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Nonlinear ultrasonic waves have demonstrated high sensitivities to various microstructural changes in metal including coherent precipitates; these precipitates introduce a strain field in the lattice structure. The thermal aging of certain alloy steels leads to the formation of coherent precipitates, which pin dislocations and contribute to the generation of a higher harmonics in an initially monochromatic wave. The objective of this research is to develop a robust technique to perform nonlinear Rayleigh wave measurements in metals using a non-contact receiving transducer. In addition a discussion about the data processing based on the two-dimensional diffraction and attenuation model is provided in order to calculate the relative nonlinearity parameter. A precipitate hardenable material, 17-4 PH stainless steel, is used to obtain different precipitation stages by thermal treatment and the influence of precipitates on the ultrasonic nonlinearity is assessed. Conclusions about the microstrucutural changes in the material are drawn based on the nonlinear Rayleigh surface wave measurement and complementary measurements of thermo-electric power, mircohardness and ultrasonic velocity. The results show that the nonlinearity parameter is sensitive to coherent precipitates in the material and moreover that precipitation characteristics can be characterized based on the obtained experimental data.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / No presente estudo, os compósitos MgO-CeO2 e ZnO-CeO2 foram obtidos via decomposição térmica de quelatos dos metais Ce, Mg e Zn com o quelante 8-hidroxiquinolina, caracterizados e testados como catalisadores na degradação do corante Vermelho Reativo BF-4B por processo de fotocatálise heterogênea. Os complexos dos metais com o quelante 8-hidroxiquinolina foram obtidos por uma rota sintética de coprecipitação em meio aquoso por elevação do pH. Análises de FTIR das misturas de complexos sintetizados comprovaram a obtenção dos complexos pela observação das bandas características que evidenciaram a ligação do quelante com os metais. Análise térmica simultânea TGA-DTG-DTA dos complexos possibilitaram traçar e caracterizar o perfil do comportamento térmico dos complexos nas condições a que foram submetidos, assim como identificar os eventos de decomposição térmica dos complexos e temperaturas de obtenção dos compósitos desejados. Resultados de DRX mostraram características de semi-cristalinidade dos complexos, e possibilitaram a identificação das fases dos compósitos obtidos, assim como a comprovação da obtenção dos mesmos. As imagens obtidas por MEV dos compósitos mostraram que as partículas dos compósitos obtidos possuíam características de aglomeração, policristalinidade e variação de tamanho de partículas para todas as amostras, onde também foi possível observar que as partículas do compósito MgO-CeO2 apresentavam a forma de bastões ocos e de base quadrada, que melhor definiram sua forma com o aumento da temperatura final de tratamento térmico utilizada, e para o compósito ZnO-CeO2, morfologia de partículas disformes juntamente com partículas no formato de placas lisas e irregulares de diversos tamanhos. Os resultados de DRS possibilitaram a obtenção dos valores de band-gap dos compósitos, que apresentaram aumento de seu valor conforme se aumentou a temperatura de tratamento térmico para obtenção dos mesmos. Os resultados dos testes aplicando os materiais como catalisadores no processo de degradação do corante têxtil Vermelho Reativo BF-4B por fotocatálise heterogênea indicaram que os materiais não são adequados, visto que a sua presença no processo tem efeito retardante na degradação do corante testado. Estes efeitos nos testes catalíticos podem ser associados à baixa afinidade entre os compósitos e o corante Vermelho Reativo BF-4B, mostrados pelos testes de adsorção do corante pelos compósitos, nas condições utilizadas para os testes. / In the present study, MgO-CeO2 and ZnO-CeO2 composites were obtained by thermal decomposition of the chelates of the Ce, Mg and Zn metals with the 8-hydroxyquinoline chelator, characterized and tested as catalysts in the degradation of BF-4B Red Reactive dye by heterogeneous photocatalysis process. The metal complexes with the 8-hydroxyquinoline chelator were obtained by a synthetic coprecipitation route in aqueous medium by raising the pH. FTIR analysis of the synthesized mixed complexes proved to obtain the complexes by observing the characteristic bands that showed the binding of the chelant to the metals. Simultaneous thermal analysis (TGA-DTG-DTA) of the complexes made it possible to trace and characterize the thermal behavior profile of the complexes