This thesis is focused on shape optimization of Venturi´s nozzle with optimization method called response surface method. The first part of this work is concerned with the description of this method as well as explaining the basic principle. Furthermore, there is an explanation of the application of this method in synchronicity with CFD and its operating algorithm. The second part of this thesis is then focused on simple example with plane wing and simplified optimization of Venturi´s nozzle in which this method was tested. In the third part there is described full multiparameter shape optimalization of the nozzle for two geometries.

<p>Insekticidi novije generacije, neonikotinoidi, odlikuju se specifičnim načinom &nbsp;delovanja na&nbsp;nervni sistem insekata. Radi dobijanja &scaron;to brže i kvalitetnije informacije o izloženosti životne sredine&nbsp;ovim insekticidima i količinama njihovih ostataka u hrani potrebno je raspolagati odgovarajućim&nbsp;instrumentalnim metodama za njihovo određivanje. Razvijene su i optimizovane analitičke metode&nbsp;zasnovane na tečnoj hromatografiji za određivanje sedam odabranih neonikotinoida (dinotefurana,&nbsp;nitenpirama, tiametoksama, klotianidina, imidakloprida, acetamiprida &nbsp;i tiakloprida) u medu i likeru od&nbsp;meda. Ispitivana je mogućnost određivanja klotianidina pomoću tečne hromatografije visoke efikasnosti&nbsp;sa detektrorom od niza dioda (HPLC-DAD) primenom kombinacije tečno-tečne i ekstrakcije na čvrstoj&nbsp;fazi iz uzoraka meda. Na osnovu preliminarnih rezultata može se zaključiti da kori&scaron;ćenje &nbsp;faznih-čvrsto&nbsp;kolona u kombinaciji sa tečno-tečnom ekstrakcijom dihlormetanom rezultira prihvatljivim prinosom&nbsp;klotianidina u uzorcima meda pri koncentraciji od oko 0,5 &micro;g g^-1&nbsp;klotianidina. Radi dobijanja većih&nbsp;prinosa odabrana je disperzna tečno-tečna mikroekstrakcija (DLLME) kao tehnika pripreme uzoraka&nbsp;meda. Testirana je upotreba acetonitrila kao disperznog sredstva. Pored hloroforma, kori&scaron;ćen je i&nbsp;dihlormetan kao drugo ekstrakciono sredstvo, kako bi se &nbsp;uporedila efikasnost ekstrakcije. Zabeleženi su&nbsp;prinosi klotianidina od 69,7 i 68,3% &nbsp;u zavisnosti da li je kori&scaron;ćen hloroform, odnosno DHM kao rastvor&nbsp;za ekstrakciju. Može se zaključiti da je prinos ekstrakcije bio povoljniji pri odnosu 0,5 mL ACN i 2,0&nbsp;mL DHM. Prinosi su se kretali od 68,4% do 92,1%, &scaron;to je ukazalo da su parametri DLLME ekstrakcije optimalni. Kako bi se detaljnije ispitali ključni parametri DLLME tehnike, kori&scaron;ćena je metodologija povr&scaron;ine odziva (RSM), kao i detekcija na osetljivijem kuplovanom masenom detektoru (MS/MS). Optimizovani su HPLC-MS/MS &nbsp;parametri kako bi se obezbedilo zadovoljavajuće hromatografsko &nbsp;razdvajanje i niske granice detekcije (GD, 0,5&ndash;1,0 &mu;g kg^-1) i određivanja (GO, 1,0&ndash;2,5 &mu;g kg^-1) ispitivanih neonikotinoida u medu. Upotrebom centralno kompozitnog dizajna konstruisani su kvadratni modeli ispitivanih faktora: zapremine ekstrakcionog (DHM, 1,0&ndash;3,0 mL) i disperznog (ACN, 0,0&ndash;1,0 mL) sredstva, izračunati statistički parametri i optimizovan proces DLLME upotrebom <em>Derringer</em>-ove funkcije poželjnih odgovora. Upotrebom MMC i SC krivih u opsegu GO&ndash;100,0 &mu;g kg^-1&nbsp;ispitan je uticaj matriksa pri čemu zaključeno je da je najveći uticaj matriksa bio na odziv analitičkog signala nitenpirama, dinotefurana i klotianidina. Ispitani su prinosi odabranih neonikotinoida (R, 74,3&ndash;113,9%), kao i preciznost metode u uslovima ponovljivosti (RSD, 2,74&ndash; 11,8%) i intermedijerne reproduktivnosti (RSD, 6,64&ndash;16,2%). Brza (retenciona vremena 1,5&ndash;9,9 min) i osetljiva metoda, koja tro&scaron;i malu količinu rastvarača, primenjena je za ispitivanje 15 realnih uzoraka meda različitog cvetnog porekla. Rezultati su pokazali da ispitivani med nije sadržao ostatke ispitivanih neonikotinoida u koncentracijama iznad GD. Dalje istraživanje je bilo usmereno ka&nbsp; razvijanju i optimizaciji HPLC-DAD analitičke metode upotrebom DLLME i QuEChERS tehnika za &nbsp;pripremu uzoraka za određivanje 7 neonikotinoida u uzorcima meda. U ovom delu istraživanja optimizovani su i hromatografski parametri, upotrebom RSM sa Box-Behnken-ovim dizajnom i Derringer-ovom funkcijom poželjnih odgovora. Od &nbsp;ispitivanih neonikotinoida dinotefuran i imidakloprid su bili u najvećoj meri izloženi uticaju matriksa, bez obzira na proceduru pripreme uzoraka. Može se istaći da je uticaj matriksa na analitički signal dinotefurana bio izraženiji u slučaju MS/MS, apostrofirajući manju robusnost ove metode određivanja. Prinosi neonikotinoida su &nbsp;bili (R, 73,1&ndash;118,3%), preciznost u uslovima ponovljivosti (RSD, 3,28&ndash;10,40%) i intermedijerne reproduktivnosti (RSD, 6,45&ndash;17,70%), a granice detekcije (GD, 1,5&ndash;2,5 &micro;g kg^-1) i određivanja (GO, 5,0&ndash;10,0 &micro;g kg^-1). Metoda je primenjena za ispitivanje 7 neonikotinoida u 104 uzorkameda različitog cvetnog porekla sa &nbsp;teritorije Autonomne Pokrajine Vojvodine. Detektovano je prisustvo tiakloprida, imidakloprida i tiametoksama u količinama koje su bile ispod MDK RS i EU. Analizirani su uzorci likera od meda - medice. Upoređivane su dve tehnike pripreme uzoraka, DLLME i QuEChERS i primenjeni optimizovani hromatografski &nbsp;uslovi i MS/MS parametri. U slučaju nitenpirama, dinotefurana i tiametoksama uticaj matriksa bio je najizraženiji. Metoda je validovana određivanjem prinosa neonikotinoida (R, 69,2&ndash;113,4%), preciznosti u uslovima ponovljivosti (RSD, 