominal sensitivity function. The method can be used in the performance assessment of controllers employing variables controlled at the setpoint and/or those controlled within ranges. This dissertation presents the results of the successful application of the method to the quadruple-tank process (JOHANSSON, 2000), for which three scenarios were evaluated. In the first scenario, the method correctly located gain and dynamic mismatches on a model-based predictive controller (MPC controller). In the second one, the method was used to evaluate the influence of an external variable to improve the performance of a controller affected by unmeasured disturbances. In the third scenario, the method located null models that should be included in the dynamic matrix of a decentralized MPC controller. The results of the three scenarios were compared with the ones obtained through the method proposed by BADWE, GUDI e PATWARDHAN (2009). The proposed method was considered more robust than the reference one for not requiring parameters estimation performed by the user to provide good results. This dissertation also includes a case study about the application of the method on the performance assessment of an industrial linear predictive controller of decentralized structure. The controller has twelve controlled variables, eight manipulated variables, and four unmeasured disturbances and is applied to a propylene-propane fractionation system of a petrochemical industry. The performance assessment allowed reducing the scope of the controller revision to nineteen channels of the models matrix, fourteen of which were null models that should be included in the controller. The efficacy of the proposed method was confirmed by repeating the model quality evaluation for all the controlled variables.

Made available in DSpace on 2016-06-02T20:34:13Z (GMT). No. of bitstreams: 1 2061.pdf: 2095607 bytes, checksum: 4c4be2ac1b6f0d4772bdd6bb16f421d8 (MD5) Previous issue date: 2008-06-16 / Financiadora de Estudos e Projetos / The synthesis and characterization of Ba1-xCaxTiO3 (BCT) for x = 5; 10; 15; 20; 40 e 80 % mol that crystallizes in a perovisquita structure were studied in this work. The BCT material was synthesized by CPM which allows obtaining structurally ordered and disordered powders. The effect of the calcium concentration was analyzed for the structurally ordered and disordered materials. The powders were crystallized at several temperatures ranging from 400 to 1200 °C for different times. The obtained materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, differential scanning calorimetry (DSC) and X-ray Absorption Near Edge Structure (XANES) and photoluminescent emission (PL). These techniques allowed to observe the evolution of the phases as well as the structural disorder of the samples. XRD results indicated that up to 20 % mol of calcium, there is formation of a solid solution with Ca2+ ion occupying the Ba2+ site in the of the BaTiO3 crystalline network. It was verified that the BCT ordered phase was obtained after calcining at 600 °C by 2 h. The presence of an intermediate oxicarbonate barium phase in temperatures below of the tetragonal BCT crystallization. The luminescent property of structurally ordered and disordered BCT powders were studied at room temperature, using two excitation wavelengths: 350,7 nm and 488,0 nm. Structurally disordered BCT present broad PL band when excited by both of wavelengths. The powders annealed at 500 oC displays the most significant PL intensity. It was verified that with the increase of the calcium concentration, the maximum of the photoluminescent emission curve tends to laser wavelength energy. XANES spectra showed in the disordered powders the coexistence of sixfold and fivefold titanium coordination. A correlation between the coexistence of this two types of coordination for the titanium atoms and PL was proposed. / Neste trabalho estudado a síntese e caracterização do Ba1-xCaxTiO3 (BCT) para x = 5; 10; 15; 20; 40 e 80 % mol que se cristaliza numa estrutura perovisquita. O material BCT foi sintetizado pelo MPC, o que possibilitou obter pós estruturalmente desordenados e ordenados. A influência da concentração de cálcio foi analisada para os materiais estruturalmente ordenados e desordenados. Em adição, foi estudada a propriedade fotoluminescente. Os pós foram calcinados na faixa de temperatura entre 400 e 1200 °C por diferentes tempos. Os materiais obtidos foram caracterizados por difração de raios X (DRX), espectroscopia Raman, calorimetria exploratória diferencial (DSC), espectros de absorção de raios X na borda K do Titânio (XANES) e emissão fotoluminescente (FL). Essas técnicas possibilitaram avaliar a evolução das fases, bem como a desordem estrutural das amostras. Os resultados de DRX indicaram que, com até 20 % em mol de cálcio, há formação de uma solução sólida com os íons Ca2+ ocupando o sítio do Ba2+ na rede cristalina do BaTiO3. Foi observado que a fase ordenada de BCT é obtida quando o material é calcinado à 600 °C por 2 h. A presença de uma fase intermediária de oxicarbonato de bário foi identificada para os materiais calcinados em temperaturas inferiores à temperatura de cristalização. A propriedade luminescente do BCT foi estudada à temperatura ambiente, utilizando-se dois comprimentos de onda de excitação: 350,7 nm e 488,0 nm. O BCT desordenado estruturalmente apresentou emissão de banda larga quando excitado nos dois comprimentos de onda investigados. Uma alta intensidade fotoluminescente foi observada para o BCT tratado termicamente à 500 °C nas diferentes composições estudadas. Foi verificado que com o aumento da concentração de cálcio, o máximo da curva de emissão fotoluminescente tende a deslocar para comprimentos de onda de maior energia. Através das análises dos espectros de XANES foi verificada a existência de dois modos de coordenação diferentes para o titânio no BCT desordenado estruturalmente: hexacoordenados e pentacoordenado. Uma correlação entre a existência desses dois modos e a FL foi proposta.