under the conditions to which they were subjected, as well as to identify the thermal decomposition events of the complexes and the temperatures of obtaining the desired composites. XRD results showed semi-crystallinity characteristics of the complexes, and enabled the identification of the phases of the composites obtained, as well as the proof of obtaining them. SEM images of the composites showed that the obtained composites particles presented characteristics of agglomeration, polycrystallinity and variation of particle size for all the samples, where it was also possible to observe that the particles of the MgO-CeO2 composite were in the form of hollow rods and square basis, which best defined their shape with the increase of the final heat treatment temperature used, and for the ZnO-CeO2 composite, morphology of deformed particles together with particles in the shape of smooth and irregular plates of various sizes. DRS results allowed to obtain the band gap values of the composites, whose values increased with the increasing in the thermal treatment temperature. Results of the tests applying the materials as catalysts in the degradation process of the BF-4B Reactive Red dye by heterogeneous photocatalysis indicated that the materials are not suitable, since their presence in the process has a retarding effect on the degradation of the dye tested. These effects on the catalytic tests may be associated with the low affinity between the composites and the BF-4B Red Reactive dye, shown by the dye adsorption tests by the composites, under the conditions used for the tests.

Atualmente estudos com óxidos de metal de terras raras com estrutura perovskitas vem sendo realizados devido as suas propriedades interessantes, como a alta condutividade eletrônica e iônica, e suas potenciais aplicações em baterias, células combustíveis, catalisadores, sensores de gás, sensores químicos, entre outros. Neste trabalho apresentam-se os resultados obtidos para obtenção da LaCoO3 a partir da decomposição térmica de 8-hidroxiquinolinatos de cobalto e lantânio, obtidos pelo método de coprecipitação, em pH final de 5 e 9, e em meio de acetona ou ácido acético. Os complexos foram caracterizados por Difratometria de Raios X (DRX), por Espectroscopia de Absorção na Região do Infravermelho (FTIR), Absorção Atômica (AAS), Análise Elementar (AE) e Microscopia Eletrônica de Varredura (MEV). O estudo do comportamento térmico foi realizado por Análise Termogravimétrica (TGA), Termogravimetria Derivada (DTG) e Análise Térmica Diferencial (DTA) em diferentes razões de aquecimento e atmosfera, até 800 ºC. Os óxidos obtidos por decomposição térmica foram caracterizados por DRX, FTIR e AAS. Com o estudo do comportamento térmico observou-se que as amostras apresentaram três etapas de decomposição térmica sob atmosfera de ar sintético e cinco etapas em atmosfera de N2, foi ainda possível observar que o percentual de resíduo final para os pH 9 foi superior ao resíduo final nos pH 5, porém as temperaturas finais de decomposição foram menores em pH 5. Os resultados indicaram maior eficiência do processo de obtenção da LaCoO3 para os pH 9 em ambos os meios reacionais, caracterizado por DRX, com rendimento médio de 93%. / Currently, studies with rare earth metal oxides with perovskite structure have been carried out due to their interesting properties, such as high electronic and ionic conductivity, and their potential applications in batteries, fuel cells, catalysts, gas sensors, chemical sensors, among others. This work presents the results obtained to obtain LaCoO3 from the thermal decomposition of cobalt and lanthanum 8-hydroxyquinolinates obtained by the coprecipitation method, at final pH of 5 and 9, and in acetone or acetic acid medium. The complexes were characterized by X-ray diffraction (XRD), Infrared Region Absorption Spectroscopy (FTIR), Atomic Absorption (AAS), Elemental Analysis (AE) and Scanning Electron Microscopy (SEM). The thermogravimetric analysis (TGA), Derived Thermogravimetry (DTG) and Differential Thermal Analysis (DTA) in different heating and atmosphere ratios up to 800 ºC were performed. The oxides obtained by thermal decomposition were characterized by XRD, FTIR and ASA. By studying the thermal behavior, it was observed that the samples presented three stages of thermal decomposition under a synthetic air atmosphere and five steps under N2 atmosphere, it was still possible to observe that the percentage of final residue for pH 9 was higher than the final residue at pH 5, but the final decomposition temperatures were lower in pH 5. Results showed higher efficiency of the process of obtaining LaCoO3 for pH 9 in both reaction media, characterized by XRD, with an average yield of 93%.

