It is increasingly evident that human development is proceeding in an unsustainable manner, and that large business organisations are significantly complicit in this process. In this context, the purpose of this study is to explore the possibilities by which business organisations could come to support sustainable development, with a particular focus on related barriers and how they may be overcome. Literature on business and sustainable development is dominated by managerialist, organisation-centric perspectives, where the focus is on business profitability rather than planetary sustainability. This study seeks to challenge this mainstream literature, engaging with more critical perspectives and exploring the subtleties of the contradictory arguments presented by these two literatures. Empirical investigation involved two major steps. First the thesis employs a) a content analysis and b) a “close reading” of corporate public utterances on sustainability. Secondly, and more substantively, the thesis comprises a series of semi-structured interviews with individuals in organisations. To obtain a range of perspectives on the sustainable development-business relationship, a number of “different types” of organisation are sampled, in the form of social enterprises, large PLCs, SMEs and co-owned businesses. Based on the research findings, it is argued that the most significant barriers within the business-sustainable development relationship in fact concern the nature of modern international financial capitalism, and the nature of business itself. Certain characteristics, such as growth, competition and self-interest, essential to both the nature of the “system” and the nature of business, are fundamentally incompatible with sustainable development. In recognising this dissonance, a blank canvas is created where new imaginings of “sustainable business” can begin to take place. Through detailed engagement with the critical and managerialist literatures, and drawing insight from the different types of organisations sampled, the thesis identifies a number of characteristics, such as collaboration, compromise and consideration of the common good, which may have the potential to enable an alternative, more “human”, and ultimately more “sustainable” form of business organisation.

The growing problem of antibiotic resistance and the lack of promising prospective antibiotics have forced us to search for new classes of antibiotics. Among the candidates to develop into future antibacterials are antimicrobial peptides (AMPs). These potent, broad spectrum compounds are important components of innate immunity of organism from all kingdoms of life. One such family of mini-proteins from plants is called cyclotides, whose members are defines by cyclic backbone and a cystine knot (CCK), which confers to them extreme stability in the face of biological, chemical and physical insults.     Some cyclotides possess Gram-negative specific antibacterial activity; the purpose of this thesis was to characterize how these molecules kill bacteria, and how bacteria would respond to treatment with cyclotides. For this purpose, Salmonella enterica and Escherichia coli mutants resistant to the cyclotides cycloviolacin O2 and cycloviolacin O19, respectively, were selected. These mutants were characterized by whole genome sequencing, genetic reconstitution, fitness measurements, and cross-resistance studies. These studies identified a number of genetic pathways for resistance development to cyclotides. These mutants displayed variable fitness profiles in laboratory growth media and in mice competition experiments, with some mutants possessing a fitness advantage in mice. Cross-resistance studies resulted in the identification of several cases of cross-resistance and collateral sensitivity between cyclotides and other AMPs/antibiotics.      Antimicrobial effects of cyclotides were assayed in different conditions and in bacterial organisms with different surface characteristics. In addition, immunolocalization experiments were performed to explore the biological distribution of cyclotides in plants and to determine the mechanism of action of cyclotides in bacteria, respectively. Antibodies raised against cyO2 were used for this purpose. Immunohistochemical techniques applied to plant cells, tissues and organs provided the information that cyclotides were distributed in all plant organs, and were found in tissues vulnerable to pathogen attack, and that cyclotides were stored in the vacuoles of plant cells. Immunogold staining of cyclotide treated cells of S. typhimurium, showed effects of cyclotide treatment on the cell envelope components as well as cytoplasm. A higher number of cyclotide molecules was associated with the cell envelope, but a considerable fraction of them penetrated into the cytoplasm.

