Les principaux modèles de comportement en fatigue des assemblages soudés par point ne prennent en compte que des paramètres géométriques. Or, les contraintes résiduelles, la microstructure de la Zone Affectée Thermiquement et la forme du fond d'entaille sont, a priori, autant de facteurs d'influence supplémentaires. L'objectif de ce travail est la compréhension des facteurs prédominants de la tenue en fatigue des assemblages soudés par point en acier THR, afin de proposer des conditions de soudage permettant un comportement amélioré. Pour analyser finement les résultats d'essais, des méthodologies et des outils d'observation sont développés : suivi de fissure, fractographie MEB, analyse métallographique. En soudage, l'observation des structures primaires permet de comprendre la formation du point de soudure. Dans certains cas, la solidification débute alors que le courant est encore délivré à l'assemblage. De nombreux essais de fatigue sont réalisés sur des assemblages de traction-cisaillement en acier Dual Phase pour étudier l'influence des conditions de soudage. Par l'utilisation combinée des différents outils, l'effet des conditions de soudage et les principaux facteurs d'influence sur la durée de vie de l'assemblage sont dégagés. L'étape de propagation de fissure est peu sensible aux conditions de soudage, une modélisation fiabiliste de cette étape est proposée. L'amorçage de fissure se révèle être l'étape cruciale. Un cycle de soudage adapté permet d'obtenir un comportement en fatigue amélioré grâce à une modification favorable du champ de contraintes résiduelles en fond d'entaille , tout en gardant des séquences de soudage sur composant acceptables. Ces résultats ouvrent de réelles perspectives d'application industrielle.

The aim of the present thesis is to understand the phase transformation behavior of embedded alloy nanoparticles embedded in immiscible matrices. Embedded alloy inclusions have been dispersed in immiscible matrix via rapid solidification method. The present work deals with synthesis of embedded particles, evolution of microstructure, morphology and crystallographic orientation relation relationships among different phases, phase transformation and phase stability behavior of embedded alloy inclusions in different matrices. In the present investigation the systems chosen are Bi-Sn and Bi-Pb in Zn matrix and Cd-Sn in Al matrix. Chapter 1 gives the brief introduction of present work Chapter 2 gives a brief review of nanoscale materials, various synthesis techniques, microstructure evolution, solidification and melting theories. Chapter 3 discusses the processing and experimental techniques used for characterization of the different samples in the present work. Melt-spinning technique used to synthesize the rapidly solidified ribbons. The structural characterization is carried out using X-ray diffraction and transmission electron microscopy. Chapter 4 illustrates the size dependent solubility and phase transformation behavior of Sn-Cd alloy nanoparticles embedded in aluminum matrix. X-ray diffraction study shows the presence of fcc Al, bct Sn, hcp Cd solid solution and hcp Cd phases. Based on Zen’s law, the amount of Sn present Cd solid solution is estimated. Using overlapped sterograms, the orientational relationships among various phases are found. Microscopy studies reveal that majority of the alloy nano inclusions exhibit a cuboctahedral shape with 111 and 100 facets and they are bicrystalline. STEM-EDS analysis shows that both phases exhibit size dependent solubility behavior and for particles size smaller than 18 nm, single phase solid solution could only be observed. Calorimetric studies reveal a depression in eutectic melting point of bimetallic particles. In situ heating studies show that melting initiates at triple line junction corner and melt first grows into the interior of the Sn rich phase of the particle and then later the melt grows into the interior of the Cd phase of the particle. During cooling first Cd phase solidifies later Sn phase solidifies and on further cooling at low temperatures entire particle transforming into complete solid solution phase particle. Size dependent melting studies show that during heating smaller particles melted first, later bigger particles melted. During cooling first bigger particle solidified later smaller particles solidified. High resolution imaging indicates presence of steps across particle-matrix interface that may get annihilated during heating. During cooling, molten particles in the size range of 16-30 nm solidify as solid solution which for molten particles greater than 30 nm solidify as biphasic particle. Insitu heating studies indicates that for solid particles less than 15 nm get dissolved in the Al matrix at temperatures at around 135°C. Differential scanning calorimetry (DSC) studies show in the first heating cycle most of the particles melt with an onset of melting of at 166.8°C which is close to the bulk eutectic temperature of Sn-Cd alooy. The heating cycle reveals that the melting event is not sharp which can be understood from in-situ microscopy heating studies. In the second and the third cycles, the