Este trabalho propõe o método de precipitação química para a produção de óxido de zinco (ZnO), por decomposição térmica de um precursor organometálico, obtido pela reação do nitrato de zinco com 8-hidroxiquinolina. Dessa forma, foram sintetizados 8-hidroxiquinolinatos de zinco sob quatro condições, em pH 5,0 e 9,0, em ácido acético ou acetona, obtendo-se quatro amostras, cujo rendimento médio da síntese foi de 92,98% em massa. Os complexos foram caracterizados pelas técnicas de difratometria de raios X (DRX), espectroscopia na região do infravermelho com transformada de Fourier (FTIR), espectroscopia na região do ultravioleta- visível (UV-Vis), análise elementar (CHN), microscopia eletrônica de varredura (MEV), Análise elementar e espectroscopia de absorção atômica (AAS). O estudo do comportamento térmico desses complexos foi realizado pelas técnicas de análise termogravimétrica (TGA) e análise térmica diferencial (DTA) em atmosfera dinâmica de ar sintético, que revelou a perda de massa em três etapas para amostras obtidas em ácido acético e quatro etapas para amostras sintetizadas em acetona devido a coprecipitação da 8-hidroxiquinolina. Em atmosfera dinâmica de nitrogênio (N2), a decomposição ocorre em duas etapas, mas sem estabilização de massa até a temperatura de 800 °C. As amostras foram submetidas à decomposição térmica em três diferentes razões de aquecimento e a partir das curvas de DTA foram determinadas as energias de ativação dos processos de desidratação e de recristalização dos compostos. Os dados instrumentais apontam que as sínteses geraram complexos na forma di-hidratada e o resíduo final de decomposição térmica o ZnO. As condições apresentadas no estudo do comportamento térmico foram utilizadas para a produção do ZnO nas temperaturas de 700 e 900 °C, com tempos de permanência de 2 e 4 h. A caracterização por DRX indicou que a estrutura do óxido obtido é hexagonal e em geral, com aumento da temperatura de calcinação e tempo de permanência, houve aumento no tamanho do cristalito, cujos valores ficaram entre 27,87 e 58,49 nm nas estimativas feitas pelo método de Williamson-Hall e pela equação de Scherrer. Os espectros de FTIR do ZnO apresentaram uma única banda em aproximadamente 400 cm-1 referente a ligação metal-oxigênio. Os espectros de UV-Vis foram utilizados para a estimativa do band-gap, obtendo-se valores que variaram entre 3,22 e 3,46 eV. Portanto, o método de precipitação química proposto, demonstrou-se tecnicamente viável para a produção do ZnO. / This work proposes chemical precipitation method for the zinc oxide (ZnO) production, by decomposition of an organometallic precursor, obtained with zinc nitrate and 8-hydroxyquinoline reaction. Therefore, zinc 8-hydroxyquinolinates were synthesized in four conditions, at pH 5.0 and 9.0, in acetic acid or acetone conditions, obtaining four samples, with an average yield of 92.98% dry matter. The compounds were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM), elemental analysis and atomic absorption spectroscopy (AAS). The thermal behavior of the complexes was performed by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) in a dynamic synthetic air atmosphere, which revealed the mass loss in three stages for samples obtained in acetic acid and four stages for samples synthesized in acetone due to the co-precipitation of 8-hydroxyquinoline. In dynamic nitrogen atmosphere (N2), the decomposition occurs in two steps, but without mass stabilization up to 800 °C. From the samples submitted to thermal decomposition in three different heating ratios and from the obtained curves, the activation energies of the dehydration and recrystallization processes of the complexes had been determined. The data indicate that the synthesis generated complexes in the dihydrate form and the final residue of thermal decomposition zinc oxide. The conditions in the study of the behavior thermal were used to produce the ZnO at temperatures of 700 and 900 ° C, with calcination times of 2 and 4 h. XRD characterization showed that the structure of the zinc oxide was hexagonal structure and increasing temperature calcination and residence time, there was an increase in the crystallite size, whose range were 27.87 to 58.49 nm in estimates by Williamson-Hall method and Scherrer's equation. FTIR spectra of ZnO showed a single band at approximately 400 cm-1 for metal-oxygen bonding. UV-Vis spectra were used to estimate the band-gap values, that varied between 3.22 and 3.46 eV. Therefore, chemical precipitation method proposed, was demonstrated technically practicable for ZnO production.