3,21&ndash;12,81%) i intermedijerne reproduktivnosti (RSD, 9,11&ndash;16,63%), kao i granice detekcije (GD, 0,5&ndash;2,5 &micro;g kg^-1) i određivanja (GO, 1,0&ndash;10,0 &micro;g kg^-1). Analizom 10 komercijalno dostupnih likera od meda otkriveno je&nbsp;prisustvo klotianidina i tiakloprida, evčzokinot&scaron; z&nbsp; na neophodnost daljeg kontrolisanja ovog proizvoda na&nbsp;prisustvo neonikotinoida. Ispitana je mogućnost uklanjanja odabranih neonikotinoida (dinotefurana,&nbsp;klotianidina i tiakloprida) iz vodene sredine (reke Dunav). Ispitivanje efikasnosti 6 različitih vrsta&nbsp;uklanjanja odabranih neonikotinoida (u prisustvu prirodne insolacije u laboratorijskim uslovima, sa&nbsp;dodatkom H2O2, sa dodatkom MWCNT, sa dodatkom MWCN+H&nbsp;₂O₂, sa dodatkom Fe-MWCNT, sa dodatkom Fe-MWCNT+H₂O₂) vr&scaron;eno je upotrebom prethodno razvijene HPLC-MS/MS metode. Krive uklanjanja odabranih neonikotinoida, pokazale su da tokom 60 minuta pri prirodnoj insolaciji&nbsp; u laboratorijskim uslovima koncentracija smanjenje oko 25%. Analitički signal dinotefurana dobijen u prisustvu H₂O_2&nbsp;pod istim uslovima ukazuje na uklanjanje ciljnog analita od oko 40%, tiakloprida od oko 70%, a klotianidina u potpunosti. Testirana je adsorpcija ciljnog analita na vi&scaron;ezidnim ugljeničnim nanocevima (MWCNT). Ovim postupkom može da se ukloni oko 30% dinotefurana, oko 50% klotianidina i 60% tiakloprida. U kombinaciji sa H₂O_2&nbsp;, MWCNT pokazuju bolju sposobnost uklanjanja za 15&ndash;50% u zavisnosti od ispitivanog neonikotinoida. Upotreba Fe-MWCNT i njihova kombinacija sa H₂O₂ otvorila je mogućnost za dalja &nbsp;ispitivanja mehanizma uklanjanja. Ustanovljeno je nastajanje intermedijera kojima odgovaraju m/z od 117,5 i 140,6 u slučaju razgradnje dinotefurana u sistemima sa H₂O₂, MWCNT+H₂O₂, Fe-MWCNT+H₂O_2&nbsp;i klotianidina u sistemu Fe-MWCNT+H₂O₂.</p> / <p>Neonicotinoid insecticides, as one of the fastest growing new generation of insecticides, have&nbsp;contributed to a significant reduction of toxicity for the environment; therefore, monitoring and&nbsp;determination of trace levels of the neonicotinoids in honey are necessary and demands highly efficient,&nbsp;selective and sensitive analytical techniques. The objective of the present work was to develop a rapid,&nbsp;sensitive, optimized and accurate analytical method based on liquid chromatography for determining&nbsp;seven neonicotinoid insecticides, dinotefuran, nitenpyram, thiamethoxam, clothianidin, imidacloprid,&nbsp;acetamiprid and thiacloprid in honey and honey liqueur samples. The possibility for determination of&nbsp;clothianidin in honey samples was investigated by HPLC with a diode array detector (HPLC-DAD).&nbsp;Based on preliminary results, it can be concluded that the use of a solid-phase column in combination&nbsp;with a liquid-liquid extraction with dichloromethane results in an acceptable recovery of clothianidin in&nbsp;the samples with a clothianidin concentration of about 0.5 &micro;g g^-1. After obtaining low recovery of&nbsp;clothianidin, dispersed liquid-liquid microextraction (DLLME) was selected as a technique for the&nbsp;preparation of honey samples.. The adequacy of acetonitrile as a dispersing agent was investigated.&nbsp;Besides the chloroform, a dichloromethane was used as a second extracting agent , in order to compare&nbsp;the relative efficiency of the extraction solvents. It can be concluded that the extraction recovery (68.4&ndash;92.1%) was more favorable with the use of 0.5 mL ACN and 2.0 mL DHM. Furthermore, LC-MS/MS&nbsp;parameters were optimized to unequivocally provide good chromatographic separation, low detection&nbsp;(LOD, 0.5&ndash;1.0 &mu;g L^&minus;1) and quantification (LOQ, 1.0&ndash;2.5 &mu;g L^&minus;1) limits for acetamiprid, clothianidin,&nbsp;thiamethoxam, imidacloprid, dinotefuran, thiacloprid and nitenpyram in honey samples. Using different&nbsp;<br />types (chloroform, dichloromethane) and volumes of extraction (1.0&ndash;3.0 mL) and dispersive&nbsp;(acetonitrile; 0.0&ndash;1.0 mL) solvent and by mathematical modeling it was possible to establish the optimal&nbsp;sample preparation procedure. Matrix-matched calibration and blank honey sample spiked in the&nbsp;<span style="font-size: 12px;">concentration range of LOQ&ndash;100.0 &mu;g kg</span>^{<span style="font-size: 12px;">&minus;1&nbsp;</span>}<span style="font-size: 12px;">were used to compensate the matrix effect and to fulfill the&nbsp;</span><span style="font-size: 12px;">requirements of SANCO/12495/2011 for the accuracy (R 74.3&ndash;113.9%) and precision (expressed in&nbsp;</span><span style="font-size: 12px;">terms of repeatability (RSD 2.74&ndash;11.8%) and within-laboratory reproducibility (RSDs &nbsp;6.64&ndash;16.2%)) of&nbsp;</span><span style="font-size: 12px;">the proposed method. The rapid (retention times 1.5&ndash;9.9 min), sensitive and low solvent consumption&nbsp;</span><span style="font-size: 12px;">procedure described in this work provides reliable, simultaneous, and quantitative method applicable for&nbsp;</span><span style="font-size: 12px;">the routine laboratory analysis of seven neonicotinoid residues in 15 real honey samples. Neonicotinoid &nbsp;</span><span style="font-size: 12px;">residues were not detected in any of the investigated samples. The objective of next study was to&nbsp;</span><span style="font-size: 12px;">develop and optimize HPLC-DAD analytical method with dispersive liquid-liquid microextraction&nbsp;</span><span style="font-size: 12px;">(DLLME) and QuEChERS sample preparation procedures for the simultaneously analysis of