onset of melting observed at still lower temperatures 164.3°C and 158.5°C .The decrease in onset melting point in subsequent heating cycles is attributed to solid solution formation of all small particles whose size range below 30 nm during cooling. cooling cycles exhibit an undercooling of 90°C with respect to Cd liquidus temperature. Thermal cycling experiments using DSC were carried out by arresting the run at certain pre-determined temperatures during cooling and reheating the sample to observe the change in the melting peak position and area under the peak. The areas of these endothermic peaks give us an estimate of the fraction of the particles solidified upto the temperature when the cycling is reversed. Based on experimental observations, a thermodynamic model is developed, to understand the solubility behavior and to describe the eutectic melting transition of a binary Sn-Cd alloy particle embedded in Al matrix. Chapter 5 discusses the phase stability and phase transformation behavior of nanoscaled Bi-Sn alloys in Zn matrix. Bi-Sn alloys with eutectic composition embedded in Zn matrix using melt spinning technique. X-ray diffraction study shows the presence of rhombohedral Bi, pure BCT Sn and hcp Zn phases. In X-ray diffractogram, there are also other new peaks observed, whose peak positions (interplanar spacings) do not coincide either with rhombohedral Bi or bct Sn or hcp Zn. Assuming these new phase peaks belong to bct Sn rich solid solution(based on earlier work on Bi-Sn rapidly solidified metastable alloys) whole pattern fitting done on x-ray diffractogram using Lebail method. The new phase peaks indicated as bct M1(metastable phase1), bct M2(metastable phase2) phases. The amount of Bi present in M1, M2 solid solution is estimated using Zens law. Two sets of inclusions were found, one contains equilibrium bismuth and tin phases and the other set contains equilibrium bismuth and a metastable phase. In-situ TEM experiments suggest that as temperature increases bismuth diffuses into tin and becomes complete solid solution. Melting intiates along the matrix–particle interface leading to a core shell microstructure. During cooling the entire inclusion solidify as solid solution and decomposes at lower temperatures. High temperature XRD studies show that as temperature increases M1, M2 phases peaks merge with Sn phase peaks and Bi phase peak intensities slowly disappear and on further increasing temperature Sn solid solution phase peaks also disappear. During cooling diffraction studies show that first Sn solid solution phase peaks appear and later Bi phase peaks appear. But, the peaks belong to metstable phases not appeared while cooling. Chapter 6 presents morphology and phase transformation of nanoscaled bismuth-lead alloys with eutectic (Pb44.5-Bi55.5) and peritectic (Pb70-Bi30) compositions embedded in zinc matrix. using melt spinning technique. In alloy1[ Zn-2at%(Pb44.5-Bi55.5)] inclusions were found to be phase separated into two parts one is rhombohedral Bi and the other is hcp Pb7Bi3 phase. X-ray diffraction study shows the presence of rhombohedral Bi, hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb44.5-Bi55.5) melt spun sample. The morphology and orientation relationships among various phases have been found. In-situ microscpy heating studies show that melt initially spreads along the matrix–particle interface leading to a core-shell microstructure. And in the core of the core-sell particles, first Bi phase melts later Pb7Bi3 phase will melt and during cooling the whole particle solidify as biphase particle with large undercooling. In-situ heating studies carried out to study the size dependent melting and solidification behavior of biphase particles. During heating smaller particles melt melt first later bigger particle will melt. In contrast, while cooling smaller particles solidifies first, later bigger particles will solidify. Detailed high temperature x-ray diffraction studies indicate there increases first Bi phase peaks disappear later Pb7Bi3 phase peaks disappear and during cooling first Pb7Bi3 phase peaks appear and later Bi phase peaks appear. In alloy2[ Zn-2at%(Pb70-Bi30)] inclusions were found to be single phase particles. X-ray diffraction study shows the presence of hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb70-Bi30) melt spun sample. The crystallographic orientation relationship between hcp Pb7Bi3 and hcp Zn phases. In-situ microscpy heating studies show that melting initiates across the matrix–particle interface grows gradually into the interior of the particle. Three phase equilibrium at peritectic reaction temperature is not observed during insitu heating TEM studies. Size dependent melting point depression of single phase particles is not observed from in-situ heating studies. Detailed high temperature x-ray diffraction studies show that while heating the Pb7Bi3 phase peak intensities start decreasing after 170°C and become zero at 234°C. And during cooling Pb7Bi3 phase peaks starts appearing at 200°C and on further cooling the Pb7Bi3 phase peak intensities increase upto 150°C, below this temperature peak intensities remain constant.