Orientador: Everson Alves Miranda / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T23:00:08Z (GMT). No. of bitstreams: 1 Lima_LeonardoHenriqueFrancade_M.pdf: 992316 bytes, checksum: 57f2f7216633dfbabec7d916c3adb88d (MD5) Previous issue date: 2006 / Resumo: A precipitação de proteínas através da adição de sais (por exemplo, o sulfato de amônio e cloreto de sódio) é uma técnica comumente utilizada em recuperação e purificação de proteínas. Contudo, a remoção de sais do precipitado e tratamento da solução remanescente contendo altas concentrações de sal são etapas limitantes, devido ao custo do processo e a regulamentação ambiental. O uso de eletrólitos voláteis é uma alternativa aos sais convencionais neste tipo de processo, visto permitirem um fácil processamento e redução do custo do tratamento de efluentes: os sais voláteis podem ser removidos com a redução de pressão ou elevação da temperatura. Neste trabalho foram determinadas as curvas de solubilidade para a lisozima e insulinas bovina e suína em soluções aquosas de sais voláteis, em sistema vedado contendo carbonato, carbamato e bicarbonato de amônio em equilíbrio com CO2 e NH3. Estas curvas de equilíbrio foram determinadas como função da concentração salina (1,00 a 7,00 mol.kg-1), da temperatura (5,0 a 25,0 °C), e razão nitrogênio por carbono (RN/C) (2,0 e 2,5) das soluções.O aumento do conteúdo de nitrogênio aumentou a solubilidade das proteínas que, de uma forma geral, apresentaram um comportamento de solubilidade retrógrada em relação à temperatura. Espectros de dicroísmo circular sugeriram uma pequena desnaturação causada pela precipitação / Abstract: Protein precipitation induced by salt addition (e.g., ammonium sulfate and sodium chloride) is a commoly used technique in the downstream processing of proteins. However, salt removal from the precipitate and disposal of the salt containing liquid phase are key steps of the process due to cost and environmental concerns. Volatile salts are alternatives to conventional salts in this process since they can allow easy processing and reduce the cost of waste disposal: the volatile salt can be removed by pressure reduction and temperature increase. In this work we reported the solubility curves for lysozyme and swine and bovine insulins in aqueous solutions of the volatile salts of the system comprised of ammonium carbonate, carbamate, and bicarbonate in equilibrium with CO2 and NH3. These equilibrium curves were determined as funciton of the salt concentration (1.0-7.0 mol/kg), temperature (5.0-25.0 ºC), and N/C ratio (2.0 and 2.5) of the solutions. The increase of the N content of the solutions increased the proteins solubility that in general had a retrograde solubility. Circular dichroism spectra suggested some denaturation caused by the procipitation / Mestrado / Desenvolvimento de Processos Biotecnologicos / Mestre em Engenharia Química

Orientadores: Pedro de Alcantara Pessoa Filho, Everson Alves Miranda / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T14:49:36Z (GMT). No. of bitstreams: 1 Watanabe_ErikaOhta_D.pdf: 2586256 bytes, checksum: af351628a929312bf64c37235f0a8f20 (MD5) Previous issue date: 2007 / Resumo: A precipitação induzida pela adição de sais (¿salting-out¿) é uma operação unitária freqüentemente empregada na purificação de proteínas. Com a adição de sal, a solução aquosa de proteína separa-se em uma fase pobre e um precipitado rico em proteína, sendo este último efetivamente uma mistura da fase sólida formada (a que chamaremos precipitado verdadeiro) e da fase líquida pobre em proteína, já que uma separação completa das fases não pode ser alcançada. A obtenção de dados completos de equilíbrio de fases na precipitação de proteínas ainda é rara, embora a determinação dos diagramas de fase possa contribuir para a caracterização deste precipitado verdadeiro e para uma melhor compreensão do fenômeno de precipitação. Neste trabalho, o equilíbrio de fases da precipitação de lisozima e albumina de soro bovino (BSA) foi estudado através de ensaios de precipitação, nos quais as composições das fases coexistentes foram analisadas. Os ensaios de precipitação de lisozima foram conduzidos utilizando-se sulfato de amônio e sulfato de sódio a diferentes valores de pH (2,0, 4,0, 7,0 e 10,0) e cloreto de sódio a pH 7,0 e o sal volátil carbamato de amônio a 5,0, 15,0 e 25,0°C como agentes precipitantes. A BSA foi precipitada em sulfato de amônio a pH 2,0, 7,0 e 9,0. A composição do precipitado verdadeiro pode ser obtida