seven&nbsp;</span><span style="font-size: 12px;">neonicotinoids in honey samples. The liquid chromatographic conditions were optimized by response&nbsp;</span><span style="font-size: 12px;">surface methodology with <em>Box-Behnken</em> design and the global <em>Derringer</em>&acute;s desirability. The optimized&nbsp;</span><span style="font-size: 12px;">method was &nbsp;validated to fulfill the requirements of SANCO/12495/2011 standard for both sample&nbsp;</span><span style="font-size: 12px;">pretreatment procedures providing results for accuracy (R, 73.1&ndash;118.3%), repeatability (RSD, 3.28&ndash;</span><span style="font-size: 12px;">10.40%) and within-laboratory reproducibility (RSD, 6.45&ndash;17.70%), limits of detection (LOD, 1.5&ndash;2.5&nbsp;</span><span style="font-size: 12px;">g&micro; kg</span>^{<span style="font-size: 12px;">-1</span>}<span style="font-size: 12px;">) and quantification (LOQ, 5.0&ndash;10.0 &micro;g kg</span>^{<span style="font-size: 12px;">-1</span>}<span style="font-size: 12px;">). For the first time, more than 100 honey samples&nbsp;</span><span style="font-size: 12px;">collected from all 7 counties of Autonomous Province of Vojvodina were analyzed. The presence of&nbsp;</span><span style="font-size: 12px;">thiacloprid, imidacloprid and thiametoxam was discovered in a small number of samples. The objective&nbsp;</span><span style="font-size: 12px;">of next study was to develop an optimized LC-MS/MS analytical method with DLLME and QuEChERS&nbsp;</span><span style="font-size: 12px;">procedures for analysis of 7 neonicotinoids in honey liqueur. The method was validated to fulfill the&nbsp;</span><span style="font-size: 12px;">requirements of SANCO/12495/2011 for both sample pretreatment procedures providing results for&nbsp;</span><span style="font-size: 12px;">accuracy (R, 69.2&ndash;113.4% for DLLME; 71.8&ndash;94.9% for QuEChERS), precision (RSD expressed in&nbsp;</span><span style="font-size: 12px;">terms of repeatability (3.21&ndash;10.20% for DLLME; 4.19&ndash;12.81% for QuEChERS) and within-laboratory&nbsp;</span><span style="font-size: 12px;">reproducibility (9.11&ndash;16.63% for DLLME; 11.32&ndash;16.40% for QuEChERS)), limits of detection (LOD,&nbsp;</span><span style="font-size: 12px;">0.5&ndash;1.5 g&micro; L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for DLLME; 1.0&ndash;2.5 g&micro; L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for QuEChERS) and quantification (LOQ, 1.0&ndash;5.0 g&micro; L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for&nbsp;</span><span style="font-size: 12px;">DLLME; 2.5&ndash;10.0 &micro;g L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for QuEChERS). Analysis of real honey liqueur samples obtained from local&nbsp;</span><span style="font-size: 12px;">markets showed the presence of clothianidin or thiacloprid in four of the analyzed samples, therefore&nbsp;</span><span style="font-size: 12px;">implicating the necessity of ongoing control of this type of traditional product. &nbsp;Removal of selected&nbsp;</span><span style="font-size: 12px;">neonicitinoid insecticides - dinotefuran, clothianidin and thiacloprid using MWCNT and H</span><span style="font-size: 12px;">₂O_2&nbsp;</span><span style="font-size: 12px;">from&nbsp;</span><span style="font-size: 12px;">Danube water matrix was investigated. &nbsp;Efficiency of different systems for neonicotinoids removal&nbsp;</span><span style="font-size: 12px;">(under natural insolation in laboratory, with H</span><span style="font-size: 12px;">₂O₂, with MWCNT, with MWCNT+ H</span><span style="font-size: 12px;">₂O₂, with Fe-MWCNT, with Fe-MWCNT+H₂O₂) was evaluated with developed LC-MS/MS method. Analysis of&nbsp;</span><span style="font-size: 12px;">degradation rates revealed loss of 25% of the initial neonicotinoid concentration under natural insolation in&nbsp;</span><span style="font-size: 12px;">the laboratory conditions during 60 min. Addition of chemical agent H₂O_2&nbsp;promoted loss of 40% of the&nbsp;</span><span style="font-size: 12px;">initial dinotefuran, 70% of thiacloprid concentration and total removal of clothianidin under same&nbsp;</span><span style="font-size: 12px;">conditions. With the addition &nbsp;of MWCNT concentration of dinotefuran, clothianidin and thiacloprid&nbsp;</span><span style="font-size: 12px;">decayed for 30, 50 and 60%, respectively. Iron modification of MWCNT in combination with H</span><span style="font-size: 12px;">₂O_2&nbsp;</span><span style="font-size: 12px;">increased the removal rate of selected neonicotinoid for 15&ndash;50%. Presence of intermediates was&nbsp;</span><span style="font-size: 12px;">discovered in systems of dinotefuran with H₂O₂, MWCNT+H</span><span style="font-size: 12px;">₂O₂, e-MWCNT+H₂O_2&nbsp;</span><span style="font-size: 12px;">and of&nbsp;</span><span style="font-size: 12px;">clothianidin in systems with Fe-MWCNT+H₂O_2&nbsp;</span><span style="font-size: 12px;">with m/z of 117,5 and 140,6.&nbsp;</span></p>

