Separation mechanisms in nanofiltration and retention changes of organic compounds

Orgaanisten yhdisteiden negatiivinen retentio nanosuodatuksessa on ilmiö, jota eiole kovin paljon tutkittu. Negatiivisen retentioon vaikuttavat syyt tai tekijäteivät ole kovin hyvin tiedossa. Erotusmenetelmänä negatiivinen retentio voi olla käyttökelpoinen tietyissä sovelluksissa. Työn kirjallisuusosa käsittelee nanosuodatuksen erotusmekanismeja ja retentioon vaikuttavia tekijöitä. Myös joitakin malleja on esitetty. Nanosuodatus on monimutkainen prosessi, josta ei voida löytää vain yhtä erotusmekanismia tai retentioon vaikuttavaa tekijää. Prosessit ovat kokonaisuuksia, joissa erottumiseen vaikuttavat syöttöliuoksen, erotettavan komponentin ja kalvon ominaisuudet, ja niiden väliset vuorovaikutukset. Työn kokeellisessa osassa koottiin mahdollisimman paljon esimerkkejä, joissa monosakkaridien negatiivinen retentio ilmenee. Muita orgaanisia ja epäorgaanisia yhdisteitä käytettiin 'häiriöyhdisteinä' syöttöliuoksessa monosakkaridien kanssa. Kokeet suoritettiin kahdella laboratoriomittakaavan suodatuslaitteella käyttäen kahta kaupallista nanosuodatuskalvoa. Negatiivinen retentio ilmeni useissa tapauksissa. Permeaattivuon ja 'häiriöyhdisteiden' pitoisuuksien havaittiin vaikuttavan voimakkaasti negatiivisen retention ilmenemiseen.

Printed low-voltage organic transistors on plastics and paper

The main advantage of organic electronics over the more widespread inorganic counterparts lies not in the electrical performance, but rather in the solution processability that opens up for low-cost flexible electronics (e.g. displays, sensors and smart tags) fabricated by using printing techniques. Replacing the commonly used laboratory-scale fabrication techniques with mass-printing techniques is, however, truly challenging, especially when low-voltage operation is required. In this thesis it is, nevertheless, demonstrated that low-voltage organic transistors can be fully printed with a similar performance to that of transistors made by laboratory scale techniques. The use of an ion-modulated type of organic field effect transistor (OFET) not only enabled low-voltage operation and printability, but was also found to result in low sensitivity to the surface roughness of the substrate. This allows not only the use of low-cost plastic substrates, but even the use of paper as a substrate. However, while absorption into the porous paper surface is advantageous in a graphical printing process, by reducing the spreading and the coffee-stain effect and by improving the adhesion, it provides great challenges when applying thin electrically active layers. In spite of these difficulties we were able to demonstrate the first low-voltage OFET to be fabricated on paper. We have also shown that low-cost incandescent lamps can be used for sintering printed metal-nanoparticles, and that the process was especially suitable on paper and compatible with a roll-to-roll manufacturing process.

Analytical methods for analyzing organic peroxides

Työn tarkoituksena oli kehittää analyyttinen erotusmenetelmä eräässä valmistusprosessissa käytettävän hapettavan aineen ja liuottimen välillä syntyvien reaktiotuotteiden tutkimiseen ja analysoimiseen. Lisäksi tarkoituksena oli tutkia prosessiolosuhteiden turvallisuutta. Kirjallisuusosassa käsitellään erilaisia orgaanisia peroksideja, niiden käyttötarkoituksia ja niiden käyttöön liittyviä huomioitavia asioita. Lisäksi tarkastellaan yleisimpiä analyysimenetelmiä, joita on käytetty erilaisten peroksidien analysoinnissa. Näitä analyysimenetelmiä on useimmiten käytetty nestemäisten näytteiden tutkimuksissa. Harvemmin on analysoitu kaasu- ja kiintoainenäytteitä. Kokeellisessa osassa kehitettiin kirjallisuuden perusteella peroksidiyhdisteille identifiointimenetelmä ja tutkittiin prosessin näytteet. Analyysimenetelmiksi valittiin iodometrinen titraus ja HPLC-UV-MS-menetelmä. Lisäksi käytettiin peroksidimittaukseen soveltuvia testiliuskoja. Tutkimus osoitti, että iodometrisen titrauksen ja testiliuskojen perusteella näytteissä oli vähäisiä määriä peroksideja viikon jälkeen peroksidilisäyksestä. HPLC-UV-MS-analyysien perusteella näytteiden analysointia häiritsi selluloosa, jota löytyi jokaisesta näytteestä.

Pulsed corona discharge as an advanced oxidation process for degradation of organic

Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

Ultrasonic and Electrokinetic Remediation of Low Permeability Soil Contaminated with Persistent Organic Pollutants

Electrokinetics has emerged as a potential technique for in situ soil remediation and especially unique because of the ability to work in low permeability soil. In electrokinetic remediation, non-polar contaminants like most organic compounds are transported primarily by electroosmosis, thus the process is effective only if the contaminants are soluble in pore fluid. Therefore, enhancement is needed to improve mobility of these hydrophobic compounds, which tend to adsorb strongly to the soil. On the other hand, as a novel and rapidly growing science, the applications of ultrasound in environmental technology hold a promising future. Compared to conventional methods, ultrasonication can bring several benefits such as environmental friendliness (no toxic chemical are used or produced), low cost, and compact instrumentation. It also can be applied onsite. Ultrasonic energy applied into contaminated soils can increase desorption and mobilization of contaminants and porosity and permeability of soil through developing of cavitation. The research investigated the coupling effect of the combination of these two techniques, electrokinetics and ultrasonication, in persistent organic pollutant removal from contaminated low permeability clayey soil (with kaolin as a model medium). The preliminary study checked feasibility of ultrasonic treatment of kaolin highly contaminated by persistent organic pollutants (POPs). The laboratory experiments were conducted in various conditions (moisture, frequency, power, duration time, initial concentration) to examine the effects of these parameters on the treatment process. Experimental results showed that ultrasonication has a potential to remove POPs, although the removal efficiencies were not high with short duration time. The study also suggested intermittent ultrasonication over longer time as an effective means to increase the removal efficiencies. Then, experiments were conducted to compare the performances among electrokinetic process alone and electrokinetic processes combined with surfactant addition and mainly with ultrasonication, in designed cylinders (with filtercloth separating central part and electrolyte parts) and in open pans. Combined electrokinetic and ultrasonic treatment did prove positive coupling effect compared to each single process alone, though the level of enhancement is not very significant. The assistance of ultrasound in electrokinetic remediation can help reduce POPs from clayey soil by improving the mobility of hydrophobic organic compounds and degrading these contaminants through pyrolysis and oxidation. Ultrasonication also sustains higher current and increases electroosmotic flow. Initial contaminant concentration is an essential input parameter that can affect the removal effectiveness.