This thesis work deals with the volume changes during the solidification of cast irons and peritectic steels. The volume changes in casting metals are related to the expansion and/or contraction of the molten metal during solidification. Often, different types of shrinkage, namely macro- and micro-shrinkage, affect the casting quality. In addition to that, exposure of the metal casting to higher contraction or expansion during the solidification might also be related to internal strain development in samples, which eventually leads to surface crack propagation in some types of steel alloys during continuous casting. In consequence, a deep understanding of the mechanisms and control of the solidification will improve casting quality and production. All of the experiments during the entire work were carried out on laboratory scale samples. Displacement changes during solidification were measured with the help of a Linear Variable Displacement Transformer (LVDT). All of the LVDT experiments were performed on samples inside a sand mould. Simultaneously, the cooling curves of the respective samples during solidification were recorded with a thermocouple. By combining the displacement and cooling curves, the volume changes was evaluated and later used to explain the influence of inoculants, carbon and cooling rates on volume shrinkages of the casting. Hypoeutectic grey cast iron (GCI) and nodular cast iron (NCI) with hypo-, hyper- and eutectic carbon compositions were considered in the experiments from cast iron group. High nickel alloy steel (Sandvik Sanbar 64) was also used from peritectic steel type. These materials were melted inside an induction furnace and treated with different types of inoculants before and during pouring in order to modify the composition. Samples that were taken from the LVDT experiments were investigated using a number of different  methods in order to support the observations from the displacement measurements:  Differential Thermal Analysis (DTA), to evaluate the different phase present; Dilatometry, to see the effect of cooling rates on contraction for the various types of alloys; metallographic studies with optical microscopy; Backscattered electrons (BSE) analysis on SEM S-3700N, to investigate the different types of oxide and sulphide nuclei; and bulk density measurements  by applying Archimedes' principle. Furthermore, the experimental volume expansion during solidification was compared with the theoretically calculated values for GCI and NCI. It was found that the casting shows hardly any shrinkage during early solidification in GCI, but in the eutectic region the casting expands until the end of solidification. The measured and the calculated volume changes are close to one another, but the former shows more expansion. The addition of MBZCAS (Si, Ca, Zr, Ba, Mn and Al) promotes more flake graphite, and ASSC (Si, Ca, Sr and Al) does not increase the number of eutectic cells by much. In addition to that, it lowers the primary austenite fraction, promotes more eutectic growth and decreases undercooled graphite and secondary dendritic arm spacing (SDAS). As a result, the volume expansion changes in the eutectic region. The expansion during the eutectic growth increase with an increase in the inoculant weight percentage. At the same time, the eutectic cells become smaller and increase in number. The effect of the inoculant and the superheat temperature shows a variation in the degree of expansion/contraction and the cooling rates for the experiments. Effective inoculation tends to homogenize the eutectic structure, reducing the undercooled and interdendritic graphite throughout the structure. In NCI experiments, it was found that the samples showed no expansion in the transversal direction due to higher micro-shrinkages in the centre, whereas in the longitudinal direction the samples shows expansion until solidification was complete.   