Ce travail est consacré à l’étude de l’incorporation volontaire des dopants dans des films de carbure de silicium épitaxiés par la technique de dépôt chimique en phase vapeur. Le rôle des principaux paramètres de croissance (température, flux de dopant, vitesse de dépôt, pression dans le réacteur et le rapport C/Si) sur l’incorporation d’azote et d’aluminium a été étudié en détail. Les travaux menés jusqu’ici ont largement exploré les caractéristiques de l’incorporation de dopants, en particulier l’incorporation d’azote et ont montré des résultats parfois très dépendants de l’équipement de croissance utilisé. Afin d’explorer cette influence, une étude expérimentale exhaustive sur l’incorporation de N et Al a été réalisée sur des couches homoépitaxiées 4H-SiC sur la face carbone et sur la face silicium de substrats 4H-SiC dans nos réacteurs CVD. Cette étude a été complétée par une analyse des propriétés structurales, optiques et électriques de couches 4H-SiC dopé Al. Aussi, la fabrication de diodes pn a été expérimentée sur les couches épitaxiées dans nos réacteurs. Nous avons pu observer différentes tendances expérimentales selon la nature du dopant, l’orientation cristalline du substrat et l’environnement chimique durant la croissance. Nous en déduisons que le mécanisme derrière les tendances observées est largement influencé par des facteurs comme les conditions de croissance (c'est-à-dire la température de croissance et/ou la pression) et la couverture de carbone à la surface de la croissance, surtout sur la face C / This work is dedicated to the investigation of intentional dopant incorporation in silicon carbide epilayers grown by chemical vapor deposition technique. The role of main process conditions (growth temperature, dopant supply, deposition rate, growth pressure and C/Si ratio) on both, Nitrogen and Aluminum incorporation was studied in details. Previous works have widely explored the characteristics of dopant incorporation, especially the nitrogen incorporation addressing a potential influence of growth equipment for the observed incorporation trends. An exhaustive experimental study of N and Al incorporation was performed for homoepitaxial 4H-SiC layers grown on Si- and C-faces of 4H-SiC substrates in our CVD setups to explore such influence. It was completed by the assessment of the structural, optical and electrical properties of the Al doped 4H-SiC films. Furthermore, the fabrication of pn diodes was tested on the grown layers. We have observed different experimental tendencies depending on dopant nature, crystal orientation and chemical environment. We conclude from these observations that the mechanism behind the experimentally obtained tendencies is widely influenced by factors such as process conditions (i.e. growth temperature and/or pressure) and the carbon coverage at the grown surface, especially on C-face

Produced water is the largest waste product by volume in the oil industry and its treatment in onshore or offshore fields poses bigger and different challenges than what water engineers are used to encounter. Process to achieve reuse quality of this water is very expensive with many technical hurdles to overcome making the optimization of the treatment steps necessary. Electrocoagulation (EC) generates coagulants in-situ responsible for destabilizing oil droplets, suspended particles, and common pollutant in produced water. Furthermore, EC is a very efficient technology compared with traditional primary treatments used in the oil & gas industry and has several advantages such as: no hazardous chemical handling (which diminishes the risk of accident and logistic costs), high efficiency potential concerning boron removal, potential small footprint and less sludge generation. In this research, the treatment of produced water using EC was investigated in a practical manner for the oilfield to aim for a cleaner effluent for further processing and help to achieve a reuse quality. For this, an EC cell was designed using different parameters normally used in the literature to fit this scenario. After preliminary tests, the treatment time was set to 3 seconds. Response surface method (RSM) was employed to optimize the operating conditions for TOC removal on a broad quality of synthetic produced water while varying: salinity, initial oil concentration and initial pH. TOC was chosen to be the main response because of its importance in legislation and sensibility on the method. Furthermore, turbidity removal, change of pH value after EC in water with lack of buffer capacity, aluminum concentration and preliminary tests involving boron removal and influence of hydrogen carbonate were also studied. Real produced water was treated with EC to assess the optimum conditions obtained by the RSM showing the results were closely related. Finally, an estimation of volume required and operating cost for EC in the different types of produced water was made to assess how realistic it is for onshore and offshore applications.:ERKLÄRUNG DES PROMOVENDEN I ACKNOLEDGEMENT III ABSTRACT V TABLE OF CONTENT VII LIST OF FIGURES IX LIST OF TABLES X LIST OF EQUATIONS XII ABBREVIATIONS XIV 1. INTRODUCTION 1 2. PRODUCED WATER 6 2.1 Characterization of Oilfield Produced Water 6 2.2 Produced Water Management 10 2.2.1 Discharge and Regulations 10 2.2.2 Efforts on Reuse 11 2.2.3 Cost 14 3. PRODUCED WATER TREATMENT 17 3.1 Most Common Primary Treatment 17 3.1.1 Hydrocyclones 17 3.1.2 Flotation unit 18 3.2 Further Water Treatment Technologies 19 3.2.1 Membrane Process 19 3.2.1.1 Microfiltration 19 3.2.1.2 Ultrafiltration 21 3.2.1.3 Nanofiltration 23 3.2.1.4 Reverse Osmosis 24 3.2.1.5 Forward osmosis 24 3.2.2 Electrodialysis 25 3.2.3 Biological treatment 28 3.2.3.1 Aerobic and anaerobic process 28 3.2.3.2 Combining membrane and bio-reactor 29 3.2.4 Oxidative process 30 3.2.4.1 Oxidation process 30 3.2.4.2 Anodic oxidation 32 3.2.5 Thermal technology 34 3.2.5.1 Evaporation 34 3.2.5.2 Eutectic freeze crystallization 35 3.2.6 Adsorption and ion-exchange 36 3.3 Electrocoagulation 39 3.3.1 Colloidal Stability Theory 39 3.3.2 Theory of Electrocoagulation 40 3.3.3 Mechanism of Abatement of Impurities 44 3.3.4 Operational parameters and efficiency 