Submitted by GUSTAVO JOSÉ CORRÊA GONÇALVES null (gustavojcgoncalves@hotmail.com) on 2017-05-19T14:19:36Z No. of bitstreams: 1 Dissertação Gustavo - Final.pdf: 5187423 bytes, checksum: 79eb54065f27a82436e48070a5494a8c (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-05-19T14:24:07Z (GMT) No. of bitstreams: 1 goncalves_gjc_me_bauru.pdf: 5187423 bytes, checksum: 79eb54065f27a82436e48070a5494a8c (MD5) / Made available in DSpace on 2017-05-19T14:24:07Z (GMT). No. of bitstreams: 1 goncalves_gjc_me_bauru.pdf: 5187423 bytes, checksum: 79eb54065f27a82436e48070a5494a8c (MD5) Previous issue date: 2017-04-26 / O uso de técnicas de controle preditivo e de sistemas inteligentes na resolução de problemas de controle de grande complexidade tem crescido significativamente na última década. Parte disso se deve ao fato destas abordagens já terem sido utilizadas com sucesso em uma vasta gama de aplicações, demonstrando sua robustez e eficiência. Porém, o uso destas técnicas ainda é pequeno quando comparado com o controle PID (proporcional integral derivativo) clássico, ainda que apresentem resultados melhores. Assim, a maioria das publicações presentes na literatura que utilizam estas técnicas de controle mais sofisticadas tem como objetivo resolver um problema específico de controle. Para isso, em geral, adota-se uma determinada abordagem sem que necessariamente se faça uma avaliação a respeito de qual dos métodos existentes seria o mais eficiente, uma vez que o foco é apenas a resolução do problema. Nesse contexto, o objetivo deste trabalho foi avaliar o desempenho de três das técnicas de controle inteligente e/ou preditivo mais aceitas para o controle de processos industriais frente ao controlador PID clássico, de uso generalizado na indústria. Mais especificamente, optou-se por utilizar o controlador MPC, o controlador Fuzzy e o controlador Neural Preditivo para o controle de um processo industrial e, então, avaliar o desempenho por meio das métricas ISE e ITSE, além de comparar o sobressinal máximo, erro estacionário e tempo de acomodação. Por fim, os resultados de desempenho de cada controlador foram confrontados com o controlador PID clássico. Os resultados indicaram que os controladores com melhor desempenho foram os controladores MPC e fuzzy de duas entradas, apresentando melhores resultados quando comparados com o controlador PID. Ainda, observou-se que o controlador fuzzy de uma entrada e preditivo neural não foram capazes de controlar o sistema em todos os patamares considerados. / The use of predictive control techniques and intelligent systems in the resolution of complex control problems has increased in the last decade. Part of this is due to the fact that these approaches have already been used successfully in a wide range of applications, demonstrating their robustness and efficiency. However, the use of these techniques is still small when compared to the classic PID (derivative proportional integral) control, although they present better results. Thus, most publications in the literature that use these more sophisticated control techniques aim to solve a specific control problem. For this, in general, a certain approach is adopted without necessarily making an evaluation as to which of the existing methods would be the most efficient, since the focus is only the resolution of the problem. In this context, the objective of this work was to evaluate the performance of three of the most accepted intelligent and / or predictive control techniques for the control of industrial processes against the classical PID controller, widely used in industry. More specifically, it was decided to use the MPC controller, the Fuzzy controller and the Neural Predictive controller to control an industrial process, and then evaluate the performance through the ISE and ITSE metrics, in addition to comparing the maximum overshoot, stationary error and accommodation time. Finally, the performance results of each controller were confronted with the classic PID controller. The results indicated that the best performing controllers were the MPC and the two input fuzzy controllers, presenting better results when compared to the PID controller. Also, it was observed that the fuzzy controller of an input and predictive neural were not able to control the system at all levels considered.