Dissertationen zum Thema „Process fluids“

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2001.
Current methods for wax fractionation result in products with large polydispersity, and due to the high temperatures required, thermal degradation of the wax is often incurred. The need for an alternative process thus exists. The purpose of this project is to investigate the technical viability of supercritical fluid processing as an alternative wax fractionation technology. The main aims of this project are to select a suitable supercritical solvent, to conduct binary phase equilibrium experiments, to determine if the process is technically viable and to investigate the ability of various equations of state to correlate the phase equilibrium data. Based on limited data from the literature, propane and a propane rich LPG (Liquefied Petroleum Gas) were selected as suitable solvents. Literature data for propane and high molecular weight alkanes is scares and incomplete, thus necessitating experimental measurements. A phase equilibrium cell was designed, constructed and commissioned. The cell was designed for pressures up to 500 bar and temperatures to 200 oC, and with the aid of an endoscope, the phase transitions were detected visually. The measurements correspond well to literature values from reliable research groups. Phase equilibrium data sets for propane with nC32, nC36, nC38, nC40, nC44, nC46, nC54 and nC60 as well as LP Gas with nC36 were measured. At temperatures just above the melting point of the alkanes, the phase transition pressures can be considered to be moderate, which will positively impact the economics of the process. The phase transition pressure increases with increasing carbon number, the relationship being found to be linear when the pressure is plotted as a function of carbon number at constant mass fractions and temperature. The increase in phase transition pressure with increasing carbon number indicates that the solvent will be able to selectively fractionate the wax. At higher temperatures the gradient of the line is larger and may thus lead to improved selectivity. The higher temperatures will also lead to better mass transfer. The linear relationship indicates that limited extrapolation to higher carbon numbers may be possible. However, this needs to be verified experimentally. The inability to measure the critical point and vapour pressure curves of the higher molecular weight normal alkanes, as well as the inability of cubic equations of state to predict liquid volumes and to capture the chain specific effects such as internal rotations, results in cubic equations of state requiring large interaction parameters to fit the data. The alternative, statistical mechanical equations of state, have difficulty in predicting the critical point of the solvent correctly and thus overpredicts the mixture critical point, yet require smaller interaction parameters to fit the data. Further work is required to improve the predictability of these non-cubic equations of state. This project has proven that wax fractionation by supercritical extraction with propane is technically feasible.

Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003.
Includes bibliographical references (leaves 106-114). Also available in electronic version. Access restricted to campus users.

Stable suspensions of superparamagnetic cobalt nanoparticles have been prepared in poly(dimethysiloxane) (PDMS) carrier fluids in the presence of poly[dimethylsiloxane-b-(3-cyanopropyl)methylsiloxane-b-dimethylsiloxane] (PDMS-PCPMS-PDMS) triblock copolymers as steric stabilizers. A series of the polysiloxane triblock copolymers with systematically varied molecular weights were prepared via anionic polymerization using LiOH as an initiator. These copolymers formed micelles in toluene or poly(dimethylsiloxane) (PDMS) carrier fluids and served as â nanoreactorsâ for thermal decomposition of the Co2(CO)8 precursor. The nitrile groups on the PCPMS central blocks are thought to coordinate onto the particle surface, while the PDMS endblocks protrude into the reaction medium to provide steric stability. The particle size can be controlled by adjusting the cobalt to copolymer ratio. Ordered self-assemblies of these cobalt nanoparticles are observed when the dispersions are cast from toluene. Electron diffraction spectroscopy reveals that the cobalt nanoparticles have fcc crystal structures. TEM shows non-aggregated cobalt nanoparticles with narrow size distributions, which are evenly surrounded with copolymer sheaths. However, some degree of surface oxidation was observed over time, resulting in a decrease in magnetic susceptibility. Novel poly[dimethylsiloxane-b-methyltriethoxysilylsiloxane-b-(3-cyanopropyl) methylsiloxane-b-methyltriethoxysilylsiloxane-b-dimethylsiloxane] (PDMS-PMTEOS-PCPMS-PMTEOS-PDMS) pentablock terpolymers were prepared. These terpolymers could fill the dual role both as steric stabilizers for preparing stable cobalt nanoparticle dispersions and precursors for the particle coating process. Silica films coated on the particles surfaces were employed to prevent the surface oxidation of the nanoparticles. Specific saturation magnetic measurement indicates that coating the nanoparticles with silica thin films can effectively inhibit the oxidation process.
Ph. D.

Durante o processo metalúrgico de usinagem de uma peça ocorre a geração de calor proveniente do atrito ferramenta/peça e cavaco/ferramenta. Para que ocorra uma menor geração de calor possibilitando o manuseio, bem como a minimização na deformação da peça, utilizam-se fluidos, que são soluções lubrificantes à base de óleos, água ou polímeros, podendo ser sintéticos ou não, diminuindo, assim, o coeficiente de atrito reduzindo-se a quantidade de calor gerado no processo. Há uma grande variedade de fluidos de corte disponíveis no mercado que são constituídos por diversos compostos como: aminas, compostos clorados e/ou aromáticos, glicóis, nitrosaminas além da presença de metais provenientes do processo de manufatura, portanto, sem tratamento, não podem ser lançados na rede de esgoto convencional. Atualmente não há um método de tratamento para os fluidos de corte nas indústrias. Nesse contexto, propõe-se um estudo sobre a viabilidade dos tipos de tratamento dos fluidos de corte para uma disposição adequada. Os processos de tratamento propostos neste trabalho compreendem hidrolise ácida e Processo Oxidativo Avançado (POA), mais especificamente, Sistema Fenton, além de propor um tratamento baseado na fotodegradação. A caracterização do fluido antes e após seu tratamento foi realizada por técnicas analíticas e espectrométricas. Os processos oxidativos mostraram-se satisfatórios para o tratamento dos efluentes, reduzindo os níveis de contaminantes aos permitidos pela legislação. O processo foto-Fenton mostrou-se mais eficiente que o processo Fenton na degradação de todos os parâmetros avaliados, incluindo BTEX e HPAs. Os processos de hidrólise ácida não apresentaram resultados satisfatórios, reduzindo apenas os metais aos níveis permitidos para descarte.
During the cutting process, part of the heat generation results from tool-part and chip-tool friction. So that it happens a smaller generation of heat making possible the handling, as well as minimization in the tool deformation, cutting fluids are used, that are the oils base, water or polymeric lubricating solutions, could be synthetic or no, decreasing the attrition coefficient being reduced the amount of heat generated in the process. There is a great variety of cutting fluids that are constituted for several composed as: amines, chlorinated and/or aromatic composed, glycols and nitrosamines besides the presence of metals proceeding of manufacture process, therefore, without a treatment, they cannot be discarded in the conventional sewerage system. At the moment there isn\'t a treatment method for the cut fluids in the industries. In that context, intends a study about the viability types of cutting fluids treatment for appropriate disposition. Treatment processes proposed in this work understand acid hydrolysis and Advanced Oxidative Process (AOP), more specifically, Fenton System, in addition proposing a treatment based on the photodegradation (photo-Fenton process). The characterization of fluid before and after treatment it was accomplished by analytical and spectrometry techniques. Oxidative processes were exposed satisfactory for cutting fluids treatment, reducing the levels of pollutants to the allowed by the legislation. Photo-Fenton process was shown more efficient than Fenton process in the oxidation of BTEX and PAHs. Acid hydrolysis processes didn\'t present satisfactory results, just reducing the metals at the levels allowed for discard.

The purpose of this thesis was to develop methods suitable for the incorporation of drug substancessuch as proteins into microparticles intended for controlled release. In particular a novel techniquefor the preparation of microparticles using supercritical fluids was investigated.

Supercritical fluids offer a considerable promise as extraction media for the formation ofmicroparticles of drugs and pharmaceutical excipients. There are two main reasons for using this technique. Firstly, the selective solvating power of supercritical fluids makes it possible to separatea particular component from a multi-component mixture. Secondly, the favourable mass transfer properties and high solubility of solvent in supercritical fluid make the formation of the microparticles rapid and efficient.

The Solution Enhanced Dispersion by Supercritical fluids process (SEDS) was used for the production of microparticles from several different biodegradable polymers. Briefly, particles were formed by the extraction of solvent from a solution which was sprayed into a supercritical fluid.

The use of a combination of supercritical N₂ and CO₂ in the SEDS process, improved the dispersion of polymer solutions, as compared with CO₂ alone. This resulted in reduction of the particle size of discrete microparticles produced from amorphous biodegradable polymers. Proteins (lysozyme and urease) were successfully incorporated into the poly(d,l-lactide-co-glycolide): copolymer composition 50:50 (DL-PLG) microparticles. The particles showed high entrapment efficiencies and the incorporated proteins retained a high degree of biological activity. Compared with conventional technologies for the preparation of such drug delivery systems, e.g. solvent-evaporation emulsion techniques, this new technique is environmentally superior, and suitable for up-scaling. Moreover the higher degree of control as indicated by the high reproducibility, makes validation of the process feasible. In conclusion, the SEDS process is an attractive way of incorporating proteins and peptides into biodegradable microparticles for controlled release.

