Orientador: Walkiria Hanada Viotto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-15T10:23:35Z (GMT). No. of bitstreams: 1 Goncalves_MonicaCorreia_M.pdf: 533762 bytes, checksum: 5ec6ee0003c8689e8b7ed49365950a6b (MD5) Previous issue date: 2010 / Resumo: A produção de requeijão culinário tem aumentado de forma significativa e sem dúvida o seu potencial de crescimento é promissor. O requeijão culinário é o terceiro queijo mais produzido no Brasil. Em 2008, o Brasil produziu 125.000 toneladas, uma produção 60% maior do que o requeijão cremoso. O requeijão culinário não é especificado pela legislação brasileira, apresentando uma consistência entre o requeijão de barra e o requeijão cremoso, permitindo o envase em bisnagas para posterior escoamento quando utilizado. É muito utilizado como ingrediente culinário, devendo suportar as altas temperaturas de assamento e fritura sem apresentar derretimento excessivo, além de não se desmanchar ou escoar quando utilizado em recheios. O teor protéico e o tempo de cozimento influenciam o desenvolvimento das propriedades funcionais. O objetivo deste trabalho foi avaliar o efeito da adição de caseinato de cálcio e o tempo de cozimento no tamanho de partícula instrumental, propriedades de textura instrumental, cor instrumental, capacidade de derretimento e aceitação sensorial do requeijão culinário. Um delineamento central composto rotacional foi utilizado. O aumento da concentração de caseinato de cálcio diminuiu o tamanho das partículas de gordura e aumentou a dureza, adesividade e gomosidade. A elasticidade e o índice de brancura foram influenciados pela concentração de caseinato de cálcio e pelo tempo de cozimento do requeijão. Houve uma tendência de diminuição da capacidade de derretimento com o aumento da concentração de caseinato de cálcio e tempo de cozimento. Provadores julgaram que o requeijão culinário fabricado com 2% de caseinato de cálcio e 2,3 min de cozimento apresentou consistência e fluidez mais próximas do ideal. A análise sensorial mostrou que os requerimentos funcionais de textura firme e baixa capacidade de derretimento de requeijões culinários se antagonizam com a conveniência do uso (ou remoção da embalagem) desse produto pelo consumidor, que prefere um produto mais fluido e menos consistente / Abstract: The manufacture of ¿requeijão culinário¿ cheese has increased significantly and its growth potential is promising. It is considered the third most produced cheese in Brazil and in 2008 its production achieved 125,000 tons, which is about 60% higher than ¿requeijão cremoso¿. ¿Requeijão culinário¿ is not specified by Brazilian legislation and its consistency is peculiar, allowing filling in tubes and disposed during the use. It is widely used as a culinary ingredient so it may have a firm consistency and must support high temperatures of baking and frying, without excessive melting, once. The development of its functional properties is influenced by protein content and cooking time.The objective of this study was to evaluate the effect of concentration of calcium caseinate and cooking time in particle size, instrumental texture properties,, color, melting capacity and sensory acceptance of ¿requeijão culinário¿. A central composite rotational design was used. The increased concentration of calcium caseinate decreased the particle size and increased hardness, adhesiveness and gumminess. The springness and whiteness index were influenced by the concentration of calcium caseinate and cooking time. There was a decreasing trend of melting capacity as the concentration of calcium caseinate and cooking time increased. Consumers judged the ¿requeijão culinário¿ cheese produced with 2% calcium caseinate and 2.3 min of cooking time with consistency and flow closer to the ideal. The experiment showed that the functional requirements of firm texture and low melting capacity of ¿requeijão culinário¿ cheese is antagonistic to the convenience of use (or unpacking) of that product by consumers, who prefer a product more fluid and less consistent / Mestrado / Mestre em Tecnologia de Alimentos

