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A retificação é um dos processos mais utilizados em operações de acabamento, geralmente caracterizada pelo resultado dimensional atingido e baixas rugosidades. Apesar de seu uso intenso na indústria, há aspectos ainda desconhecidos do processo e de sua estabilidade, sendo considerados tempos excessivos de centelhamento para atingir boas condições dimensionais. Este trabalho propõe um novo modelo para determinar o menor tempo de centelhamento necessário para que as deformações do sistema máquina-rebolo-peça sejam absorvidas e a dimensão objetivo da peça alcançada. Esse modelo partiu do equacionamento descrito por S. Malkin para obtenção da rigidez da máquina e avançou na obtenção da constante característica do tempo τ de forma experimental. A comprovação do modelo proposto deu-se em dois experimentos, sendo o primeiro experimento aplicado para determinar o valor de τ em função da velocidade de avanço, segundo o modelo de Malkin. Comprovou-se que o τ varia, principalmente em baixas velocidades de avanço. O segundo experimento teve como objetivo determinar qual o menor tempo de centelhamento necessário para que as deformações do sistema máquina-rebolo-peça sejam plenamente absorvidas e compará-las com o modelo proposto. Os resultados teórico e experimental comprovaram que, para as velocidades de mergulho 3,0 e 2,5 mm/min, com τ = 0,219 e 0,204 s, respectivamente, o tempo mínimo de centelhamento de 1,0 s foi suficiente para absorver as deformações elásticas inseridas no sistema. De forma comparativa, o modelo proposto foi mais eficaz que o de Malkin para o cálculo do tempo de centelhamento e do erro diametral da peça para relações t1/τ menores ou iguais a 20, sendo t1 o tempo em segundos da fase de retificação em desbaste. Conclui-se que o modelo proposto neste trabalho mostrou-se eficiente para predizer o tempo mínimo necessário para centelhamento e a redução diametral da peça, considerando o valor experimental de τ. / Grinding is one of the processes most commonly used in finishing operations, usually characterized by good dimensional results and low roughness values. Despite the extensive use in industry, there are still unknown aspects of the grinding process and its stability, with excessive spark-out times being used to achieve good dimensional requirements. This research work proposed a new model to determine the shortest spark-out time required to absorb the machine-wheel-workpiece system deformations and to achieve the desired workpiece diameter. This model derived from the equation described by S. Malkin to obtain the machine stiffness and consisted in experimentally obtaining the time characteristic constant τ. The verification of the proposed model was done in two experiments. The first one was performed to determine the value of τ according to the radial infeed velocity (vf), as proposed by S. Malkin. It was shown that the τ varies, especially at low feed rates. The second objective was to determine the shortest spark-out time needed, in which all machine-wheel-workpiece system deformations were fully eliminated and to compare it to the one calculated by the proposed model. The theoretical and experimental results showed that for radial infeed velocities of 3.0 and 2.5 mm/min, with τ = 0.219 and 0.204 s, respectively, the spark-out time of 1 s was long enough to ensure that the elastic deformations introduced into the system were fully absorbed. Comparatively, the proposed model was more effective than the Malkin\'s one to predict the spark-out time and the diametric error for the ratio t1/τ lower that 20, being t1 the time in seconds for the rough grinding stage. As a conclusion, the proposed model proved to be effective in predicting the minimum spark-out time and the workpiece diameter reduction, when considering the experimental value of τ.