49 4. MATERIALS AND METHODS 51 4.1 Analytical Techniques and Synthetic Solutions 51 4.1.1 Analytical Techniques 51 4.1.2 Synthetic Produced Water 51 4.2 Design of Experiment and Models 54 4.3 Experimental Protocol for EC 56 4 .4 Development of the new Electrocoagulation cell 57 4.5 Real Produced water 58 5. RESULTS AND DISCUSSION 59 5.1 Designing EC Cell Process 59 5.1.1 Computational Fluid Dynamics for EC manufacturing 59 5.2 Preliminary Experiments 61 5.2.1 TOC Removal and Residence Time Determination 61 5.2.2 Aluminum Concentration 64 5.3 Models Quality and Range of Validity 66 5.3.1 TOC Removal 66 5.3.2 Turbidity Removal 69 5.3.3 Final pH value 71 5.3.4 Ionic Strength and Interpolation for Different Salinities 73 5.3.5 Partial Conclusions 76 5.4 Evolution of the Final pH Value 78 5.5 Operation Region for Effective Treatment of Produced Water with EC 80 5.5.1 Produced Water with Low Salinity 80 Organic Compounds Removal 80 Turbidity Removal 83 5.5.2 Produced Water with Medium Salinity 84 Organic Compounds Removal 84 Turbidity Removal 86 5.5.3 Produced Water with High Salinity 87 Organic Compounds Removal 87 5.6 Influence of Hydrogen Carbonate 90 5.7 Real Produced water 91 5.8 Boron Removal 93 5.9 Estimation of the Size for EC in Full scale 94 5.10 Produced Water with Very Low Salinity and EC 95 5.11 Estimation of Operation Cost 96 6. CONCLUSION AND RECOMMENDATIONS 98 6.1 Conclusion 98 6.2 Recommendations for Future Work 101 Scale up on EC for upstream 101 Further processing and reuse 101 Online optimization for EC 101 Recommendations for any research related to upstream produced water 101 BIBLIOGRAPHY 102 APPENDIX A 117 APPENDIX B 120

Avec l'intégration croissante des fonctions, les systèmes embarqués modernes deviennent très intelligents et sophistiqués. Les exemples les plus emblématiques de cette tendance sont les téléphones portables de dernière génération, qui offrent à leurs utilisateurs un large panel de services pour la communication, la musique, la vidéo, la photographie, l'accès à Internet, etc. Ces services sont réalisés au travers d'un certain nombre d'applications traitant d'énormes quantités d'informations, qualifiées d'applications de traitements intensifs de données. Ces applications sont également caractérisées par des comportements multi-horloges car elles comportent souvent des composants fonctionnant à des rythmes différents d'activations lors de l'exécution. Les systèmes embarqués ont souvent des contraintes temps réel. Par exemple, une application de traitement vidéo se voit généralement imposer des contraintes de taux ou de délai d'affichage d'images. Pour cette raison, les plates-formes d'exécution doivent souvent fournir la puissance de calcul requise. Le parallélisme joue un rôle central dans la réponse à cette attente. L'intégration de plusieurs cœurs ou processeurs sur une seule puce, menant aux systèmes multiprocesseurs sur puce (en anglais, "multiprocessor systems-on-chip - MPSoCs") est une solution-clé pour fournir aux applications des performances suffisantes, à un coût réduit en termes d'énergie pour l'exécution. Afin de trouver un bon compromis entre performance et consommation d'énergie, l'hétérogénéité des ressources est exploitée dans les MPSoC en incluant des unités de traitements aux caractéristiques variées. Typiquement, des processeurs classiques sont combinés avec des accélérateurs (unités de traitements graphiques ou accélérateurs matériels). Outre l'hétérogénéité, l'adaptativité est une autre caractéristique importante des systèmes embarqués modernes. Elle permet de gérer de manière souple les paramètres de performances en fonction des variations de l'environnement et d'une plate-forme d'exécution d'un système. Dans un tel contexte, la complexité du développement des systèmes embarqués modernes paraît évidente. Elle soulève un certain nombre de défis traités dans nos contributions, comme suit : 1) tout d'abord, puisque les MPSoC sont des systèmes distribués, comment peut-on aborder avec succès la correction de leur conception, de telle sorte que les propriétés fonctionnelles des applications multi-horloges déployées puissent être garanties ? Cela est étudié en considérant une méthodologie de distribution "correcte-par-construction" pour ces applications sur plates-formes multiprocesseurs. 2) Ensuite, pour les applications de traitement intensif de données à exécuter sur de telles plates-formes, comment peut-on aborder leur conception et leur analyse de manière adéquate, tout en tenant pleinement compte de leur caractère réactif et de leur parallélisme potentiel ? 3) Enfin, en considérant l'exécution de ces applications sur des MPSoC, comment peut-on analyser leurs propriétés non fonctionnelles (par exemple, temps d'exécution ou énergie), afin de pouvoir prédire leurs performances ? La réponse à cette question devrait alors servir à l'exploration d'espaces complexes de conception. Nos travaux visent à répondre aux trois défis ci-dessus de manière pragmatique, en adoptant une vision basée sur des modèles. Pour cela, ils considèrent deux paradigmes complémentaires de modélisation flot de données : la "modélisation polychrone" liée à l'approche synchrone réactive, et la "modélisation de structures répétitives" liée à la programmation orientée tableaux pour le parallélisme de données. Le premier paradigme permet de raisonner sur des systèmes multi-horloges dans lesquels les composants interagissent, sans supposer l'existence d'une horloge de référence. Le second paradigme est quant à lui suffisamment expressif pour permettre la spécification du parallélisme massif d'un système.