através da intersecção de extrapolações das linhas de amarração determinadas experimentalmente, técnica de análise cuja utilização extensiva e sistemática foi realizada pela primeira vez neste trabalho. Os diagramas de fases, para o sistema contendo lisozima e sulfato de amônio e sulfato de sódio, mostraram dois tipos de precipitado verdadeiro: um composto de proteína-água e um complexo de proteína, água e sal. Diferentes valores de pH não influenciaram na composição do precipitado verdadeiro. Para os sistemas lisozima-sulfato de amônioágua a pH 7,0 e a 5,0 e 15,0°C, uma região de ¿salting-in¿ na curva de solubilidade pode ser observada. Duas fases correspondentes a diferentes precipitados foram obtidas para as regiões ¿salting-in¿ e ¿salting-out¿. Os sistemas lisozima-cloreto de sódio e lisozima-carbamato de amônio apresentaram um precipitado verdadeiro composto de proteína-água e apenas proteína, respectivamente. A atividade enzimática da lisozima mostrou-se dependente da concentração de sal, enquanto nenhuma desnaturação foi verificada para a lisozima precipitada em carbamato de amônio. Para o sistema contendo BSA, em cada valor de pH utilizado foi obtido um único precipitado verdadeiro cuja composição é dependente do pH / Abstract: Salt induced protein precipitation (¿salting-out¿) is a unit operation commonly used to protein purification. By adding a salt, an aqueous protein solution is forced to undergo a phase separation into a protein-lean liquid phase and a protein rich phase. Nevertheless, as a complete phase separation cannot be achieved, the protein rich phase is actually a mixture of the solid phase (herein called true precipitate) and the protein-lean liquid phase. The determination of equilibrium diagrams can contribute to the characterization of this true precipitate and to the understanding of the phenomena underlying this so widely used technique but, in spite of this, the experimental determination of phase equilibrium diagrams of protein precipitation is scarce. In this work, phase equilibrium of salt-induced precipitation of lysozyme and bovine serum albumin (BSA) was studied through precipitation assays, in which the compositions ofthe coexisting phases were analysed. Lysozyme precipitation experiments were carried out using ammonium sulfate and sodium sulfate at different values of pH (2.0, 4.0, 7.0 e 10.0) and sodium chloride at pH 7.0 and the volatile salt ammonium carbamate at 5.0, 15.0 and 25.0°C as precipitant agents. Precipitation of BSA was carried out in ammonium sulfate solution at pH 2.0, 7.0 and 9.0. The composition of the true precipitate phase was inferred by the intersection of the extensions of the experimentally determined tie-lines ¿ an analysis not previously carried out to such extent. Phase diagrams of lysozyme-ammonium sulfate and sodium sulfate-water showed two different types of precipitate: a salt-free protein-water phase and a proteinrich phase formed by lysozyme, water and salt. No significant difference was observed in the composition of the true precipitate when the pH value is changed. For systems formed by ammonium sulfate at pH 7.0 at 5.0 and 15.0°C, a salting-in region in the solubility curve was observed. Two different true precipitates were found, corresponding to the salting-in and salting-out regions. The systems lysozyme-sodium chloride and lysozyme-ammonium carbamate showed only one true precipitate composed by protein-water and protein, respectively. Lysozyme activity depends on the salt concentration used to protein precipitation, while no protein denaturation was verified in the lysozyme precipitated by ammonium carbamate. Phase diagrams of BSA-salt-water showed only one true precipitate, whose composition depends on the pH studied. / Doutorado / Engenharia de Processos / Doutor em Engenharia Química

Nickel-base superalloys have been emerged as materials for gas turbines used for jet propulsion and electricity generation. The strength of the superalloys depends mainly from an ordered precipitates of L12 structure, so called gamma prime (γ’) dispersed within the disorder γ matrix. The Ni-base alloys investigated in this dissertation comprise both model alloy systems based on Ni-Al-Cr and Ni-Al-Co as well as the commercial alloy Rene N5. Classical nucleation and growth mechanism dominates the γ’ precipitation process in slowed-cooled Ni-Al-Cr alloys. The effect of Al and Cr additions on γ’ precipitate size distribution as well as morphological and compositional development of γ’ precipitates were characterized by coupling transmission electron microscopy (TEM) and 3D atom probe (3DAP) techniques. Rapid quenching Ni-Al-Cr alloy experiences a non-classical precipitation mechanism. Structural evolution of the γ’ precipitates formed and subsequent isothermal annealing at 600 °C were investigated by coupling TEM and synchrotron-based high-energy x-ray diffraction (XRD). Compositional evolution of the non-classically formed γ’ precipitates was determined by 3DAP and Langer, Bar-on and Miller (LBM) method. Besides homogeneous nucleation, the mechanism of heterogeneous γ’ precipitation involving a discontinuous precipitation mechanism, as a function of temperature, was the primary focus of study in case of the Ni-Al-Co alloy. This investigation coupled SEM, SEM-EBSD, TEM and 3DAP techniques. Lastly, solute partitioning and enrichment of minor refractory elements across/at the γ/ γ’ interfaces in the commercially used single crystal Rene N5 superalloy was investigated by using an advantage of nano-scale composition investigation of 3DAP technique.

Groundwater chemistry is a function of recharge and the input chemistry of the rain, which gets transformed as it moves through the soil matrix. Apart from mineral transformations, anthropogenic activities are other external factors, which affect the groundwater chemistry. Stream – aquifer interactions alter the chemistry of groundwater in the regions nearer to the stream. A study is carried out to analyse the hydrogeochemical behavior under the influence of lithologic, precipitation and anthropogenic controls in the upper Cauvery basin. This is followed by the analysis of contributions made by the components of the hydrogeochemical cycle. A geochemical model is developed, which is used to study the spatiotemporal variations in groundwater chemistry of a silicatic rock group in a small experimental watershed. In order to study the effects of precipitation control on the groundwater chemistry the Upper Cauvery river basin (~ 10000 km2) is selected for the analysis, which stretches along three climatic zones – ‘semi-arid’ (500 – 800 mm/year rainfall), ‘sub-humid’ (1000 - 1200 mm/year) and ‘humid’ (1200 – 1500 mm/year) zones. The basin is mainly formed by granitic gneissic group of rocks with some traces of amphibolites and charnockites. Groundwater is observed to occur either in the saprolite or in the deeper hard rock zone based on the geomorphology even at the scale of a small watershed. Parts of this basin are under canal irrigation and are drained by Kabini and Cauvery Rivers. Groundwater – surface water interactions play an important role in these regions. Irrigation with different levels of intensities is practiced through groundwater in the upland areas. Observation wells considered in these three zones are classified into four classes based on the mean annual groundwater fluctuations. Wells in each of these four classes are further classified into ‘shallow’ and ‘deep’ categories based on the depth to groundwater. Analysis of the groundwater chemistry in the basin (widely spread with 120 wells in the three zones) shows a gradient in chemistry along the climatic gradient with sub-humid zone bridging between the semi-arid and humid zones. Ca/Na and Mg/Na ratios decrease from humid zone (unimodal rainfall) to semi-arid (bimodal rainfall) zone since both Na and Mg concentrations in groundwater increase along this gradient. These elements are mainly controlled by weathering reactions. Apart from the weathering of Ca, calcrete formations also play an important role in the semi-arid zone. Ion exchange process cycles between Cl and SO4 and between Ca and Na. Dissolution of CaCO3, silicate weathering and evaporation are the major mineralogical reactions. Variations in Na/Cl and Ca/Cl molar ratios indicate that shallow wells have higher molar ratios with higher variance than the deeper wells. Semi-arid zone is more silicaceous (higher Na/Cl value) than the humid zone, which has higher Ca/Cl ratio (~ 14). Effective seasonal patterns are identified using ‘recharge – discharge’ concept based on the rainfall intensity. Wells under normal scenario have low Na/Cl and Ca/Cl ratios in the ‘recharge period’ than in the corresponding ‘discharge period’ (dilution chemistry). Wells in the relatively higher pumping regions, which receive sufficient annual recharge exhibit dilution chemistry though groundwater level fluctuations are higher. However, wells in regions with insufficient recharge show ‘anti - dilution’ chemistry. Thus, the ‘recharge – discharge’ concept is useful in identifying the pumped wells from deeper wells and helps in characterizing the anthropogenic effects on the basin. Rainfall and its chemistry are to be analysed to understand the groundwater chemistry. Hence, data from various monitoring stations in India are analyzed for assessing the influence of several major factors such as, topographic location of the area, its distance from sea and annual rainfall. These stations are categorized as ‘urban’, ‘suburban’ and ‘rural’. pH, HCO3, NO3 and Mg concentrations have not changed much from coast to inland. On the other hand, SO4 and Ca concentrations changes are subjected to local emissions. Cl and Na (marine elements) originate solely from sea and a model is developed to quantify the variation in concentration of these elements under the influence of inland distance and annual rainfall. Non – linear regression model for the various categories shows that both rainfall amount and precipitation chemistry follow a power law reduction with distance from sea. Cl and Na decrease rapidly for the first 100 km distance from sea, then decrease marginally for the next 100 km and then later stabilize. Regression parameters estimated for different cases are found to be consistent (R2 ~ 0.8). Variation in one of the regression parameters accounts for the effect of urbanization. Model developed for precipitation chemistry is validated using stations from the southern peninsular region of the country. Model predictions are found to be in good correlation with observations with a relative error of ~ 5%. This relationship between the three parameters – rainfall amount, coastline distance, and concentration (in terms of Cl and Na) was validated with experiments conducted at Mule Hole SEW and Kalekere. Monthly variations in precipitation chemistry at these stations are predicted from a downscaled (in time) model and then compared with the observed data. Models developed at both annual and monthly scale are found to perform well with the field observations. Hence, this model is used for predicting the precipitation chemistry (in terms of Cl and Na) of different station points in the upper Cauvery basin. Comparative performance of alternate methods of recharge estimation i.e. Chloride mass balance (CMB) and water table fluctuation (WTF) approaches, is analyzed at various stations in the basin. Annual rainfall, Cl concentration in rain (predicted from precipitation model) and the concentration of Cl in the groundwater are the inputs for the CMB approach. Since main source of Na is from atmosphere, Na is taken as an alternative for Cl in the CMB approach and recharge is estimated using sodium mass balance (SMB) approach. Na concentrations contributed from weathering are quantified and eliminated in the analysis. Recharge estimated using SMB approach is found to be higher than CMB estimate in the semi-arid and the sub-humid zones. Water table fluctuation (WTF) method is used to compare the recharge obtained from both CMB and SMB approaches. Estimates using WTF approach are found to be higher than both CMB and SMB in the semi-arid and the sub-humid zones while SMB is found to be higher than CMB estimates. SMB and WTF estimates match well in the humid zone. An exponential relationship between recharge and annual rainfall is observed. Recharge coefficient estimated on an annual scale varied from 0.1 to 0.25 across the basin. Among CMB and SMB approaches, SMB is a better alternative for recharge estimation in semi-arid zones, where WTF approach performed poorly. Water – rock reactions are driven by the inequilibrium reactions of water with the mineral assemblage in the rock. These reactions evolve towards equilibrium with the primary minerals while a series of secondary minerals precipitate. Mass balance approach is adopted to quantify the rate at which the water – rock interactions occur in order to reach the equilibrium. Field experiments in the experimental watershed (Mule Hole SEW, ~ 4.5 km2) are carried to identify the minerals present in the region and their composition. Quartz, oligoclase, sericite, epidote and chlorite are the primary minerals while kaolinite and Fe-oxides are the secondary minerals present in this region. Percentages of oxides of different elements in each of these minerals are determined from the field experiments. Stoichiometric coefficients of different elements in each of these minerals are determined from these