The theoretical and measured volume changes agreed with each other. The austenite fraction and number of micro-shrinkage pores decreased with increase in carbon content. The nodule count and distribution changes with carbon content. The thermal contraction of NCI is not influenced by the variation in carbon content at lower cooling rates. The structural analysis and solidification simulation results for NCI show that the nodule size and count distribution along the cross-sections at various locations are different due to the variation in cooling rates and carbon concentration. Finer nodule graphite appears in the thinner sections and close to the mold walls. A coarser structure is distributed mostly in the last solidified location. The simulation result indicates that finer nodules are associated with higher cooling rate and a lower degree of microsegregation, whereas the coarser nodules are related to lower cooling rate and a higher degree of microsegregation. As a result, this structural variation influences the micro-shrinkage in different parts. The displacement change measurements show that the peritectic steel expands and/or contracts during the solidification. The primary austenite precipitation during the solidification in the metastable region is accompanied by gradual expansion on the casting sides. Primary δ-ferrite precipitation under stable phase diagram is complemented by a severe contraction during solidification. The microstructural analysis reveals that the only difference between the samples is grain refinement with Ti addition. Moreover, the severe contraction in solidification region might be the source for the crack formation due to strain development, and further theoretical analysis is required in the future to verify this observation. / <p>QC 20170228</p>

A proposta da modificação química da superliga MAR-M247 através da substituição do Ta pelo Nb (em átomos) foi baseada nas seguintes informações: (1) O Nb desempenha funções muita parecidas com as do Ta nas superligas à base de Ni, como endurecedor via solução sólida da fase ? e elemento formador de fases secundárias (?? e carbonetos); (2) O Brasil tem as maiores reservas de Nb do mundo e (3) O Nb já é adicionado em diversas classes de superligas à base de Ni - fundidas convencionalmente e solidificadas direcionalmente e monocristalinas. Neste trabalho o objetivo principal foi de avaliar a viabilidade da substituição do Ta pelo Nb na superliga à base de Ni MAR-M247. As amostras da MAR-M247 e da liga modificada - MAR-M247[Nb] utilizadas na caracterização microestrutural foram obtidas por solidificação direcional no forno a vácuo do tipo forno Bridgman (Lab. de Solidificação/FEM-UNICAMP) nas seguintes condições de processamento: v = 5, 10 e 18 cm/h e G = 80°C/cm. As simulações de cálculo termodinâmico utilizando o programa Thermo-Calc foram realizadas com o objetivo de se avaliar se as temperaturas de transformação mudariam com a substituição do Ta pelo Nb. Para avaliação das propriedades mecânicas em alta temperatura e a estabilidade estrutural da superliga MAR-M247[Nb] foram realizados ensaios de fluência a 750 e 850 °C nas tensões de 840, 780 e 440 MPa. A estabilidade microestrutural da MAR-M247[Nb] foi testada por meio de ensaios de oxidação isotérmica a 1000 °C no intervalo de tempo de 30 minutos a 100 h. A substituição do Ta pelo Nb promoveu mudanças significativas principalmente nas temperaturas de formação do eutético ?/??, solvus - ?? e de fusão incipiente. As microestruturas das ligas após os experimentos de solidificação direcional a v = 5, 10 e 18 cm/h eram constituídas por dendritas da fase gama - ? e precipitados coerentes da fase gama linha - ?? (morfologia cuboidal). Na região interdendrítica da MAR-M247 e MAR-M247[Nb] solidificadas a v = 5 e 10 cm/h foram encontrados os eutéticos ?/?? e ?/Ni5(Hf,Zr). Na v = 18 cm/h a região interdendrítica era constituída apenas do eutético ?/??. A exposição a 1250 °C por 15 e 30 dias promoveu a decomposição total e a re-precipitação de carbonetos do tipo MC. No entanto, devido à contaminação por oxigênio e nitrogênio durante os tratamento térmicos, não foi atingido o equilíbrio termodinâmico em decorrência de mudanças das composições dos carbonetos MC. Nos ensaios de fluência a 750 °C, os tempos de ruptura foram de 49 h para MAR-M247 e de 39,4 h para MAR-M247[Nb] apesar dos elevados valores das tensões terem sido superestimados. A 850 °C o tempo de ruptura da MAR-M247[Nb] (trup = 359 horas) foi reduzido em 32 % em relação ao valor observado para MAR-M247 (trup = 476 horas). Os resultados dos ensaios de oxidação a 1000 °C da superliga MAR-M247[Nb] mostraram que o período transiente foi de 20 h com ganho de massa expressivo. A partir de 50 h o efeito do descolamento das camadas oxidadas durante o resfriamento das amostras foi significativo e promoveu