Cette thèse s’inscrit au croisement de plusieurs domaines de la recherche économique de l’innovation. Notre démarche fait appel à des résultats empiriques issus de l’économétrie de l’innovation. Pour étudier la relation entre innovation et demande, l’outil le plus adapté nous semble être le modèle de la croissance endogène fondé sur l’innovation par opposition au modèle de la croissance exogène. La nature et la direction de cette relation ont été explorées par différents courants économiques qui peuvent être classés selon deux grandes écoles. Les premiers sont les tenants de la thèse dite de la poussée technologique de l’innovation (« Technology-Push Innovation ») que l’on peut considérer très globalement comme « tirés » par les travaux de Joseph Schumpeter. Les seconds sont les tenants de l’approche dite de l’impulsion par la demande de l’innovation (« Demand-Pull Innovation ») dont les travaux pionniers ont été baptisés par Jacob Schmookler. Les travaux de Kleinknecht et Verspagen (1990) nous ont fortement inspiré pour démarrer cette thèse. Notre démarche constitue un prolongement et une complexification de leur analyse. En effet, l’objectif de cette thèse est double : monter que la relation entre innovation et demande n’est pas unidirectionnelle et, ce constat vérifié, examiner la possibilité d’étudier l’hétérogénéité des industries au sens de ces deux approches en fonction de leurs niveaux technologiques.Il nous semble que notre travail contribue à la compréhension des déterminants de l’innovation tels qu’ils ressortent de la controverse « Demand-Pull » versus « Technology-push », de trois façons :1) En proposant un survey problématisé de la littérature sur l’innovation,2) En présentant de façon originale des données sur la R&D et la productivité des industries des pays de l’OCDE,3) En suggérant que les modèles à correction d’erreur, maintenant très bien maîtrisés, peuvent apporter d’utiles éclairages à la question des modèles d’innovation (« Demand-Pull » versus « Technology-push »). / This thesis is at the intersection of several fields of economic research of innovation. Our approach uses empirical results from the econometrics of innovation. To study the relationship between innovation and demand, the most suitable seems to be the endogenous growth model based on innovation as opposed to the exogenous growth model. The nature and the direction of this relationship have been explored by various economic flows that can be classified into two major schools. The first are the proponents of so-called “Technology-Push Innovation” which may be regarded very broadly as “learned” by the work of Joseph Schumpeter. The latter are the proponents of the approach “Demand-Pull Innovation”, whose pioneering works have been baptized by Jacob Schmookler.The works of Kleinknecht and Verspagen (1990) have greatly inspired us to start this thesis. Our approach is an extension of this analysis. The purpose of this thesis is twofold: 1) showing that the relationship between innovation and demand is not unidirectional, 2) and this finding verified, examining the heterogeneity of industries within the meaning of these two approaches based on their technology levels.It seems to us that our work contributes to understanding the determinants of innovation as they emerge from the controversy “Demand-Pull” versus “Technology-push”, in three ways: 1) By offering a problematized survey of the literature on innovation, 2) By presenting, in an original way, data on R&D and productivity of industries in OECD countries, 3) By suggesting that the error correction models, now very well controlled, can provide useful insights to the issue of innovation models (“Demand-Pull” versus “Technology-push”).

Cette thèse a pour objectif de caractériser et d'analyser les variations de concentration atmosphérique en CO2, CO et O3 et en aérosols ultrafins mesurées au dessus de la Sibérie, lors de trois campagnes intensives aéroportées en avril et septembre 2006 et en août 2007. La Sibérie est éloignée des grandes sources de pollution de l'hémisphère nord. La distribution, mal connue, de polluants et de gaz à effet de serre dans cette région est cruciale pour la modélisation du transport à grande échelle des polluants. Les mesures ont permis de mettre en évidence l'impact de (1) l'advection de polluants chinois dans des perturbations baroclines, (2) l'advection de polluants européens à diverses altitudes, (3) des feux de biomasse en Asie Centrale, à travers une nouvelle technique (clustering de fonction d'influence lagrangiennes). Les gradients estivaux importants de CO2 sont utilisés pour contraindre le mélange vertical du modèle de circulation globale. Un possible maximum de nucléation dans la moyenne troposphère continentale propre en été est mis en évidence à partir de mesures de particules ultrafines.