The demand for high performance electronic devices is ever increasing in today's world with advent of digital technology in every field. In order to support this fast paced growth and incursion of digital technology in society, smarter, smaller integrated circuits are required at a lower cost. This primary requirement drives semiconductor industries towards the integration of larger number of smaller transistors on a given circuit area. The past decades have seen a rapid evolution of material processing and fabrication techniques, as focus shifts from submicron to sub-nanometer length scales in device configuration. As the functional feature size of an integrated circuit decreases, the threshold of defect causing impurities rises drastically. Huge amount of resources are spent in downstream and upstream processing in order to restore system from contamination upsets and in the upkeep of Ultra-High-Purity (UHP) process streams to meet these stringent requirements. Contamination once introduced into the system also drastically reduces process yield and throughput resulting in huge losses in revenue. Regular UHP fluid distribution system maintenance as well as restorative operations involve a purging operation typically known as Steady State Purge (SSP). This purge operation involves large amount of expensive UHP gas and time. Depending on the scale of the system and type of process involved this results in significant tool, process downtimes and can have a wide range of environment, health and safety (ESH) ramifications. A novel purge process, referred to as Pressure Cyclic Purge (PCP) was studied for establishing gas phase contamination control in UHP applications. In understanding the basic mechanism of this technique and to analyze its extent of application in aiding purging operations, a coupled approach involving experimental investigation and computational process modelling was used. Representative and generic distribution sections such as main supply lines and sections with laterals were contaminated with a known amount of moisture as impurity. The dynamics of the impurity transport through the system from purging with SSP as well as PCP was captured by a highly sensitive analyzer. The surface interactions between the moisture and EPSS were characterized in terms of adsorption and desorption rate constants and surface site density. A computational process model trained using experimental data was then validated and used to study the steady and cyclic purge mechanisms and predict complex purge scenarios. Industrially relevant and applicable boundary conditions and system definitions were used to increases the utility of the computational tool. Although SSP compared closely with PCP on simple systems without laterals, a drastic difference in dry-down efficiency was noticed in systems with dead volumes in the form of capped laterals. Studies on system design parameters revealed that the disparity in performance was observed to increase with larger number and surface area of dead volumes, opening a path to critical understanding of the differences in process mechanisms. Beneficial transient pressure gradient induced convective flow in the dead volumes during cyclic purge was identified to be the main factor driving the enhanced dry down rate. Similar trends were observed on using surface concentration as the purge metric. Hybrid purge schemes involving a combination of SSP and PCP were found to yield higher benefit in terms of efficient use of purge gas. Removal of strongly interacting contaminant species showed a higher benefit from use of controlled PCP scheme. Although, parametric analysis carried out on the operating factors of cyclic purge suggested that the enhancement in dry down increased with higher pressure range, it was highly conditional towards configurational factors in design and operation such as system dimensions, holding time, cycling pattern, valve loss coefficients and the complex inter coupling between them. The robustness of the process simulator allows the development of optimal purge scenarios for a given set of system parameters in order to perform a controlled purge. The benefit of using a hybrid PCP scheme was evaluated in terms of UHP purge gas and process time as a function of purity baseline required. Apart from UHP gas distribution systems, process vessels, chambers and components along the process stream are also prone to molecular contamination and pose a threat to product integrity. The dead volumes acting as areas of contaminant accumulation represent cavities or dead spaces in flow control elements such as mass flow controllers (MFCs), gauges, valves or dead spaces in process chambers. Steady purge has very little effect in cleanup of such areas and more efficient methods are necessitated to raise purge efficiency. The analysis of application of PCP is extended to such components through the development of a robust and comprehensive process simulator. The computational model applies a three dimensional physical model to analyze purge scenarios with steady and cyclic purge. The results presented pertain to any generic gas phase contaminant and electronic grade steel surfaces. Close investigation of the purge process helped elaborate the cleaning mechanism. Critical steps driving the purge process were identified as - dilution of chamber by introduction of fresh gas during re-pressurization and chamber venting during depressurization. Surface and gas phase purging of chambers with dead spaces using steady and cyclic purge were studied and compared. Cyclic purge exhibited a higher rate of dry down. The effect of system, design and purge operating parameters on surface cleaning were studied. Although higher frequency cycles and larger operating pressure ranges optimized for a given geometry are found to deliver better pressure cyclic purge (PCP) performances, the benefit is found to be contingent to a strong interplay between system parameters. PCP is found to be advantageous than steady state purge (SSP) in terms of purge gas usage and operation time in reaching a certain purity baseline. Specialty process gases supplied to the fabrication facility are typically stored in the form of liquids in enormous tanks outside the fab. Ammonia is a widely used in UHP concentrations for a variety of process including epitaxial growth, MOCVD, etching and wet processes in the semiconductor industry. The recent development in LED research has risen the demand and supply for Ammonia based compounds. Stringent baselines are maintained for the impurities associated with the manufacturing of such gases (e.g. Moisture in Ammonia). Apart from the difference in the rates of evaporation of the individual species from the storage cylinder causing accumulation of slower evaporating species, external temperature fluctuations also generate unsteady flux of desired species. When concentrations rise above this threshold additional purification or in most cases discarding large volumes of unused gas is warranted, causing loss of resources and causing ESH issues. Bulk gases are usually delivered over long lengths of large diameter pipes which produce large density of adsorption sites for contaminants to accumulate and eventually release into the gas stream. In order to establish contamination control in the gas delivery system, the surface interactions of the multispecies system with the delivery line surface was characterized. Desired concentrations of moisture in ammonia and UHP nitrogen mixtures were produced in a gas mixing section capable of delivering controlled mass flow rates to an EPSS test bed. Transient moisture profiles during adsorption and desorption tests at various test bed temperatures, mass flow rates and moisture concentration were captured by a highly sensitive analyzer. A mathematical model for single and multi-species adsorption was used in conjunction with experimental data to determinate kinetics parameters for moisture, ammonia system in EPSS surface. The results indicate competitive site binding on EPSS between ammonia and water molecules. Also, the concentration distribution of each species between surface, gas phase is interdependent and in accordance to the kinetic parameters evaluated. Back diffusion of impurity is a major source of contaminant introduction into UHP streams. Back diffusion refers to the transport of contaminants against the flow of bulk process stream. Molecular species can back diffuse from dead volumes, during mixing operations etc., simply when there is a gradient of concentration. A steady state approach was used to analyze the mechanism and effects of various geometrical and operational parameters on back diffusion. High sensitivity moisture detectors were used to capture the dynamics of contamination in a section of a generic distribution system. Results showed that back diffusion can occur through VCR fittings, joints and valves under constant purge. General trends on the effect of design parameters on back diffusion were derived from studies on various orifice sizes, system dimensions, flow rates and test moisture concentrations. Coupled parametric studies helped identify critical variable groups to perform dimensionless analysis on back diffusion of moisture. Crucial points where back diffusion can be minimized or completely eliminated are identified to help set up guidelines for cyclic and steady purge parameters without excessive use of expensive UHP gas or installation of unnecessarily large factors of safety. Wet cleaning of micro/nano sized features is a highly frequent process step in the semiconductor industry. The operation is a huge consumer of ultra-pure water and one of the main areas where process time minimization is focused. Comprehensive process model is developed to simulate the mechanism and capture the dynamics of rinsing high aspect ratio Silicon features in the nanometer scale. Rinsing of model trench, post etch contaminated with ammonium residue is studied. Mass transport mechanisms such as convection, diffusion are coupled with surface processes like adsorption and desorption. The effect of charged species on the trench surface and in the bulk, the resultant induced electric field on the rinse dynamics and decay of surface species concentration is studied. General rinsing trends and critical points in change in mechanisms were identified with critical groups such as mass transfer coefficient and desorption coefficient. The model is useful in evaluating process efficiency in terms of rinse time and DI water consumption under varying process temperature, contaminant concentration, and rinse fluid flow rate. The generic build of the model allows extension of its functionality to other impurity-substrate material couples.

Thesis (PhD)--University of Stellenbosch, 2004.
ENGLISH ABSTRACT: In this study an equation of state has been developed for the specific purpose of representing systems of simple non-polar spherical and chain-like components and their mixtures for practical applications. To be applied in engineering calculations, the model has to be accurate, be able to represent mixtures with large size asymmetry without the use large binary interaction parameters, and be mathematically simple enough to ensure rapid computations. The model is developed through a sequential evaluation of the statistical mechanical theory of particles and the various approaches available to extend it to real fluid systems. The equation of state developed in this work models the real fluid systems as interacting with a highly simplified two step potential model. The repulsive interactions are represented by a newly developed simplified form of the hard sphere equation of state, capable of representing the known hard sphere virial coefficients and phase behaviour to a high degree of accuracy. This equation has a realistic closest packed limiting density in between the idealised hard sphere fluid random and crystal structure limits. The attractive interactions between the particles are incorporated into the model through a perturbation expansion represented in the form of a double summation perturbation approximation. The perturbation matrix was optimised to have the lowest order in density necessary to still be able to accurately represent real fluid properties. In a novel approach to obtain simple mixing rules that result in the theoretically correct second virial coefficient composition dependence, the perturbation matrix is constrained in such a manner that only the first perturbation term has a term that is first order in density. From a detailed evaluation of the various methods available to represent chain-like non-spherical systems it was finally concluded that the Perturbed Hard Chain Theory provided an ideal compromise between model simplicity and accuracy, and this method is used to extend the equation to chain-like systems. Finally the model is extended to fluid mixtures by uniquely developed mixing rules resulting in the correct mixture composition dependence both at low and high system densities. The newly developed equation of state is shown to be capable of representing the pure component systems to a comparable degree of accuracy as the generally applied equations of state for non-spherical systems found in the literature. The proposed equation is furthermore also shown equal or improve on the predictive ability of these models in the representation offluid mixtures consisting out of similar chainlike or size and energetic asymmetric components. Finally, the computational time required to model the behaviour of large multi-component fluid mixtures using the new equation of state is significantly shorter that that of the other semi-empirical equations of state currently available in the literature.
AFRIKAANSE OPSOMMING: Hierdie werkstuk behels die ontwikkeling van ‘n toestandsvergelyking wat spesifiek gerig is op toepassings in alledaagse, praktiese ingenieurstipe berekeninge en daartoe instaat is om sisteme bestaande uit nie-polêre spferiese- en ketting-tipe komponente en hulle mengsels teKettingteorie (PHCT) die mees geskikde metode is vir hierdie doel en is op die vergelyking toegepas. As ‘n laaste stap in die toestandsvergelykingontwikkelling is daar mengreëls ontwikkel vir die vergelyking wat die korrekte samestellingsafhanklikheid toon vir beide die lae en hoë digtheidskondisies. Die model wat in hierdie studie ontwikkel is, is met verskeie ander bekende toestandsvergelykings, wat daartoe instaat is om nie-spferiese sisteme te modelleer, vergelyk en daar is gevind dat die nuwe model daartoe instaat is om suiwer sisteme net so goed as die bestaande vergelykings te modelleer. Verder is daar ook gevind dat die nuwe vergelyking die modellering van verskeie mensels van kettingtipe komponente en komponente van uiteenlopende groottes of interaksie energieë kan ewenaar of verbeter. Laastens is daar ook gevind dat die tyd nodig vir die modellering van die termodinamiese gedrag van mengsels van ‘n groot hoeveelheid komponente aansienlik korter is vir die nuwe model as die ander bekende semi-empiriese vergelykings. kan beskyf. Om aan hierdie vereistes te voldoen moet die toestandsvergelyking die relevante sisteme akkuraat kan modelleer, slegs klein interaksie parameters benodig om mengsels van komponente met groot verskille in molekulêre groottes akkuraat voor te stel en steeds wiskundig eenvoudig genoeg wees om vinnige berekeninge te verseker. Die vergelyking is ontwikkel deur ‘n sistematiese evaluering van die statisitiese meganiese teorie van partikels en die verskillende metodes om hierdie teorië op werklike sisteme toe te pas. Die toestandsvergelyking beskryf die intermolekulêre interaksie tussen die verskillende komponente met ‘n hoogs vereenvoudigde twee-stap interaksie potensiaal model. Die afstotende kragte tussen die komponente word in ag geneem deur ‘n nuwe vergelyking wat ontwikkel is om die gedrag van ‘n ideale harde spfeer sisteem te modelleer. Hierdie hardespfeermodel is daartoe instaat om die viriale koeffisiënte en die fase gedrag van teoretiese harde spfeer sisteme akkuraat te modelleer, en het ‘n maksimum digtheidslimiet wat tussen teoretiese waardes van ‘n perfek geordende en nie-geordende harde spheer sisteem lê. Die aantrekkinskragte tussen die partikels word beskou as ‘n perturbasie van die harde-spheer vergelyking. ‘n Term bestaande uit ‘n dubbelle sommasiefunksie word gebruik om hierdie perturbasie uitbreiding voor te stel. Die sommasie term is geoptimiseer sodat die finale toestandsvergelyking die laagste digtheidsgraad het wat steeds tot ‘n akkurate voorstelling van die termodinamiese gedrag van werklike sisteme lei. Die sommasiefunksie is so gespesifiseer dat die eerste term van die perturbasie uitbreiding slegs ‘n eerste graadse orde in digtheid het in ‘n unieke benadering om te verseker dat die mengreëls van die toestandsvergelyking die teoreties korrekte samestellingafhanklikheid van die mengselvirialekoeffisiente tot gevolg het. ‘n Deeglike ondersoek van die verskillende metodes om die toepassing van die toestandsvergelyking uit te brei tot die moddellering van nie-spheriese ketting-tipe molekules is gedoen en daar is uiteindelik tot die gevolgtrekking gekom dat die Geperturbeerde Harde

The reason for the writing of this doctoral thesis arises from the commitment adopted by COMEXI in order to put its products in the market making his products more sustainable and environmentally friendly. Is in this process of continuous improvement that the company has set the goal to reduce the energy consumption of the flexographic presses, rotogravure presses as well as laminators. All these machines have in common that all of them have a drying system mainly based on forced convection drying, whose consumption can reach values near to 60% of total machine’s consumption. The drying process consists on evaporating the solvent (the more commonly used are acetates, alcohols or water), whose function is to facilitate the application of pigments and resins over the substrate to be printed. The main focus of this work has been put on the study of the drying system between drying decks on a flexographic printer. The improvement and redesign process has been based on achieving an uniform speed distribution all over the length nozzle, as well as improving the balance of the drying deck (reduce the suction flow necessary to collect all the air that is fed into each screen). The redesign process of the screen has been based on experimental measurements made in the available designs of current screens, and their validation by means of CFD simulations done in OpenFOAM. The final design is achieved by using CFD simulations until the obtained results are the expected according to the requirements
La motivació per a la redacció d'aquesta tesi doctoral neix de la voluntat de COMEXI de posicionar els seus productes en el mercat fent que aquests siguin més sostenibles i respectuosos amb el medi ambient. Tot seguint aquest compromís, es pretén reduir el consum energètic de les impressores flexogràfiques, impressores de rotogravat o laminadores, a les quals el consum energètic corresponent al sistema d'assecatge pot arribar a valors de l'ordre del 60% del consum energètic total de la màquina. El procés d'assecatge de les màquines consisteix en evaporar la quantitat de solvent (habitualment acetats, alcohols o bé aigua) contingut en la tinta que s'utilitza durant el procés d'impressió, la funció del qual és facilitar l'aplicació de pigments i resines sobre el substrat que es desitja imprimir. L'atenció principal d'aquest treball s'ha focalitzat en la millora de les pantalles d'assecatge entre tinters d'una impressora flexogràfica, en el sentit d'aconseguir una major uniformitat en la distribució de la velocitat a la sortida del llavi de la pantalla, així com millorar-ne també el seu balanç (abaixar la quantitat d'aire que cal aspirar per recollir tot l'aire que s'impulsa). El procés de redisseny es basa en la caracterització experimental del comportament de les pantalles d'assecatge actuals, la seva validació i ajust del model mitjançant simulació CFD amb el software OpenFOAM i la posterior millora del disseny a través de simulacions CFD fins assolir un concepte que proporcioni els requeriments exigits
Programa de Doctorat en Tecnologia

