The use of a CO2 infrared (IR) laser and photocatalysis for water treatment microorganism disinfection purposes was investigated. During CO2 infrared (IR) laser treatment E. cloacae inactivation was comparable to inactivation via ultraviolet (UV) treatment; however no inactivation of the more resistant B. subtilis endospores occurred. Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR) spectroscopy of the bacterial cells displayed increased polysaccharide contents after IR treatment. FTIR and Raman spectroscopy of simple carbohydrates before and after IR laser treatment displayed no spectral changes, with the exception of N-acetyl-D-glucosamine (NAG), which was partially attributed to sampling techniques. E. cloacae inactivation during IR treatment was attributed to localised and overall temperature increases within the water. Due to the inability to inactivate B. subtilis endospores this technique is not suitable for water treatment purposes. Photocatalytic water treatment using novel TiO2 colloids prepared via a postsynthetic microwave-modification process (MW-treated) was also examined. These colloids were characterised using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analyses and compared to Degussa P25 and convection hydrothermally-treated (HT-treated) TiO2. Slurry suspensions displayed comparable E. coli inactivation rates, so the colloids were examined in immobilised form using both a model organic degradant, oxalic acid, and E. coli. Oxalic acid degradation studies showed that the MW-treated colloids displayed similar inactivation rates to the HT-treated TiO2, due to their pure anatase composition, while Degussa P25 displayed higher inactivation rates. Investigations into the effect of shortening UV wavelength were also performed. Degussa P25 was the only catalyst which displayed higher apparent quantum yields upon shortening the UV wavelength, which was attributed to its mixed-phase anatase-rutile composition. As E. coli inactivation was observed using distilled water, photocatalysis in natural river water was trailed. It was discovered that the pH had to be lowered from 7.5 to 5.0 and the initial cell concentration must be approximately 1 x 103 colony forming units (CFU) per cm3 or less for inactivation to be observed during a 5 hour treatment period. At a catalyst loading of 1.0 mg per cm2, Degussa P25 absorbed all the applied UVA irradiation; however the MW- and HT-treated TiO2 colloids did not due to their smaller particle size. Therefore sandwich experiments were devised to evaluate the effect of unabsorbed UV irradiation within the system. Small colony variants were identified after photocatalytic and UV treatment, which pose a potential threat to public health. Further investigation of the different TiO2 colloids was performed using in situ FTIR, both with and without an applied potential and compared to a thermally prepared TiO2 catalyst. The latter displayed potential dependent photocatalysis, while the mesoporous TiO2 catalysts displayed potential independent photocatalysis. All catalyst types displayed increased degradation rates upon the application of a positive bias, which was followed in situ via the production of CO2. Sodium oxalate and NAG was examined for photocatalytic degradation, both of which were degraded to CO2, with proposed break-down products identified when using NAG.