Non-centrosymmetric materials that can be polarized under applied mechanical stress or electric field are piezoelectric in nature and the phenomenon is called piezoelectric effect. They are broadly classified as direct and converse piezoelectric effects. Piezo-ceramics have a wide range of applications such as piezoelectric actuators, sensors, and transducers. Among piezoceramics, ferroelectric based materials are imperative owing to the existence of spontaneous polarization in these systems. Several materials are investigated starting from naturally occurring crystals to synthetic ceramics but are limited in their application range. The piezoelectric and ferroelectrics properties of the solid-solutions based on lead zirconate and lead titanate called lead zirconate titanate (PZT), lead magnesium niobate-lead titanate (PMN-PT), lead zinc niobate-lead titanate (PZN-PT) (near morphotrophic phase boundary (MPB)) demonstrate their potential for myriad device applications besides inciting a great deal of academic interest. They have been widely used for commercial applications such as ultra sound transducers, ultrasonic motors, fuel injector actuators, nano positioners in scanning electron microscope etc. However, these materials contain more than 60% lead by weight and volatization of Pb at higher temperature, and disposal of lead results in environmental pollution and are fatal to human health. This gave an insight to search for lead-free solid solutions covering a wide spectrum of applications akin to that of PZT. The search for alternatives to lead based piezoelectric materials is now being focused on modified barium titanates and alkali niobates in which the incidence of MPB was reported similar to that of PZT. In this thesis the results pertaining to the various investigations carried out on modified barium titanates, Ba(Zr0.2Ti0.8)O3- x(Ba0.7Ca0.3)TiO3(BCZT), and alkali niobates, potassium sodium niobate (KNN), are presented. Especially, lead-free piezoelectric material Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3(BCZT) with x= 0.5 has attracted great attention due to its excellent piezoelectric properties. Contrary to the other Pb-free systems, the BZT–BCT phase diagram shows a Morphotropic Phase Boundary (MPB) characterized by the existence of a tri-critical point (TCP), which is also the case for PZT and PMN–PT. One drawback of the BZT–xBCT (x=0.5) is its high sintering temperature (where it exhibits the largest d33 of 550 – 620pC/N). Several methods have been adopted and various additives are being added to bring down the sintering temperature, since high d33 requires an optimized sintering temperature of around 1540oC which also shows excellent ferroelectric properties. However, the methods that were reported in the literature to synthesize the above materials do not guarantee compositional homogeneity and also there is a limitation in obtaining ceramics of enhanced grain size as the ceramics comprising larger grains are demonstrated to exhibit high piezoelectric coefficients. Therefore to address these issues, the simple soft chemical route was adopted to synthesize chemically homogenous powder and the influence of microstructure (grain size) and ferroelectric domains on piezoelectric properties of the BCZT at nano and micron sized crystallites was studied. The results obtained are classified into chapter 3 and chapter 4 accordingly apart from introduction, materials, and methods. Another challenging area of research in lead free piezoceramics for nanoscale device application is to synthesize materials and to visualize the piezoelectric properties at nanoscale with controlled shapes and sizes. For that, Mg2+ ion was chosen as the dopant especially on Ba2+ sites to synthesize Ba0.95Mg0.05Zr0.1Ti0.9O3 (BMZT) nanocrystals, as MgO is known to be an effective grain growth inhibitor in many functional and structural ceramics. Therefore in the present thesis Mg2+ ion was chosen to exercise a strict control over the grain size. The results obtained from this title compound are discussed in chapter 5. Another class of material is K0.5Na0.5NbO3 (KNN), which has been considered a good candidate for lead-free piezoelectric materials. KNN exhibits an MPB around 50% K and 50% Na separating two orthorhombic phases from the complete solid solution of NaNbO3 (Anti-ferroelectric) and KNbO3 (ferroelectric). The major problem associated with KNN ceramic is its complex densification process; difficulty in processing and volatilization of sodium at higher sintering temperature leading to stoichiometric discrepancy. To overcome these difficulties, in the present investigations, an attempt has been made to fabricate KNN ceramics by employing the liquid phase sintering method. In this chapter, B2O3 and borate based glass (0.5 Li2O - 0.5K2O- 2B2O3) were chosen to improve the densification, grain size and their effects on the physical properties of the KNN ceramics are discussed in chapter 6. In chapter 7, KNN crystallites (with size varying from nano to micrometers) were dispersed in the Polyvinylidene fluoride (PVDF) matrix to obtain a polymer/nano or micro crystal composites and the effect of nano and micron sized KNN fillers on the structural, dielectric and piezoelectric properties were investigated. The results obtained pertaining to these aforementioned investigations are organized as follows. In Chapter 1, a brief introduction to the field of ferroelectricity, piezoelectricity, and piezoelectric materials. The emphasis has been on the ferroelectric based piezoelectric materials belonging to the perovskite family of oxides. A