The efficiency of boron-doped diamond electrodes (BDD) has been investigated by electrolysis of an aqueous solution containing sodium sulfate. A Synthesis StarterKit from Condias was used, which contained the BDD anode with an active surface area of 3.14 cm2, and electrosynthesis was performed in a batch mode reactor. In this report, the electrooxidation of sodium sulfate to sodium persulfate is well reported. The production of persulfate was studied at different cell voltages and electrolyte concentrations. The amount of persulfate produced was determined by the iodometric titration and itwas found that its concentration in the electrolyte was directly proportional to the persulfate concentration, i.e, a larger amount of persulfate could be obtained when the electrolyte was highly concentrated, up to 1 M. For each of the samples the amount of persulfate that theoretically is possible to produce was calculated and subsequently compared to the actual amount of persulfate that was formed, ie. current efficiencies. These current efficiencies were unexpectedly low for all experiments except for one data point. Hydrogen gas was also produced as a by-product at the cathode, but it couldn ot be collected in the present setup. The results and some possible improvements are discussed in the report. / Effektiviteten av att använda bor-dopad diamant (BDD) för elektrosyntes med en vattenlösning innehållande natriumsulfat för att producera persulfat har undersökts. Den utrustningen som använde svar ett Syntes StarterKit från företaget Condias, denna innehöll en cell med BDD som anodmaterial vilken hade en aktiv area på 3,14 cm2. Produktionen av persulfat studerades vid olika cellspänningar och elektrolytkoncentrationer. Mängden av producerad persulfat bestämdes genom titrering. Detv isade sig att koncentrationen av elektrolyten var proportionell mot persulfatkoncentrationen, dvs. mer persulfat producerades vid högre elektrolytkoncentrationer. För varje prov beräknades även det teoretiska antalet mol persulfat som kan åstadkommas och jämfördes sedan med det faktiska antalet mol som producerades, detta gav strömeffektiviteten för den önskade reaktionen. Denna effektivitet var oväntat låg för alla prov förutom ett i experiment 4. Vätgas producerades som en biprodukt vid katoden, men på grund av begränsad tillgång till utrustning och tid kunde denna gas inte samlas uppför vidare analys. Resultaten och möjliga förbättringar diskuteras även i rapporten.

In order to inject solar power to the utility grid, among various types of inverters, Grid Connected Transformerless Solar Inverters (GCTSI) are mostly preferred for residential or commercial applications. This preference is because of the high energy efficiency and low cost due to the absence of a line frequency or a high frequency transformer. Peak value of the efficiency characteristics of GCTSIs can reach 98%, which are selected topology, component optimization, switching strategy and operating condition dependent. In spite of the attractive energy efficiency characteristics of GCTSIs, due to the lack of galvanic isolation, these inverters are vulnerable to leakage currents, which are prohibitive for the safety and the maintenance reasons. The purpose of this research is to analyze GCTSIs in terms of their leakage current and energy efficiency characteristics. In the research, the leakage current mechanisms of GCTSIs are identified and grid connected solar inverters are classified in terms of their leakage current characteristics including the GCTSIs. In addition to the existing ones, several novel topologies are proposed enriching the family of GCTSIs. The leakage current and the inductor current ripple performances of GCTSI topologies are analyzed and evaluated by detailed simulations for 3 kVA and 10 kVA single-phase systems. In addition, the energy efficiency characteristics of GCTSIs are investigated in these power levels by making use of Calculated Average Power Per Switching Cycle (CAPPSC) method. The efficiency studies with CAPPSC method provide design guidelines and comparison of the GCTSI topologies in terms of their energy efficiency characteristics.