O objetivo do presente trabalho consistiu no desenvolvimento de fios de liga de cobre-cromo-zircônio (CuCrZr) em uma composição estabelecida em Cu-0,7%Cr- 0,1%Zr (em massa). Nas etapas desenvolvidas, foram feitos botões de cobrecromo (CuCr) e cobre-zircônio (CuZr) em um forno a arco elétrico de eletrodo não consumível, sendo esses botões, posteriormente, fundidos junto com cargas de cobre em um cadinho de alumina (Al2O3) inserido no interior de um vaso de aço inoxidável, que serviu como suporte. Após a fusão dos botões e cargas, o banho foi vazado em uma coquilha de cobre, obtendo-se os tarugos da liga de cobre. Dos tarugos em estado bruto de fusão, foram retiradas amostras para ensaios de dureza Vickers. Nesses tarugos foi feito um tratamento térmico de homogeneização a 910 °C por 2 h. Os tarugos foram posteriormente trabalhados mecanicamente a frio por forjamento rotativo seguido de trefilação, para obtenção final dos fios no calibre de 2,174 mm. Os fios passaram por dois tratamentos térmicos de recristalização, um a 510 °C por 1 h e outro de 480 °C por 5 h. Os fios foram caracterizados mecanicamente por ensaios de tração e de dureza e os resultados foram comparados com dados experimentais da literatura. / The objective of this work is the development of copper alloy wire-chromiumzirconium (CuCrZr) in a chemical composition Cu-0,7% Cr-0,1% Zr (weight). The main steps were, buttons were made of copper-chromium (CuCr) and copperzirconium (CuZr) in an electric arc furnace, these buttons were later melted with copper charge in a alumina crucible, placed inside a stainless steel can which served as a support. After melting buttons and charge, the bath was poured into a copper chill mold obtaining copper alloy billets. From the as cast cooper alloy billets, small samples were cut for Vickers hardness and then, a homogenizing heat treatment at 910 °C for 2 h was performed. The billets were then mechanically cold worked by swaging followed by drawing to obtain the wires with a diameter of 2,174 mm. The wires are mechanically characterized using tensile and hardness testing after recrystallization heat treatment at 510 °C for 1 h and at 480 °C for 5 h and the results were compared with experimental data from literature.

A demanda por energia fotovoltaica vem aumentando a razão de mais de 20% ao ano no mercado internacional nos últimos dez anos. O silício com pureza entre 99,999% e 99,99999% é utilizado na fabricação de células fotovoltaicas. O silício metalúrgico tem pureza entre 98,5% e 99%. Este estudo visa investigar o refino a vácuo como um processo alternativo de menor custo para se obter o silício para células fotovoltaicas. Este processo pode remover o fósforo do silício, que é um dos elementos prejudiciais à célula fotovoltaica. Isso permitiria agregar valor à produção brasileira de silício metalúrgico, que alcança um preço de aproximadamente US$2,5 por quilo, enquanto o silício para células fotovoltaicas varia entre US$20 e 60 por quilo. Foram realizados experimentos de fusão em forno de indução a vácuo, variando parâmetros como temperatura, tempo e pressão. O teor de fósforo caiu de 33 ppm para cerca de 0,1 ppm e os resultados foram comparados com um modelo matemático da literatura. Conclui-se que o refino por este processo é tecnicamente viável. / The demand for photovoltaics is increasing at a ratio over 20 % per year in the international market in the last ten years. Silicon with purity of 99.999 % and 99.99999 % is used in the manufacture of photovoltaic cells. The purity of metallurgical silicon is between 98.5% and 99%. This study aims to investigate the vacuum refining process as a lower cost alternative to obtain silicon for photovoltaic cells. This process can remove phosphorus from silicon, which is a harmful element to the photovoltaic cell. This would add value to Brazilian production of metallurgical silicon, that reaches a price of approximately U.S.$ 2.5 per kilogram, while the silicon for photovoltaic cells varies between U.S.$ 20 and 60 per kilo . Melting experiments were performed in a vacuum induction furnace by varying such parameters as temperature, time and pressure. The phosphorus content dropped from 33 ppm to about 0.1 ppm and the results were compared with a mathematical model from literature. It is concluded that refining of this process is technically feasible.