uma variação de massa importante no intervalo de tempo de 50 a 100 h. Ensaios de oxidação em tempos mais longo deverão ser feitos para determinação da estrutura de formação das camadas e seus respectivos constituintes. / The chemistry modification in the Ni-based superalloy MAR-M247 through the replacing all Ta by Nb was based on in these statements: (1) Nb does the same function in Ni-based superalloys as Ta does, solid solution strenghtening and ?? e carbides element formers, (2) Brazil has the major ores of Nb in the world and (3) Nb has been added in all classes of Ni superalloy conventional casting, columnar and single crystal processed by directional solidification. In this study the main focus was to evaluate the feasibility of replacing Ta by Nb in the Ni - based superalloy MAR-M247. The samples of MAR-M247 and the Nb modified MAR-M247[Nb] were produced by directional solidification in a Bridgman vacuum furnace at the Solidification Research Lab/FEM - UNICAMP) in the following processing conditions: v = 5, 10 and 18 cm/h and G = 80 °C/cm. The thermodynamic simulations using Thermo-Calc program were performed to evaluate whether or not the transformation temperatures would change with the replacing of Ta by Nb. For the evaluation of mechanical properties at high temperature were performed creep rupture tests at 750 and 850 °C under the stress values of 840, 780 and 440 MPa. The isotermal oxidation tests at 1000 °C were done during the time interval of 30 min to 100 h. The replacing of Ta by Nb promoted some changes in eutectic-?/??, ??-solvus and incipient melting temperatures. After the directional solidification experiments at the v = 5, 10 and 18 cm/h the microstructural characterization has shown that for all condition the microstructures were composed by dendrites - ? and ?? - cuboidal precipitates in it. In the interdendritic region was observe the ?/?? and ?/Ni5(Hf,Zr) eutectics for v = 5 and 10 cm/h and only the ?/?? eutectics for v = 18 cm/h. The exposure at 1250 °C for the extended times promoted the formation of fine MC carbides but the equilibrium compositions have not been achieved due to the oxygen and nitrogen contamination. In the creep rupture tests at 750 °C the MAR-M247[Nb] have shown more shorter lifetime than the MAR-M247 even with overestimated tensile stress. At 850 °C the lifetime for MAR-M247[Nb] (trup = 359 h) was reduced by 32 % compared to the MAR-M247 (trup = 476 h). It was discussed that the changes in the composition of the ? phase induced Ta by Nb replacing which would led to the weakness of matrix in the MAR-M247[Nb]. The samples were oxidized at 1000 °C showed 20 h to the transient period and significant weight gain in that time. However at the extended period the weight gain had changed significantly and was precluded to predict the structure formation of oxides layer properly.

A proposta da modificação química da superliga MAR-M247 através da substituição do Ta pelo Nb (em átomos) foi baseada nas seguintes informações: (1) O Nb desempenha funções muita parecidas com as do Ta nas superligas à base de Ni, como endurecedor via solução sólida da fase ? e elemento formador de fases secundárias (?? e carbonetos); (2) O Brasil tem as maiores reservas de Nb do mundo e (3) O Nb já é adicionado em diversas classes de superligas à base de Ni - fundidas convencionalmente e solidificadas direcionalmente e monocristalinas. Neste trabalho o objetivo principal foi de avaliar a viabilidade da substituição do Ta pelo Nb na superliga à base de Ni MAR-M247. As amostras da MAR-M247 e da liga modificada - MAR-M247[Nb] utilizadas na caracterização microestrutural foram obtidas por solidificação direcional no forno a vácuo do tipo forno Bridgman (Lab. de Solidificação/FEM-UNICAMP) nas seguintes condições de processamento: v = 5, 10 e 18 cm/h e G = 80°C/cm. As simulações de cálculo termodinâmico utilizando o programa Thermo-Calc foram realizadas com o objetivo de se avaliar se as temperaturas de transformação mudariam com a substituição do Ta pelo Nb. Para avaliação das propriedades mecânicas em alta temperatura e a estabilidade estrutural da superliga MAR-M247[Nb] foram realizados ensaios de fluência a 750 e 850 °C nas tensões de 840, 780 e 440 MPa. A estabilidade microestrutural da MAR-M247[Nb] foi testada por meio de ensaios de oxidação isotérmica a 1000 °C no intervalo de tempo de 30 minutos a 100 h. A substituição do Ta pelo Nb promoveu mudanças significativas principalmente nas temperaturas de formação do eutético ?/??, solvus - ?? e de fusão incipiente. As microestruturas das ligas após os experimentos de solidificação direcional a v = 5, 10 e 18 cm/h eram constituídas por dendritas da fase gama - ? e precipitados coerentes da fase gama linha - ?? (morfologia cuboidal). Na região interdendrítica da MAR-M247 e MAR-M247[Nb] solidificadas a v = 5 e 10 cm/h foram encontrados os eutéticos ?/?? e ?/Ni5(Hf,Zr). Na v = 18 cm/h a região interdendrítica era constituída apenas do eutético ?/??. A exposição a 1250 °C por 15 e 30 dias promoveu a decomposição total e a re-precipitação de carbonetos do tipo MC. No entanto, devido à contaminação por oxigênio e nitrogênio durante os tratamento térmicos, não foi atingido o equilíbrio termodinâmico em decorrência de mudanças das composições dos carbonetos MC. Nos ensaios de fluência a 750 °C, os tempos de ruptura foram de 49 h para MAR-M247 e de 39,4 h para MAR-M247[Nb] apesar dos elevados valores das tensões terem sido superestimados. A 850 °C o tempo de ruptura da MAR-M247[Nb] (trup = 359 horas) foi reduzido em 32 % em relação ao valor observado para MAR-M247 (trup = 476 horas). Os resultados dos ensaios de oxidação a 1000 °C da superliga MAR-M247[Nb] mostraram que o período transiente foi de 20 h com ganho de massa expressivo. A partir de 50 h o efeito do descolamento das camadas oxidadas durante o resfriamento das amostras foi significativo e promoveu uma variação de massa importante no intervalo de tempo de 50 a 100 h. Ensaios de oxidação em tempos mais longo deverão ser feitos para determinação da estrutura de formação das camadas e seus respectivos constituintes. / The chemistry modification in the Ni-based superalloy MAR-M247 through the replacing all Ta by Nb was based on in these statements: (1) Nb does the same function in Ni-based superalloys as Ta does, solid solution strenghtening and ?? e carbides element formers, (2) Brazil has the major ores of Nb in the world and (3) Nb has been added in all classes of Ni superalloy conventional casting, columnar and single crystal processed by directional solidification. In this study the main focus was to evaluate the feasibility of replacing Ta by Nb in the Ni - based superalloy MAR-M247. The samples of MAR-M247 and the Nb modified MAR-M247[Nb] were produced by directional solidification in a Bridgman vacuum furnace at the Solidification Research Lab/FEM - UNICAMP) in the following processing conditions: v = 5, 10 and 18 cm/h and G = 80 °C/cm. The thermodynamic simulations using Thermo-Calc program were performed to evaluate whether or not the transformation temperatures would change with the replacing of Ta by Nb. For the evaluation of mechanical properties at high temperature were performed creep rupture tests at 750 and 850 °C under the stress values of 840, 780 and 440 MPa. The isotermal oxidation tests at 1000 °C were done during the time interval of 30 min to 100 h. The replacing of Ta by Nb promoted some changes in eutectic-?/??, ??-solvus and incipient melting temperatures. After the directional solidification experiments at the v = 5, 10 and 18 cm/h the microstructural characterization has shown that for all condition the microstructures were composed by dendrites - ? and ?? - cuboidal precipitates in it. In the interdendritic region was observe the ?/?? and ?/Ni5(Hf,Zr) eutectics for v = 5 and 10 cm/h and only the ?/?? eutectics for v = 18 cm/h. The exposure at 1250 °C for the extended times promoted the formation of fine MC carbides but the equilibrium compositions have not been achieved due to the oxygen and nitrogen contamination. In the creep rupture tests at 750 °C the MAR-M247[Nb] have shown more shorter lifetime than the MAR-M247 even with overestimated tensile stress. At 850 °C the lifetime for MAR-M247[Nb] (trup = 359 h) was reduced by 32 % compared to the MAR-M247 (trup = 476 h). It was discussed that the changes in the composition of the ? phase induced Ta by Nb replacing which would led to the weakness of matrix in the MAR-M247[Nb]. The samples were oxidized at 1000 °C showed 20 h to the transient period and significant weight gain in that time. However at the extended period the weight gain had changed significantly and was precluded to predict the structure formation of oxides layer properly.

<p>Predmet doktorske disertacije je uklanjanje neorganskih i organskih polutanata iz efluenata ofset tehnike štampe (otpadnog razvijača i otpadnog sredstva za vlaženje) u cilju minimiziranja njihovog štetnog uticaja na životnu sredinu. Uklanjanje polutanata sprovedeno je primenom elektrokoagulaciono/ flotacionog (EKF) tetmana, adsorpcionog (AD) tretmana i kombinacijom navedenih tretmana. Izvodljivost i efikasnost tretmana analizirana je ispitivanjem uticaja karakterističnih operativnih promenljivih u okviru procesa na smanjivanje količine polutanata. Mehanizmi EKF i AD tretmana definisani su na osnovu teorijskih matematičko kinetičkih modela. Za rešavanje problema odlaganja mulja nastalog nakon EKF tretmana primenjen je solidifikaciono/stabiliza-cioni tretman sa odgovarajućim imobilizacionim agensima. Razvijen je efikasan model kombinacije tretmana efluenata grafičkih procesa ofset štampe kojim je omogućena konverzija efluenata u proizvode kompatibilne sa principima i normativima životne sredine.</p> / <p>The topic of this doctoral dissertation is the removal of inorganic and organic pollutants from the offset printing effluents (waste developer and waste fountain solution) in order to minimize their damaging influence onto the environment. The removal of the pollutants has been performed by electrocoagulation/flotation (ECF) treatment, adsorption (AD) treatment and the combination of the two said treatments. Feasibility and efficacy of the treatments has been analyzed by investigating the effect of characteristic operational variables within the process on the decrease in the quantity of pollutants. The mechanisms of ECF and AD treatments have been defined on the basis of theoretical mathematical-kinetic models. For the solution of the problem of sludge disposal, originating from the ECF treatment, a solidification/stabilization treatment with immobilization agents has been applied. An efficient model that combines the offset printing effluent treatments has been developed, the one which enables the conversion of effluents into products compatible with environmental principles and norms.</p>

Submitted by JOSIANE SANTOS DE OLIVEIRA (josianeso) on 2018-12-21T13:22:18Z No. of bitstreams: 1 José Henrique Nazzi Ehms_.pdf: 4808489 bytes, checksum: b590c723912ffe1d5d90006182f8cff2 (MD5) / Made available in DSpace on 2018-12-21T13:22:18Z (GMT). No. of bitstreams: 1 José Henrique Nazzi Ehms_.pdf: 4808489 bytes, checksum: b590c723912ffe1d5d90006182f8cff2 (MD5) Previous issue date: 2018-10-31 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Armazenamento térmico apresenta grande potencial de utilização em diversas aplicações, como energia solar, climatização, conservação de alimentos ou aproveitamento de calor residual em processos industriais. O armazenamento térmico de calor latente é realizado com materiais de mudança de fase (PCM), através dos processos de fusão e solidificação. A representação destes processos através de simulação numérica é realizada com o acréscimo ao modelo matemático básico, composto pelas equações da conservação da massa, quantidade de movimento e energia, modelos para descrever o calor latente e a transição na velocidade entre as fases, tais como: Darcy STM (source term method), VVM (variable viscosity method) e SOM (switch-off method). No entanto, a grande maioria das pesquisas nesta área utiliza o primeiro método. Além disso, são poucos os estudos comparativos de diferentes métodos para descrever processos de mudança de fase. Assim, o objetivo do presente estudo é comparar os métodos Darcy STM, VVM e misto (utilizando elementos dos dois anteriores) na simulação numérica de processos de fusão e de solidificação do PCM RT27 no interior de uma esfera. O estudo foi realizado utilizando-se fluidodinâmica computacional, através do método dos volumes finitos. O Modelo numérico foi validado com resultados experimentais da literatura. Os resultados quantitativos e qualitativos de fração líquida mostram que o método Darcy STM é mais adequado ao processo de solidificação, enquanto o método VVM produz resultados mais próximos aos experimentais no processo de fusão. O custo computacional foi menor para o método Darcy STM e maior para o método VVM, enquanto o método misto apresenta custo computacional pouco inferior ao do método VVM. Na análise da camada líquida na fusão de contato, foram analisadas a velocidade descendente do sólido, a espessura da camada e a vazão na camada. Os resultados referentes a camada líquida indicaram significativa influência das configurações do método Darcy STM. No entanto, são pouco influenciados pelas configurações do método VVM. / Thermal energy storage presents great potential of utilization in several applications, such as solar energy, HVAC systems, food conservation or waste heat recovery