L’usinage par électroérosion est un procédé d’enlèvement de matière par fusion, vaporisation et érosion, réservé aux matériaux conducteurs et semi-conducteurs.Il peut être utilisé pour usiner les métaux et alliages, les aciers trempés, les alliages céramiques, les carbures métalliques, certaines céramiques et même des matériaux plus durs tels que le diamant polycristallin. La pièce ainsi chauffée voit ses caractéristiques mécaniques chuter et modifier, ce qui augmente son usinabilité. Les travaux réalisés ont porté sur l'influence de l'usinage par électroérosion à fil sur; l'intégrité de surface, l'usinabilité, la productivité et la précision de procédé, de plusieurs matériaux, tels que, le titane pur, l'alliage de titane Ti-6Al-4V, le composite intermétallique à base Ti-Al, le composite Ti17 et le composite Ti6242.En usinage par électro-érosion à fil, et plus précisément en finition, le procédé est caractérisé par un débit de matière, une largeur de kerf, un durcissement superficiel, une zone affectée thermiquement et un état de surface variant en fonction de plusieurs paramètres tels que, le courant de décharge, le temps d’impulsion, la tension d’amorçage, la vitesse de coupe, la pression d'injection de lubrifiant et la tension de fil.Toutefois, il s’agit d’une étude d’optimisation et de modélisation empirique des conditions de coupe des matériaux composites à base métallique et des alliages de titane, afin de maitriser et d'améliorer l'intégrité de surface usinée, d'augmenter la productivité et de perfectionner la précision du procédé. Par la suite, atteindre les exigences de la qualité et de la sûreté de fonctionnement des pièces aéronautiques.Dans cette étude, on a utilisé des méthodes de type Plan d'expériences, méthode de Taguchi et la Méthodologie des surfaces de réponses pour le calage et le contrôle des paramètres de l’usinage par électroérosion à fil, et ses conditions opératoires. / EDM machining is a process for the removal of material by melting, spraying and erosion, which is reserved for conductive and semiconductor materials.It can be used for machining metals and alloys, hardened steels, ceramic alloys, metal carbides, some ceramics and even harder materials such as polycrystalline diamond. The heated part has its mechanical characteristics drop, which increases its machinability. The work carried out focused on the influence of WEDM machining on surface integrity, machinability, productivity and process precision, of several materials: pure titanium, Ti6Al4V alloy, composite intermetallicTi-Al based, Ti17 composite and Ti6242 composite.In ripping, and more precisely in finishing, the process is characterized by a flow of material,kerf width, surface hardening, heat affected zone and surface condition varying with discharge current, pulse time and voltage, cutting speed, lubricant injection pressure and wire tension.In fact, the machining conditions of metal-based composite materials and titanium alloys have been modeled and optimized to improve machined surface integrity, increase productivity, and improve process accuracy. Subsequently, meet the quality and safety requirements of aeronautical parts.Methods such as Experimental Design, Taguchi and Surface of Response were used for calibration and process control parameters and operating conditions.

El cultivo protegido bajo invernadero tiene altos costes energéticos derivados de la ventilación forzada. En cambio, la ventilación natural puede ser una solución barata que reduzca el consumo energético. No obstante, un diseño que permita la ventilación natural del invernadero supone un reto debido a la complejidad del fenómeno físico. Frente a otros métodos de diseño, como los métodos experimentales o analíticos, en los últimos tiempos la dinámica de fluidos computacional (CFD por sus siglas en inglés) se ha convertido en la herramienta más utilizada para estudiar este tipo de fenómenos, gracias a su relativo bajo coste y a la rapidez en la obtención de resultados. No obstante, los modelos CFD deben refrendarse mediante validaciones realizadas a través de datos experimentales. Un análisis bibliográfico detallado del uso de la CFD aplicada a invernaderos muestra, en general, que los trabajos carecen de suficientes datos experimentales, seguramente debido al alto coste de los sensores para adquirirlos y la dificultad que conlleva el trabajo en condiciones de campo. Además, se observa que las simulaciones CFD en invernaderos no se realizan con un procedimiento sistematizado. Por ello, la presente tesis, por un lado describe un dispositivo y unos métodos sencillos y baratos para obtener datos atmosféricos, y por otro, propone una visión crítica sobre la investigación realizada hasta el momento, con el fin de sistematizar la manera de generar modelos CFD aplicados a la ventilación natural de invernaderos. Finalmente, la tesis se complementa con un ejemplo sobre un caso práctico. Para ello, en primer lugar, se realizó una revisión bibliográfica de las diferentes guías de buenas prácticas en diferentes campos de la tecnología principalmente en edificación, para sistematizar y adaptar las recomendaciones para generar modelos CFD en invernaderos. En segundo lugar, se desarrolló un sistema de adquisición de datos sencillo, consistente en una red de sensores, que permite medir simultáneamente la velocidad y dirección de viento en 20 puntos. Este sistema de sensores fue calibrado y probado en campo satisfactoriamente obteniendo una precisión similar a los anemómetros comerciales con un precio 30 veces superior. En tercer lugar, se generaron 24 modelos del flujo de aire alrededor del invernadero, resultantes de la combinación de cuatro modelos de turbulencia (k- ¿; RNG k-¿; k-¿ y RSM); dos esquemas de discretización (primer orden y segundo orden) y tres velocidades de viento exterior (3; 3,5 y 4 m/s) con el fin de analizar sus diferencias y demostrar sus ventajas e inconvenientes. Por este motivo, en cuarto lugar, se comprobó su capacidad de ajustarse a los datos de campo, validando los modelos con un análisis de regresión lineal sobre los datos experimentales. Con este estudió se reveló que los modelos SST k-¿ y el RSM (segundo orden) son los que mejor representan el flujo de ventilación y se demostró que el modelo k-¿ estándar (primer orden), el más utilizado en la bibliografía, no sólo ofrece resultados diferentes al resto de modelos, sino que su rendimiento es pobre para predecir el flujo de ventilación. / Granell Ruiz, R. (2014). Análisis del flujo ambiental y propuesta metodológica para simulaciones CFD aplicadas a la ventilación natural de invernaderos [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/37194 / TESIS