Le procédé de fabrication directe de pièces thermoplastiques est un procédé innovant qui permet de créer sans outillage, à partir d'une modélisation géométrique numérique, des pièces de géométrie complexe en quelques heures. La fabrication dite additive est réalisée par étalement successif de couches de poudre thermoplastique de quelques dizaines de micromètres, dont une partie est fondue sous rayonnement laser et refroidie lentement afin de permettre la densification de la poudre par diffusion de l'air emprisonné. La résistance mécanique finale du matériau dépend fortement de cette densification. Un grand nombre de paramètres procédé et matériau influencent les mécanismes physiques mis en jeu qui sont contrôlés par la thermique du procédé. La clé de la maîtrise de ce procédé réside dans la parfaite maîtrise de la thermique du lit de poudre. Cette étude a pour objectif de modéliser le procédé de fabrication directe de pièces thermoplastiques haute température de type PEEK. Dans un premier temps, une simulation microscopique de la fusion laser d'un lit de poudre préchauffé et de la coalescence des grains est développée à l'aide de la méthode C-NEM implémentée sur le logiciel Matlab. Les cycles thermiques, la densification et le soudage des grains sont étudiés en fonction des paramètres matériau et procédé. Dans un second temps, l'étude de la thermique d'une couche de poudre à l'état liquide refroidie par apport d'une nouvelle couche de poudre par-dessus est menée à l'aide d'un logiciel éléments finis commercial. L'objectif est de définir les conditions d'étalement permettant au polymère fondu de rester à l'état liquide. / Direct manufacturing technology using Selective Laser Sintering of thermoplastic powder allows obtaining final parts in a short time, with a high degree of geometry flexibility and evolution. Parts are built layer by layer, a specific area of each layer is melted by the laser radiation and the whole part is cooled down slowly to induce a good densification, permitting the gas diffusion through the melted material. The mechanical properties of parts made by this process highly depend on the final polymer density. A lot of process and material parameters control the parts properties. The key of the process master lies in its perfect thermal control. The aim of this work is to model the selective laser sintering process for high temperature polymers like PEEK at two scales. Firstly, a microscopic simulation of the melting and the grain coalescence of preheated polymer powder bed is performed using the C-NEM method implemented on Matlab. This tool allows to study the material thermal cycles, the powder densification and the welding quality of grains for different material and process parameters. Then, the thermal study of the additional powder layer spreading on the melted layer is performed on a commercial finite element software. This study aims to determine the good spreading conditions allowing the melted material not to decrease below its crystallization temperature to enhance material densification.

La fabrication directe et additive regroupe un ensemble de technologies de mise en forme des matériaux en rupture avec les procédés conventionnels. L'industrie aéronautique et aérospatiale s'intéresse fortement à ces nouveaux procédés, dont la fusion sélective par laser de lits de poudre métallique (SLM). Cette thèse présentera les enjeux de la fabrication additive ainsi que certains procédés. Une étude bibliographique a été menée sur deux alliages aéronautiques utilisés dans ces travaux : l'alliage de titane TA6V et le superalliage base nickel Nimonic 263. Les travaux présentés dans ce rapport comprennent l'étude de la poudre métallique brute d'atomisation (morphologie, granulométrie, composition chimique). D'autre part, l'étude de la recyclabilité de la poudre utilisée en SLM est présentée pour le TA6V, tant en ce qui concerne l'évolution de la poudre elle-même que celle des propriétés mécaniques des pièces qui en sont issues. Par ailleurs ce travail traite d'un modèle de consolidation du lit de poudre permettant également d'évaluer la productivité du procédé. Enfin, une étude paramétrique et thermique menée sur le Nimonic 263 en vue de l'établissement d'une solution de contrôle procédé est présentée. / Direct and additive manufacturing regroups several new technologies that are very different from conventional manufacturing processes such as casting. Aeronautic and space industries are really interested in those new processes such as the selective laser melting of metallic powder beds know as the SLM process. This PhD thesis report will show the issues of additive manufacturing and will describe some processes. A bibliography study has been done on two aeronautical alloys used in this work: titanium alloy TA6V and nickel-based superalloy Nimonic 263. This work also presents powder characterization (granulometry, morphology chemical composition) for the gas atomized powder. Besides, study has been done on the recyclability of the TA6V powder for the SLM process, for the powder itself and the mechanical properties of parts built from recycled powder. Moreover, this works deals with a powder bed consolidation model to estimate the productivity of the process. Then, a parametric and thermal study has been done on the Nimonic 263. The coaxial system for thermal visualization is described such as the image processing algorithm used. Finally, this reports deals with the study of thermal signature of typical SLM defects.