The anodic films formed on CP-Ti in sulphuric and phosphoric acids using potentiodynamic polarization and potentiostatic anodizing were investigated. Single-barrier anodic films were created in sulphuric and phosphoric acids from 10 to 60 V. Oxygen evolution was initiated within both stages, leading to the suppression of current efficiency for the growth of anodic films. The crystalline phases assisted gas bubbles to develop within the film, resulting in the formation of the blister textures. The rupture of the anodic film was found from anodizing at 20 V in the sulphuric acid but occurred at 50 V in the phosphoric acid. The corrosion behaviour of the anodic oxide films formed on CP-Ti was studied in a 3.5% NaCl electrolyte. Ruptures and blisters of the films were found as a result of the release of a huge pressure by the bursting of oxygen bubbles. More ruptures were observed when anodizing to higher anodic voltages in the sulphuric and phosphoric acids. Further, the anodic films showed more ruptures after the anodized titanium specimens at higher anodic voltages were immersed for 60 days in the NaCl electrolyte compared with the immediate immersions. Additionally, the corrosion behaviours of the anodic films were examined by potentiodynamic polarization and electrochemical impedance spectroscopy. The corrosion resistance of the anodized titanium in the NaCl electrolyte increased with increased anodic voltage. Porous anodic films were formed on CP-Ti after anodizing at 100, 150 and 200 V for 900 s respectively. Nano-particulates were found within the pores; the size and quantity of the pores increased due to the dissolution of the particulates. The amorphous-to-crystalline transition was initiated during anodizing. It was revealed that the degree of crystallinity was greater at a higher voltage. An increased content of phosphorus species was incorporated into the porous oxide film as the voltage increased. The formation of anodic oxide films on CP-Ti in the NaTESi electrolyte was investigated. Barrier-type titanium anodic films generated after anodizing to 5, 10 and 20 V were of thickness 30, 37 and 67 nm respectively. Further, a porous anodic film of ~80.0 nm thickness was generated after anodizing to 40 V. Significant amounts of sodium species were found, which were incorporated into the anodic films. The current efficiency for the film growth was reduced at higher anodic voltages due to the formation of crystalline phases and more oxygen generation. The degree of crystallinity of the anodic film increased at higher voltages. The dielectric permittivity of the anodic film was estimated as ~2.35 according to EIS and the TEM evidence. The degradation test was carried out in a continuous climatic chamber with a humidity of 90% at 50 oC. The anodic films formed on CP-Ti in the NaTESi electrolyte showed an excellent degradation resistance. Single-lap bonding tests were operated for the study of the adhesion joint performance, and the bonding strength increased with increase of the voltage associated with a thicker anodic TiO2 coatings. The formation of anodic oxide films on the Ti6Al4V alloy in the NaTESi electrolyte at a constant current density of 20 mA cm-2 was studied. An anodic film with shallow pores was formed after anodizing to 10 V. Porous anodic films were created after anodizing to 20, 30 and 40 V respectively. Significant amounts of sodium species were incorporated into the films. The current efficiency for the anodic film growth increased from 10 to 30 V but decreased from 30 to 40 V due to oxygen evolution. The film thicknesses determined by RBS were ~15 nm, ~39 nm, ~1100 nm and 1800 nm for voltages of 10, 20, 30 and 40 V respectively. The film thickness at 10 V showed good agreement with 11 nm which was evident by TEM. The degree of crystallinity of the films was greater at a higher voltage. The dielectric permittivity of the film was ~118 according to the results of TEM and EIS. The degradation test was carried out in a continuous climatic chamber with a humidity of 90% at 50oC. Without the evidence of damages, the anodic films formed on Ti6Al4V alloy in the NaTESi electrolyte showed an excellent degradation resistance. In addition, it was evident that the film formed after anodizing to 40 V was crystallized at the thermal temperature of 50 oC. Single-lap bonding tests were employed to compare the strength of adhesively joined titanium alloy anodized with different film thicknesses, the results revealing a significant benefit from a thicker film. The ~100 nm thick 99.6% pure titanium layers were sputter-deposited on electropolished aluminium substrates by magnetron sputtering technique to investigate the anodic film growth behaviour of titanium in H3PO4. The TiO2 and the Ti layer were ruptured by the bursting of oxygen bubbles. The phosphoric acid electrolyte penetrated into the ruptured regions of the sputter-deposited titanium layer, leading to the growth of Al2O3. The thickness of TiO2 increased from 10 to 100 V but decreased from 100 to 150 V. Above 80 V, some regions of the titanium layer where were completely ruptured did not generate TiO2. Important structural details of anodic films with high quality images were obtained using the STEM-in-SEM technique, enabling the study of film morphologies, film thicknesses and oxygen bubble features. STEM-in-SEM would be used to study a large-scale morphology of the anodic film. Additionally, a 6-specimen carousel holder would provide an increase in productivity by ~20% compared with a conventional single-specimen STEM or TEM. An air-formed oxide film was stripped from CP-Ti substrate by chemical etching in the bromine-methanol electrolyte, exposing the bare titanium substrate and grain boundaries with defects. After that, pitting corrosion occurred on the bare titanium due to the attack of bromine. The corrosion pits propagated with etching time from 10 to 300 s and were displayed using white light interferometry. Increased surface roughness was identified with etching time due to the occurrence of more pitting corrosion attacks. Bromine species and TiBr4 compounds were detected by EDS and X-ray diffraction patterns, indicating that the dissolution of the titanium substrate was induced in each etching.