Le conditionnement, opération unitaire clé du processus industriel de fabrication des produits fromagers, consiste à remplir par un jet de façon homogène des emballages de formes variées par des produits à propriétés rhéologiques complexes tout en assurant des cadences optimisées. L’objectif de cette étude est de prédire le remplissage d’un emballage, à partir de la connaissance de la rhéologie des produits et des paramètres opératoires pour le dimensionnement de nouveaux procédés de conditionnement ou l’optimisation de procédés existants.Nécessaire à la poursuite de l’étude, le comportement rhéologique des produits fromagers dans les domaines de sollicitation du procédé à 80°C a été caractérisé comme rhéofluidifiant, à seuil de contrainte, élastique en-dessous et au-dessus du seuil d’écoulement.L’hydrodynamique des jets et du remplissage lors du conditionnement a été étudiée avec trois types de produits grâce au pilote à l’échelle laboratoire du procédé, dimensionné pour reproduire les conditions opératoires industrielles. Après avoir vérifié la cohérence des résultats obtenus avec le dispositif expérimental avec ceux de la littérature pour un fluide newtonien, l’étude s’est portée sur des fluides modèles viscoplastiques, gels de Carbopol®, et sur des produits fromagers.Cinq régimes d’écoulement ont été observés et caractérisés à partir des évolutions du diamètre de jet et de la vitesse d’atteinte des bords pendant le remplissage et de la hauteur de motte finale du dépôt après le remplissage, paramètre décisif de la qualité du conditionnement. Des diagrammes de fonctionnement adimensionnels d’observation des régimes ont été déterminés à partir des forces en jeu dans le système. Ainsi, le régime d’écoulement peut être prédit par ces diagrammes à partir des propriétés rhéologiques du produit et des paramètres géométriques et opératoires du procédé
Packaging is a key step of cheese products industrial manufacturing process. It consists in filling containers of various shapes with non-Newtonian products while ensuring optimized rates. The aim of the present work is to describe the influence of cheese rheological properties as well as process parameters onto packaging, thereby contributing towards its optimization.Necessary for the study, the rheological behavior of cheese products on the process stress range at 80°C has been identified as shear-thinning with a yield stress, with elasticity both below and above the yield stress.Jets and filling hydrodynamics during packaging have been studied with three types of products by the means of the laboratory-scale process pilot, which is able to reproduce the industrial process conditions. After checking for consistency between experimental and litterature results for Newtonian products, the study focused on viscoplastic model fluids, Carbopol® hydrogels, and on cheeses.Five flow patterns have been observed and characterized through jet diameter, spread velocity during filling and final mound height after filling, which is a key factor of the packaging quality. Flow patterns dimensionless distributions have been determined from the forces involved in the system. Thus, the flow pattern can be predicted thanks to theses distributions from product rheological properties and geometrical and process parameters

Orientador: Marcos Akira d'Ávila
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica
Made available in DSpace on 2018-08-22T01:11:51Z (GMT). No. of bitstreams: 1 Lima_NicolaoCerqueira_M.pdf: 2608433 bytes, checksum: 1f09fc99d86a78b7861be6972463c29c (MD5) Previous issue date: 2013
Resumo: A eletrohidrodinâmica trata basicamente dos efeitos de um campo elétrico em meios contínuos. Um fluido sob o efeito de um campo elétrico tende a se deformar devido a uma força elétrica que age sobre ele. Essa força elétrica é consequência de alguns fatores que têm como base as próprias propriedades do fluido. Entre elas estão à condutividade elétrica (capacidade do fluido de ionizar-se ou de conduzir corrente elétrica) e a permissividade elétrica (capacidade do fluido de polarizar-se). Diversos processos que utilizam efeitos elétricos em fluidos foram desenvolvidos nas últimas décadas. O fato de estes processos envolverem uma alta complexidade de parâmetros faz com que seja consumido bastante tempo e material durante a fase de testes. Por esse motivo, as simulações numéricas passaram a ser uma boa alternativa para otimizar tais processos, além de aumentar o conhecimento sobre eles. Nesse contexto, no presente trabalho foi implementado um código numérico (solver) no pacote de CFD OpenFOAM baseado no modelo para fluidos pouco condutores (leaky dieletric model) no intuito de descrever escoamentos eletrohidrodinâmicos. Entre eles estão o efeito de um campo elétrico em uma gota condutora e o afinamento de um jato na saída de um tubo capilar. Eventualmente, em processos eletrohidrodinâmicos, são utilizados polímeros. Entretanto, não há na literatura muitos estudos sobre a simulação de escoamentos eletrohidrodinâmicos utilizando fluidos viscoelásticos. Assim, um segundo código foi implementado, baseado em um código já existente. Este é capaz de simular efeitos elétricos em fluidos viscoelásticos, utilizando a equação constitutiva de Giesekus como modelo viscoelástico. Os resultados obtidos para a deformação da gota condutora foram comparados com resultados analíticos para fluidos newtonianos e com observações experimentais para fluidos viscoelásticos. Para o caso do jato na saída de um tubo capilar, ambos os tipos de fluidos (newtonianos e viscoelásticos) foram comparados com resultados experimentais e teóricos
Abstract: Electrohydrodynamics deals basically on the effects of an electric field on a continuum media. A fluid under the effect of an electric field tends to deform due to an electric force that acts on it. This electric force is a consequence of some factors which are based on the fluid properties, including the electric conductivity (ability of the fluid to ionize or to conduct electrical current) and the permittivity (ability of the fluid to polarize). Many processes using electrical effects in fluids have been developed in recent decades. The fact that these processes involve a high complexity of parameters, it consumes time and materials during the test phase. For that reason, the numerical simulations start being a good alternative to optimize such processes, and also to increase the knowledge about them. In this context, on the present work was implemented a solver on the open CFD software OpenFOAM, based on the leaky dielectric model, in order to describe electrohydrodynamic flows. Among them, are the effect of an electric field on a conducting droplet and the thinning of a jet on the exit of a nozzle. Eventually, in electrohydrodynamic processes, polymers are used. However, there aren't many studies about electrohydrodynamic flow simulation using viscoelastic fluids. So, a second solver was made, based on another existing solver. This second solver is able to simulate electric effects on viscoelastc fluids, using the Giesekus model as a constitutive equation. The results of the deformation of a conducting droplet were compared to analytical results, for Newtonian fluids, and with experimental observations, for viscoelastic ones. As for the jet, both types of fluids, Newtonians and viscoelastics, were compared to experimental and theoretical results
Mestrado
Materiais e Processos de Fabricação
Mestre em Engenharia Mecânica

L'objectif est d'élaborer un nouveau procédé de fabrication de mousses métalliques par voie de fonderie en modélisant l'infiltration et la solidification d'un métal liquide dans un milieu poreux. La modélisation est faite en deux étapes.Tout d'abord, à l'échelle locale un brin de la mousse métallique est considéré comme un tube capillaire et l'infiltration et solidification d'un métal liquide dans un moule cylindrique est étudiée. Deuxièmement,le modèle macroscopique de la solidification diffusive d'un métal liquide dans un milieu poreux est obtenu par prise de moyenne volumique. Le modèle local est codée dans un outil CFD opensource et trois études paramétriques ont été faites permettant la détermination des relations de la longueur et le temps d'infiltration en fonction de paramètres de fonctionnement. La modélisation de la solidification d’un métal liquide dans un milieu poreux est simplifié en considérant que le moule est complètement saturé par un métal liquide au repos,par suite la solidification se produit par diffusion pure (pas de convection). L'équilibre thermique local (LTE) est considéré entre les phases solide et liquide du métal tandis qu'un non équilibre thermique local (LTNE) est retenue entre la phase métallique et le moule. Les problèmes de fermeture associés ainsi que le problème macroscopique ont été résolus numériquement
The objective of this work is to elaborate a new manufacturing process of metal foams via casting by modelling the infiltration and solidification of liquid metal inside a porous medium.However, due to the complexity of this problem the study is divided into two steps. First, at local scale one strut of the metal foam is considered as a capillary tube and the infiltration and solidification of liquid metal inside a cylindrical mould is studied. Second, a macroscopic model of diffusive solidification is derived using the volume average method. The local model is coded in an open source CFD tool and three parametric studies were done where the relations between the infiltration length and time as function of the operating parameters are determined. The modelling of the solidification of liquid metal inside a porous medium is simplified by considering that the mould is fully saturated by liquid metal at rest, solidification occurs by pure diffusion. Local thermal equilibrium (LTE) is considered between the solid and liquid phases of the metal while local thermal non equilibrium (LTNE) is retained between the metallic mixture and the mould. The associated closure problems as well as the macroscopic problem were numerically solved

Metalworking fluids (MWFs) are petroleum emulsions employed for metal machining processes as coolants and lubricants. To date, they have been irreplaceable in modern heavy and manufacturing industries, with annual usage exceeding two billion litres worldwide. However, the large amount of MWFs, the highly concentrated complex recalcitrant and toxic petroleum components contained in them continue to cause significant concern in terms of sustainable routes of end-of-life treatment and disposal. Compared with other treatment methods, the anaerobic treatment method has significant advantages, such as the low capital, operating and maintenance costs and energy recovery. This latter factor has the potential benefit of generating bio-energy from waste organic matter whilst aerobic route leads to CO₂ emission. However, the bio-toxicity of MWFs is a huge challenge in terms of employing bio-treatment of waste MWFs. In this study, the anaerobic biodegradability of a typical MWF was investigated employing an activated sludge experimental system. Furthermore, the toxic effects of the MWF on the anaerobic ecosystem, particularly on methanogen species, were investigated using bio-molecular analytical methods and a biosensor. In order to overcome its toxicity, the indigenous anaerobic bacteria isolated from spent MWFs were employed in the treatment of the MWF since they were assumed to be acclimated to the conditions. The major findings include: (1) approximately 80% of the MWF (5,000mgCOD/L) was found to be anaerobically biodegradable, with around 35% of the biodegraded COD could be converted to methane; (2) the MWF appeared to be toxic to the anaerobic ecosystem, especially to methanogen species; and (3) however, treatment employing the anaerobic bacteria successfully reduced the toxicity of the MWF and enhanced the methane production in the process.

Transformers are electrical devices used in practice to increase or decrease voltages. Transformers are of various sizes and used mainly in power distribution. To provide cooling and insulation, transformer oils are used together with cellulose that acts as a solid insulation. The most common type of transformer oil is mineral oil and is a product derived from the refining of crude oil. Its low cost and good compatibility with cellulose are two factors that have led to its predominant position as the common transformer oil. There are also synthetic ester based transformer oils, and following an increased interest in environmentally friendly products, transformer oils made from natural esters such as sunflower, soybean and rapeseed. Mineral oil is not biodegradable and is deemed as hazardous waste. The ester based oils are biodegradable and promoted as a more environmentally friendly alternative to mineral oil. In this thesis, the possibility of re-refining used mineral transformer oil is assessed from a financial perspective in the form of a business case and an LCA study has been done to compare the environmental impacts between ester based transformer oils and mineral based transformer oil. The results from the LCA study showed that from a cradle-to-gate perspective, mineral oil has a lower environmental impact than ester-based transformer oils. The re-refining of used mineral transformer oil further reduces the environmental impact. The results from the business case showed that a small scale re-refining facility is financially feasible but highly dependent on the supply and demand of used transformer oil. It is recommended to pursue further studies before making any decision. There is lack of data regarding the re-refining market in Eastern Europe and the accuracy of the LCA study can be further improved by having emissions data from re-refining used mineral transformer oil.
Transformatorer är elektriska komponenter som tillämpas vid spänningsregleringar. Dessa transformatorer har olika storlekar och används i eldistribution. Transformatorolja tillsammans med cellulosa används som elektrisk isolering och kylning av transformatorer. Den vanligaste typen av transformatorolja är mineralolja och är en produkt som erhålls vid raffinering av råolja. Dess låga kostnad och goda kompatibilitet med cellulosa är två faktorer som har lett till dess dominerande ställning. Det finns också syntetisk esterbaserad transformatorolja och efter ett ökat intresse för miljövänliga produkter så tillverkas även transformatoroljor av naturliga estrar så som solros, soja och raps. Mineralolja är inte nedbrytbar och anses vara farligt avfall. De esterbaserade oljorna är nedbrytbara och anses vara ett mer miljövänligt alternativ till mineralolja. I denna rapport utvärderades möjligheten till att återraffinera använd mineralolja ur ett ekonomiskt perspektiv i form av en affärsplan och en LCA-studie där esterbaserad olja och mineralolja har jämförts ur ett miljöperspektiv. Resultaten från LCA-studien visade att mineralolja från ett ”cradle-to-gate” perspektiv har en lägre miljöpåverkan än esterbaserade transformatoroljor. Återraffinering av använd mineralolja minskar dess miljöpåverkan ytterligare. Resultatet från affärsplanen visade att en småskalig återraffineringsanläggning är ekonomiskt hållbar men samtidigt väldigt beroende av utbud respektive efterfrågan på använd mineralolja. Det rekommenderas att göra en djupare analys innan man fattar ett beslut. Det finns brist på information med avseende på återraffineringsmarknaden i Östeuropa. Noggrannheten på LCA-studien kan förbättras ytterligare genom att emissionsdata från en återraffineringsanläggning är tillgänglig.