Στην παρούσα διδακτορική διατριβή μελετάται η φωτοηλεκτροχημική παραγωγή υδρογόνου και ηλεκτρικής ενέργειας με υβριδικές ανόργανες/οργανικές διατάξεις. Η παραγωγή ηλεκτρικής ενέργειας και υδρογόνου, με φωτοαποικοδόμηση οργανικών αποβλήτων σε μία φωτοηλεκτροχημική (ΦΗΧ) κυψελίδα είναι μία ελκυστική διεργασία με διπλό περιβαλλοντικό όφελος: Τα απόβλητα καταναλώνονται και η ηλιακή ακτινοβολία μετατρέπεται σε χρήσιμες μορφές ενέργειας, όπως η ηλεκτρική και το υδρογόνο. Οι κύριες συνιστώσες ενός φωτοηλεκτροχημικού κελιού είναι: (α) το ηλεκτρόδιο ανόδου, το οποίο φέρει τον φωτοκαταλύτη και ονομάζεται «φωτοάνοδος». Όταν ο φωτοκαταλύτης είναι ένας n-τύπου ημιαγωγός, η φωτοάνοδος παράγει ηλεκτρόνια, δηλαδή είναι το αρνητικό ηλεκτρόδιο και εκεί πραγματοποιούνται οι αντιδράσεις οξείδωσης, (β) το ηλεκτρόδιο καθόδου, το οποίο φέρει τον ηλεκτροκαταλύτη, δηλαδή ένα υλικό το οποίο διευκολύνει την μεταφορά ηλεκτρονίων από την κάθοδο στην υγρή φάση. Αντιδράσεις αναγωγής πραγματοποιούνται στην κάθοδο, όπως για παράδειγμα, αναγωγή των ιόντων υδρογόνου σε μοριακό υδρογόνο, (γ) ο ηλεκτρολύτης, που προστίθεται προκειμένου να αυξηθεί η αγωγιμότητα και να ρυθμιστεί το pH του διαλύματος. Τα φωτόνια που προσπίπτουν στην κυψελίδα απορροφώνται από την φωτοάνοδο, δημιουργώντας ζεύγη ηλεκτρονίων-οπών. Οι οπές οξειδώνουν τις προς φωτοαποικοδόμηση ουσίες, απελευθερώνοντας ιόντα υδρογόνου τα οποία διαχέονται στην υγρή φάση. Τα ηλεκτρόνια διοχετεύονται μέσω εξωτερικού κυκλώματος στην κάθοδο, όπου και ανάγουν τα ιόντα υδρογόνου. Η παραγωγή υδρογόνου συνοδεύεται από τη ροή ηλεκτρονίων, δηλαδή ηλεκτρικό ρεύμα, στο εξωτερικό κύκλωμα. Το μοριακό υδρογόνο σχηματίζεται υπό αναερόβιες συνθήκες ενώ παρουσία οξυγόνου, οδηγείται στο σχηματισμό νερού. Η νανοκρυσταλλική τιτάνια (TiO2¬), είναι ένας από τους καταλληλότερους φωτοκαταλύτες που χρησιμοποιούνται για την ετερογενή φωτοκαταλυτική αποικοδόμηση ρύπων. Ωστόσο το TiO2 αν και είναι ένας ικανός φωτοκαταλύτης με κατάλληλο ενεργειακό χάσμα, βαρύνεται με το μειονέκτημα της απορρόφησης μόνο υπεριώδους ακτινοβολίας και έτσι στην παρούσα μελέτη έχουν γίνει προσπάθειες φωτοευαισθητοποίησής του με ημιαγωγούς μικρότερου ενεργειακού χάσματος που απορροφούν στο ορατό τμήμα της ακτινοβολίας (π.χ. CdS). Η ορατή ακτινοβολία απορροφάται από τον φωτοευαισθητοποιητή, ο οποίος διεγείρεται και εφόσον το ενεργειακό επίπεδο του διεγερμένου ηλεκτρονίου είναι ηλεκτραρνητικότερο από τη στάθμη αγωγιμότητας του TiO2, μεταπηδά στο TiO¬2 και συμμετέχει στην φωτοηλεκτροχημική διαδικασία. Η οπή που διαχωρίζεται από το διεγερμένο ηλεκτρόνιο, παραμένει στον φωτοευαισθητοποιητή και συμμετέχει σε αντιδράσεις οξείδωσης. Η ποιότητα και η αποτελεσματικότητα της καθόδου, παίζει εξίσου σπουδαίο ρόλο όπως και η απόδοση της ανόδου. Η κυψελίδα μπορεί να λειτουργήσει ακόμα και με ένα μεταλλικό σύρμα για κάθοδο. Όμως η απόδοση γίνεται κατά πολύ μεγαλύτερη όταν η κάθοδος έχει μεγάλη ενεργό επιφάνεια, πράγμα που αντανακλάται άμεσα στον συντελεστή πληρότητας (fill factor) της κυψελίδας. Βέλτιστη απόδοση της φωτοηλεκτροχημικής κυψελίδας έχει επιτευχθεί με τη χρήση ηλεκτροδίου Carbon Cloth εμπλουτισμένου με νανοσωματίδια Pt (0.5mg Pt/cm2). Η φωτοηλεκτροχημική διαδικασία παρουσία φωτοκαταλύτη απαιτεί τη δημιουργία φορέων φορτίου, συγκεκριμένα ιόντων, η συγκέντρωση των οποίων επηρεάζει την ιοντική αγωγιμότητα. Για την έκλυση μοριακού υδρογόνου είναι απαραίτητη η παραγωγή ιόντων υδρογόνου μέσω της αντίδρασης οξείδωσης. Επομένως χημικές ουσίες που απελευθερώνουν ιόντα υδρογόνου κατά τη φωτοκαταλυτική οξείδωση έχουν δώσει τη μεγαλύτερη παραγωγή υδρογόνου και ηλεκτρικής ενέργειας. Το υψηλό pH του ηλεκτρολύτη εκτός από την αύξηση της αγωγιμότητας είναι επίσης απαραίτητο για την φωτοαποικοδόμηση οργανικών ρύπων. Όταν η φωτοηλεκτροχημική διεργασία, πραγματοποιείται σε αλκαλικό περιβάλλον, οι μεγάλες συγκεντρώσεις ΟΗ- εξασφαλίζουν τη δέσμευση των φωτοπαραγόμενων οπών και τον επιτυχή διαχωρισμό τους από τα ηλεκτρόνια. Κυριότερες κατηγορίες αυτών των «θυσιαζόμενων» ενώσεων είναι οι αλκοόλες, τα σάκχαρα, οι πολυόλες και από τη δική μας μελέτη προκύπτει ότι συγκεκριμένα αιθανόλη και γλυκερόλη είναι οι πιο αποδοτικοί οργανικοί «ρύποι». / In the present study a detailed investigation has been carried out in an attempt to obtain photoelectrochemical hydrogen and electricity production by using hybrid organic- inorganic structures. Production of electricity and hydrogen by photocatalytic degradation of organic wastes in a photoelectrochemical (PEC) cell is an attractive project with double environmental benefit: waste material can be consumed and solar radiation can be converted into useful forms of energy, such as electricity and hydrogen. The main components of a PEC cell are: (a) the anode electrode, which carriers the photocatalyst and thus it is usually named “photoanode”. When the photocatalyst is an n-type semiconductor, the photoanode produces electrons, i.e. it is the negative electrode. Oxidation reactions take place at the photoanode, (b) the cathode electrode, which carries the electrocatalyst, i.e. a material which facilitates transfer of electrons from the cathode to the liquid phase. Reductive interactions take place at the cathode, for example reduction of hydrogen ions to molecular hydrogen, (c) the electrolyte, which is added in order to increase conductivity and define the pH. Photons are absorbed by the photoanode, generating electron-hole pairs. Holes oxidize the photodegradable substance, liberating hydrogen ions which diffuse in the liquid phase. Electrons are channeled through an external circuit towards the cathode, where they reduce hydrogen ions producing hydrogen molecules. This production of hydrogen is accompanied by flow of electrons, i.e. an electric current, in the external circuit. Hydrogen is detected in the absence of oxygen, otherwise in its presence, hydrogen is retained regenerating water. Nanocrystalline titania is the most successful photocatalyst for heterogeneous photocatalytic degradation of organic wastes. Even though, TiO2 is a capable catalyst with suitable energy band gap, it is burdened with the disadvantage of the absorption by only UVA light. Thus in the present study there have been efforts for its photo-activation through smaller energy band gap semiconductors that absorb in the visible part of solar spectrum, for example, CdS. CdS acts as titania sensitizer in the visible and at the same time prevents electron-hole recombination, since electrons are transferred to a separate nanoparticle. The quality and efficiency of the cathode plays an equally important role as the performance of the anode. The cell can operate even with a single metal wire being used as cathode. Nevertheless the performance is much higher when the cathode has a large active surface, a fact that is reflected on the fill factor of the cell. The optimal performance of the photo-electrochemical cell has been achieved using Carbon Cloth electrode, loaded with nanoparticles Pt (0.5mg Pt/cm2). The photoelectrochemical process, in the presence of a photocatalyst, requires the creation of charge carriers, more specifically ions, the concentration of which affects the ionic conductivity. For the release of the molecular hydrogen, the production of hydrogen ions is first necessary through the oxidation reaction. Thus chemical substances that release hydrogen ions during the photo-catalytic oxidation have yielded the greatest hydrogen and electricity production. In the presence of high OH− concentration, efficient hole scavenging and production of hydroxyl radicals is ensured. This is particularly important when an organic sacrificial agent is added, which is expected to be photodegraded during PEC cell operation. Major categories of these sacrificial agents are alcohols, sugars and polyols and our research shows that specifically ethanol and glycerol are the most efficient organic “wastes”.

Poor indoor air quality is a source of adverse health effects. TiO2 coatings deposited on well-illuminated surfaces, such as window panes, can be used to fully mineralize indoor air pollutants by photocatalysis. In such applications it is important to ensure stable photocatalytic activity for a wide range of operating conditions, such as relative humidity and temperature, and to avoid deactivation of the catalyst. In this thesis photocatalytic removal of the indoor-pollutant acetaldehyde (CH3CHO) on nanostructured TiO2 films is investigated, and in particular it is proposed how such films can be modified and operated for maximum performance. Catalyst deactivation can be reduced by purposefully changing the surface acidity of TiO2 by covalently attaching SO4 to the surface. Moreover, the overall photocatalytic activity on anatase TiO2 films can be improved by increasing the fraction of exposed reactive {001} surfaces, which otherwise are dominated by {101} surfaces. In the first part of the thesis mode-resolved in-situ FTIR is used to elucidate the reaction kinetics of CH3CHO adsorption and photo-oxidation on the TiO2 and SO4 – modified TiO2 surfaces. Surface concentrations of main products and corresponding reaction rates were determined. Formate is the major reaction product, whose further oxidation limits the complete oxidation to gaseous species, and is responsible for photocatalyst deactivation by site inhibition. The oxidation reaction is characterized by two reaction pathways, which are associated with two types of surface reaction sites. On the sulfate modified TiO2 catalyst fewer intermediates are accumulated, and this catalyst resists deactivation much better than pure TiO2. A hitherto unknown intermediate – surface-bound acetaldehyde dimer with an adsorption band at 1643 cm−1 was discovered, using interplay between FTIR spectroscopy and DFT calculations. The second part of the thesis treats the effect of increasing the relative abundance of exposed {001} facets on the photocatalytic activity of anatase TiO2 films prepared by DC magnetron sputtering. A positive effect was observed both for liquid-phase photo-oxidation of methylene blue, and for gas-phase photocatalytic removal of CH3CHO. In both cases it was found that the exposed {001} surfaces were an order of magnitude more reactive, compared to the {101} ones. Furthermore, it was found that the reactive films were more resilient towards deactivation, and exhibited almost unchanged activity under varying reaction conditions. Finally, a synergetic effect of SO4 – modification and high fraction of exposed {001} surfaces was found, yielding photocatalysts with sustained high activity. The results presented here for facet controlled and chemically modified TiO2 films are of interest for applications in the built environment for indoor air purification and as self-cleaning surfaces. / GRINDOOR

>Magister Scientiae - MSc / Tuberculosis still remains one of the world’s killer diseases. Pyrazinamide (PZA) is one of the most commonly prescribed anti-tuberculosis (anti-TB) drugs due to its ability to significantly shorten the TB treatment period. However, excess PZA in the body caused hepatotoxicity and liver damage. This, together with the resistance of the bacteria to treatment drugs, poor medication and inappropriate dosing, contribute significantly to the high incidents of TB deaths and diseases (such as liver damage). This, therefore, calls for new methods for ensuring reliable dosing of the drug, which will differ from person to person due to inter-individual differences in drug metabolism. A novel biosensor system for monitoring the metabolism of PZA was prepared with a nanocomposite of multi-walled carbon nanotubes (MWCNTs), polyaniline (PANI) and cytochrome P450 2E1 (CYP2E1) electrochemically deposited on a glassy carbon electrode (GCE). The nanocomposite biosensor system exhibited enhanced electro-activity that is attributed to the catalytic effect of the incorporated MWCNTs. The biosensor had a sensitivity of 7.80 μA/ μg mL-1 PZA and a dynamic linear range (DLR) of 4.92 – 160 ng/mL PZA. Bisphenol A (BPA) is a hormone-disrupting chemical used in production of epoxy resins and polycarbonates, which produce various products used on a daily basis. However, BPA can leach out of plastic during normal use and cause health effects such as cancer or disrupt the endocrine system. Moreover, BPA has also been proven to degrade from the containers in landfills and accumulate in groundwater and streams, thereby, polluting the environment while destroying aquatic organisms. Therefore, this also calls for new selective and sensitive methods for the monitoring of BPA. A novel biosensor system for monitoring the oxidation of BPA was prepared from a nanocomposite of polyaniline, polymethyl methacrylate and titanium dioxide nanoparticles, also electrochemically deposited on the GCE. Biosensor fabrication was conducted by immobilization of the enzyme manganese peroxidase (MnP) iii onto the nanocomposite film. The nanobiosensor also revealed enhanced electro activity, attributed to the incorporation of TiO2 nanoparticles. The biosensor system had a sensitivity of 0.3 μA/nM and a detection limit of 0.12 nM. This detection limit falls within the range of the allowed daily intake of BPA as recommended by the Food and Drug Administration (FDA, USA) and other regulatory bodies.

O dióxido de titânio, TiO2, é o pigmento branco mais importante na indústria de tintas devido à sua capacidade de refletir o espectro da radiação solar nas regiões do visível e do infravermelho. Ao refletir os comprimentos de onda da região do visível, o observador percebe a cor branca. A região do infravermelho é percebida pelo ser humano na forma de calor e a radiação ao ser refletida pelo pigmento diminui o aquecimento da superfície pintada. Neste trabalho foram investigados os aspectos morfológicos do TiO2 e avaliado o seu impacto nas propriedades ópticas de tintas base água. Quatro tipos de TiO2 foram utilizados, um de tamanho nanométrico, dois pigmentos comercias com diferentes tamanhos de partículas e o quarto obtido da calcinação do pigmento nanométrico. A calcinação objetivou a alteração da estrutura cristalina da fase anatase para rutilo do TiO2 nanométrico. Os pigmentos e carga (CaCO3) utilizados foram caracterizados através de análises morfológicas (tamanho e formato das partículas, estrutura cristalina, área superficial), absorção de óleo e espectroscopia de refletância difusa (regiões do ultravioleta, visível e infravermelho próximo). Foram produzidas tintas com diferentes teores de pigmentos (5%, 10%, 15% e 20%) As tintas foram caracterizadas através dos seguintes ensaios: viscosidade, espessura do filme seco, determinação de cor e brilho e espectroscopia de refletância difusa. Constatou-se que as propriedades ópticas das tintas são fortemente dependentes do tamanho de partícula do pigmento TiO2. A refletância da região do visível (400 a 700 nm) apresentou valores ótimos nas tintas produzidas com 15 e 20% dos pigmentos comerciais com tamanho médio de partícula entre 140 e 600 nm, produzindo um filme branco com elevada opacidade. A tinta com TiO2 nanométrico (15 a 60 nm para as partículas unitárias) apresentou baixos valores de refletância difusa nas regiões do visível e do infravermelho. As tintas produzidas com TiO2 calcinado, com elevado tamanho de partícula, refletiram mais eficientemente a região do infravermelho (700 – 2500 nm). O tratamento térmico do TiO2 nanométrico resultou num pigmento com tamanho de partícula adequado para aplicação de tintas reflexivas ao calor. / Titanium dioxide, TiO2, is the most important white pigment in coating industry due to its ability to reflect solar radiation spectrum in visible and infrared regions. When TiO2 reflects the light wavelengths in the visible region, the observer perceives the white color. The infrared region is perceived by human being in the form of heat and when the radiation is reflected by pigment decreases the heating of painted surface. In this work, the morphological aspects of TiO2 were investigated and evaluated their impact on optical properties of waterborne paints. Four types of TiO2 were used; one nanosized pigment, two commercial pigments with different particle sizes and the last one was obtained from the calcination of nanoparticles pigments. The main objective of calcination was to alter the crystalline structure of anatase phase to rutile phase of nanometric TiO2. The pigments and filler used (CaCO3) were characterized by morphological analysis (particle size distribution and shape analysis, crystalline structure, surface area), oil absorption and diffuse reflectance spectroscopy (ultraviolet, visible and near-infrared regions) Paints were prepared using different pigments concentrations (5%, 10%, 15% and 20%). The followings tests were carried out to characterize the paints: viscosity, dry film thickness, color and brightness determination and diffuse reflectance spectroscopy. It was observed that the optical properties of the paints are strongly dependent on TiO2 pigment particle size. The reflectance of the visible region (400 to 700 nm) showed better results in the paints produced with 15% and 20% of commercial pigment whose average particle size ranges were between 140 and 600 nm, producing a white film with high opacity. The paint with nanosized TiO2 showed lowest values of diffuse reflectance in visible and infrared regions. The paints formulated with calcined TiO2, pigment showing higher particle sizes, reflected more efficiently the infrared region (700 to 2500 nm). Thermal treatment of nanometric TiO2 resulted in a pigment with particle size suitable for application of heat reflective paints.

Submitted by Alison Vanceto (alison-vanceto@hotmail.com) on 2017-05-02T11:56:47Z No. of bitstreams: 1 DissNESS.pdf: 3543889 bytes, checksum: 8aff5fb0c19f74c48e698260a94c29d2 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-04T12:15:07Z (GMT) No. of bitstreams: 1 DissNESS.pdf: 3543889 bytes, checksum: 8aff5fb0c19f74c48e698260a94c29d2 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-04T12:15:15Z (GMT) No. of bitstreams: 1 DissNESS.pdf: 3543889 bytes, checksum: 8aff5fb0c19f74c48e698260a94c29d2 (MD5) / Made available in DSpace on 2017-05-04T12:21:59Z (GMT). No. of bitstreams: 1 DissNESS.pdf: 3543889 bytes, checksum: 8aff5fb0c19f74c48e698260a94c29d2 (MD5) Previous issue date: 2015-10-08 / Outra / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The titanium dioxide nanoparticles (NP-TiO2) has achieved into aquatic ecosystems through different sources, such as sewer and leaching. Abiotic factors such as pH, ionic strength, water hardness may change the chemical aggregation of NPs as well as the bioavailability of metals in waters result of speciation and /or complexation with other compounds. Considering the pH variations can occur in the environment naturally or as a result of ecological accidents and the increasing use of NP-TiO2 in many different industries, this study aimed to determine the CL-50; 48 hours of NPTiO2 in different pH (acidic, neutral and basic) in juvenile Prochilodus lineatus (curimbatá) and evaluating the effects of exposure to sublethal NP-TiO2 these pH using biochemical, physiological and morphological biomarkers. After sensitivity test with KCl, the animals were tested with different concentrations of NP-TiO2 at pH 5.0, 7.0 and 8.0 for 48 hours to determine the CL-50; 48h. Subsequently, the animals were exposed to 1 mg L-1 NP-TiO2 for 48 hours at different pH. After the exposure period, blood samples were obtained via caudal puncture for ion plasma analysis and hematologic variables, and samples of gills were collected and fixed. The analytical characterization of NP-TiO2 suggest the aggregation ability are modified of the NP at different pH and at pH 5.0, the hydrodynamic diameter of the NP is much larger then the others pH, which may have create difficults for the entry of NP in organisms and caused less damage. The NP-TiO2 were considered non-toxic in pH 5,0, 7,0 and 8,0. Exposure to NP-TiO2 pH 5.0 and ionic imbalance caused in the exposed animals, possibly due to changes in the concentration of Cl- ions. Exposure to pH 5.0 and 8.0 and NP-TiO2 at pH 7.0 inhibited AC enzyme. In animals exposed to NP at pH 5.0 were not identified cloride cells with crypt surface, possibly due the blocking of these surfaces by the large NP aggregates. Changes in concentrations of ROS and SOD, CAT and GCL activity may indicate an imbalance in antioxidant system due to different pH and NPTiO2 exposure. NP exposure caused major damage at pH 7.0, where have lower hydrodynamic diameter , supporting the hypothesis that the smaller the size of the cluster,it’s easier the NP enter the body of the exposed animals. / As nanopartículas de dióxido de titânio (NP-TiO2) têm alcançado os ecossistemas aquáticos através de diferentes fontes, como esgotos e lixiviação das culturas agrícolas. Fatores abióticos como pH, força iônica, dureza da água podem alterar a agregação química das NPs e a biodisponibilidade de metais nas águas. Considerando as variações de pH que podem ocorrer no ambiente, naturalmente ou não, e a crescente utilização de NP-TiO2 nos mais diferentes segmentos industriais, o presente estudo teve por objetivo determinar a CL-50;48h das NP-TiO2 em diferentes pH (ácido, neutro e básico) em juvenis de Prochilodus lineatus (curimbatá) e avaliar os efeitos da exposição subletal a NP-TiO2 nesses pH, utilizando biomarcadores bioquímicos, fisiológicos e morfológicos. Após a realização do teste de sensibilidade com KCl, os animais foram submetidos a testes com diferentes concentrações de NP-TiO2 nos pH 5,0, 7,0 e 8,0 durante 48h para determinar a CL-50;48h. Posteriormente, os animais foram expostos à concentração de 1 mg L-1 de NP-TiO2 durante 48h nos diferentes pH. Após a exposição, amostras de sangue e de brânquias foram coletadas. Análises de caracterização das NP-TiO2 sugerem que em diferentes pH a capacidade de agregação das NP se modificam e que em pH 5,0, o diâmetro hidrodinâmico das NP é maior em relação aos outros pH, o que pode ter dificultado a entrada das NP nos organismos e causado danos menores. As NP-TiO2 foram consideradas não-tóxicas nos diferentes pH. A exposição a NP-TiO2 e a pH 5,0 causou desequilíbrio iônico nos animais expostos, possivelmente em função das alterações na concentração de Cl-. A exposição a pH 5,0 e 8,0 e a NP-TiO2 em pH 7,0 inibiu a enzima anidrase carbônica. Nos animais expostos a NP em pH 5,0 não foram identificadas CC em cripta, possivelmente devido ao bloqueio das superfícies dessas CC pelos grandes agregados de NP. As alterações nas concentrações de espécies reativas de oxigênio e da atividade das enzimas superóxido dismutase, catalase e glutamato cisteína ligase podem indicar um desequilíbrio no sistema antioxidante. A exposição as NP causou danos maiores em pH 7,0, onde os agregados apresentam diâmetro hidrodinâmico menor, corroborando com a hipótese de que quanto menor o tamanho dos aglomerado, maior a facilidade das NP entrarem no organismo dos animais expostos.