[pt] Uma análise experimental é desenvolvida para avaliação da transferência de calor durante a fusão ao redor de um cilindro isotérmico vertical imerso em um meio de mudança de fase. A posição e forma da interface sólido-líquido é determinada como função do tempo, para diferentes temperaturas do cilindro. A relação altura/diâmetro é de cinco, para comparação com resultados já existentes. A faixa de Número de Stefan investigado foi de 0,017 a 0,33 o que equivale a uma faixa de Número Rayleigh de 7x10 elevado a quarta potência a 2x10 elevado a sexta potência. Os dados obtidos foram utilizados para a determinação dos números de Nusselt locais na interface e médios para a superfície do cilindro. A dependência da massa fundida com o tempo foi também determinada, parametrizada por Rayleigh. Soluções do problema de fusão sem os efeitos de convecção natural (Problema tipo STEFAN) foram obtidos via método de elementos finitos e estes resultados foram comparados com os dados experimentais obtidos. Isto permitiu a determinação do tempo quando os efeitos de convecção natural tornam-se importantes. Comparações com resultados numéricos publicados, para a mesma condição física, foram desenvolvidas obtendo excelentes concordâncias. / [en] An experimental investigation was performed to determine heat transfer coefficients during the outward melting of a phase-change material (PCM),maintained at its fusion temperature, around an isothermal cylinder positioned vertically. The position and shape of the Solid-liquid interface were determined as a function of time, for diferent temperatures of the cylinder. The ratio height-to-diameter of the cylinder was chosen to be five, in order to allow comparisons with available results. The Stefan number range investigated was 0,017 - 0,33 corresponding to a Rayleigh number variation from 7x10 to the fourth power to 2x10 to the sixth power. The data obtained was used in the determination of local Nusselt numbers for the interface and average Nusselt numbers for cylinder surface. The dependence of the molten mass on time was also determined, for several combinations of the relevant parameters. Solutions of the axisymmetric melting problem without natural convection effects (Stefan-like problem) were obtained via finite-element analysis. These numerical results were compared with the experimental data, which permitted the determination of times when the natural convection effects in the liquid region become of importance. The experimental data were compared with the results of an available numerical analysis of the same physical situation, and excellent agreement was obtained.

L'objectif de cette thèse est l'étude de la population de bulles générée entre deux morceaux de verre mis en contact et portés à 1100 °C sans matières premières. Comprendre la transition gaz dissous/gaz est un sujet scientifique majeur, par ailleurs les bulles sont le principal défaut dans les verres industriels et la quantité de verre recyclé introduite dans les fours est destinée à augmenter. Nous étudions la vie d'une bulle de sa nucléation à sa remontée dans le verre fondu en passant par sa croissance. Nous montrons que la nucléation homogène n'existe pas dans un verre car les réactions chimiques ne génèrent pas les sursaturations suffisantes. L'écoulement du verre après la transition vitreuse enferme des poches de gaz qui sont les précurseurs naturels des bulles. Nous modélisons la sursaturation à l'interface entre deux verres et montrons son influence sur le nombre de nuclei stables qui forment des bulles. Nous modélisons la dynamique de croissance des bulles en utilisant la même caractérisation de l'état d'oxydation que pour la nucléation. Nous constatons que la croissance des bulles à l'interface entre un verre réduit et un verre oxydé est plus rapide que celle des bulles situées dans un verre oxydé seul. Nous attribuons cette accélération à l'interaction entre les verres qui décale l'équilibre du soufre vers la formation de SO2 gazeux. Pour finir, nous présentons un montage expérimental qui permet de mesurer des champs de vitesse dans du verre grâce à l'utilisation de rayons X et à un algorithme de flot optique. Cette mesure permet d'évaluer la capacité d'une population de bulles à favoriser le mélange du verre au début de la fusion. / This thesis focuses on the bubbles population that appears between two glass pieces when heated at 1100 °C without any reactive raw materials. Understanding the mechanisms involved in the transition from dissolved gas to gas is still a fundamental issue of materials science. Industrially, bubbles are the major sources of defects in the final glass product and the amount of recycled glass introduced in glass furnaces will likely increase.We have studied the life of a bubble at different times, from its creation to its growth behavior, and to its rise in the molten glass. We show that homogeneous nucleation cannot exist in molten glass because chemical reactions are not able to generate the needed supersaturations by themselves. Thus, right after glass transition, glass flow is responsible for the entrapment of gas pockets, which then become natural precursors of bubbles.We model the supersaturation at the interface between two glasses, and we show its influence over the number of stable nuclei that can form bubbles.We also model the growth dynamic by using the same characterization of glasses' oxidation states than for nucleation. We experimentally show that bubbles located at the interface between a reduced glass and an oxidized glass grow faster than bubbles located in an oxidized glass only. The main effect of the interaction between the two glasses is to move the sulfur equilibrium towards the formation of gaseous SO2.Finally, using X-rays and an optical flow algorithm, we present a new experimental setup which measure velocity fields in an opaque medium to assess bubbles ability to promote glass mixing.