Thesis (PhD (Chemical Engineering))--Cape Peninsula University of Technology, 2019 / Simultaneous nitrification and aerobic denitrification (SNaD) is a preferred method for single stage total nitrogen (TN) removal, which was recently proposed to improve wastewater treatment plant design. However, SNaD processes are prone to inhibition by toxicant loading with free cyanide (CN-) possessing the highest inhibitory effect on such processes, rendering these processes ineffective. Despite the best efforts of regulators to limit toxicant disposal into municipal wastewater sewage systems (MWSSs), free cyanide (CN-) still enters MWSSs through various pathways; hence, it has been suggested that CN- resistant or tolerant microorganisms be utilized for processes such as SNaD. To mitigate toxicant loading, organisms in SNaD have been observed to adopt a multiphase growth strategy to sequentially degrade CN- during primary growth and subsequently degrade TN during the secondary growth phase. However, CN- degrading microorganisms are not widely used for SNaD in MWSSs due to the inadequate application of suitable microorganisms (Chromobacterium violaceum, Pseudomonas aeruginosa, Thiobacillus denitrificans, Rhodospirillum palustris, Klebsiella pneumoniae, and Alcaligenes faecalis) commonly used in single-stage SNaD. The use of CN- degrading or resistant microorganisms for SNaD is a cost-effective method compared to the use of other methods of CN- removal prior to TN removal, as they involve multi-stage systems (as currently observed in MWSSs). The use of CN- degrading microorganisms, particularly when used as a consortium, presents a promising and sustainable resolution to mitigate inhibitory effects of CN- in SNaD. However, SNaD is known to be completely inhibited by CN- thus it is imperative to also study some thermodynamic parameters of SNaD under high CN- conditions to see the feasibility of the process. The Gibbs free energy is significant to understand the feasibility of SNaD, it is also vital to study Gibbs free energy to determine whether or not the biological reaction is plausible. The relationship between the rate of nitrification and Gibbs free energy was also investigated. The attained results showed that up to 37.55 mg CN-/L did not have an effect on SNaD. The consortia degraded CN- and achieved SNaD, with degradation efficiency of 92.9 and 97.7% while the degradation rate of 0.0234 and 0.139 mg/L/hr for ammonium-nitrogen (NH4-N) and CN- respectively. Moreover, all the free Gibbs energy was describing the individual processes were found to be negative, with the lowest Gibbs free energy being -756.4 and -1830.9 Kcal/mol for nitritation and nitratation in the first 48 h of the biological, reaction respectively. Additionally, a linear relationship between the rate of NH4-N and nitrite-nitrogen (NO2-N) degradation with their respective Gibbs free energy was observed. Linear model was also used to predict the relationship between NH4-N, NO2-N degradation and Gibbs free energy. These results obtained showed a good correlation between the models and the experimental data with correlation efficiency being 0.94 and 0.93 for nitritation, and nitratation, respectively. From the results found it can be deduced that SNaD is plausible under high cyanide conditions when cyanide degrading or tolerant microorganisms are employed. This can be a sustainable solution to SNaD inhibition by CN- compounds during wastewater treatment. Furthermore, a single strain was purified from the consortium and identified as Acinetobacter courvalinii. This bacterial strain was found to be able to perform sequential CN- degradation, and SNaD; an ability associated with multiphase growth strategy of the microorganism when provided with multiple nitrogenous sources, i.e. CN- and TN. The effect of CN- on nitrification and aerobic denitrification including enzyme expression, activity and protein functionality of Acinetobacter courvalinii was investigated. It was found that CN- concentration of up to 5.8 mg CN-/L did not affect the growth of Acinetobacter courvalinii. In cultures whereby the A. courvalinii isolate was used, degradation rates of CN- and NH4-N were found to be 2.2 mg CN-/L/h and 0.40 mg NH4-N/L/h, respectively. Moreover, the effect of CN- on NH4-N, nitrate-nitrogen (NO3-N) and NO2-N oxidizing enzymes was investigated, with findings indicating CN- did not affect the expression and activity of ammonia monooxygenase (AMO), but affected the activity of nitrate reductase (NaR) and nitrite reductase (NiR). Nevertheless, a slow decrease in NO2-N was observed after the addition of CN- thus confirming the activity of NaR and the activation of the denitrification pathway by the CN-. Moreover, five models’ (Monod, Moser, Rate law, Haldane, and Andrew’s model) ability to predict SNaD under CN- conditions, indicated that only Rate law, Haldane and Andrew’s models, were suited to predict both SNaD and CN- degradation. Due to low degradation rates of NH4-N and CN-, optimization of SNaD was essential. Therefore, response surface methodology was used to optimize the SNaD under CN- conditions. The physiological parameters that were considered for optimization were temperature and pH; with the result showing that the optimum for pH and temperature was 6.5 and 36.5oC respectively, with NH4-N and CN- degradation efficiency of 50 and 80.2%, respectively. Furthermore, the degradation kinetics of NH4-N and CN- were also studied under the optimum conditions in batch culture reactors, and the results showed that up to 70.6% and 97.3% of NH4-N and CN- were simultaneously degraded with degradation rates of 0.66 and 0.41 mg/L/h, respectively. The predictive ability of RSM was further compared with cybernetic models, and cybernetic models were found to better predict SNaD under CN- conditions. These results exhibited a promising solution in the management of inhibition effected of CN- towards SNaD at an industrial scale.