Made available in DSpace on 2014-10-09T12:35:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:01Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

O dióxido de titânio, TiO2, é o pigmento branco mais importante na indústria de tintas devido à sua capacidade de refletir o espectro da radiação solar nas regiões do visível e do infravermelho. Ao refletir os comprimentos de onda da região do visível, o observador percebe a cor branca. A região do infravermelho é percebida pelo ser humano na forma de calor e a radiação ao ser refletida pelo pigmento diminui o aquecimento da superfície pintada. Neste trabalho foram investigados os aspectos morfológicos do TiO2 e avaliado o seu impacto nas propriedades ópticas de tintas base água. Quatro tipos de TiO2 foram utilizados, um de tamanho nanométrico, dois pigmentos comercias com diferentes tamanhos de partículas e o quarto obtido da calcinação do pigmento nanométrico. A calcinação objetivou a alteração da estrutura cristalina da fase anatase para rutilo do TiO2 nanométrico. Os pigmentos e carga (CaCO3) utilizados foram caracterizados através de análises morfológicas (tamanho e formato das partículas, estrutura cristalina, área superficial), absorção de óleo e espectroscopia de refletância difusa (regiões do ultravioleta, visível e infravermelho próximo). Foram produzidas tintas com diferentes teores de pigmentos (5%, 10%, 15% e 20%) As tintas foram caracterizadas através dos seguintes ensaios: viscosidade, espessura do filme seco, determinação de cor e brilho e espectroscopia de refletância difusa. Constatou-se que as propriedades ópticas das tintas são fortemente dependentes do tamanho de partícula do pigmento TiO2. A refletância da região do visível (400 a 700 nm) apresentou valores ótimos nas tintas produzidas com 15 e 20% dos pigmentos comerciais com tamanho médio de partícula entre 140 e 600 nm, produzindo um filme branco com elevada opacidade. A tinta com TiO2 nanométrico (15 a 60 nm para as partículas unitárias) apresentou baixos valores de refletância difusa nas regiões do visível e do infravermelho. As tintas produzidas com TiO2 calcinado, com elevado tamanho de partícula, refletiram mais eficientemente a região do infravermelho (700 – 2500 nm). O tratamento térmico do TiO2 nanométrico resultou num pigmento com tamanho de partícula adequado para aplicação de tintas reflexivas ao calor. / Titanium dioxide, TiO2, is the most important white pigment in coating industry due to its ability to reflect solar radiation spectrum in visible and infrared regions. When TiO2 reflects the light wavelengths in the visible region, the observer perceives the white color. The infrared region is perceived by human being in the form of heat and when the radiation is reflected by pigment decreases the heating of painted surface. In this work, the morphological aspects of TiO2 were investigated and evaluated their impact on optical properties of waterborne paints. Four types of TiO2 were used; one nanosized pigment, two commercial pigments with different particle sizes and the last one was obtained from the calcination of nanoparticles pigments. The main objective of calcination was to alter the crystalline structure of anatase phase to rutile phase of nanometric TiO2. The pigments and filler used (CaCO3) were characterized by morphological analysis (particle size distribution and shape analysis, crystalline structure, surface area), oil absorption and diffuse reflectance spectroscopy (ultraviolet, visible and near-infrared regions) Paints were prepared using different pigments concentrations (5%, 10%, 15% and 20%). The followings tests were carried out to characterize the paints: viscosity, dry film thickness, color and brightness determination and diffuse reflectance spectroscopy. It was observed that the optical properties of the paints are strongly dependent on TiO2 pigment particle size. The reflectance of the visible region (400 to 700 nm) showed better results in the paints produced with 15% and 20% of commercial pigment whose average particle size ranges were between 140 and 600 nm, producing a white film with high opacity. The paint with nanosized TiO2 showed lowest values of diffuse reflectance in visible and infrared regions. The paints formulated with calcined TiO2, pigment showing higher particle sizes, reflected more efficiently the infrared region (700 to 2500 nm). Thermal treatment of nanometric TiO2 resulted in a pigment with particle size suitable for application of heat reflective paints.

Nesse trabalho foram fabricados filmes finos de TiO2 por RF magnetron sputtering reativo sobre substrato de silício (1 0 0). A pressão parcial do oxigênio na câmara foi variada de 5 a 100% em relação ao argônio. Após a deposição os filmes foram submetidos a tratamento térmico em atmosfera de oxigênio. A estequiometria dos filmes e o perfil de profundidade foram obtidos por RBS. A estrutura cristalina foi obtida por XRD. As propriedades ópticas foram obtidas por interferometria e reflectância e as elétricas por meio das curvas C-V. Os valores de espessura dos filmes sem tratamento térmico aumentaram aproximadamente 41% com o aumento do oxigênio na câmara de deposição. Essa variação está ligada ao aumento da eficiência do sputtering do alvo. Os índices de refração dos filmes sem tratamento térmico se mantiveram dentro de um intervalo de aproximadamente 2,3 a 2,4. A diminuição do band gap com o tratamento térmico é consequência da mudança de fase cristalográfica de anatase para rutila. A estequiometria TiOx dos filmes antes do tratamento térmico apresentaram valores de x entre 2,0 e 2,4. A espessura em TFU dos filmes aumentou com o percentual de oxigênio na câmara. As amostras que receberam tratamento térmico apresentaram difusão de titânio na interface do substrato e incorporação de oxigênio no filme. Os valores da constante dielétrica aumentaram com o percentual de oxigênio na câmara, em contraposição com o efeito do tratamento térmico que diminuiu o valor. Todos os resultados observados são coerentes do ponto de vista da mudança de fase anatase rutila e aumento do percentual de oxigênio na câmara. / In this work thin films of TiO2 were produced by reactive RF magnetron sputtering on silicon substrate (1 0 0). The oxygen partial pressure in the chamber was varied from 5 to 100% in relation to argon. After deposition the films were submitted to thermal treatment under an oxygen atmosphere. The stoichiometry of the films and the depth profile were obtained by RBS. The crystal structure was obtained by XRD. Its optical properties were obtained by interferometry and reflectance and the electrical were obtained by means of the C-V curves. The thickness values of films without heat treatment increased approximately 41% with the increase of oxygen in the deposition chamber. This variation is linked to the increased sputtering efficiency of the target. The refractive indexes of films without heat treatment remained within a range of about 2.3 to 2.4. The decrease of the band gap with the heat treatment is a consequence of the change of crystallographic phase from anatase to rutile. The TiOx stoichiometry of the films before the heat treatment showed values of x between 2.0 and 2.4. The TFU thickness of the films increased with the percentage of oxygen in the chamber. The samples that received heat treatment shows diffusion of titanium at the interface of the substrate and incorporation of oxygen in the film. The values of the dielectric constant increased with the percentage of oxygen in the chamber, as opposed to the effect of the thermal treatment that decreased the value. All the results observed are consistent from the point of view of the anatase - rutile phase transition and the increase in the oxygen percentage in the chamber.