Wall-bounded turbulent flows such as plane Couette flow, channel, pipe flows and boundary layer flows are fundamental problem of interest that we often meet in many scientific and engineering situations. The goal of the present thesis is to investigate the origin of large-scale streaky motions observed in the wall-bounded turbulent flows. Under a hypothesis that the large-scale streaky motions sustain with a process similar to the well-known near-wall self-sustaining cycle, the present thesis have pursued on four separate subjects: (i) non-modal amplification of streaks, (ii) the secondary instability of the finite amplitude streaks, (iii) existence of a self-sustaining process at large scale and (iv) turbulent skin friction reduction by forcing streaks. First, using a linear model with turbulent mean flow and the related eddy viscosity, it is shown that the streaks are largely amplified by harmonic and stochastic forcing. The largely amplified streaks undergo the secondary instability and it has been associated with the formation of the large-scale motions (bulge). The existence of a self-sustaining process involving the amplification and instability of streaks at large scale is proved by quenching the smaller-scale energy carrying eddies in the near-wall and logarithmic regions. Finally, it is shown that artificially forcing of large-scale streaks reduce the turbulent skin friction up to 10\% by attenuating the near-wall streamwise vortices.

This thesis presents investigations into the design and synthesis of nanomaterials in supercritical carbon dioxide (sc-CO₂) as well as novel experimental design methodologies. First, the process-structure-property relationships are studied for the deposition of materials from organometallic precursors in sc-CO₂. The materials that were investigated in these studies were: (1) the semiconductor material copper zinc tin sulfide (Cu₂ZnSnS₄, or CZTS), which has application in solar energy capture; (2) zinc sulfide nanoparticles deposited onto carbon nanotubes, which have application in optoelectronics; and (3) silver nanoparticles deposited on silicon and glass wafer surfaces, which find application as biosensors via surface enhanced Raman spectroscopy. Next, two novel experimental design methodologies were implemented. The first is termed layers of experiment with adaptive combined design (LoE/ACD), which efficiently optimizes a process that is expensive and time consuming to study by zooming in on the process optimum through successive layers. The mean silver nanoparticle size was optimized as a function of temperature in the sc-CO₂ system using the LoE/ACD approach. The second experimental design methodology is called initial experimental design (IED). The IED methodology was developed to choose the first round of experiments for a system that is expensive to study (in terms of time and money), poorly understood, and possesses a related, non-identical system that is well-studied. The IED approach was used to optimize the mean iridium nanoparticle size as a function of temperature given expert opinion, prior data, and an engineering model for silver nanoparticles synthesized in sc-CO₂.

L’objectif de ce travail est d’étudier l’influence de jets d’impact libres utilisés comme mode de mise en contact des phases dans les procédés de recristallisation utilisant un fluide supercritique comme anti-solvant. L’influence des variations de plusieurs paramètres opératoires sur l’hydrodynamique des jets et sur les caractéristiques des poudres de Sulfathiazole a été étudiée. Les paramètres sont la vitesse des jets (de 0,25 m.s-1 à 25,92 m,s-1), le rapport molaire solvant/CO2 (de 2,5 % à 20 %), la température (de 313 K à 343 K), la pression (10 MPa à 20 MPa) et la concentration du soluté dans la solution (de 0,5 % à 1,8 %). Les conditions de mélange ont été caractérisées par l’estimation des puissances dissipées par les jets d’impact, variant de 0,1 à 158 W.kg-1 dans les conditions étudiées. Les résultats ont montré que la vitesse des jets et la sursaturation sont deux paramètres-clés contrôlant la cristallisation avec un effet prépondérant de la sursaturation. Les cristaux obtenus ont des tailles, distributions de taille, faciès et nature polymorphique différents selon les conditions. La forme polymorphique la plus stable a été obtenue pure ou en mélange. Une comparaison avec le procédé SAS classique a montré que les particules sont significativement plus petites lorsqu’elles sont cristallisées avec les jets d’impact, ce qui confirme que ce dispositif créant un mélange plus intense, permet d’accélérer la cinétique de nucléation.Ce travail devrait contribuer à une meilleure maîtrise des procédés de cristallisation en milieu supercritique
The aim of this work is to study the influence of free impinging jets used for the fluids’introduction in supercritical anti-solvent (SAS) processes. The influence of the variations of several operating parameters upon jets’ hydrodynamics and upon the powder characteristics is studied. Parameters are jets velocity (0.25 m.s-1 to 25.92 m.s-1), molar ratio solvent / CO2 (2.5 % to 20 %), temperature (313 K to 343 K), pressure (10 MPa to 20 MPa) and solute concentration in the organic solution (0.5 % to 1.8 %). Mixing conditions have been characterized estimating the dissipated powers of the impinging jets, varying from 0,1 à 158 W.kg-1 in the studied conditions. The results showed that jets velocity and supersaturation are two key-parameters controlling the crystallization with a preponderant effect of supersaturation. The obtained crystals have different size, particle size distribution, habit and polymorphic nature depending on the conditions. The most stable polymorphic form has been obtained pure or in mixture.A comparison with the classical SAS process showed that mean particle sizes are significantly smaller with impinging jets device proving that this device, creating a more efficient mixing, enhances the nucleation kinetics.This work may contribute to a better control of processes of crystallization in supercritical media

The main task of this work was to compare the being used process fluids in mechanical engineering with a focus on polymer and additive fluids. Selected polymer and nanoadditive fluids were compared based on a thread forming test, during which different concentrations of individual fluids were tested. All data from experiments were evaluated, assessed in terms of their properties, and recommended for further practice.

This doctoral thesis has integrated biological models (activated sludge models “ASM”) with simulation tools of computational fluid dynamics “CFD”, and has applied them to the design of two advanced technologies for wastewater treatment: “Microbial Fuel Cells” and the “Anammox” process. Wastewater treatments based on Microbial Fuel Cells use the catalytic bioelectrochemical activity of certain microorganisms to oxidise organic compounds and produce electricity without needing additional chemical compounds. In Anammox process (Anaerobic Ammonium Oxidation) microorganisms also play a main role in the autotrophic removal of nitrogen compounds.
Aquesta tesi doctoral ha integrat models biològics - en concret, models de fangs activats “ASM” amb eines de simulació de dinàmica de fluids computacional “CFD”, i les ha aplicat al disseny de dues tecnologies avançades per al tractament de les aigües residuals: les “Microbial Fuel Cells” o piles bioelectroquímiques i el procés “Anammox”. El sistemes de tractament d’aigües residuals basats en Microbial Fuel Cells aprofiten l’activitat catalítica bioelectroquímica de determinats microorganismes per oxidar compostos orgànics i produir electricitat sense necessitat d’addicionar compostos químics. També en el procés Anammox (Anaerobic Ammonium Oxidation) els protagonistes són els microorganismes, en aquest cas per eliminar de manera autotròfica compostos de nitrogen, i reduir així la quantitat de fangs generats i les necessitats d’aeració.

La trempe est une méthode de traitement thermique où un métal chaud est refroidi rapidement à l’aide d’un medium. Le but est de donner au métal une certaine microstructure afin d’atteindre les performances mécaniques requises. Ce procédé a des impacts directs sur l’évolution propriétés mécaniques, contrôle de la microstructure et libération des contraintes résiduelles. Afin de réaliser un procédé optimal, il est essentiel de contrôler correctement les transformations de phase qui ont lieu dans l’alliage, et ainsi obtenir la microstructure présentant les propriétés thermomécaniques souhaitées. Cette thèse est réalisée en collaboration avec la société Linamar Montupet spécialisée dans la fabrication de composants en aluminium pour l’industrie automobile. Ils s’intéressent à la trempe des pièces métalliques dans les liquides pouvant vaporiser. La vaporisation est le principal phénomène qui anime le système. L’objectif de cette thèse est donc de définir un cadre numérique capable de simuler le procédé de trempe à l’échelle industrielle. Différents aspects seront étudiés: (i) analyser et simuler les interactions liquide-vapeur-solide avec changement de phase, (ii) simuler des interactions fluide-solide pour pouvoir prédire le comportement thermomécanique du solide. Les résultats des développements numériques seront validés par des confrontations avec les expériences proposées par le partenaire industriel
Quenching is a heat treatment method where a hot metal part is cooled down rapidly with the help of a quenchant. The purpose of such process is to give a certain microstructure to the metal in order to achieve the required mechanical performance. This process has direct impacts on changing mechanical properties, controlling microstructure and releasing residual stresses. Good control of quenching is essential for correctly controlling the phase changes that take place within the alloy, and obtain the microstructure exhibiting the desired thermomechanical properties. This Phd is done in collaboration with the company Linamar Montupet specialized in the manufacture of complex cast alumnium components for the automotive industry. They are interested in the quenching of metallic parts in liquid quenchants that can vaporize. The vaporizationis generally the leading phenomenon that drives the system. Indeed, the cooling of the part is strongly conditioned by the behavior of the surrounding fluid that extracts the heat therein.Thus, the objective of this thesis is to set a numerical framework able to simulate the quenching process at an industrial scale. In this thesis, different aspects will be studied: (i) analyze and simulate the liquid-vapor-solid interactions with phase change, (ii) simulate fluid-solid interactions to be able to predict the thermomechanical behavior of the solid. The results coming from these numerical development will be validated by confrontations with the experiments proposed in agreement with the industrial partner

A partir de três premissas essenciais para a apreensão e construção da Paisagem, entende-se o Sistema Paisagem como um organismo vivo, aberto e fluido. A introdução da categoria tempo, influenciou o processo de formulação imagética, de apreensão espacial, e também abriu diversas possibilidades de aproximação à Paisagem, enquanto Sistema Liquido, caracterizado pelos seus conteúdos particulares e pela sua permanente transformação. Optando por uma metodologia organicista, inclusiva de todas as possibilidades operativas, cruzam-se componentes ecológicas, figurais e processuais, identificando a matriz líquida, estruturante das transformações do Sistema Paisagem de Lisboa. O parcelamento e os movimentos de extensão e coesão, que promovem a fixação e a propulsão na Paisagem, são registos de uma matriz liquida, em que o principal motor e ativador transversal é o elemento água, determinante na diferenciação e consequente construção da Paisagem de Lisboa; ABSTRACT: LANDSCAPE LIQUID SYSTEM From three essential premises for the apprehension and construction of the contemporary landscape, understanding the System Landscape as a living organism, open and fluid. The introduction of time category influenced the idea process, spatial dimension, and also open more possibilities of approach to the Landscape, while Liquid System, characterized by its particular content and its constant transformation. With an organic methodology, inclusive of all operative possibilities, intersection of ecological components, figural and processes, identifying the liquid matrix, structural transformations of Lisbon System Landscape. The subdivision, extension and cohesion movements, which promote attachment and propulsion in the Landscape, are records of a liquid matrix, in which the main motor and activator is the water element in determining differentiation and consequent construction of the Lisbon Landscape.