percentages. Long – term weathering rates are determined using these stoichiometric coefficients along with the mass fluxes of each element. Set of minerals present at different depths are found to vary among the thirteen observation wells of Mule Hole SEW. Hence, the mass balance calculations resulted in different weathering rates for a particular mineral based on the spatial location and the particular depth of the occurrence of the mineral. These weathering rates are tested for the sensitivity to carbonates with the inclusion of calcite in the mass balance calculations. With this sensitivity analysis it is observed that the presence of carbonates in the nodular form in the shallow wells has not changed the weathering reactions and their rates, and hence these wells are termed to be in the ‘silicate with secondary carbonate’ system. On the other hand, carbonates are not present in deeper wells, inclusion of which alters the equilibrium of the mass balance calculations. Thus, these wells are said to belong to the ‘silicate’ system. Anorthite present in some of the wells (MH2 and MH6) dissolves accompanied with the dissolution of carbonates. These wells are observed to belong to the third group the ‘amphibolites with primary carbonate’ system. Weathering rates of all the minerals present in these three different systems are also determined annually (short term rates). Mean of these short – term rates are observed to be the same as the long – term (over a period of 4 years) weathering rates with a minor difference of 3 – 10% in values. Thus, the weathering rates determined using mass balance approach is used to determine the quantities of concentrations of different elements contributed from the mineralogical reactions. Temporal variations in the concentrations of different chemical species in this small experimental watershed are simulated using a hydrogeochemical model. The model is developed based on a mixing cell approach, which considers the spatiotemporal variations in the recharge and the weathering inputs. Most of the weathering reactions are observed to take place in the saturated zone, which is termed as the ‘mixing zone’. This zone extends from few meters above the groundwater table to few meters below the water table. Mixing zone is discretized into series of ‘cells’ and concentrations in this zone are simulated. This group of cells is assumed to move along with the groundwater fluctuation. Sensitivity of the model is analysed subject to the variations in the recharge and the weathering fluxes. The developed model is used to simulate the concentrations of the groundwater in the three systems – ‘silicate’, ‘silicate with secondary carbonate’ and ‘amphibolites with primary carbonate’. Field data for chemical species is observed to vary in this mixing zone, boundaries of which are defined from the model simulations. Simulations corresponding to the cell at the mid depth of this mixing zone are observed to correlate well with the field data. Hence, the model developed is able to simulate the temporal variations in the groundwater chemistry. In summary, the study analyses the effects of lithological, climatic and anthropogenic factors on groundwater chemistry. The transformations in the rainwater chemistry as it reaches groundwater are analysed along different stages. A hydrogeochemical model is developed to simulate the groundwater concentrations in three different mineralogical settings over a period of three years.

The impact of particle size, size distribution, and particle shape on the rheology of precipitated calcium carbonate (PCC) based coatings was studied. Evaluating the interactions between different particle sizes and shapes leads to a better understanding of the packing fraction of PCC. HIgh packing fraction is desirable because of the positive impact on the fluidity of suspensions. Suspension with higher levels of fluidity can potentially load larger amounts of solids while keeping low viscosities. High solids suspensions are key factors to improve the efficiency of coating processes. To address this issue, PCC of different sizes and shapes where mixed in different ratiosto find mixtures with higher packing fractions that could result in coatings with lower viscosities. When coatings containing 90% of large particles and 10% by weight of small particles of different shape, viscosity decreases by 50% for one combination. The effect is caused by the higher packing fraction achieved. Future research is also described here.