The selective laser sintering (SLS) process or the additive manufacturing (AM) enables the construction of a three-dimensional object through melting and solidification of metal powder. The primary advantage of AM over the conventional process is providing the manufacturing flexibility, especially for highly complicated products. The quality of AM products depends upon various processing parameters such as laser power, laser scanning velocity, laser scanning pattern, layer thickness, and hatch spacing. The improper selection of these parameters would lead to parts with defects, severe distortion, and even cracking. I herein perform the numerical and experimental analysis to investigate the interplay between processing parameters and the defect generation. The analysis aims to resolve issues at two different scales, micro-scale and product-scale. At the micro-scale, while the numerical model is developed to investigate the interaction of the laser and materials in the AM process, its advantages and disadvantages compared to an analytical approach (Rosenthal’s equation), which provides a quicker thermal solution, are thoroughly studied. Additionally, numerical results have been verified by series of experiments. Based on the analysis, it is found that the simultaneous consideration of multiple processing parameters could be achieved using the energy density. Moreover, together with existing criteria, a processing window is numerically developed as a guideline for AM users to avoid common defects at this scale including the lack of fusion, balling effect, and over-melting. Thermal results at a micro-scale are extended as an input to determine the residual stress initiation in AM products. The effect of energy density and substrate temperature on a residual stress magnitude is explored. Results show that the stress magnitude within a layer is a strong function of the substrate temperature, where a higher substrate temperature results in a lower stress. Moreover, the stress formation due to a layer’s addition is studied, in which the stress relaxation at locations away from a top surface is observed. Nevertheless, even though the micro-scale analysis can resolve some common defects in AM, it is not capable of predicting product-scale responses such as residual stress development and entire product’s distortion. As a result, the multiscale modeling platform is developed for the numerical investigation at the product level. Three thermal models at various scales are interactively used to yield an effective thermal development calculation at a product-scale. In addition, the influence of the multiple layers, energy densities and scanning patterns on the residual stress formation has been addressed, which leads to the prediction of the residual stress development during the fabrication. The distortion of products due to the residual stress can be described by the product-scale model. Furthermore, among many processing parameters, the energy input and the scanning length are found to be important factors, which could be controlled to achieve the residual stress reduction in AM products. An optimal choice of a scanning length and energy input can reduce an as-built residual stress magnitude by almost half of typically encountered values. Ultimately, the present work aims to illustrate the integration of the computational method as tools to provide manufacturing qualification for part production by the AM process.