brief exposure to the conventional lead based piezoceramics, lead zirconate titanate (PZT) is discussed. Furthermore, drawbacks associated with lead based ceramics are highlighted and alternatives to PZT based ceramics such as modified barium titanate and alkali niobate solid solutions are focused, leading to the motivation and objectives of our work. Chapter 2 describes the various experimental techniques that are employed to synthesize and characterize the materials under investigation. Chapter 3 deals with details concerning the characterization of Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) nanocrystals prepared via complex oxalate precursor route at a relatively low temperature (800°C/5h). The phase formation temperature of BCZT at nanoscale was confirmed by thermogravimetric (TG), differential thermal analysis (DTA) followed by X-ray powder diffraction (XRD) studies. Fourier Transform Infrared (FTIR) spectroscopy was carried out to confirm the complete decomposition of oxalate precursor into BCZT phase. The XRD and profile fitting revealed the coexistence of cubic and tetragonal phases and was also corroborated by Raman study. Transmission electron microscopy (TEM) studies carried out at 800°C and 1000°C/5h heat treated BCZT powder revealed the crystallite size to be in the range of 20 – 50 nm and 40 – 200 nm respectively. The optical band gap for BCZT nanocrystalline powder was obtained using Kubelka Munk function and was found to be around 3.12 ± 0.02 eV and 3.03± 0.02 eV respectively for 800°C (20 – 50 nm) and 1000°C/5h (40 – 200 nm) heat treated samples. The piezoelectric properties were studied for two different crystallite sizes (30 and 70 nm) using piezoresponse force microscope (PFM). The d33 coefficients obtained for 30 nm and 70 nm sized crystallites were 4 pm/V and 47 pm/V respectively. These were superior to those of BaTiO3 nanocrystal (≈ 50 nm) and promising from the technological/industrial applications perspective. Chapter 4 deals with the studies concerning the effect of microstructure (Grain size) and ferroelectric domains on physical properties of Ba0.85Ca0.15Zr0.1Ti0.9O3 ceramics. Fine powders comprising nanocrystallites of Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) were synthesized via oxalate precursor method which facilitated to obtain homogenous and large grain sized ceramics at a lower sintering temperature. The compacted powders were sintered at various temperatures in the range of 1200°C - 1500°C for an optimized duration of 10h. Interestingly the one that was sintered at 1450°C/10h exhibited well resolved Morphotrophic Phase Boundary (MPB). The average grain size associated with this sample was 30 µm accompanied by higher domain density mostly with 90° twinning. These were believed to make a significant contribution towards obtaining large strain of about 0.2 % and piezoelectric coefficient as high as 563 pC/N. The maximum force that was generated by BCZT ceramic (having 30 µm grain size) was found to be 161 MPa which is much higher than that of known actuator materials such as PZT (40 MPa) and NKN-5-LT (7 MPa). Chapter 5 reports the details involving the synthesis, structural, optical, and piezoelectric response of lead free Ba0.95Mg0.05Zr0.1Ti0.9O3 nanocrystalline powder. Nanocrystalline powders of Ba1-xMgxZr0.1Ti0.9O3 (x=0.025 - 0.1) were synthesized via citrate assisted sol-gel method. Interestingly, the one with x=0.05 in the system Ba1-xMgxZr0.1Ti0.9O3 exhibited fairly good piezoelectric response apart from the other physical properties. The phase and structural confirmation of synthesized powder was established by X-ray powder diffraction (XRD) and Raman Spectroscopic techniques. Two distinct Raman bands i.e., 303 cm-1 and 723 cm-1 characteristic of the tetragonal phase were observed. Thermogravimetric analysis (TGA) was performed to evaluate the phase decomposition of the as-synthesized Ba0.95Mg0.05Zr0.1Ti0.9O3 sample as a function of temperature. The average crystallite size associated with Ba0.95Mg0.05Zr0.1Ti0.9O3 was calculated using Scherrer formula based on the XRD data and was found to be 25 nm. However, Scanning and Transmission Electron Microscopy studies revealed the average crystallite size to be in the range of 30-40 nm. Kubelka-Munk function was employed to determine the optical band gap of these nanocrystallites. The piezoelectric response of 26 pm/V was observed for Ba0.95Mg0.05Zr0.1Ti0.9O3 nanocrystal by Piezoresponse Force Microscopy (PFM) technique. Photoluminescence (PL) study carried out on these nanocrystals exhibited a blue emission (470 nm) at room temperature. Chapter 6 describes the effect of the addition of B2O3 on the density, microstructure, dielectric, piezoelectric and ferroelectric properties of K0.5Na0.5NbO3 ceramics. Boron oxide (B2O3) addition to pre-reacted K0.5Na0.5NbO3 (KNN) powders facilitated swift densification at relatively low sintering temperatures which was believed to be a key to minimize potassium and sodium loss. The base KNN powder was synthesized via solid-state reaction route. The different amounts (0.1 to 1 wt %) of B2O3 were added, and ceramics were sintered at different temperatures and durations to optimize the amount of B2O3 needed