In this study, the application of bipolar electrocoagulation (EC) with iron electrode has been assessed for color removal of simulated wastewater containing Reactive Red 195. The influence of initial pH, sodium sulfate concentration, initial dye concentration, electrolysis time, and electric current were examined. The optimum operational parameters were found to be pH =11, concentration of dye = 50 mg L-1, sodium sulfate concentration = 1200 mg L-1, electrolysis time = 5 min and electric current = 4 A. In such condition, color removal efficiency achieved over 99%. This result indicates that EC can be used as an efficient and “green” method for color removal from reactive dye solution. / Trong nghiên cứu này, quá trình khử màu nhuộm hoạt tính (Reactive Red 195) được khảo sát bằng hệ thống keo tụ điện hóa điện cực kép, với vật liệu sắt. Các yếu tố ảnh hưởng đến quá trình khử màu như pH, nồng độ màu nhuộm, nồng độ muối Na2SO4, thời gian phản ứng và cường độ dòng được lựa chọn nghiên cứu. Kết quả cho thấy hệ thống điện hóa trên loại gần như hoàn toàn màu nhuộm với hiệu suất đạt trên 99 % tại pH 11, nồng độ màu 50 mgL-1 và nống độ muối Na2SO4 1200 mgL-1 trong khoảng thời gian 5phút. Kết quả trên cho thấy keo tụ điện hóa có thể xem là một phương pháp xử lý hiệu quả và “xanh” trong việc loại bỏ hoàn toàn màu từ nước thải nhuộm hoạt tính.

Στην παρούσα εργασία μελετάται πειραματικά η ανάπτυξη μεμβρανών πορώδους αλουμίνας με ελεγχόμενο πάχος, διάμετρο πόρου, σε ηλεκτρολύτη οξαλικού οξέος συγκεντρώσεως 0.3Μ με εφαρμοζόμενη τάση 40V και 50V. Για την κατανόηση του μηχανισμού της δημιουργίας των μεμβρανών πορώδους αλουμίνας γίνεται μια βιβλιογραφική παρουσίαση των μοντέλων ανάπτυξης της. Από τα πειράματα προκύπτει ότι ο ρυθμός ανάπτυξης του πάχους της μεμβράνης ακολουθεί τον νόμο του Faraday με απόδοση που εξαρτάται από την τάση ανοδίωσης. Τέλος υπολογίζεται η ενέργεια ενεργοποίησης για την αντίδραση του σχηματισμού της πορώδους αλουμίνας. Η ενέργεια ενεργοποίησης που αφορά την αντίδραση του αλουμινίου με τον ηλεκτρολύτη. / Ιn the present study, the synthesis of porous alumina membranes with controlled thickness and pore diameter is investigated. More specifically, the experimental condition under study was oxalic acid 0.3M under an applied voltage of 40V and 50V. In order to understand the growth mechanism of the porous alumina membrane formation, a bibliographic view of the growth models is presented. The experiments result in the conclusion that the thickness growth rate of the porous alumina membrane obeys the Faraday law for electrolysis with an efficiency being dependent on the anodization applied voltage. Finally, the activation energy for the porous alumina formation concerning the reaction of aluminum with the electrolyte, is calculated.

Diploma thesis mainly describes the theoretical knowledge of the topic photoimpedance spectroscopy characterization of optical and electrical properties of the photovoltaic cells, which contains development and princip of cells working, material properties of photovoltaic cells, explanation of electromagnetic waves, spectrophotometry and impedance spectroscopy, followed by a discription of the measuring device and used measuring methods. The experimental section for each measurement method describes the steps of setting the program, then the tables with measured values are involeved in some parts and a part of each method are summary graphs of measured values with subsequent evaluation.

>Magister Scientiae - MSc / A comparative study of electrolysers using different anodic materials for the electrolysis of brine (sodium chloride) for the production of sodium hypochlorite as a source of A comparative study of electrolysers using different anodic materials for the electrolysis of brine (sodium chloride) for the production of sodium hypochlorite as a source of available chlorine for disinfection of rural water supplies has been undertaken. The electrolyser design used was tubular in form, having two chambers i.e. anode inside and cathode outside, separated by a tubular inorganic ceramic membrane. The anode was made of titanium rod coated with a thin layer of platinum and a further coat of metal oxide. The cathode was made of stainless steel wire. available chlorine for disinfection of rural water supplies has been undertaken. The electrolyser design used was tubular in form, having two chambers i.e. anode inside and cathode outside, separated by a tubular inorganic ceramic membrane. The anode was made of titanium rod coated with a thin layer of platinum and a further coat of metal oxide. The cathode was made of stainless steel wire. An assessment of these electrolysers was undertaken by studying the effects of some variable parameters i.e. current, voltage and sodium chloride concentration. The flow rate was kept unchanged at 50ml/h anolyte and 140ml/h catholyte since it was found to be optimum flow rate for chlorine generation. Figures of merit of the electrolysers were calculated on the basis of three sets of measurements. Analytical methods used for the determination of sodium hypochlorite concentration were iodometric and N, N-Diethyl-p- Phenylenediamine (DPD) titration methods. The DPD titration method was used to determine the chlorine concentration of less than 1mg/L, while the iodometric titration method was used to determine chlorine concentration of ImgIL and above. Sodium chlorate present in the hypochlorite solution was also determined using a spectrophotometric method. The cobalt oxide electrolyser has been shown to be superior as compared to the ruthenium dioxide and manganese dioxide electrolysers in terms of hypochlorite generation. Sodium chlorate was present but at concentration levels not hazardous for use in dosing water for drinking purposes. Analysis of hydroxyl radicals was undertaken since there were claims that these are produced during brine electrolysis. Hydroxyl radical analysis was not successful, since sodium hypochlorite and hypochlorous acid interfere using the analytical method described in this study.