A retificação é um dos processos mais utilizados em operações de acabamento, geralmente caracterizada pelo resultado dimensional atingido e baixas rugosidades. Apesar de seu uso intenso na indústria, há aspectos ainda desconhecidos do processo e de sua estabilidade, sendo considerados tempos excessivos de centelhamento para atingir boas condições dimensionais. Este trabalho propõe um novo modelo para determinar o menor tempo de centelhamento necessário para que as deformações do sistema máquina-rebolo-peça sejam absorvidas e a dimensão objetivo da peça alcançada. Esse modelo partiu do equacionamento descrito por S. Malkin para obtenção da rigidez da máquina e avançou na obtenção da constante característica do tempo τ de forma experimental. A comprovação do modelo proposto deu-se em dois experimentos, sendo o primeiro experimento aplicado para determinar o valor de τ em função da velocidade de avanço, segundo o modelo de Malkin. Comprovou-se que o τ varia, principalmente em baixas velocidades de avanço. O segundo experimento teve como objetivo determinar qual o menor tempo de centelhamento necessário para que as deformações do sistema máquina-rebolo-peça sejam plenamente absorvidas e compará-las com o modelo proposto. Os resultados teórico e experimental comprovaram que, para as velocidades de mergulho 3,0 e 2,5 mm/min, com τ = 0,219 e 0,204 s, respectivamente, o tempo mínimo de centelhamento de 1,0 s foi suficiente para absorver as deformações elásticas inseridas no sistema. De forma comparativa, o modelo proposto foi mais eficaz que o de Malkin para o cálculo do tempo de centelhamento e do erro diametral da peça para relações t1/τ menores ou iguais a 20, sendo t1 o tempo em segundos da fase de retificação em desbaste. Conclui-se que o modelo proposto neste trabalho mostrou-se eficiente para predizer o tempo mínimo necessário para centelhamento e a redução diametral da peça, considerando o valor experimental de τ. / Grinding is one of the processes most commonly used in finishing operations, usually characterized by good dimensional results and low roughness values. Despite the extensive use in industry, there are still unknown aspects of the grinding process and its stability, with excessive spark-out times being used to achieve good dimensional requirements. This research work proposed a new model to determine the shortest spark-out time required to absorb the machine-wheel-workpiece system deformations and to achieve the desired workpiece diameter. This model derived from the equation described by S. Malkin to obtain the machine stiffness and consisted in experimentally obtaining the time characteristic constant τ. The verification of the proposed model was done in two experiments. The first one was performed to determine the value of τ according to the radial infeed velocity (vf), as proposed by S. Malkin. It was shown that the τ varies, especially at low feed rates. The second objective was to determine the shortest spark-out time needed, in which all machine-wheel-workpiece system deformations were fully eliminated and to compare it to the one calculated by the proposed model. The theoretical and experimental results showed that for radial infeed velocities of 3.0 and 2.5 mm/min, with τ = 0.219 and 0.204 s, respectively, the spark-out time of 1 s was long enough to ensure that the elastic deformations introduced into the system were fully absorbed. Comparatively, the proposed model was more effective than the Malkin\'s one to predict the spark-out time and the diametric error for the ratio t1/τ lower that 20, being t1 the time in seconds for the rough grinding stage. As a conclusion, the proposed model proved to be effective in predicting the minimum spark-out time and the workpiece diameter reduction, when considering the experimental value of τ.

Ball mill grinding is an important operation in the processing of most minerals, in that it may be used to produce particles of the required size and shape, to liberate minerals from each other for concentration purposes, and to increase the powder surface area. Grinding of minerals is probably the most energy consuming task and optimization of this operation has vital importance in processing plant operations to achieve the lowest operating costs. Predicting the complete product size distribution, mill specifications and power draw are important parameters of this optimization. In this study, a computer simulation program is developed in MATLAB environment to simulate grinding operations using the kinetic model in which comminution is considered as a process continuous in time. This type of model is commonly and successfully used for tumbling grinding mills having strongly varying residence time as a function of feed rate. The program developed, GRINDSIM, is capable of simulating a ball mill for a specified set of model parameters, estimating grinding kinetic parameters from experimental batch grinding data and calculating continuous open and closed-circuit grinding behavior with mill power input. The user interacts with the program through graphical user interfaces (GUI&rsquo / s).

La rectification est un procédé de fabrication permettant d’obtenir des états de surface avec une rugosité très faible. Elle est généralement utilisée sur des matériaux très durs pour lesquels les autres procédés d’usinage ne sont pas adaptés, cependant, ce procédé fait intervenir des mécanismes d’enlèvement matière complexes et difficiles à mettre en oeuvre. Lors du processus de rectification, l'énergie de rectification est principalement convertie en chaleur entre la pièce, la meule, le liquide d'arrosage et les copeaux. Les températures et les flux de chaleur à l'interface meule/pièce dépendent de la géométrie du contact, du matériau rectifié, de la meule (taille de grains, géométrie, densité, porosité, usure), de son dressage, des paramètres de rectification (profondeurs de passe, vitesse d'avance, vitesse de meule, conditions de dressage), des conditions d'arrosage et de lubrification. Les températures élevées peuvent engendrer des transformations métallurgiques superficielles, des gradients de contraintes résiduelles, ainsi que des variations dimensionnelles notables. D’une façon générale l’intégrité de surface peut être grandement modifiée par cette interaction. Les conditions de rectification doivent garantir les critères de qualité et d'intégrité du matériau tout en répondant aux besoins d’augmentation de la productivité en milieu industriel. L'objectif cette thèse a été l'étude mécanico-thermique de l'interface meule/pièce/lubrifiant, dans le but de réduire le risque d'endommagement lors de la rectification d’une denture d’engrenage en acier nitruré et de qualifier les transformations éventuelles impactant l’intégrité de la pièce qui lui est associé. Pour cela nous avons développé plusieurs axes de recherche. Nous avons proposé et vérifié expérimentalement à partir d’une méthode inverse et de mesures de température par thermocouple rectifiable, un modèle de flux thermique permettant, en utilisant une mesure d’effort de prédire le profil de température à l’interface meule/pièce/lubrifiant. Nous avons effectué un comparatif détaillé de meules dans le but de déterminer celle qui permettra pour un état de surface donné de limiter le risque d’endommagement thermique du matériau rectifié. Pour effectuer cette étude, nous nous sommes intéressés à la profondeur de passe maximale admissible de chaque meule avant brûlure. Ce comparatif a été mené à la fois en laboratoire et en milieu industriel. Nous avons ensuite étudié l’influence des endommagements thermiques provoqués par la rectification en étudiant et en qualifiant la microstructure de l’acier nitruré. L’utilisation de moyens de mesure classiques (dureté, MEB EBSD, DRX) ou inédits et peu utilisés sur les brûlures de rectification (bruit Barkhausen, spectroscopie Raman) nous a permis de définir les modifications du matériau endommagé en termes de contraintes résiduelles, de dureté, de tailles de grain et de création d’oxydes. Enfin, nous avons mené une étude détaillée sur l’influence de la lubrification lors de la rectification de notre acier nitruré. Nous avons pour cela modifié indépendamment les débits et vitesses d’arrosage en sortie de buse et observé les changements que cela engendrait sur le profil température dans la zone de rectification et sur le coefficient de répartition de la pièce / The grinding process is very useful to obtain a very precise surface finish. It is generally used on very hard materials which cannot be machined by other conventional machining processes. However grinding involves very complex material removal mechanisms and most of the time is difficult to set up. During the grinding process, the main grinding energy is converted into heat between chip, lubricant, wheel and workpiece. Temperature and heat flux in the grinding zone depend on the contact geometry, on the material, on the wheel (grit size, geometry, porosity, wear), on the dressing, on the grinding parameters (depth of cut, workpiece speed, wheel speed) and on lubrication conditions. High temperatures result in thermal damage such as metallurgical changes, stress gradients, and changes in workpiece dimensions. In general terms, because of this process, surface integrity may be seriously damaged. Grinding parameters have to guarantee the workpiece quality and have to respond to the productivity improvement in machining and cutting industry. The target of this thesis was the mechanical and thermal study of the grinding zone between workpiece, wheel and lubricant in order to reduce the burn risk during the grinding of a nitrided steel gear. The purpose was also to define possible transformations associated to this damage. To achieve it, we developed several research topics. We proposed an experimentally verified heat flux model, usable to predict accurately the nitrided steel temperature in the lubricated grinding zone. This model is based on an inverse method and temperature measurements with a workpiece/foil thermocouple. We made a grinding wheel comparative study in order to determine the wheel capable, for a given workpiece roughness, of limiting the risk of burn. To perform this study, we focused, for each wheel, on the maximum allowable depth of cut before burning. This comparative study was led both in laboratory and industrial conditions. We also studied the influence of thermal damages in grinding by studying and qualifying the nitrided steel microstructure. The use of classical measurement techniques such as: hardness, SEM, EBSD and DRX or original and underused techniques such as Barkhausen noise or Raman spectroscopy permitted to define changes in the burned grinded materials. Between the two states of materials (burned and no burned), we observed differences in hardness, grain size and ferrous oxides creation. At last, we made a detailed study on the lubrication efficiency during grinding of the nitrided steel. For this purpose we changed independently fluid flow and jet speed in outlet nozzle. Then we observed the modifications this could cause on the temperature distribution in the grinding zone and on the workpiece heat partition ratio

Orientador: Eduardo Carlos Bianchi / Banca: Manoel Cleber de Sampaio Alves / Banca: Reginaldo Teixeira Coelho / O programa de Pós Graduação em Ciência e Tecnologia de Materiais PosMat, tem carater institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Os materiais compósitos estão se tornando essenciais e amplamente utilizados na indústria moderna, principalmente nas indústrias aeronáuticas e aeroespacial. Essa notável demanda por este tipo de material, proveniente da junção entre dois ou mais materiais distintos, pode ser explicada pelo resultado alcançado com essa combinação: propriedades específicas e otimizadas para cada aplicação. Devido à anisotropia do material, há a tendência de aparecimento de tensões residuais ou distorções estruturais, após o seu processamento. Para o devido controle destas distorções, é imperativo o processo de usinagem denominado retificação. Nesse processo de usinagem, há a necessidade da utilização de grande quantidade de fluido de corte (refrigeração convencional). Referente a preocupações ambientais, surgem métodos que visam reduzir a utilização abundante de fluidos de corte, como: a refrigeração otimizada, a técnica de mínima quantidade de lubrificação (MQL) e a retificação a seco. O presente trabalho analisou os métodos de lubri-refrigeração citados, na retificação plana de compósitos plásticos reforçados com fibras de carbono (PRFC'S), como alternativas à retificação convencional, buscando mitigar o uso de fluidos de corte no meio industrial. Essa análise através da coleta de dados sobre a eficiência do processo e a qualidade superficial das peças, através das seguintes variáveis de saída: o comportamento de força tangencial de corte, rugosidade, energia específica, relação G (volume de material removido/volume de rebolo desgastado) e microscopia eletrônica de varredura (MEV). Com os resultados obtidos, verificou-se que a técnica de MQL gerou valores mais baixos de força tangencial de corte e energia específica de retificação. Já os métodos convencional e otimizado proporcionaram um menor desgaste da ferramenta de corte, bem como um melhor acabamento superficial / Abstract: Composite materials are becoming essential and largely used in modern industry, mainly is aeronautics and aerospace industries. This notable demand for these materials, generated from the combination of two or more distinct materials, can be explained by some results obtained: unique and optimized properties specific for each application. One of the main reasons for its large use it is their structural composition, which comes from the fusion of two different materials, resulting into excellent structural properties. Due to the material anisotropy, there is a trend of appering residual stresses and structural distortions, after its processing. For the adequade control of these distortions, it is necessary a machining process called grinding. When grinding these materials, there is a need of a great quantity of cutting fluids (conventional lubrication). In relation to the environmental concerns, new methodologies arise, which intend to reduce this large quantity of cutting fluid, like optimized cooling, the minimum quantity lubrification (MQL) technique and dry grinding. The present work analyzed the aforementioned lubri-cooling methods, on surface grinding of carbon fiber reinforced plastic composities (CFRP's), as alternatives to conventional cooling, in order to mitigate the deleterious effects of cutting fluids. This analysis was conducted through data gathering concerning the process efficiency and the the workpiece surface quality, using the following output variables: bahavior of the tangential force, surface roughness, specific grinding energy, G relation and scanning electron microscopy (SEM). With the results obtained, it can be verified that the MQL technique generated the lowest values of tangential cutting force and griding specific energy. The optimized and conventional methods provided the lowest wear of the grinding wheel, as well as the better surface finishing / Mestre

Made available in DSpace on 2014-06-11T19:28:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-09-24Bitstream added on 2014-06-13T18:34:25Z : No. of bitstreams: 1 damasceno_rf_me_bauru.pdf: 2382441 bytes, checksum: c07ae566c39a8420db844725306f470e (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho teve o propósito de contribuir com informações sobre a aplicação de fluidos de corte na operação de retificação plana de aço, em especial do ano ABNT 4340 temperado e revenido. Desta forma testados e comparados três métodos de lubri-refrigeração, os quais são: MQL (Mínima Quantidade de Lubrificante), convencional e otimizado. Os testes foram realizados em retificadora plana universal, utilizando um rebolo de cBN Vitrificado. Os fluidos de corte utilizados para os testes foram: emulsão com diluição a 5% para os métodos convencinal e Otimizado, enquanto que para MQL utilizou-se fluido sintético. A fim de obter uma análise comparativa dos desempenhos entre os três métodos, o parâmetro profundidade de corte foi variado em três valores (0,02mm;0,05mm e 0,08mm). Os outros parâmetros de corte, os quais foram mantidos constantes. Como variáveis de saída foram analisadas: força tangencial de corte, rugosidade, desgaste diametral do rebolo, relação G, dureza por microindentação, tensão residual superficial da pela e imagens obtidas no Microscópio Eletrônico de Varredura foram também obtidas para analisar a superfície das peças usinadas. Os resultados indicaram que a técnica MQL, permite obter menor desgaste diametral do rebolo, no entanto há prejuízos quanto ao acabamento superficial (rugosidade) em profundidades de corte até 0,05mm, acima deste valor o método MQL mostrou-se incapaz de realizar a lubrirefrigeração de forma eficaz. Já o método otimizado permitiu obter os melhores resultados de rugosidade, menor desgaste diametral do rebolo e induziu menor tensão residual superficial, mas em profundidade de corte de 0,02mm apresentou os maiores valores de força de corte tangencial comparados aos outros métodos. Por fim, o método convencional apresentou resultados medianos em quase todas as variáveis de saída analisadas / This work aims to investigate the comparative efficiency of three different colling and lubrificatins system e applied to surface grinding operation. Systems compared are MQL (Minimal Quantify Lubrification), conventional and conventional optimized. Grinding tests were performed on universal grinding machine using a vitrified cBN grinding wheel for grinding, steel samples of ABNT4340 (grade SAE4340) hardened and tempered to 55HRc. The cutting fluid used for testing was soluble oil at 5% for methods and conventional and conventional optimized and synthetic fluid for MQL technique tested. In order to obtain a comparative analysis of performance among the three methods, the depth of cut parameter was varied in three values (0,02mm, 0,05 mm, 0,08mm), the other cutting parameters were kept constant. Which one output variables investigated were: tangential cutting force, surface roughness, wheel diametrical wear, G ratio, workpiece microhardness and surface residual stress. Images obtained by scanning electron microscopy of the ground surface were used to analyze machined surfaces. The results indicated that the MQL technique allowed to prolong tool life of wheel, however there is damage on the surface finish of machined surfaces (roughness) at depths of cut up values to 0.05 mm. Above this value the MQL method proved did not provide efficiente lubrification and cooling functions. Conventional optimized method showed the best results of roughness, residual stress and least wear of wheel, bur in depth of cut 0.02 mm gave the highest values of tangential cutting force compared to other methods under conditions investigated. Finally, the conventional coolant method presented relatively satisfatory results for most output variables analyzed

Made available in DSpace on 2014-06-11T19:30:20Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-10Bitstream added on 2014-06-13T18:47:32Z : No. of bitstreams: 1 varasquim_fmfa_me_bauru.pdf: 3736893 bytes, checksum: d77b1a71d89e0f0dfcd0ffcd80e0ad43 (MD5) / Os materiais compósitos estão se tornando essenciais e amplamente utilizados na indústria moderna, principalmente nas indústrias aeronáuticas e aeroespacial. Essa notável demanda por este tipo de material, proveniente da junção entre dois ou mais materiais distintos, pode ser explicada pelo resultado alcançado com essa combinação: propriedades específicas e otimizadas para cada aplicação. Devido à anisotropia do material, há a tendência de aparecimento de tensões residuais ou distorções estruturais, após o seu processamento. Para o devido controle destas distorções, é imperativo o processo de usinagem denominado retificação. Nesse processo de usinagem, há a necessidade da utilização de grande quantidade de fluido de corte (refrigeração convencional). Referente a preocupações ambientais, surgem métodos que visam reduzir a utilização abundante de fluidos de corte, como: a refrigeração otimizada, a técnica de mínima quantidade de lubrificação (MQL) e a retificação a seco. O presente trabalho analisou os métodos de lubri-refrigeração citados, na retificação plana de compósitos plásticos reforçados com fibras de carbono (PRFC'S), como alternativas à retificação convencional, buscando mitigar o uso de fluidos de corte no meio industrial. Essa análise através da coleta de dados sobre a eficiência do processo e a qualidade superficial das peças, através das seguintes variáveis de saída: o comportamento de força tangencial de corte, rugosidade, energia específica, relação G (volume de material removido/volume de rebolo desgastado) e microscopia eletrônica de varredura (MEV). Com os resultados obtidos, verificou-se que a técnica de MQL gerou valores mais baixos de força tangencial de corte e energia específica de retificação. Já os métodos convencional e otimizado proporcionaram um menor desgaste da ferramenta de corte, bem como um melhor acabamento superficial / Composite materials are becoming essential and largely used in modern industry, mainly is aeronautics and aerospace industries. This notable demand for these materials, generated from the combination of two or more distinct materials, can be explained by some results obtained: unique and optimized properties specific for each application. One of the main reasons for its large use it is their structural composition, which comes from the fusion of two different materials, resulting into excellent structural properties. Due to the material anisotropy, there is a trend of appering residual stresses and structural distortions, after its processing. For the adequade control of these distortions, it is necessary a machining process called grinding. When grinding these materials, there is a need of a great quantity of cutting fluids (conventional lubrication). In relation to the environmental concerns, new methodologies arise, which intend to reduce this large quantity of cutting fluid, like optimized cooling, the minimum quantity lubrification (MQL) technique and dry grinding. The present work analyzed the aforementioned lubri-cooling methods, on surface grinding of carbon fiber reinforced plastic composities (CFRP's), as alternatives to conventional cooling, in order to mitigate the deleterious effects of cutting fluids. This analysis was conducted through data gathering concerning the process efficiency and the the workpiece surface quality, using the following output variables: bahavior of the tangential force, surface roughness, specific grinding energy, G relation and scanning electron microscopy (SEM). With the results obtained, it can be verified that the MQL technique generated the lowest values of tangential cutting force and griding specific energy. The optimized and conventional methods provided the lowest wear of the grinding wheel, as well as the better surface finishing

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The synthesis of twelve NH-pyrazoles from the cyclocondensation reaction of β-dimethylaminovinylketones ([R1C(O)C(R2)=CHN(Me)2], where R1 = Me, C6H5, 3- MeO-C6H4, 4-Me-C6H4, 4-MeO-C6H4, 4-F-C6H4, 4-Cl-C6H4, 4-Br-C6H4, 4-O2N-C6H4, fur-2-il, tien-2-il; R2 = H, 2-MeO-C6H4 and R1, R2 = -(CH2)3C(O)- with hydrazine sulfate is reported. In this work, it was also demonstrated the synthesis of twelve isoxazoles from the cyclocondensation reaction of β-dimethylaminovinylketones where R1 = Me, C6H5, 3-MeO-C6H4, 4-Me-C6H4, 4-MeO-C6H4, 4-F-C6H4, 4-Cl-C6H4, 4-Br-C6H4, 4-biphenyl, naphthalen-2-yl, 4-O2N-C6H4, thien-2-yl and R2 = H, 2-MeOC6H4 with hydroxylamine hydrochloride. The reactions were performed in the presence of p-toluene sulfonic acid as the catalyst through two methodologies: (i) by the solvent-free grinding method, and (ii) using the conventional method, ethanol reflux. In addition, the Grindstone Chemistry methodology demonstrated that largescale synthesis is also possible. Making a comparison with the classical reaction conditions, which employ molecular solvent (ethanol), the grinding method has as main advantages of shorter reaction time (5-15 min), higher product yields (60-92%), mild reaction conditions as well as being environmentally friendly. / Neste trabalho é descrita a síntese de uma série de doze NH-pirazóis a partir da reação de ciclocondensação de β-dimetilaminovinilcetonas ([R1C(O)C(R2)=CHN(Me)2], onde R1 = Me, C6H5, 3-MeO-C6H4, 4-Me-C6H4, 4-MeOC6H4, 4-F-C6H4, 4-Cl-C6H4, 4-Br-C6H4, 4-O2N-C6H4, fur-2-il, tien-2-il; R2 = H, 2-MeOC6H4 e R1, R2 = -(CH2)3C(O)- com sulfato de hidrazina. Também foi realizada a síntese de uma série de doze isoxazóis a partir da reação de ciclocondensação de β-enamino cetonas, onde R1 = Me, C6H5, 3-MeO-C6H4, 4-Me-C6H4, 4-MeO-C6H4, 4- F-C6H4, 4-Cl-C6H4, 4-Br-C6H4, 4-bifenil, naft-2-il, 4-O2N-C6H4, tien-2-il e R2 = H, 2-MeO-C6H4 com cloridrato de hidroxilamina. As reações para obtenção dos compostos heterocíclicos foram realizadas na presença de ácido p-tolueno sulfônico (ác. p-TsOH) como catalisador através de duas metodologias: (i) utilizando o método grinding na ausência de solvente, e (ii) utilizando metodologia convencional, refluxo em etanol. O método Grindstone Chemistry foi testado e demonstrou que a síntese em grande escala também é possível. Os resultados obtidos mostraram que o grinding proporciona uma redução no tempo da reação (5-15 min), altos rendimentos (60-92%), condições de reação brandas, além de ser uma metodologia ambientalmente aceitável.