[ES] El comportamiento acústico de una sala viene determinado, entre otros factores, por el coeficiente de absorción acústica de las soluciones constructivas de las superficies interiores que lo forman. El coeficiente de absorción se halla a través de ensayos de laboratorio o de las propuestas de la literatura científica. En teatros habitualmente el volumen de la caja de escena es equiparable sino superior al volumen de la sala propiamente dicho, y se comunica con la sala a través de la boca de escena. Para calcular el comportamiento acústico de un teatro no se tiene en cuenta el volumen de la caja de escena, sino que éste se sustituye en el modelo por la superficie de la boca de escena. El coeficiente de absorción de la boca de escena se toma de la literatura científica. Siendo la boca de escena un gran vacío, no es posible encontrar sus valores de absorción en laboratorio. Se desconoce cómo los distintos autores que han propuesto valores para el coeficiente de absorción de la boca de escena han llegado a dichos valores. En el presente trabajo se ha hallado el coeficiente de absorción de la boca de escena de seis teatros de diferentes características y épocas. Para ello, se ha recopilado información gráfica y constructiva de los espacios, se han realizado mediciones acústicas normalizadas con la boca de escena abierta y cerrada, y se han elaborado modelos informáticos tridimensionales que han sido calibrados con las mediciones tomadas "in situ". En una primera fase se ha calibrado el modelo con la boca de escena cerrada y en una segunda se ha repetido el proceso con la boca de escena abierta. El ajuste de los modelos virtuales se ha ejecutado mediante el empleo del método de las superficies de respuesta. Este método ha permitido considerar hasta dos soluciones constructivas con comportamiento acústico desconocido. De esta forma se ha podido deducir el coeficiente de absorción de la boca de escena en cada caso. Finalmente, los coeficientes de la boca de escena hallados en cada teatro se han comparado con los propuestos por diversos autores. Además, se ha evaluado la influencia de la absorción de la boca de escena en cada modelo. Constatando que los valores propuestos en las obras de referencia son adecuados en teatros antiguos, no así en los modernos en los que son válidos sólo en frecuencias medias y altas. / [CA] El comportament acústic d'un espai ve determinat, entre altres factors, pel coeficient d'absorció acústica de les solucions constructives de les superfícies interiors que el formen. El coeficient d'absorció és troba mitjançant assajos de laboratori o de les propostes de la literatura científica. En teatres habitualment el volum de la caixa d'escena és equiparable, sinó superior al volum de la sala, i es comunica amb la sala mitjançant la boca d'escena. Per calcular el comportament acústic d'un teatre no es té en compte el volum de la caixa d'escena, sinó que es substitueix al model per la superfície de la boca d'escena. Com que la boca d'escena és un gran buit, no és possible trobar els seus valors d'absorció al laboratori. Perla qual cosa els seus valors es prenen de la literatura científica Es desconeix com els autors que han proposat valors per al coeficient d'absorció de la boca d'escena han arribat a aquests valors. En aquest treball s'ha trobat el coeficient d'absorció de la boca d'escena de sis teatres de característiques i èpoques diferents. Per fer-ho, s'ha recopilat informació gràfica i constructiva dels espais, s'han realitzat mesures acústics normalitzades amb la boca d'escena oberta i tancada, i s'han elaborat models informàtics tridimensionals que han estat calibrats amb les mesures preses "in situ". En una primera fase el model s'ha calibrat amb la boca d'escena tancada i en una segona s'ha repetit el procés amb la boca d'escena oberta. L'ajust dels models virtuals s'ha executat mitjançant la utilització del mètode de les superfícies de resposta. Aquest mètode ha permès considerar fins a dues solucions constructives amb un comportament acústic desconegut. D'aquesta manera, s'ha pogut deduir el coeficient d'absorció de la boca d'escena en cada cas. Finalment, els coeficients de la boca d'escena trobats a cada teatre s'han comparat amb els proposats per diversos autors. A més, s'ha avaluat la influència de l'absorció de la boca d'escena a cada model. Constatant que els valors proposats a les obres de referència són adequats en teatres antics, no així als moderns en què són vàlids només en freqüències mitjanes i altes. / [EN] The acoustic behavior of a room is determined, among other factors, by the acoustic absorption coefficient of the interior surfaces that make it up. The absorption coefficient is found through laboratory tests or proposals from the scientific literature. In theaters, the volume of the stage house is usually equivalent to the volume of the room itself, if not greater; and it is connected to the room through the proscenium opening. To calculate the acoustic behavior of a theater, the volume of the fly tower is not considered, but instead it is replaced in the model by the surface of the stage opening. Since the proscenium opening is a large recess, it is not possible to find its absorption values in the laboratory; that's why they are taken from the scientific literature. It is not known how the different authors who have proposed values for the absorption coefficient of the stage opening have found these values. In the present work, the absorption coefficient of the proscenium opening of six theaters of different characteristics and periods has been found. For this, graphic and constructive information of the spaces has been compiled, standardized acoustic measurements have been made with the stage opening opened and closed, and three-dimensional computer models that have been calibrated with the on-site measurements have been prepared. In the first phase, the model has been calibrated with the stage opening closed and in the second one the process has been repeated with the stage opening opened. The adjustment of the virtual models has been carried out using the response surface method. This method has allowed to consider up to two constructive solutions with unknown acoustic behavior. This way it has been possible to deduce the absorption coefficient of the stage opening in each case. Finally, the coefficients of the proscenium opening found in each theater have been compared with those proposed by several authors. In addition, the influence of the absorption of the stage opening in each model has been evaluated. Noting that the values proposed in the reference works are adequate in old theaters, but not in modern ones, where they are valid only in medium and high frequencies. / Pérez Aguilar, BN. (2023). Revisión de los valores del espectro de absorción de la caja de escena en teatros, mediante la aplicación del método de superficies de respuesta [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/196753

Orientador: Aneirson Francisco da Silva / Resumo: A Estampagem a Frio é um processo de conformação plástica de chapas metálicas, que possibilita, por meio de ferramentas específicas, obter componentes com boas propriedades mecânicas, geometrias e espessuras variadas, diferentes especificações de materiais e com boa vantagem econômica. A multiplicidade destas variáveis gera a necessidade de utilização de técnicas estatísticas e de simulação numérica, que suportem a sua análise e adequada tomada de decisão na elaboração do projeto das ferramentas de conformação. Este trabalho foi desenvolvido em uma empresa brasileira multinacional de grande porte que atua no setor de autopeças, em seu departamento de engenharia de projetos de ferramentas, com o propósito de reduzir o estiramento e a ocorrência de trincas em uma travessa de 6,8 [mm] de aço LNE 380. A metodologia proposta obtém os valores dos fatores de entrada e sua influência na variável resposta com o uso de técnicas de Delineamento de Experimentos (DOE) e simulação pelo método de Elementos Finitos (FE). Uma Função Empírica é desenvolvida a partir desses dados, com o uso da técnica de regressão, obtendo-se a variável resposta y (espessura na região crítica), em função dos fatores influentes xi do processo. Com a Otimização via Simulação Monte Carlo (OvSMC) insere-se a incerteza nos coeficientes desta Função Empírica, sendo esta a principal contribuição deste trabalho, pois é o que ocorre, por via de regra, na prática com problemas experimentais. Simulando-se por FE as ferram... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre