Electrochemical Characterisation of Filter Media Properties and Their Exploitation in Enhanced Filtration

Streaming potential measurements for the surface charge characterisation of different filter media types and materials were used. The equipment was developed further so that measurements could be taken along the surfaces, and so that tubular membranes could also be measured. The streaming potential proved to be a very useful tool in the charge analysis of both clean and fouled filter media. Adsorption and fouling could be studied, as could flux, as functions of time. A module to determine the membrane potential was also constructed. The results collected from the experiments conducted with these devices were used in the study of the theory of streaming potential as an electrokinetic phenomenon. Several correction factors, which are derived to take into account the surface conductance and the electrokinetic flow in very narrow capillaries, were tested in practice. The surface materials were studied using FTIR and the results compared with those from the streaming potentials. FTIR analysis was also found to be a useful tool in the characterisation of filters, as well as in the fouling studies. Upon examination of the recorded spectra from different depths in a sample it was possible to determine the adsorption sites. The influence of an external electric field on the cross flow microflltration of a binary protein system was investigated using a membrane electroflltration apparatus. The results showed that a significant improvement could be achieved in membrane filtration by using the measured electrochemical properties to help adjust the process conditions.

Electrochemical and spectroelectrochemical characterization of alkylated and thiolated polyanilines

Vi omges i vardagen av alla sorters plaster, som kemiskt kallas för polymerer. Vi anknyter dem oftast till vardagliga föremål såsom muggar, leksaker eller platskassar. Det finns dock en särklass av polymerer som fås elektriskt ledande genom en så kallad dopningsprocess. Dopning innebär i detta fall oxidation eller reduktion av konjugerade dubbelbindningar i polymerstrukturen. Detta har lett till utveckling av elektriska apparater där dyra, och i vissa fall även sällsynta, metall och halvledarmaterial ersätts genom av elektriskt ledande polymerer (plaster). Utöver elektronisk ledningsförmåga uppvisar dessa polymerer också jonisk ledningsförmåga. Denna kombination av unika egenskaper möjliggör skapandet av t.ex. nya sensormaterial som kan överföra kemisk information till en mätbar elektronisk signal. Detta öppnar i sin tur möjligheter att göra snabba, billiga och känsliga sensorer för bl.a. mediciniska analyser. I denna avhandling karakteriserades elektrokemiskt och spektroelektrokemiskt N- och ring-substituerade polyanilinfilmer. Polyanilin (PANI) hör till de mest studerade elektriskt ledande polymererna. Den är stabil och lätt att framställa. Substituerade polyaniliner har ändå studerats måttligt, mest p.g.a. att substituerade PANIs ledningsförmåga är lägre än PANIs och deras framställning kan vara svår. De nya grupperna i PANI-kedjan ger dock en möjlighet att binda ytterligare molekyler av intresse till PANI-kedjan, som t.ex. jonselektiva grupper. Kovalent bundna selektiva molekyler ger upphov till stabila, känsliga och selektiva sensormaterial. Karakteriseringen av de studerade polymerer är viktig för den fundamentala förståelsen av deras unika egenskaper och för utvecklingen av framtidens sensormaterial. -------------------------------------- Käytämme joka päivä monenlaisia muoveja, joita kutsutaan kemiassa myös polymeereiksi. Olemme tottuneet yhdistämään muovit arkisiin esineisiin kuten mukeihin, leluihin tai muovikasseihin. On kuitenkin olemassa erityisiä polymeerejä, jotka voidaan saada sähköä johtaviksi hapetus- ja pelkistysreaktioiden avulla. Tästä johtuen on kehitteillä sähköisiä laitteita, joissa kalliit ja jossain tapauksissa myös harvinaisia metalleja sisältävät osat ja puolijohteet voidaan korvata johdepolymeereillä (eli muoveilla). Sähkönjohtavuuden lisäksi johdepolymeereillä on myös ionijohtavuutta. Näiden erityislaatuisten ominaisuuksien yhdistelmä on mahdollistanut mm. sensorimateriaalin kehittämisen, sillä kemiallinen tieto voidaan kääntää mitattavaksi sähköiseksi signaaliksi. Tämä taas omalta osaltaan mahdollistaisi nopeiden, halpojen ja herkkien sensorien valmistuksen, mm. diagnostiikkaan. Tässä väitöksessä on tutkittu sähkökemiallisesti valmistettuja N- ja rengassubstituoituja polyaniliinikalvoja. Polyaniliini (PANI) on yksi eniten tutkituista johdepolymeereistä. Se on stabiili ja helppo valmistaa. Substituoidut polyaniliinit ovat herättäneet vain kohtalaista tieteellistä kiinnostusta, lähinnä, koska niiden sähköinen johdekyky on alhaisempi kuin PANIn. Myös niiden valmistus voi olla vaikeaa. Substituoidut molekyylit PANI-ketjussa mahdollistavat kuitenkin, että niihin voi liittää uusia molekyylejä, esim. ioniherkkiä ryhmiä. Kovalentisti sitoutuneilla selektiivisillä molekyyleillä saadaan tehtyä stabiileja, herkkiä ja selektiivisiä sensorimateriaaleja. Väitöksessä käytettyjen polymeerien karakterisointi on tärkeää, jotta niiden erityisominaisuuksia pystyttäisiin ymmärtämään paremmin ja myös kehittämään sopivia tulevaisuuden sensorimateriaaleja.

Electrochemical Treatment of Wastewaters

Electrocoagulation is a process in which wastewater is treated under electrical current. Coagulant is formed during the process through the metal anode dissolution to respective ions which react with hydroxyl ions released in cathode. These metal hydroxides form complexes with pollutant ions. Pollutants are removed among metal hydroxide precipitates. This study was concentrated on describing chemistry and device structures in which electrochemical treatment operations are based on. Studied pollutants were nitrogen compounds, sulphate, trivalent and pentavalent arsenic, heavy metals, phosphate, fluoride, chloride, and bromide. In experimental part, removal of ammonium, nitrate, and sulphate during electrochemical treatment was studied separately. Main objective of this study was to find suitable metal plate material for ammonium, nitrate, and sulphate removal, respectively. Also other parameters such as pH of solution, concentration of pollutant and sodium chloride, and current density were optimized. According to this study the most suitable material for ammonium and sulphate removal by electrochemical treatment was stainless steel. Respectively, iron was the optimum material for nitrate removal. Rise in the pH of solution at the final stage of electrochemical treatment of ammonium, nitrate, and sulphate was detected. Conductivities of solutions decreased during ammonium removal in electrochemical processes. When nitrate and sulphate were removed electrochemically conductivities of solutions increased. Concentrations of residual metals in electrochemically treated solutions were not significant. Based on this study electrochemical treatment processes are recommended to be used in treatment of industrial wastewaters. Treatment conditions should be optimized for each wastewater matrix.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.