to obtain KNN pellets with the highest possible density and grain size. The 0.1 wt% B2O3 added KNN ceramics sintered at 1100°C for 7h exhibited higher density (98%) with grain size of ~5 µm. Scanning electron microscopy (SEM) studies confirmed an increase in average grain size with increasing B2O3 content at the appropriate temperature of sintering and duration. The B2O3 added KNN ceramics exhibited improved dielectric and piezoelectric properties at room temperature. For instance, 0.1 wt% B2O3 added KNN ceramic exhibited d33 value of 116 pC/N which is much higher than that of pure KNN ceramics. Interestingly, all the B2O3 added (0.1 to 1wt %) KNN ceramics exhibited polarization – electric field (P vs E) hysteresis loops at room temperature. The remnant polarization (Pr) and coercive field (Ec) values are dependent on the B2O3 content and crystallite size. The details pertaining to the effect of the addition of borate based glass (0.5 Li2O - 0.5K2O- 2B2O3) on the physical properties of K0.5Na0.5NbO3 ceramics are also reported in this chapter. The addition of powdered 0.5 Li2O - 0.5K2O- 2B2O3 (LKBO) glass (0.5 to 2 wt%) to potassium sodium niobate, K0.5Na0.5NbO3 (KNN) powder facilitated higher densification which resulted in improved physical properties that include dielectric, piezoelectric and ferroelectric. The required polycrystalline powders of KNN were synthesized through solid-state reaction route, while LKBO glass was obtained via the conventional melt-quenching technique. Pulverized glass was added to KNN powders in different wt% and compacted at room temperature and these were sintered around 1100°C. Indeed the addition of optimum amount (1 wt %) of LKBO glass to KNN ceramics facilitated lowering of sintering temperature accompanied by larger grains (8 µm) with improved density. The dielectric constant (εr) measured at room temperature was 475 (at 10 kHz), whereas it was only 199 for the LKBO glass free KNN. The piezoelectric coefficient (d33) was found to be 130 pC/N for 1wt% LKBO added glass, which was much higher than that of pure KNN ceramics (85 pC/N). Indeed, the LKBO glass added samples did exhibit well saturated P versus E hysteresis loops at room temperature. Though there was no particular trend observed in the variation of Pr with the increase in glass content, the Pr values were higher than those obtained for KNN ceramics. The improved physical properties of KNN ceramics encountered in these studies were primarily attributed to enhancement in density and grain size. Chapter 7 presents a comparative study on the structural, dielectric and piezoelectric properties of nano and micron sized K0.5Na0.5NbO3 fillers in PVDF composites. Polymer nanocrystal composites were fabricated by embedding polyvinylidene fluoride (PVDF) with different vol% of K0.5Na0.5NbO3 (KNN) nanocrystallites using hot-pressing technique. For comparison, PVDF-KNN microcrystal composites of the same compositions were also fabricated which facilitated the crystallite size (wide range) effect studies on the dielectric and piezoelectric properties. The structural, morphological, dielectric, and piezoelectric properties of these nano and micro crystal composites were investigated. The incorporation of KNN fillers in PVDF at both nano and micrometer scale above 10vol% resulted in the formation of polar β-form of PVDF. The room temperature dielectric constant as high as 3273 at 100Hz was obtained for PVDF comprising 40 vol% KNN nanocrystallites due to dipole –dipole interactions (as the presence of β-PVDF is prominent), whereas it was only 236 for PVDF containing the same amount (40 vol%) of micron sized crystallites of KNN at the same frequency. Various theoretical models were employed to predict the dielectric constants of the PVDF-KNN nano and microcrystal composites. PVDF comprising 70 vol% micronmeter sized crystallites of KNN exhibited d33 value of 35pC/N, while the nanocrystal composites of PVDF-KNN did not exhibit any piezoelectric response perhaps due to unrelieved internal stress within each grain besides having less number of domain walls. The Thesis ends with summary and conclusions, though each chapter is provided with conclusions and a complete list of references.

No description available.

A indústria têxtil gera grandes volumes de efluentes com elevada carga orgânica, forte coloração e toxicidade. Neste trabalho, estuda-se o tratamento de solução aquosa contendo o corante Solophenyl Yellow Arle 154% por meio dos processos O3-H2O2/UV e foto-Fenton, avaliando-se as repostas: remoção de cor em 5 minutos, remoção de cor em 60 minutos, taxa máxima de remoção de cor e remoção de COT em 60 minutos. Os experimentos foram realizados em semibatelada com circulação usando um reator fotoquímico com campo de radiação anular coaxial, constituído de corpo cilíndrico em aço com refletor interno de alumínio para 12 lâmpadas fixadas simetricamente na superfície refletora e um tubo reator em quartzo de 0,7 L, posicionados verticalmente no eixo do refletor. Para o processo O3-H2O2/UV foram utilizadas lâmpadas Phillips TUV (36 W, 254 nm). A corrente gasosa contendo O3 foi introduzida no reator por meio de um difusor. Para o processo foto-Fenton foram utilizadas lâmpadas