Orientador: Nelson Eduardo Duran Caballero / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T05:06:09Z (GMT). No. of bitstreams: 1 Donaire_PatriciaPulciniRosvald_D.pdf: 1368968 bytes, checksum: 36ddc25863076b787c4847f7b99b272a (MD5) Previous issue date: 2007 / Resumo: O presente trabalho trata do desenvolvimento de um reator tubular fotocatalítico aplicado ao tratamento de águas superficiais e subterrâneas contaminadas com compostos orgânicos voláteis, mais especificamente benzeno, tolueno, etilbenzeno e xileno (BTEX). O reator opera com recirculação da amostra e é constituído por dois catalisadores semicondutores, o dióxido de titânio e o dióxido de zircônio (TiO2/ZrO2). Estes catalisadores foram depositados sobre substratos de vidro na forma de filme misto e ativados com luz artificial proveniente de 2 lâmpadas de luz negra de 15 W cada, representando uma intensidade luminosa total de 3,6 mW cm. Os resultados demonstraram a viabilidade da utilização da fotocatálise heterogênea através da deposição de 15 camadas do filme misto sobre a matriz de vidro. A irradiação de água deionizada contaminada com 10 mg L de BTEX resultou em 95,9% de remoção destes compostos em pH 6,6 e vazão de recirculação de 280 mL min , onde somente o benzeno não alcançou o limite permitido pela legislação. A quantificação dos analitos foi realizada utilizando-se microextração em fase sólida (SPME). Observou-se uma cinética de pseudo-primeira ordem sendo a concentração inicial um fator limitante na taxa de degradação. A acetofenona foi a espécie intermediária detectada durante o processo fotocatalítico. No experimento de toxicidade utilizando Daphnia similis como organismo teste, a remoção de toxicidade foi atingida após 30 min de tratamento de água contaminada com gasolina onde o CE50-48 h inicial médio foi de 14,1% atingindo um CE50-48 h final médio de 84,3% / Abstract: The present work deals with the development of a photocatalytic tubular reactor to treat superficial and groundwaters contaminated with organic volatile compounds, more specifically benzene, toluene, ethylbenzene and xylene (BTEX). The reactor was operated with sample recirculation and it was constituted by two semiconductors catalysts, the titanium dioxide and the zirconium dioxide (TiO2/ZrO2). These catalysts were deposited over glass substrate in the form of mixed film and activated with artificial light originated from two 15 W black light lamps representing an average light intensity of 3.6 mW cm. The results showed the viability of heterogeneous photocatalysis using a deposition of 15 mixed film layers over the glass matrix. The photodegradation of deionized water contaminated with 10 mg L of BTEX gave a 95.9% of BTEX removal at pH 6.6 with a recirculation flow of 280 mL min . Among the other components of BTEX, only the benzene did not reach the permitted limit by legislation. The analytes were quantified by solid phase microextraction (SPME). The kinetic of pseudo-first order was observed and being the initial concentration a limiting factor in the degradation rate. The acetophenone was the intermediate species detected during photocatalytic process. In the toxicity experiment using Daphnia similis as organism test, the toxicity removal was reached after 30 min of treatment of contaminated water with gasoline where the initial average CE50-48 h was 14.1 % and reaching a final average CE50-48 h of the 84.3% / Doutorado / Quimica Analitica / Doutor em Quimica