In this study, the application of bipolar electrocoagulation (EC) with iron electrode has been assessed for color removal of simulated wastewater containing Reactive Red 195. The influence of initial pH, sodium sulfate concentration, initial dye concentration, electrolysis time, and electric current were examined. The optimum operational parameters were found to be pH =11, concentration of dye = 50 mg L-1, sodium sulfate concentration = 1200 mg L-1, electrolysis time = 5 min and electric current = 4 A. In such condition, color removal efficiency achieved over 99%. This result indicates that EC can be used as an efficient and “green” method for color removal from reactive dye solution. / Trong nghiên cứu này, quá trình khử màu nhuộm hoạt tính (Reactive Red 195) được khảo sát bằng hệ thống keo tụ điện hóa điện cực kép, với vật liệu sắt. Các yếu tố ảnh hưởng đến quá trình khử màu như pH, nồng độ màu nhuộm, nồng độ muối Na2SO4, thời gian phản ứng và cường độ dòng được lựa chọn nghiên cứu. Kết quả cho thấy hệ thống điện hóa trên loại gần như hoàn toàn màu nhuộm với hiệu suất đạt trên 99 % tại pH 11, nồng độ màu 50 mgL-1 và nống độ muối Na2SO4 1200 mgL-1 trong khoảng thời gian 5phút. Kết quả trên cho thấy keo tụ điện hóa có thể xem là một phương pháp xử lý hiệu quả và “xanh” trong việc loại bỏ hoàn toàn màu từ nước thải nhuộm hoạt tính.

La presente Tesis Doctoral consiste en la determinación de las propiedades de transporte de diferentes especies catiónicas a través de membranas de intercambio catiónico. Las membranas de intercambio iónico son un componente clave de los reactores electroquímicos y de los sistemas de electrodiálisis, puesto que determinan el consumo energético y la eficiencia del proceso. La utilización de este tipo de membranas para el tratamiento de efluentes industriales no es muy extendida debido a los requisitos de elevada resistencia química y durabilidad que deben cumplir las membranas. Otro asunto importante radica en la eficiencia en el transporte de los iones que se quieren eliminar a través de la membrana. Normalmente, existe una competencia por el paso a través de las membranas entre diferentes especies debido al carácter multicomponente de los efluentes a tratar. Sin embargo, una mejora en las propiedades de las membranas de intercambio iónico permitiría la implantación del tratamiento mediante reactores electroquímicos de efluentes industriales con un contenido importante en compuestos metálicos, tales como los baños agotados de las industrias de cromado. La utilización de una tecnología limpia como la electrodiálisis conllevaría diferentes ventajas, entre las cuales destacan la recuperación de los efluentes para su reutilización en el proceso industrial, el ahorro en el consumo de agua y la disminución de la descarga de contaminantes al medio ambiente. La determinación de las condiciones de operación óptimas así como la mejora de las propiedades de transporte de las membranas constituye el principal tema de la presente investigación. Para ello, se emplearán diferentes tipos de membrana. En primer lugar, se estudiará el comportamiento de las membranas poliméricas comerciales que poseen unas propiedades de resistencia química elevadas, las cuales se tomarán como referencia. De forma paralela, se producirán membranas conductoras de iones a partir de materiales cerámicos económicos, ya que la resistencia de los materiales cerámicos a sustancias oxidantes y muy ácidas es mayor que la de los materiales poliméricos. Este punto constituye la parte más innovadora de la investigación, puesto que la mayoría de las membranas de intercambio iónico comerciales están basadas en materiales poliméricos que no pueden resistir las condiciones específicas de los efluentes industriales. Una vez determinadas las condiciones de operación óptimas, se realizarán ensayos en plantas piloto con el fin de confirmar los resultados obtenidos mediante las técnicas de caracterización y determinar el grado de recuperación y coste energético asociado a los procesos electrodialíticos de tratamiento de efluentes industriales. / Martí Calatayud, MC. (2014). STUDY OF THE TRANSPORT OF HEAVY METAL IONS THROUGH CATION-EXCHANGE MEMBRANES APPLIED TO THE TREATMENT OF INDUSTRIAL EFFLUENTS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/46004 / Premios Extraordinarios de tesis doctorales