Los materiales compuestos nanoestructurados son considerados una opción prometedora para la concepción de materiales multifuncionales. Sin embargo, la falta habitual de interacción entre los componentes orgánicos e inorgánicos en los materiales híbridos nanoestructurados comporta unas propiedades macroscópicas anisotrópicas que limitan su uso. Por ello, se hace necesario el diseño de la interfase formada entre los componentes mencionados a fin de mejorar sus prestaciones. En esta Tesis Doctoral se ha optado por el uso de dióxido de carbono supercrítico (scCO2) para la modificación superficial de nanopartículas inorgánicas y para la preparación de materiales híbridos nanoestructurados. Estos procesos supercríticos, diseñados como sostenibles, se proponen como sustitutos de técnicas convencionales que empleen disolventes orgánicos. El tratamiento superficial de nanopartículas de dióxido de titanio (TiO2) con octiltrietoxisilano se ha empleado como sistema de estudio para evaluar el uso de recubrimientos de alcoxisilanos bifuncionales como promotores de adhesión de partículas inorgánicas nanométricas. El scCO2 se emplea como disolvente del alcoxisilano para la silanización del TiO2. También se han llevado a cabo estudios fundamentales de solubilidad de octiltrietoxisilano en CO2 y de la cinética del proceso de silanización del TiO2. La modulación de las propiedades fisicoquímicas del scCO2 con la presión y la temperatura permite el control de las características del recubrimiento con silano. El proceso de silanización supercrítico se ha extendido a diferentes sistemas alcoxisilano-nanopartículas inorgánicas. Asimismo, se ha evaluado la tecnología de scCO2 para la preparación de materiales híbridos nanoestructurados que contengan nanopartículas inorgánicas silanizadas. El tratamiento superficial de las nanopartículas favorece la distribución homogénea de éstas en el material híbrido y mejora la interacción relleno-matriz orgánica. Se han procesado matrices biopoliméricas de interés en ingeniería tisular, compuestas de ácido poliláctico o la mezcla iv polimetilmetacrilato/policaprolactona, con adiciones de nanopartículas de TiO2 o hidroxiapatita, respectivamente. Para su procesado, se ha empleado scCO2 como no-disolvente utilizando la técnica Particles from a Compressed Anti-Solvent (PCA). Además, se han preparado partículas híbridas formadas por una mezcla lipídica de aceite de ricino hidrogenado y glicerilmonoestearato con adiciones de TiO2 y cafeína, con posibles aplicaciones en cremas para uso tópico. Estas partículas sólidas lipídicas se han obtenido usando la técnica Particles from Gas Saturated Solutions (PGSS) que emplea scCO2 como soluto. Por último, el proceso de silanización supercrítico se ha ensayado para materiales híbridos complejos multiescalados. Se han procesado materiales de base cemento empleando un proceso supercrítico de carbonatación-silanización en dos etapas. Primero, el cemento se carbonata de manera acelerada usando scCO2 como agente de carbonatación. Este cemento, ya carbonatado, se somete, finalmente, a un tratamiento hidrofóbico mediante silanización supercrítica, para su posible aplicación en confinamiento de residuos peligrosos en ambientes húmedos o como material de construcción duradero.
Nowadays, society is asking for a global changing in the way of manufacturing goods in a more sustainable manner. Indeed, the weight of the classical factors (cost, quality, appearance) influencing the acceptance of a certain good in the market have currently changed. Manufacturing requirements and regulations concerning environment protection (e.g., resource consumption, sustainability, toxicity, CO2 footprint, recycling potential) and quality features (e.g., product guarantees, durability against aggressive environments, corporate vision) are aspects of increasing concern. The competitive position of a company is influenced by seizing the opportunities and challenges and by managing the risks that the changeable market has. As a consequence, the industry is continuously looking for smart and innovative solutions for the design and manufacturing of materials with novel properties and increased added value, and for the production of materials already existing in the market in a more efficient manner. Nanostructured hybrid composites have emerged as a promising class of innovative materials for many industrial sectors (e.g., energy, optoelectronics, biomedicine, cosmetics). The multicomponent composition of these materials provides them with unique properties arising from the synergistic combination of the characteristics of their individual components structured at the nanolevel. Nevertheless, in numerous hybrid materials, the lack of coupling or bonding between the components often leads to anisotropic macroscopic properties, limiting their use. Hence, the interaction at the interphase between hybrid components must be properly engineered to enhance materials properties. In this PhD Thesis, the quest for sustainable and environmentally friendly processes led to the use of supercritical carbon dioxide (scCO2) for both the surface modification of nanometric inorganic particles and the preparation of nanostructured hybrid materials. These processes are designed for the replacement of conventional methods using organic solvents. vi Bifunctional alkoxysilane molecules, acting as adhesion promoters, are, herein, investigated for the surface modification of nanometric inorganic particles. The surface treatment of titanium dioxide (TiO2) nanoparticles with octyltriethoxysilane is taken as the model system for study. In terms of processing, scCO2 is used as the solvent of choice for alkoxysilanes for the surface modification of TiO2. Fundamental studies on the solubility of the used silane in CO2 in the pressure range 8-18 MPa at two different temperatures (318 and 348 K) and on the kinetics of the TiO2 silanization process are performed. For the scCO2-aided silanization process, studies are conducted to ascertain the effects and interactions of the operating variables on the properties of the final material. Results show that the tunable physicochemical properties of scCO2 with pressure and temperature (e.g., density, solvation power) allows the engineering control of the characteristics of the silane coating. Examples of the extension of the application of the supercritical silanization process to other sets of alkoxysilanes and inorganic nanoparticles are also presented. The preparation of hybrid materials including silanized inorganic nanoparticles and organic matrices is further tested using scCO2 technology. Surface treated nanoparticles are used to facilitate the homogeneous distribution of the nanoparticles within the matix and to improve the inorganic filler-organic matrix interaction. Biopolymeric matrices of either poly(L-lactic acid) (L-PLA) or the blend poly(methylmethacrylate)/poly(ε-caprolactone) (PMMA/PCL) loaded with nanometric titanium dioxide or hydroxyapatite, respectively, are prepared. To obtain these hybrid materials, scCO2 is employed as an anti-solvent, using the Particles from a Compressed Anti-Solvent (PCA) technique. Studies are performed to pursue the effect of the processing conditions on the morphology of the precipitated hybrid materials. The resulting material, obtained in the form of fibers, has suitable properties for its potential application in tissue engineering. In a different system, hybrid particles composed of a lipidic matrix (hydrogenated castor oil/glyceryl monostearate) loaded with silanized titanium dioxide and caffeine are prepared. The Particles from Gas Saturated Solutions (PGSS) technique, assisted by the use of scCO2 as a solute, is employed for the production of these solid lipid particles. The obtained hybrid material is evaluated concerning the drug carrier and release ability and the UV-shielding capacity. The UV-light protection and photoaging prevention capacity of the lipid-based hybrid material provide excellent properties for the use of these particles in the formulation of sunscreens and pharmaceutical dermal products. vii Finally, the possibility of extending the supercritical silane treatment to multiscale complex hybrid materials is assessed. The technology based on the use of scCO2 is presented for the two-step carbonation-silanization process of cement-based materials. In the first step, the carbonation of cement is accelerated using scCO2 as the carbonation agent. The effects of the cement formulation and process operation conditions on the microstructure and physicochemical properties of carbonated samples are evaluated. The carbonation process is followed by the hydrophobic treatment of the carbonated samples using a supercritical silanization method. The surface modification of carbonated cement with octyltriethoxysilane confers water repellence to the material. The carbonation-silanization process is scheduled and integrated to mitigate the consumption of raw materials and the use of facilities.

La thèse a pour but d’étudier les effets de changements de mouillabilité de roches dans des conditions d’injections d’eau douce en tant que méthode de récupération d’hydrocarbures. Afin d’identifier le ou les mécanismes à l’origine du gain additionnel de récupération nous avons utilisé un microtomographe RX. Nous avons ainsi imagé les états de saturations finales d’un milieu poreux rempli de saumures et d’huiles. Une fois le drainage primaire réalisé nous avons effectué deux phases d’imbibitions : avec une saumure (récupération secondaire) puis une imbibition d’eau douce (récupération tertiaire). L’analyse de la mouillabilité à l’échelle du pore a permis de mettre en évidence l’effet de la température et de la salinité sur la mouillabilité. Nous avons montré que les changements de mouillages des roches n’étaient pas occasionnées par la seule expansion de la couche électrique en revanche des changements de mouillabilité ont été montrés. Ces changements s’expliquant par des transitions de mouillages de second ordre observées non seulement pour des gouttes d’huiles sur de l’eau mais également sur un substrat en verre. Au final, la mouillabilité en milieux poreux doit être mise en évidence à une échelle sous-Micrométrique ce qui est relativement nouveau dans le domaine pétrolier
The aim of the thesis is to study rock wettability change effects caused by Low Salinity brine injection as tertiary recovery method. To identify the underlying mechanism or mechanisms of additional oil recovery X-Ray imaging technology was applied. We have also imaged the end-Point saturations of filled by brine and water core samples. Once the primary drainage is realized we carried out two phases imbibitions: with high salinity brine (waterflooding) and with low salinity brine (tertiary recovery mode). The wettability analysis at pore scale permitted to put in evidence the thermal and saline effects playing a decisive role in rock wettability. We have showed wettability changes are not caused by only electrical double layer expansion, however wettability changes was shown. These changes are explained by wettability transition of second order and observed not only for oil droplet on brine, but also for oil deposited on glass substrate. Finally, the pore space wettability needs to be evidenced at sub-Micrometric scale that is new for the petroleum domain