in industrial processes. Latent heat thermal energy storage is realized with phase change materials (PCM), through solidification and melting processes. Representation of such processes through numerical simulation is performed with the addition to the basic numerical model, composed of the conservation equations of mass, momentum and energy, models to account the latent heat and the velocity transition between the phases, such as: Darcy STM (source term method), VVM (variable viscosity method) and SOM (switch-off method). However, the large majority of the research on such area employ the first method. Besides that, there are few comparative studies of different methods to describe phase change processes. Thus, the objective of the present work is compare Darcy STM, VVM and mixed method (using elements of the two prior) in the simulation of melting and solidification processes of PCM RT27 inside a sphere. The study was realized using computational fluid dynamics, with the finite volume method. The numerical model was validated with experimental results from literature. Quantitative and qualitative results of liquid fraction show that Darcy STM is most suitable to solidification process, while VVM produces results closer to experimental in the melting process. Computational cost was smaller for Darcy STM and greater for VVM, while mixed method presents computational cost slightly lower than the one of VVM. In the analysis of the liquid layer in close contact melting, were analyzed descending velocity of the solid, liquid layer thickness and the flow in the liquid layer. The results regarding the liquid layer denote significant influence of the configurations for Darcy STM. However, such results are little influenced by the configurations of VVM.

Dans le domaine de l'élaboration des alliages métalliques, les principaux enjeux industriels résident dans la possibilité de maîtriser la structure métallurgique ainsi que les défauts qui surviennent lors de la phase de solidification. Lors de la solidification, les mouvements hydrodynamiques dans la phase liquide ont une influence importante sur les propriétés du produit solidifié. Dans cette étude, la conception d'un nouveau dispositif BATMAF (Bridgman Apparatus with a Travelling MAgnetic Field) constitué d'un four de solidification dirigée et d'une bobine de Bitter permettant de produire un champ magnétique glissant a permis d'étudier l'influence d'une convection forcée sur la solidification dirigée des alliages métalliques binaires. Notre attention s'est plus particulièrement portée sur deux effets majeurs influencés par la présence de convection forcée ou non : la macroségrégation et la structure de grains pour un alliage d'Al-3.5%pdsNi en présence ou non de particules affinantes. La vitesse ainsi que le sens de l'écoulement forcé peuvent être contrôlés par l'application du champ magnétique glissant. Nous avons montré que dans le cas de notre alliage, la macroségrégation peut-être contrôlée et que de plus, l'espacement primaire dendritique est modifié en fonction du champ appliqué. En ce qui concerne les structures de grains, à l'aide d'un modèle analytique, nous montrons que l'extension de la couche solutale en avant du front de solidification varie en fonction du sens de l'écoulement au voisinage de la zone pâteuse. Ceci conditionne la possibilité pour les grains équiaxes de germer puis de croître et, par conséquent, l'obtention du régime équiaxe ou non. Enfin, dans le cas des alliages non affinés, dans un domaine d'intensité de brassage, un régime de grains libres allongés a pu être obtenu probablement par fragmentation. Cette étude démontre s'il en était besoin, l'importance cruciale de la maîtrise de la convection sur les macroségrégations et la structure des grains et ouvre des perspectives quant à l'utilisation du champ magnétique glissant pour leur contrôle

The effect of solidification conditions on microstructural and mechanical properties of eutectic TiFe alloy cast under different conditions was examined. Samples exhibit different ultrafine eutectic structures (β-Ti(Fe) solid solution + TiFe). Different cooling conditions lead to the evolution of ultrafine eutectic oval-shaped colonies or elongated lamellar colonies with preferred orientation. Isotropic as well as anisotropic mechanical properties were obtained. Alloys exhibit compressive strengths between 2200 and 2700 MPa and plastic strains between 7 and 19 pct. in compression.

On aborde quelques problèmes de durabilité posés par l'utilisation de géomatériaux en génie civil dans lesquels interviennent de forts couplages thermo-hydro-physico-chimio-mécaniques : (i) perméabilité à l'eau liquide des matériaux cimentaires ; (ii) perméabilité électro-osmotique dans les argiles ; (iii) comportement mécanique des bétons au gel/dégel.