Abstract During the past decade submicron and nanoparticles have aroused a wide interest and gained new applications due to their high surface area and strength. Grinding with a wet stirred media mill is usually the last process step before the submicron or nanoparticles are added to an application, and the step where the final particle size distribution is achieved. Since stirred media milling is an energy-intensive process, energy efficiency should be optimized. This can be done by determining the optimum operational parameters for the mill and using the highest possible solids concentration. The solids concentration can be increased by controlling particle-particle interactions with stabilization chemicals, e.g. polymers. This thesis concerns parameters and grinding aids affecting the particle size distribution and suspension stability of the aqueous submicron grinding of calcium carbonate (CaCO3) and titanium dioxide (TiO2) in stirred media mills. TiO2 particles are aggregates produced via a bottom-up method, while CaCO3 are primary mineral particles produced by a top-down method. The most energy efficient grinding of TiO2 to a 300 nm particle size with the narrowest possible particle size distribution was obtained with the lowest stress energy, implying the smallest grinding medium size. It was observed that electrosteric stabilization with sodium polyacrylates was effective for TiO2, and sodium polyacrylate with a molecular weight of 12500 g/mol was found to be the most effective for reducing the viscosity of the suspension. As with TiO2, electrosteric stabilization with sodium polyacrylates was also found to be effective for CaCO3, but in this case sodium polyacrylate with a lower polydispersity index was more effective, showing a better stabilization potential in micron and submicron grinding and reducing the viscosity and particle size to a greater extent. Nanogrinding experiments were performed for a CaCO3 suspension with low PDI sodium polyacrylate and it was found to be possible to obtain a particle size of 26 nm, smaller than any size previously reported when grinding CaCO3. / Tiivistelmä Viimeisen kymmenen vuoden aikana alle yhden mikrometrin partikkelit ovat herättäneet kiinnostusta ja niille on kehitetty uusia sovelluksia niiden suuren pinta-alan ja lujuuden ansiosta. Ultrahienojauhatus märkähelmimyllyllä on useimmiten viimeinen prosessivaihe ennen partikkelien lisäämistä sovelluskohteeseen ja siinä saavutetaan partikkelien lopullinen partikkelikokojakauma. Helmimyllyjauhatuksen energiankulutus minimoidaan etsimällä optimioperointiparametrit kullekin jauhatusprosessille ja käyttämällä korkeinta mahdollista suspension kuiva-ainepitoisuutta. Suspension kuiva-ainepitoisuutta voidaan nostaa hallitsemalla partikkelien välisiä vuorovaikutuksia stabilointiaineilla, kuten polymeereillä. Tässä väitöskirjassa tutkittiin operointiparametrien ja jauhatusapuaineiden vaikutusta titaanidioksidin (TiO2) ja kalsiumkarbonaatin (CaCO3) partikkelikokojakaumaan ja lietteen stabiilisuuteen submikronijauhatuksessa. Tutkitut TiO2-partikkelit olivat aggregaatteja, jotka oli valmistettu sulfaattiprosessilla saostamalla, ja tutkitut CaCO3-partikkelit olivat primäärisiä mineraalipartikkeleita. TiO2-partikkeleille saavutettiin energiatehokkain jauhatus ja samalla toivottu partikkelikokojakauma, eli mediaani 300 nm ja mahdollisimman kapea jakauma, pienillä helmillä, jotka aiheuttavat partikkeleihin pienimmän puristusenergian. Elektrosteerinen stabilointi käyttämällä natriumpolyakrylaatteja stabilointiaineena havaittiin tehokkaaksi menetelmäksi hallita TiO2-partikkelien välisiä vuorovaikutuksia. Natriumpolyakrylaatti, jonka molekyylimassa oli 12500 g/mol, oli tehokkain TiO2-partikkeleille alentaen suspension viskositeettiä eniten. Myös CaCO3-partikkeleille elektrosteerinen stabilointi natriumpolyakrylaatteja käyttäen oli tehokkain stabilointimenetelmä. Myös natriumpolyakrylaattien polydispersiteetti-indeksin vaikutusta tutkittiin CaCO3-suspensioille. Tulokset osoittivat matalan polydispersiteetti-indeksin olevan tehokkaampi alentaen viskositteettia ja pienentäen partikkelikokoa tehokkaammin kuin natriumpolyakrylaatti, jolla oli korkeampi polydispersitetti-indeksi. Tämän vuoksi natriumpolyakrylaatti, jolla oli matala polydispersiteetti-indeksi, valittiin nanojauhatuskokeisiin. Kokeissa CaCO3-partikkelit saatiin jauhettua 26 nm kokoon, joka on pienin koskaan aiemmin jauhamalla saavutettu koko CaCO3-partikkeleille.