Sylvania (12 W cada, 300 400 nm) e concentração de Fe(II) de 0,25 mmol/L. Em ambos os processos, solução de peróxido de hidrogênio foi adicionada durante os 30 minutos iniciais de tratamento. As amostras foram analisadas por medidas de carbono orgânico total (COT) e remoção de cor (absorbância medida em 405 nm em espectrofotômetro UV-visível). Em ambos os processos utilizou-se o planejamento experimental Doehlert, definindo os valores mínimo e máximo para cada variável adotada. No caso do processo O3- H2O2/UV (ETAPA I), foram estudados os efeitos da potência elétrica total das lâmpadas (144 432 W), concentração de H2O2 (5 30 mmol/L), concentração inicial de corante (20 100 mg/L), concentração de ozônio (10 40 mg/L) e pH (3 10). No processo foto-Fenton (ETAPA II), estudaram-se os efeitos da potência (160 480 W), concentração de H2O2 (5 30 mmol/L) e concentração inicial de corante (20 100 mg/L). Os resultados da ETAPA I indicaram que o aumento da concentração do corante, em meio ácido, aumenta a remoção de cor em 5 e 60 minutos, sugerindo a eficiência da ação via ozônio molecular sob o grupo cromóforo do corante. Os melhores resultados apresentaram remoção acima de 95% em 5 e 60 minutos de tratamento. Entretanto, para a remoção de COT em 60 minutos o processo não foi eficiente, apresentando resultado máximo de 35,6%. Na ETAPA II obtiveram-se resultados menos satisfatórios para remoção de cor se comparados aos da ETAPA I (56,1% em 5 minutos e 78% em 60 minutos de tratamento), mas melhores em relação à remoção de COT em 60 minutos atigindo 45,1% de remoção. As maiores taxas de remoção de cor foram observadas nos 5 primeiros minutos de tratamento para todos os experimentos. Experimentos complementares realizados em uma terceira etapa (ETAPA III) mostraram que a aplicação do processo O3 seguido do processo foto-Fenton permitiu resultados satisfatórios tanto para remoção de cor (97,2%), quanto para remoção de COT (69,5%). O estudo da ação do processo O3 em modo contínuo e a avaliação econômica preliminar do processo integrado O3 - foto-Fenton sugerem o potencial de aplicação do tratamento integrado a indústrias têxteis. / The textile industry generates large volumes of wastewater with high organic load, strong coloration and toxicity. In this work, the treatment of an aqueous solution containing the dye Solophenyl Yellow Arle 154% was studied by the O3-H2O2/UV and photo-Fenton processes, in order to evaluate the responses color removal after 5 minutes; color removal after 60 minutes; maximum rate of color removal; and TOC removal after 60 minutes. The experiments were carried out in the semi-batch mode with circulation using a photochemical reactor with annular coaxial radiation field, consisting of a cylindrical stainless steel support with an aluminum internal reflector with 12 lamps fixed symmetrically in the internal reflecting surface, and a quartz tube reactor of 0.7 L, positioned vertically along the axis of the reflector. For the O3- H2O2/UV process, Phillips TUV lamps (36 W, 254 nm) were used; the gas stream containing zone was introduced into the reactor through a diffuser. For the photo- Fenton process, Sylvania lamps (12 W each, 300 - 400 nm) and a concentration of Fe (II) of 0.25 mmol/L were used. In both cases, the hydrogen peroxide solution was added in the first 30 minutes of treatment. The samples were analyzed by the measurement of total organic carbon (TOC) and color removal (absorbance measured at 405 nm in a UV-visible spectrophotometer). In both cases the Doehlert experimental design was used, defining the minimum and maximum values of each variable adopted. In the case of O3-H2O2/UV process (PHASE I), the effects of the total electric power of the lamps (144 - 432 W), H2O2 concentration (5 - 30 mmol/L), initial dye concentration (20 - 100 mg/L), ozone concentration (10 - 40 mg/L), and pH (3 - 10) were studied. For the photo-Fenton process, the studied variables were: total electric power of the lamps (160 - 480 W), H2O2 concentration (5 - 30 mmol/L), and initial dye concentration (20 - 100 mg/L). The results of PHASE I indicated that the increase of dye concentration in acidic conditions increases color removal after 5 and 60 minutes, thus suggesting the efficiency of molecular ozone action upon the chromophore group of the dye. The best results showed color removal above 95% after 5 and 60 minutes of treatment. However, for the TOC removal the process was not efficient, with maximum removal after 60 minutes of only 35.6%. In PHASE II less satisfactory results for color removal were obtained in comparison with PHASE I (56.1% after 5 minutes and 78% after 60 minutes of treatment), but with higher TOC removal after 60 minutes, achieving over 45.1%. The highest color removal rates were observed within the first 5 minutes of treatment for all runs. Additional experiments carried out in PHASE III showed that the oxidation by O3 followed by the photo-Fenton process enabled to achieve suitable results for both color (97.2%) and TOC removals (69.5%). The study of the O3 process in the continuous mode and a preliminary economic evaluation suggests a high potential for the use of the integrated O3-photo-Fenton process in textile industries.

A indústria têxtil gera grandes volumes de efluentes com elevada carga orgânica, forte coloração e toxicidade. Neste trabalho, estuda-se o tratamento de solução aquosa contendo o corante Solophenyl Yellow Arle 154% por meio dos processos O3-H2O2/UV e foto-Fenton, avaliando-se as repostas: remoção de cor em 5 minutos, remoção de cor em 60 minutos, taxa máxima de remoção de cor e remoção de COT em 60 minutos. Os experimentos foram realizados em semibatelada com circulação usando um reator fotoquímico com campo de radiação anular coaxial, constituído de corpo cilíndrico em aço com refletor interno de alumínio para 12 lâmpadas fixadas simetricamente na superfície refletora e um tubo reator em quartzo de 0,7 L, posicionados verticalmente no eixo do refletor. Para o processo O3-H2O2/UV foram utilizadas lâmpadas Phillips TUV (36 W, 254 nm). A corrente gasosa contendo O3 foi introduzida no reator por meio de um difusor. Para o processo foto-Fenton foram utilizadas lâmpadas Sylvania (12 W cada, 300 400 nm) e concentração de Fe(II) de 0,25 mmol/L. Em ambos os processos, solução de peróxido de hidrogênio foi adicionada durante os 30 minutos iniciais de tratamento. As amostras foram analisadas por medidas de carbono orgânico total (COT) e remoção de cor (absorbância medida em 405 nm em espectrofotômetro UV-visível). Em ambos os processos utilizou-se o planejamento experimental Doehlert, definindo os valores mínimo e máximo para cada variável adotada. No caso do processo O3- H2O2/UV (ETAPA I), foram estudados os efeitos da potência elétrica total das lâmpadas (144 432 W), concentração de H2O2 (5 30 mmol/L), concentração inicial de corante (20 100 mg/L), concentração de ozônio (10 40 mg/L) e pH (3 10). No processo foto-Fenton (ETAPA II), estudaram-se os efeitos da potência (160 480 W), concentração de H2O2 (5 30 mmol/L) e concentração inicial de corante (20 100 mg/L). Os resultados da ETAPA I indicaram que o aumento da concentração do corante, em meio ácido, aumenta a remoção de cor em 5 e 60 minutos, sugerindo a eficiência da ação via ozônio molecular sob o grupo cromóforo do corante. Os melhores resultados apresentaram remoção acima de 95% em 5 e 60 minutos de tratamento. Entretanto, para a remoção de COT em 60 minutos o processo não foi eficiente, apresentando resultado máximo de 35,6%. Na ETAPA II obtiveram-se resultados menos satisfatórios para remoção de cor se comparados aos da ETAPA I (56,1% em 5 minutos e 78% em 60 minutos de tratamento), mas melhores em relação à remoção de COT em 60 minutos atigindo 45,1% de remoção. As maiores taxas de remoção de cor foram observadas nos 5 primeiros minutos de tratamento para todos os experimentos. Experimentos complementares realizados em uma terceira etapa (ETAPA III) mostraram que a aplicação do processo O3 seguido do processo foto-Fenton permitiu resultados satisfatórios tanto para remoção de cor (97,2%), quanto para remoção de COT (69,5%). O estudo da ação do processo O3 em modo contínuo e a avaliação econômica preliminar do processo integrado O3 - foto-Fenton sugerem o potencial de aplicação do tratamento integrado a indústrias têxteis. / The textile industry generates large volumes of wastewater with high organic load, strong coloration and toxicity. In this work, the treatment of an aqueous solution containing the dye Solophenyl Yellow Arle 154% was studied by the O3-H2O2/UV and photo-Fenton processes, in order to evaluate the responses color removal after 5 minutes; color removal after 60 minutes; maximum rate of color removal; and TOC removal after 60 minutes. The experiments were carried out in the semi-batch mode with circulation using a photochemical reactor with annular coaxial radiation field, consisting of a cylindrical stainless steel support with an aluminum internal reflector with 12 lamps fixed symmetrically in the internal reflecting surface, and a quartz tube reactor of 0.7 L, positioned vertically along the axis of the reflector. For the O3- H2O2/UV process, Phillips TUV lamps (36 W, 254 nm) were used; the gas stream containing zone was introduced into the reactor through a diffuser. For the photo- Fenton process, Sylvania lamps (12 W each, 300 - 400 nm) and a concentration of Fe (II) of 0.25 mmol/L were used. In both cases, the hydrogen peroxide solution was added in the first 30 minutes of treatment. The samples were analyzed by the measurement of total organic carbon (TOC) and color removal (absorbance measured at 405 nm in a UV-visible spectrophotometer). In both cases the Doehlert experimental design was used, defining the minimum and maximum values of each variable adopted. In the case of O3-H2O2/UV process (PHASE I), the effects of the total electric power of the lamps (144 - 432 W), H2O2 concentration (5 - 30 mmol/L), initial dye concentration (20 - 100 mg/L), ozone concentration (10 - 40 mg/L), and pH (3 - 10) were studied. For the photo-Fenton process, the studied variables were: total electric power of the lamps (160 - 480 W), H2O2 concentration (5 - 30 mmol/L), and initial dye concentration (20 - 100 mg/L). The results of PHASE I indicated that the increase of dye concentration in acidic conditions increases color removal after 5 and 60 minutes, thus suggesting the efficiency of molecular ozone action upon the chromophore group of the dye. The best results showed color removal above 95% after 5 and 60 minutes of treatment. However, for the TOC removal the process was not efficient, with maximum removal after 60 minutes of only 35.6%. In PHASE II less satisfactory results for color removal were obtained in comparison with PHASE I (56.1% after 5 minutes and 78% after 60 minutes of treatment), but with higher TOC removal after 60 minutes, achieving over 45.1%. The highest color removal rates were observed within the first 5 minutes of treatment for all runs. Additional experiments carried out in PHASE III showed that the oxidation by O3 followed by the photo-Fenton process enabled to achieve suitable results for both color (97.2%) and TOC removals (69.5%). The study of the O3 process in the continuous mode and a preliminary economic evaluation suggests a high potential for the use of the integrated O3-photo-Fenton process in textile industries.