Additive Manufacturing (AM) is a group of manufacturing technologies which are capable to produce 3D solid parts by adding successive layers of material. Parts are fabricated in an additive manner, layer by layer; and the geometric data can be taken from a CAD model directly. The main revolutionary aspect of AM is the ability of quickly producing complex geometries without the need of tooling, allowing for greater design freedom. As one of AM methods, Selective Laser Melting (SLM) is a process for producing metal parts with minimal subtractive post-processing required. It relies on the generation and distribution of laser generated heat to raise the temperature of a region of a powder bed to above the melting point. Due to high energy input to enable full melting of the powder bed materials, SLM is able to build fully dense metal parts without post heat treatment and other processing. Successful fabrications of parts by SLM require a comprehensive understanding of the main process controlling parameters such as energy input, powder bed properties and build conditions, as well as the microstructure formation procedure as it can strongly affect the final mechanical properties. It is valuable to control the parts' microstructure through controlling the process parameters to obtain acceptable mechanical properties for end-users. In the SLM process, microstructure characterisation strongly depends on the thermal history of the process. The temperature distribution in the building area can significantly influence the melting pool behaviour, solidification process and thermal mechanical properties of the parts. Therefore, it is important to have an accurate prediction of the temperature distribution history during the process. The aim of this research is to gain a better understanding of process control parameters in SLM process, and to develop a modelling methodology for the prediction of microstructure forming procedure. The research is comprised of an experiment and a finite element modelling part. Experimentation was carried out to understand the effect of each processing control parameters on the final part quality, and characterise the model inputs. Laser energy input, build conditions and powder bed properties were investigated. Samples were built and tested to gain the knowledge of the relationship between samples' density and mechanical properties and each process control factor. Heat transfer model inputs characterisation, such as defining and measuring the material properties, input loads and boundary conditions were also carried out via experiment. For the predictive modelling of microstructure, a methodology for predicting the temperature distribution history and temperature gradient history during the SLM process has been developed. Moving heat source and states variable material properties were studied and applied to the heat transfer model for reliable prediction. Multi-layers model were established to simulate the layer by layer process principles. Microstructure was predicted by simulated melting pool behaviour and the history of three dimensional temperature distribution and temperature gradient distribution. They were validated by relevant experiment examination and measurement.

The Sutherland group recently demonstrated that from a mixture of oligoribonucleotide-2'- or 3'-phosphates the latter is chemoselectively acetylated. This is shown to mediate a template-directed ligation to give predominantly 3',5'-linked RNA that is acetylated at the ligation junction (acetyl-RNA). It was suggested that RNA emerged prebiotically via acetyl-RNA and also is proposed to have favourable genotypic properties due to greater propensity to form duplex structure. To study the properties of acetyl-RNA, their synthesis by solid-phase chemistry was required and described is the design of a 2'/3'-O-acetyl orthogonal protecting group strategy. Key to the orthogonal protecting group strategy is the use of (2-cyanoethoxy)carbonyl for the protection of the nucleobase exocyclic amines and a photolabile solid-phase linker group that allowed partial on-column deprotection. The synthesis of the 2'/3'-O-acetyl and 2'/3'-O-TBDMS phosphoramidites, in addition to preparation of a photolabile solid-phase support, are described. With the materials to hand the procedures for an automated synthesis of acetyl-RNA were optimised and several acetyl-RNA oligonucleotides were synthesised. The duplex stability of acetyl-RNA with up to four sites of 2'-O-acetylation were assessed by UV melting curve analysis. Remarkably, the acetyl groups caused a consistent decrease in Tm of between 3.0-3.2 °C. Thermodynamic parameters indicated a decrease in duplex stability that was consistent with a decrease in hydration of the minor groove resulting in a reduction of the stabilising hydrogen bonding network. The stability of a tetraloop was also found to decrease on acetylation. The acetylated- tetraloop it is able to form duplex at lower concentrations than the natural tetraloop. Additionally, it is more stable at high concentrations, indicating that acetyl-RNA favours duplex over other secondary structure. These properties are considered to give acetyl-RNA competitive advantage for their non-enzymatic replication. Aminoacylation of RNA is an important process in modern biology but the intermediacy of aminoacyl-adenylates is considered to be prebiotically implausible. A potentially prebiotic aminoacylation of nucleoside-3'-phosphates, selective for the 2'-hydroxyl, is presented. However, it was thought the aminoacylation yields could be improved and so a search for an alternative activator was conducted. Oligoribonucleotide-3'-phosphates were exposed to the aminoacylation conditions and selective aminoacylation at only the 2'-hydroxyl of the 3'-end was observed. In particular, the aminoacylation of a trimer lends support to Sutherland’s theory of a linked origin of RNA and coded peptide synthesis.