Thesis (PhD)--Stellenbosch University, 2014.
ENGLISH ABSTRACT: Data on the process performance at different operating conditions are required to determine the feasibility of a separation process. Such data can be experimentally measured, but due to the time and costs associated with pilot plant scale experiments, the use of predictive process models are often preferred. The main aim of this project is to establish a working process model in Aspen Plus® that can be used to predict the separation performance of a supercritical fluid fractionation process aimed at the separation of mixtures of detergent range alkanes and alcohol isomers where similar boiling points or low relative volatilities can occur. Currently, an azeotropic distillation process is employed for the separation of detergent range alkanes and alcohols. Although this process shows good separation performance, some concerns regarding the operating conditions are raised: the preferred entrainer, diethylene glycol, is toxic to humans; very low operating pressures of 0.016 – 0.031 MPa and high temperatures of 473 K are required; additional processing units and materials are required to remove the entrainer from the product streams. An alternative process, supercritical fluid fractionation, is proposed in this work after previous studies have reported that this process have potential for the separation of alkanes and alcohols. The supercritical fluid fractionation process addresses the concerns of the azeotropic distillation process in the following ways: a non-toxic solvent, CO2, is used as the separating agent; mild temperatures of 344 K is proposed, but at the cost of the low operating pressures of the azeotropic process; and a single process unit and no additional material is required to separate the solvent from the product streams. A process model was developed in Aspen Plus® to evaluate the separation performance of the newly proposed supercritical fluid fractionation process and compare it to the current azeotropic distillation process. The development of the process model included the development of an accurate thermodynamic model in Aspen Plus®. After thorough evaluation of a number of cubic equations of state, the RK-ASPEN model was found to be superior in its representation and prediction of phase transition pressures for multi-component mixtures of detergent range alkanes and alcohols in the temperature range 318 – 348 K. Phase transition pressures could be predicted with an error of less than 6 % with the inclusion of regressed polar parameters and binary solute-solvent interaction parameters for two multi-component mixtures: CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol) and CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol). Polar parameters were regressed from pure component vapour pressure data predicted with correlations available in Aspen Plus®. Binary interaction parameters were regressed from experimental bubble and dew point data. Binary bubble and dew point data were measured for a number of systems containing ethane or CO2 and a C10-alkane or C10-alcohol isomer at temperatures between 308 K and 353 K, and compositions ranging between 0.01 and 0.7 mass fraction solute. A comparison between the phase equilibrium data measured for these systems revealed that the structure of the molecule, and not only the molecular weight, influences its solubility in the supercritical solvent. The phase transition pressures of n-decane, 2-methylnonane, 3-methylnonane and 4-methylnonane did not differ significantly in CO2 or ethane, and these compounds will in all likelihood not be separated in a supercritical fluid fractionation process. The phase transition pressures measured for the C10-alcohol isomers decreased in both CO2 and ethane in the following order: 1-decanol, 3,7-dimethyl-1-octanol, 2-decanol, 2,6-dimethyl-2-octanol and 3,7-dimethyl-3-octanol. The position of the hydroxyl group and the number, length and position of the side branches, all influence the solubility behaviour and phase transition pressures of the isomeric alcohols in the supercritical solvent. Since the use of ethane did not show any significant benefits with regard to selectivity, the use of the less harmful and less expensive solvent, CO2, in further investigations was justified. The RK-ASPEN thermodynamic model, with the inclusion of the regressed polar and binary solute-solvent interaction parameters, was implemented in the process model and the separation performance of the process was simulated at different operating conditions for the CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) mixture. A comparison to experimental pilot plant data revealed that the model cannot be used to predict the separation performance at low fractionation temperatures (316 K) due to shortcomings in the thermodynamic model. However, the performance of the process at high fractionation temperatures (344 K) could be predicted well, with an error of 10 – 36 %. Simulations for the CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) and CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol) mixtures showed that the composition of the feed mixture have a significant effect on the location and size of the operating window and optimum operating conditions. The optimum operating conditions were defined as the conditions where an acceptable selectivity ratio and alcohol recovery occurred simultaneously. Since the selectivity ratio and alcohol recovery have opposing optimization approaches, a number of possible optimum operating conditions exist, based on the product specifications. When an alcohol and an alkane with similar phase behaviour exist in a mixture, a distinct minimum selectivity ratio will occur at a point within the extract-to-feed ratio limits of the process. When the alkanes and alcohols present in a mixture do not have similar or overlapping phase transition pressures, the minimum selectivity ratio will typically cover a small range of extract-to-feed ratios at the high end limit of the extract-to-feed ratio range. To summarize: A process model was established in Aspen Plus® that can be used to determine the feasibility and separation performance of a supercritical fractionation process for a feed mixture of detergent range alkane and alcohol isomers. The model was used to prove that an SFF process is a feasible alternative process to consider for the removal of alkanes from mixtures of detergent range alcohol isomers, even where overlapping boiling points or low relative volatilities occur. During the development of the process model, the following significant novel contributions were made: · New phase equilibrium data were measured for C10-alkane and C10-alcohol isomers in supercritical ethane, as published in The Journal of Supercritical Fluids 58 (2011) 330 – 342. · New phase equilibrium data were measured for C10-alkane and C10-alcohol isomers in supercritical CO2, as published in The Journal of Supercritical Fluids 59 (2011) 14 – 26. · A thermodynamic model was developed in Aspen Plus® that can accurately predict the phase transition pressures of binary, ternary and multi-component mixtures of detergent range alkanes and alcohols in supercritical CO2, as published in The Journal of Supercritical Fluids 84 (2013) 132 – 145. · A process model was developed in Aspen Plus® that can be used to predict the separation performance of a supercritical fluid fractionation process for the separation of mixtures of detergent range alkanes and alcohols. · Experimental and simulated results indicated that a supercritical fluid fractionation process can be implemented successfully to separate an alkane from a mixture of alcohol isomers, as was shown for two mixtures: CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) and CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol).
AFRIKAANSE OPSOMMING: Data oor die omvang van skeiding by verskillende bedryfstoestande word benodig om die lewensvatbaarheid van ’n skeidingsproses te bepaal. Sulke data kan eksperimenteel gemeet word, maar as gevolg van die tyd en kostes geassosieer met eksperimente op loodsaanlegskaal, word die gebruik van prosesmodelle verkies. Die hoofdoel van hierdie projek is om ’n werkende prosesmodel, wat daarop gemik is om C8 – C20 alkane en alkohol isomere te skei, in Aspen Plus® tot stand te bring om die omvang van die skeiding van ’n superkritiese fraksioneringsproses te meet. Tans word azeotropiese distillasie gebruik vir die skeiding van C8 – C20 alkane en alkoholisomere. Alhoewel goeie skeiding met hierdie proses bewerkstellig word, is daar sekere eienskappe van die proses wat aandag vereis: die voorgestelde skeidingsagent, dietileen glikol, is giftig vir mense; baie lae bedryfsdrukke van 0.016 – 0.031 MPa en hoë temperature van 473 K word benodig; addisionele proseseenhede en materiaal is nodig om die skeidingsagent van die produkte te verwyder. Die gebruik van ’n alternatiewe proses - superkritiese fraksionering - word in hierdie werk voorgestel nadat vorige studies getoon het dat hierdie proses die potensiaal het om alkane en alkohole te skei. Die superkritiese fraksioneringsproses spreek al die kommerwekkende eienskappe van azeotropiese distillasie aan soos volg: ’n veilige oplosmiddel, CO2, word as die skeidingsagent gebruik; gemiddelde temperature van 344 K word voorgestel, maar ten koste van lae bedryfsdrukke; ’n enkele proseseenheid en geen addisionele materiaal word benodig om die oplosmiddel van die produkte te skei nie. ’n Prosesmodel is in Aspen Plus® ontwikkel om die omvang van die skeiding wat deur die voorgestelde superkritiese fraksioneringsproses teweeggebring is, te evalueer en te vergelyk met die azeotropiese distillasieproses wat tans in gebruik is. Die ontwikkeling van die prosesmodel sluit die ontwikkeling van ’n akkurate termodinamiese model in Aspen Plus® in. Na deeglike evaluasie van ’n aantal kubiese toestandsvergelykings is gevind dat die RK-ASPEN-model die faseoorgangsdrukke van multi-komponentmengsels van C8 – C20 alkane en alkohole die beste voorspel binne die temperatuurbereik van 318 – 348 K. Faseoorgangsdrukke kon voorspel word met ’n fout van minder as 6 % met die insluiting van voorafbepaalde polêre parameters en binêre interaksie-parameters vir twee multi-komponentmengsels: CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol) and CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol). Polêre parameters is bepaal met dampdruk data, wat voorspel is met korrelasies in Aspen Plus®. Binêre interaksieparameters is van eksperimentele faseoorgangsdata bepaal. Binêre faseoorgangsdata is vir ’n aantal sisteme wat uit etaan of CO2 en ’n C10-alkaan- of C10-alkohol-isomeer bestaan, gemeet by temperature tussen 308 K en 353 K en samestellings van tussen 0.01 en 0.7 massafraksie van die opgeloste stof. ’n Vergelyking tussen die gemete fase-ewewigsdata het onthul dat die struktuur van die molekuul, en nie net die molekulêre massa nie, die oplosbaarheid van die stof in die superkritiese oplosmiddel beïnvloed. Die faseoorgangsdrukke van n-dekaan, 2-metielnonaan, 3-metielnonaan en 4-metielnonaan het geen skynbare verskille getoon in etaan of CO2 nie en dus sal hierdie stowwe in alle waarkynlikheid nie met ’n superkritiese fraksioneringsproses geskei kan word nie. Die faseoorgangsdrukke wat vir die C10-alkohol gemeet is, het in beide etaan en CO2 afgeneem in die volgende volgorde: 1-dekanol, 3,7-dimetiel-1-oktanol, 2-dekanol, 2,6-dimetiel-2-oktanol en 3,7-dimetiel-3-oktanol. Die posisie van die hidroksielgroep en die aantal, lengte en posisie van die sytakke beïnvloed die oplosbaarheidsgedrag van die alkohol-isomere in die superkritiese oplosmiddel. Aangesien die gebruik van etaan nie enige voordele ten opsigte van selektiwiteit inhou nie, is die gebruik van die minder skadelike en goedkoper oplosmiddel, CO2, vir verdere ondersoeke geregverdig. Die ontwikkelde termodinamiese model, met die insluiting van die polêre parameters en binêre interaksieparameters, is in die prosesmodel ingesluit en die omvang van die skeiding van die proses is gesimuleer by verskillende bedryfstoestande vir die CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) mengsel. ’n Vergelyking tussen die gesimuleerde data en die eksperimentele loodsaanlegdata het onthul dat die model nie die omvang van die skeiding kan voorspel by lae fraksioneringstemperature (316 K) nie as gevolg van die tekortkominge in die termodinamiese model. Die omvang van die skeiding by hoë temperature (344 K) kon egter goed voorspel word met ’n fout van 10 – 36 %. Simulasies van die CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) en CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol) mengsels het getoon dat die samestelling van die voermengsel ’n beduidende effek op die grootte van die bedryfsvenster en optimum bedryfstoestande het. Die optimum bedryfstoestande word gedefinieer as die toestande waar ’n aanvaarbare selektiwiteitsverhouding en alkoholherwinning terselfdertyd voorkom. Aangesien die selektiwiteitsverhouding en alkoholherwinning teenstrydige optimeringsbenaderings het, bestaan daar ’n aantal optimum bedryfstoestande gebaseer op die produkspesifikasies. Wanneer ’n alkohol en ’n alkaan met ooreenstemmende fasegedrag saam in ’n mengsel voorkom, bestaan daar ’n duidelike minimum selektiwiteitsverhouding by ’n punt binne die ekstrak-tot-voer-verhoudingslimiete van die proses. Wanneer die alkane en alkohole in ’n mengsel nie ooreenstemmende fasegedrag toon nie, sal die minimum selektiwiteitsverhouding oor ’n reeks ekstrak-tot-voer-verhoudings voorkom, tipies by die hoë limiet van die ekstrak-tot-voer-verhoudingsreeks. Om op te som: ’n Prosesmodel is in Aspen Plus® tot stand gebring wat die lewensvatbaarheid en omvang van die moontlike skeiding van ’n superkritiese fraksioneringsproses vir voermengsels van C8 – C20 alkane en alkohol-isomere kan voorspel. Die model is gebruik om te bewys dat ’n superkritiese proses ’n lewensvatbare alternatiewe proses is om te oorweeg vir die verwydering van alkane uit mengsels van alkohol-isomere, self waar ooreenstemmende kookpunte of lae relatiewe vlugtigheid tussen komponente voorkom. Tydens die ontwikkeling van die prosesmodel is die volgende beduidende nuwe bydraes gemaak: · Nuwe fase-ewewigsdata is gemeet vir C10-alkaan- en C10-alkohol-isomere in superkritiese etaan, soos gepubliseer in The Journal of Supercritical Fluids 58 (2011) 330 – 342. · Nuwe fase-ewewigsdata is gemeet vir C10-alkaan and C10-alkohol isomere in superkritiese CO2, soos gepubliseer in The Journal of Supercritical Fluids 59 (2011) 14 – 26. · ’n Termodinamiese model is ontwikkel in Aspen Plus® wat die faseoorgangsdrukke van binêre, ternêre en multi-komponent mengsels van C8 – C20 alkane en alkohol-isomere in superkritiese CO2 akkuraat kan voorspel, soos gepubliseer in The Journal of Supercritical Fluids 84 (2013) 132 – 145. · ’n Prosesmodel is ontwikkel in Aspen Plus® wat die omvang van die moontlike skeiding van ’n superkritiese fraksioneringsproses, gemik op die skeiding van mengsels van C8 – C20 alkane en alkohol-isomere, kan voorspel. · Eksperimentele en gesimuleerde resultate toon aan dat ’n superkritiese fraksioneringsproses suksesvol geïmplementeer kan word vir die skeiding van ’n alkaan vanuit ’n mengsel van alkohol-isomere, soos bewys vir twee mengsels: CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) en CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol).

Orientador: Maria Angela de Almeida Meireles
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos
Made available in DSpace on 2018-08-26T11:16:03Z (GMT). No. of bitstreams: 1 Moraes_MoysesNavesde_D.pdf: 11795880 bytes, checksum: 816fd6cdb3996f8cf9ea868d729c0050 (MD5) Previous issue date: 2015
Resumo: A busca por produtos naturais que apresentem elevado grau de pureza tem impulsionado pesquisas por processos de extração e, preferencialmente, que não agridam o meio ambiente. Assim, processos de extração com fluido supercrítico (SFE ¿ Supercritical Fluid Extraction) vêm ganhando espaço por propiciar extratos diferenciados. O resíduo obtido da SFE é a matriz sólida livre do extrato de interesse, sendo que esse resíduo pode ser utilizado como matéria-prima em outros processos. Atualmente há grande interesse também em processos que utilizem integralmente a matéria-prima, minimizando a produção de resíduo, e garantindo uma produção mais diversificada oriunda de uma mesma matéria-prima, mas não se pode desconsiderar o processo industrial, e para isso, é necessário desenvolver processos que possam ser integrados sem perder a continuidade da produção, mesmo que o processo, por definição, seja intitulado pseudocontínuo. Para a implementação da SFE em escala industrial uma opção é a operação pseudocontínua de extração com CO2 supercrítico (ScCO2), para que isso seja possível é necessário que a unidade de extração possua no mínimo n+1 extratores, tal que n seja um número inteiro positivo. Então, neste trabalho foi estudada a obtenção de dois tipos de extratos em operação pseudocontínua: (1) óleo volátil de cravo-da-índia, para a validação do processo de extração em modo pseudocontínuo e (2) extrato rico em tocotrienóis de sementes de urucum. Nos dois casos as matrizes vegetais após a SFE podem ser utilizadas para obtenção de outros produtos. No caso do urucum, as sementes desengorduradas possuem grande quantidade de bixina, a qual tem grande aceitabilidade no mercado devido ao seu poder corante, e por isso, utilizou-se esse resíduo como matéria-prima para a obtenção de bixina, promovendo, uma integração de processo. Ademais, o resíduo da extração da bixina e o material lignocelulósico obtido após a SFE do cravo-da-índia podem ser hidrolisados a alta pressão catalisada ou não por CO2 para produzir biopolímeros úteis para serem utilizados na fabricação de nanoestruturas porosas. Para que o processo pseudocontínuo pudesse ser desenvolvido foi necessário o conhecimento atual da área supercrítica, principalmente a nível regional (América Latina e Brasil), além da necessidade de entender as limitações que as diferentes técnicas de extração apresentam para as diferentes classes de compostos de interesse. Então o processo de extração pseudocontínuo foi avaliado, e se mostrou eficaz, permitindo aproveitamento do tempo, pois durante o período de carga e descarga de um leito extrativo o outro estava em período de extração. Deste modo, houve a manutenção de ao menos um extrator em período de extração, caracterizando-se assim a operação pseudocontínua. A extração pseudocontínua do óleo de cravo-da-índia apresentou uma taxa média 3,6 vezes maior que o processo em batelada. A manutenção da razão S/F e do tempo de extração iguais pode ser usada satisfatoriamente para mudança de escala para o cravo e o urucum, ao se utilizar extratores de relação Hb/Db distintas. Por fim, a composição química do óleo de cravo-da-índia foi distinta, sendo então aconselhado uma avaliação prévia dessa composição química antes de definir qual a relação Hb/Db será utilizada
Abstract: The demand for natural products with high purity is promoting studies focused on extraction processes that avoid environmental damages. Supercritical fluid extraction (SFE) processes are gaining emphasis because they afford the extraction of selective compounds when compared with conventional techniques. The residue from SFE is the solid matrix free of target compounds; this residue can be a raw material in other processes. Recently, the appeal for green technologies and the searching for integral use of raw materials are receiving attention. These green technologies minimize the residue generation and promote a diversified production of bioactive compounds from the same raw material. Regarding the industrial scale, integrated processes with continuous productive lines are needed, even that in some cases the processes are named pseudo continuous. Thus, the pseudo continuous extraction using supercritical CO2 (ScCO2) is an important issue for implementing SFE processes in industrial scales. To make it possible, the extraction equipment needs to contain at least n+1 extractors, where n should be a positive integer number. Based on these aspects, we performed in this study the pseudo continuous extraction of two classes of compounds: (1) volatile oil from clove buds for validating the process and (2) tocotrienol rich-extracts from annatto seeds. In both cases the material from SFE can be used to obtain other products. Defatted annatto seeds contain bixin, a coloring pigment that finds several applications. Then, we selected annatto to obtain bixin by using process integration. Furthermore, the residue from the extraction of bixin and the lignocellulosic fraction from the extraction of clove compounds can be hydrolyzed applying high pressure. The reaction can be catalyzed with CO2 to produce biopolymers useful for manufacturing porous nanostructures. To become the pseudo continuous process feasible, we evaluated the information available on the scientific community, especially in Latin America and Brazil. With this search, we could find some limitations about extracting different classes of compounds. Then, we performed the proposed operation, and it yielded good results with respect to optimizing the time. While one bed was in extraction step, the other was in charge/discharge step, characterizing the pseudo continuous extraction mode. In this case, at least one bed was maintained in extraction step along the time. The pseudo continuous extraction of clove oil presented an extraction rate 3.6-fold higher when compared with batch extraction. Besides, process scale up using the studied raw materials might be accomplished by maintaining the S/F ratio equal (for a fixed time) in different Hb/Db ratios. Finally, we observed significant difference (5 % of probability) in the chemical composition of clove oil obtained in both extractors. An evaluation of the oil composition is needed to define the suitable Hb/Db ratio for extraction processes
Doutorado
Engenharia de Alimentos
Doutor em Engenharia de Alimentos

Made available in DSpace on 2014-06-11T19:34:58Z (GMT). No. of bitstreams: 0 Previous issue date: 2004-10Bitstream added on 2014-06-13T19:44:44Z : No. of bitstreams: 1 catai_re_dr_guara.pdf: 5048506 bytes, checksum: 92a0c290f63def07988a569548fd0d34 (MD5)
Universidade Estadual Paulista (UNESP)
Diante do elevado desenvolvimento tecnológico mundial, o processo de retificação surge cada vez mais como um dos processos de usinagem mais importantes dentro das indústrias. Diante disto, na procura incessante por processos mais capazes e econômicos é que as empresas vêm buscando a otimização da retificação, por exemplo, através da redução da quantidade de fluido de corte a ser utilizada. Desta forma este projeto pretendeu explorar o conceito da utilização racional de fluidos de corte no processo de retificação, e a utilização de defletores aerodinâmicos para minimizar os efeitos das camadas de ar provindas da rotação do rebolo. Foram utilizados dois fluidos de corte (uma solução sintética e um óleo emulsionável), duas ferramentas abrasivas (um rebolo convencional e outro superabrasivo de CBN com ligante vitrificado), um bocal convencional (para o sistema de lubri-refrigeração convencional) e um bocal otimizado de formato arredondado (para o sistema otimizado, que conta ainda com o emprego ou não dos sistemas defletores). Nas condições de aplicação otimizada, fez-se quatro variações da velocidade de saída do fluido, partindo-se de uma relação unitária (velocidade de saída do fluido de corte igual à velocidade de corte do rebolo), tentando verificar se uma velocidade de fluido um pouco menor poderia afetar negativamente às variáveis de saída analisadas (força tangencial de corte, energia específica de retificação, emissão acústica, rugosidade, desgaste diametral, circularidade, tensão residual e microscopia eletrônica de varredura), com o intuito de se buscar a mínima quantidade de fluido de corte possível de ser aplicada sem prejudicar o processo e a qualidade final das peças. Os resultados mostraram a eficiência na utilização dos defletores aerodinâmicos na condição otimizada, os quais para todas... .
Given the high world technological development, the grinding process appears like one of the most important processes inside the industries. Thus, companies are looking for the optmization of the grinding process, for example, through the reduction of the amount of cutting fluid used as the incessant search for more capable and economical processes takes place. Therefore, this project intended to explore the concept of the rational use of cutting fluids in the grinding process, and the utilization of the aerodynamics deflectors to minimize the effects of the air layers created by the grinding wheel rotation. Two cutting fluids (a synthetic cutting fluid and an emulsion oil), two grinding wheels (a conventional and other CBN superabrasive grinding wheel with vitrified bond), a conventional nozzle (for the conventional system of coolant and lubrication) and an optimized nozzle with round format (that was used with and without the deflector system) were used. For conditions of optimized coolant and lubrication, four variations of the coolant jet speed were developed, starting from the unitary relationship (coolant jet speed equal to the wheel peripheral speed), trying to verify whether a minor coolant jet speed could affect negatively the output variables (tangential cutting force, grinding specific energy, acoustic emission, roughness, diametrical wear of grinding wheel, roundness, residual stress and scanning electron microscopy), with the intention of looking for the minimal quantity of cutting fluid that can be applied without harming the process and the final quality of the workpieces. The results showed the efficiency of the aerodynamic deflectors in the optimized coolant/lubrication for all the machining conditions. In relation to the different coolant jet speeds used, it has been noticed that the tendency was to improve the final... (Complete abstract, click electronic address below).

The mixing processes are present in the hydraulics engineering field as well as in the environmental field, and they appear in many different situations that are of great interest for humankind. The mechanisms that rule these processes can be very diverse and complex, these being able to interact with each other. However, when a fluid has a turbulent behavior, it is highly unstable and three-dimensional, modifying greatly the other mixing processes. In these cases, the resolution for the fluid mechanics with classical methods can be extremely difficult, making the use of approximations and models necessary. On the other hand, in the last few years, numerical simulation techniques have advanced a lot, and with the velocity increase and the computational capacity, Computational Fluids Dynamics (CFD) allows the development of simulations of these complex processes. This doctoral thesis is motivated by the importance of analyzing the physics of the turbulent flow by numerical methods in different mixing processes of interest in the field of hydraulics engineering and the environmental fluid mechanics. It is intended to illustrate the utility and potentiality of the CFD through the application and analysis in four specific steps, grouped together in two groups of mixing processes: the ones influenced by a turbulent jet in a water tank, and the ones influenced by the turbulent structures due to the curved geometry of the meander channels. The four studied cases are: i) mixing processes in drinking water storage tanks, ii) inlet influence in the thermal stratification in hot water storage tanks, iii) turbulent flow and mixing in a meandering channel, and iv) turbulent flow and mixing in compound meandering channels. The developed work is focused in a practical context. To that effect, test simulations on each studied case have been developed. The experimental data is useful for validating the models and, overall, to thoroughly study the problem. Two CFD techniques are used to solve the Navier-Stokes equations, together with turbulence models, dispersion and/or heat transference, depending on the case. For the jet mixing cases, the chosen technique was the URANS (Unsteady Reynolds-Averaged Navier-Stokes). In the meander cases the LES (Large Eddy Simulation) technique was required. The first work shows a procedure for the study of the fluid dynamic in the mixing processes in potable water tanks. The procedure can be applied in the design and improvement of these elements by using the URANS technique together with experimental methods. In the second case, the URANS simulations in the hot water tank could determine the distribution of the temperature in the whole computational domain. Besides, the model, validated with a high level of adjustment, was developed for the study of the influence of some inlet configurations and to improve the degree of stratification. With respect to the third study, the suitability of the LES technique has been proved in the thorough study of the flow and the turbulence in meanders, even by using relatively coarse grids. The great influence of the secondary flows (due to the curved shape of the channel) on the mixing process has been clarified. Finally, the LES technique was very effective upon adding information about the flow and the turbulence in meanders with different flooding levels. A very good consistency with the experimental data was obtained, despite the use of relatively coarse grids. The mixing process between the flooding flow and the meander has been observed with more clarity.
Los procesos de mezcla están presentes tanto en el campo de la ingeniería hidráulica como en el del medio ambiente y aparecen en infinidad de situaciones que son de gran interés para el ser humano. Los mecanismos que gobiernan estos procesos pueden ser muy diversos y complejos, pudiendo interaccionar entre sí. Sin embargo, cuando un fluido tiene un comportamiento turbulento, éste es altamente inestable y tridimensional, modificando en gran medida los otros mecanismos de mezcla. En estos casos, la resolución con métodos clásicos de la mecánica de fluidos puede llegar a ser extremadamente difícil, siendo necesario utilizar aproximaciones o modelos. Por otro lado, en los últimos años, se ha avanzado mucho en las técnicas de simulación numérica, y junto con el aumento de la velocidad y capacidad computacional, la Dinámica de Fluidos Computacional (en inglés Computational Fluid Dynamics, CFD) permite desarrollar simulaciones de estos complejos procesos. Esta Tesis Doctoral está motivada por la importancia de analizar mediante métodos numéricos la física del flujo turbulento en diferentes procesos de mezcla de interés en el campo de la ingeniería hidráulica y la mecánica de fluidos medioambiental. Se pretende ilustrar la utilidad y potencialidad de la CFD a través de la aplicación y análisis a cuatro casos concretos, agrupados en dos grupos de procesos de mezcla: los dominados por un chorro turbulento de entrada en un tanque de agua y los dominados por las estructuras turbulentas debidas a la propia geometría curva de los canales meándricos. Los cuatro casos de estudio son: i) procesos de mezcla en tanques de agua potable, ii) influencia del chorro de entrada en la estratificación térmica en tanques de agua caliente, iii) flujo turbulento y mezcla en canales con meandros, y iv) flujo turbulento y mezcla en canales con meandros inundables. El trabajo desarrollado está centrado en un contexto práctico donde, a partir de casos concretos, se buscan los métodos y modelos más adecuados en cada uno de ellos. A tal efecto, se han desarrollado simulaciones de ensayos llevados a cabo en cada uno de los casos de estudio. Aunque los datos experimentales empleados fueron generados por diferentes equipos de investigación, en todo momento existió una estrecha relación y colaboración con todos los grupos. Dichos datos experimentales sirvieron para validar los modelos y, en conjunto, para estudiar en profundidad el problema. El trabajo en el que se analiza el primero de los cuatro casos muestra un procedimiento para el estudio de dinámica de fluidos de los procesos de mezcla en tanques de agua potable. El procedimiento puede aplicarse en el diseño y mejora de de estos elementos mediante la técnica URANS junto con métodos experimentales. En el segundo caso, las simulaciones URANS en el tanque de agua caliente permitieron determinar la distribución de temperatura en todo el dominio computacional. Además, el modelo, validado con un alto nivel de ajuste, fue desarrollado para el estudio de la influencia de algunas configuraciones de entrada y mejorar el grado de estratificación inicial. Con el tercer caso de estudio, se ha mostrado la idoneidad de la técnica LES en el estudio en profundidad del flujo y la turbulencia en meandros, incluso habiendo empleado mallas relativamente gruesas. La mayor influencia de los flujos secundarios (resultado de la forma curva del canal) sobre el proceso de mezcla ha podido ser clarificada. Por último, la técnica LES resultó ser muy eficaz a la hora de ampliar la información disponible sobre el flujo y la turbulencia en meandros con diferentes planos de inundación. Se obtuvo una muy buena concordancia con los datos experimentales, pese al uso de mallas relativamente gruesas. El proceso de mezcla entre el flujo de la inundación y el del meandro ha podido ser observado con mayor claridad.
Els processos de mescla estan presents tant en el camp de l'enginyeria hidràulica com en el del medi ambient i apareixen en infinitat de situacions que són de gran interès per a l'ésser humà. Els mecanismes que governen aquests processos poden ser molt diversos i complexos, podent interaccionar entre si. No obstant això, quan un fluid té un comportament turbulent, aquest és altament inestable i tridimensional, modificant en gran mesura els altres mecanismes de mescla. En aquests casos, la resolució amb mètodes clàssics de la mecànica de fluids pot arribar a ser extremadament difícil, sent necessari utilitzar aproximacions o models. D'altra banda, en els últims anys, s'ha avançat molt en les tècniques de simulació numèrica, i juntament amb l'augment de la velocitat i capacitat computacional, la Dinàmica de Fluids Computacional (en Anglès Computational Fluids Dynamics, CFD) permet desenvolupar simulacions d'aquests complexos processos. Aquesta Tesi Doctoral està motivada per la importància d'analitzar mitjançant mètodes numèrics la física del flux turbulent en diferents processos de mescla d'interès en el camp de l'enginyeria hidràulica i la mecànica de fluids mediambiental. Es pretén il¿lustrar la utilitat i potencialitat de la CFD a través de l'aplicació i anàlisi a quatre casos concrets, agrupats en dos grups de processos de mescla: els dominats per un doll turbulent d'entrada en un tanc d'aigua i els dominats per les estructures turbulentes degudes a la pròpia geometria corba dels canals meàndrics. Els quatre casos d'estudi són: i) processos de mescla en tancs d'aigua potable, ii) influència del doll d'entrada en l'estratificació tèrmica en tancs d'aigua calenta, iii) flux turbulent i mescla en canals amb meandres, i iv) flux turbulent i mescla en canals amb meandres inundables. El treball desenvolupat està centrat en un context pràctic on, a partir de casos concrets, es busquen els mètodes i models més adequats en cadascun d'ells. A aquest efecte, s'han desenvolupat simulacions d'experiments duts a terme en cadascun dels casos d'estudi. Tot i que les dades experimentals emprats van ser generats per diferents equips d'investigació, en tot moment va existir una estreta relació i col¿laboració amb tots els grups. Aquests dades experimentals varen servir per validar els models i, en conjunt, per estudiar en profunditat el problema. El treball en el qual s'analitza el primer dels quatre casos mostra un procediment per a l'estudi de dinàmica de fluids dels processos de mescla en tancs d'aigua potable. El procediment pot aplicar-se en el disseny i millora d'aquests elements mitjançant la tècnica URANS juntament amb mètodes experimentals. En el segon cas, les simulacions URANS en el tanc d'aigua calenta van permetre determinar la distribució de temperatura en tot el domini computacional. A més, el model, validat amb un alt nivell d'ajust, va ser desenvolupat per a l'estudi de la influència d'algunes configuracions d'entrada i millorar el grau d'estratificació inicial. En el tercer cas d'estudi, s'ha mostrat la idoneïtat de la tècnica LES en l'estudi en profunditat del flux i la turbulència en meandres, fins i tot havent emprat malles relativament gruixudes. La major influència dels fluxos secundaris (resultat de la forma corba del canal) sobre el procés de mescla ha pogut ser aclarida. Per últim, la tècnica LES va resultar ser molt eficaç a l'hora d'ampliar la informació disponible sobre el flux i la turbulència en meandres amb diferents plànols d'inundació. Es va obtenir una molt bona concordança amb les dades experimentals, malgrat l'ús de malles relativament gruixudes. El procés de mescla entre el flux de la inundació i el del meandre ha pogut ser observat amb major claredat.
Moncho Esteve, IJ. (2017). Procesos de Mezcla en Flujos Turbulentos con Técnicas de la Mecánica de Fluidos Computacional (CFD) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/90573
TESIS

The thesis deals with an analysis of an existing technology of thread forming under various technological parameters used in car industry. Furthermore, it characterizes metric threads, their production and quality control, forming taps, process fluids and other process parameters. In the experimental part the experimental tests with a conventional and CNC drilling machines were carried out. The influence of various process fluids on surface and thread quality have been assessed statistically. The technical-economic evaluation of the process fluids and their effect on the technology has been made. The work supports a beneficial role of soap and polymers as convenient tribological means at thread forming.

Le transport de particules solides dans un matériau poreux saturé, sujet à l'écoulement de fluide se produit dans les milieux naturels et dans diverses applications liées au génie civil. Ces particules solides peuvent colmater les interstices du matériau poreux et par conséquent réduire sa perméabilité ou au contraire se détacher du matériau poreux et provoquer son érosion. Ainsi, cette thèse s'attache à étudier à l'échelle des grains du matériau poreux les mécanismes du transport de particules en présence d'écoulement de fluide incompressible et de calculer les interactions fluide-solide pour contribuer à la connaissance des phénomènes de colmatage ou d'érosion. Le travail est réalisé principalement par la voie numérique utilisant un couplage original entre deux codes de calcul : PFC3D pour la matrice granulaire - CFD FINAS pour l'écoulement du fluide, validé par des expériences de visualisation menées sur des modèles de laboratoire.
Les études numérique et expérimentale de la filtration dans un milieu poreux bidimensionnel montrent l'influence des particules sur le champ de vitesse du fluide qui se met à son tour en mouvement et accélère la filtration. L'étude des interactions particules-fluide par l'approche couplée DEM-CFD (Distinct Element Method-Computational Fluid Dynamics) a abouti à proposer une formulation de la traînée en fonction de la porosité du milieu poreux. Le couplage avec la loi de Darcy conduit à une relation pratique qui prédit la perméabilité en fonction de la porosité. L'étude est étendue à la filtration de particules solides dans un milieu poreux constitué d'un empilement désordonné de sphères dans lequel un fluide s'écoule en permanence. L'analyse à l'échelle des grains montre des zones de colmatage qui se développent dans le milieu poreux. L'étendue du colmatage est analysée en fonction de combinaisons des forces prédominantes que sont les forces de gravité et de viscosité. Des courbes de distribution des particules selon la profondeur sont trouvées.

Quantitative analysis by means of discrete-state stochastic processes is hindered by the well-known phenomenon of state-space explosion, whereby the size of the state space may have an exponential growth with the number of objects in the model. When the stochastic process underlies a Markovian process algebra model, this problem may be alleviated by suitable notions of behavioural equivalence that induce lumping at the underlying continuous-time Markov chain, establishing an exact relation between a potentially much smaller aggregated chain and the original one. However, in the modelling of massively distributed computer systems, even aggregated chains may be still too large for efficient numerical analysis. Recently this problem has been addressed by fluid techniques, where the Markov chain is approximated by a system of ordinary differential equations (ODEs) whose size does not depend on the number of the objects in the model. The technique has been primarily applied in the case of massively replicated sequential processes with small local state space sizes. This thesis devises two different approaches that broaden the scope of applicability of efficient fluid approximations. Fluid lumpability applies in the case where objects are composites of simple objects, and aggregates the potentially massive, naively constructed ODE system into one whose size is independent from the number of composites in the model. Similarly to quasi and near lumpability, we introduce approximate fluid lumpability that covers ODE systems which can be aggregated after a small perturbation in the parameters. The technique of spatial aggregation, instead, applies to models whose objects perform a random walk on a two-dimensional lattice. Specifically, it is shown that the underlying ODE system, whose size is proportional to the number of the regions, converges to a system of partial differential equations of constant size as the number of regions goes to infinity. This allows for an efficient analysis of large-scale mobile models in continuous space like ad hoc networks and multi-agent systems.

Le procédé d’enduction grande vitesse d’un filament de carbure de silicium de type SCS-6 par du titane liquide constitue une voie d’élaboration innovante pour la réalisation de composites à matrice métallique. Cependant, un mauvais mouillage entre le filament et le titane liquide et la formation de perles de titane le long de ce filament au cours de l’enduction ne permettaient pas de maîtriser le procédé pour la réalisation des matériaux composites. Les travaux de la thèse ont donc consisté à identifier et comprendre l’ensemble des mécanismes entrant en jeu lors de l’enduction à grande vitesse. Une double approche numérique et expérimentale a été mise en place pour estimer les paramètres influents sur l’épaisseur de fluide emportée et sa stabilité en proposant une analyse paramétrique du phénomène physique grâce à l’étude d’enductions avec des liquides modèles. Cette analyse a ensuite été confrontée à une analyse physique et chimique d’enduction de filaments par un fluide métallique. Les différences et similitudes de ces analyses ont permis notamment grâce à des études de mouillage, à identifier les conditions pour lesquelles l’enduction d’un filament céramique de carbure de silicium par un alliage de titane seraient possibles
High speed coating of SCS-6 silicon carbide fiber by liquid titanium is a new industrial process designed to manufacture metallic matrix composites at a lower cost. However, due to expected high speed in the coating process, a lack of reactivity is observed between liquid titanium and ceramic fiber. Because of these high speeds, large titanium drops are also formed on the coated fiber. The work presented in this doctoral thesis aimed to identify and understand the several mechanisms occurring in this high speed coating in order to propose an improvement of the industrial process.Both experimental and numerical studies are used to determine the parameters responsible of the coating and the ones of thickness stability. Standard coatings with model fluids were firstly studied to understand the physical phenomenon alone. The understandings of chemical influence in fiber coating and especially on wetting properties were done in a second time. Using the previous results, an optimization of titanium high speed coating on ceramic fiber is then described

Resumo: Diante do elevado desenvolvimento tecnológico mundial, o processo de retificação surge cada vez mais como um dos processos de usinagem mais importantes dentro das indústrias. Diante disto, na procura incessante por processos mais capazes e econômicos é que as empresas vêm buscando a otimização da retificação, por exemplo, através da redução da quantidade de fluido de corte a ser utilizada. Desta forma este projeto pretendeu explorar o conceito da utilização racional de fluidos de corte no processo de retificação, e a utilização de defletores aerodinâmicos para minimizar os efeitos das camadas de ar provindas da rotação do rebolo. Foram utilizados dois fluidos de corte (uma solução sintética e um óleo emulsionável), duas ferramentas abrasivas (um rebolo convencional e outro superabrasivo de CBN com ligante vitrificado), um bocal convencional (para o sistema de lubri-refrigeração convencional) e um bocal otimizado de formato arredondado (para o sistema otimizado, que conta ainda com o emprego ou não dos sistemas defletores). Nas condições de aplicação otimizada, fez-se quatro variações da velocidade de saída do fluido, partindo-se de uma relação unitária (velocidade de saída do fluido de corte igual à velocidade de corte do rebolo), tentando verificar se uma velocidade de fluido um pouco menor poderia afetar negativamente às variáveis de saída analisadas (força tangencial de corte, energia específica de retificação, emissão acústica, rugosidade, desgaste diametral, circularidade, tensão residual e microscopia eletrônica de varredura), com o intuito de se buscar a mínima quantidade de fluido de corte possível de ser aplicada sem prejudicar o processo e a qualidade final das peças. Os resultados mostraram a eficiência na utilização dos defletores aerodinâmicos na condição otimizada, os quais para todas... (Resumo completo, clicar acesso eletrônico abaixo).
Abstract: Given the high world technological development, the grinding process appears like one of the most important processes inside the industries. Thus, companies are looking for the optmization of the grinding process, for example, through the reduction of the amount of cutting fluid used as the incessant search for more capable and economical processes takes place. Therefore, this project intended to explore the concept of the rational use of cutting fluids in the grinding process, and the utilization of the aerodynamics deflectors to minimize the effects of the air layers created by the grinding wheel rotation. Two cutting fluids (a synthetic cutting fluid and an emulsion oil), two grinding wheels (a conventional and other CBN superabrasive grinding wheel with vitrified bond), a conventional nozzle (for the conventional system of coolant and lubrication) and an optimized nozzle with round format (that was used with and without the deflector system) were used. For conditions of optimized coolant and lubrication, four variations of the coolant jet speed were developed, starting from the unitary relationship (coolant jet speed equal to the wheel peripheral speed), trying to verify whether a minor coolant jet speed could affect negatively the output variables (tangential cutting force, grinding specific energy, acoustic emission, roughness, diametrical wear of grinding wheel, roundness, residual stress and scanning electron microscopy), with the intention of looking for the minimal quantity of cutting fluid that can be applied without harming the process and the final quality of the workpieces. The results showed the efficiency of the aerodynamic deflectors in the optimized coolant/lubrication for all the machining conditions. In relation to the different coolant jet speeds used, it has been noticed that the tendency was to improve the final... (Complete abstract, click electronic address below).
Orientador: Eduardo Carlos Bianchi
Coorientador: Marcos Valério Ribeiro
Banca: Paulo Roberto de Aguiar
Banca: Marcos Tadeu Tibúrcio Gonçalves
Banca: Leonardo Roberto da Silva
Banca: Anselmo Eduardo Diniz
Doutor

Crystallization is one of the most important separation and purification processes in chemical and especially in pharmaceutical industries. Currently most crystallization processes in the industry are based on batch crystallization; however, due to the variation of product quality per batch, efforts are made to move to continuous processes instead. In this respect, micro and meso scale reactors represents a promising technology due to enhanced heat and mass transfer rates, which, translated to particle generation, provide control of size, morphology, and composition. In this study, a meso-scale continuous crystallizer has been characterized and optimized. A stirred tubular continuous-crystallizer has been characterized and optimized in which the crystallization of active pharmaceutical ingredients (APIs) can be performed under controlled conditions. The crystallizer is formed by two tubes, one for nucleation and the other one for growth, in order to separate different phenomena to control better the process and hence the crystal size distribution. The optimized nucleation tube has a length of 35 cm and a diameter of 3 cm with a long axial blade across the tube with the length of 30 cm and 2.5 cm of diameter. The phenomena of mixing helps to achieve homogeneous supersaturation along the tube to prevent growth during the nucleation and enables narrow residence time distribution of the crystals in the tube with the help of gravity to achieve narrower crystal size distribution. Computational fluid dynamics (CFD) is used to optimize the process. CFD is the application of numerical methods to solve systems of partial differential equations related to fluid dynamics. The continuity and the momentum equations are the most commonly applied equations within CFD, and together they can be used to calculate the velocity and pressure distributions in a fluid.