Avec l’usage intensif de dispositifs microélectroniques modernes, il existe un besoin croissant de mémoires non volatiles. La FeRAM (mémoire ferroélectrique à accès aléatoire) est une des mémoires de nouvelle génération les plus prometteuses en raison de sa faible consommation et de sa vitesse élevé de lecture/écriture. Parmi les différents matériaux ferroélectriques, le PZT (Pb (Zr1-x,Tix)O3) présente une polarisation rémanente élevée et un faible champ coercitif qui en font un candidat de choix pour les FeRAM.Dans cette thèse, la croissance épitaxiale de couches de PZT (52/48) d’épaisseurs variables (33 à 200 nm), sur un substrat de SrTiO3 et une électrode inférieure interfaciale de SrRuO3, a été réalisé par deux méthodes pour comparaison : pulvérisation cathodique et sol – gel. Trois matériaux conducteurs différents (SrRuO3, Pt et ITO) ont été utilisés comme électrode supérieure. L’objectif a été une étude détaillée des propriétés électriques et ferroélectriques de ces structures MFM (métal-ferroélectrique-métal), avec une attention particulière sur l’influence des conditions d’élaboration et de la nature des électrodes sur le courant de fuite et la dynamique de basculement de domaines.Les capacités élaborées par pulvérisation ou sol-gel présentent des caractéristiques semblables : Au-delà d’une épaisseur minimum d’environ 100 nm, pour une structure capacitive à base de PZT de 100 × 100 μm2, elles montrent un faible courant de fuite, une permittivité relative maximale élevée (600 - 1300) et une polarisation rémanente élevée (30 - 40 μC/cm2). Les mécanismes dominants dans le courant de fuite ont été identifiés par un fit des résultats, manifestant différentes contributions en fonction du champ électrique. Des caractérisations par PFM (microscopie à force piézoélectrique) confirme l’existence de domaines ferroélectriques de directions opposées. Il est aussi montré que le champ coercitif dépend fortement de la fréquence de travail. D’autre part, les propriétés d’impression dépendent de l’électrode supérieure, de la nature du recuit et de l’épaisseur de l’électrode inférieure. / With the intensive use of modern microelectronic devices in numerous areas, there is an increasing demand for non-volatile memories. FeRAM (ferroelectric random access memory) is one of the most potential next-generation memories for its ultra-low power consumption and high read/write rate. Among various ferroelectrics, PZT (Pb(Zr1-x,Tix)O3) exhibits high remnant polarization and low coercive field, which make it a promising candidate for FeRAM.In this dissertation, PZT(52/48) layers of various thicknesses (from 33 nm to 200 nm) have been epitaxially grown on SrTiO3 substrate, with a SrRuO3 interlayer as bottom electrode, using two deposition methods for comparison: sol-gel and sputtering. Three different conductive materials (SrRuO3, Pt and ITO) have been deposited as top electrode. The objective was a detailed study of the electrical and ferroelectric properties of these MFM (metal-ferroelectric-metal) capacitors, with a particular investigation of the influence of elaboration conditions and electrode material on leakage currents and domain switching dynamics.Sputtered and sol-gel-derived PZT capacitors showed similar properties: Above a minimum workable thickness of about 100 nm for a 100 × 100 μm2 PZT capacitor, they showed low leakage current, high maximum relative permittivity (600 - 1300) and high remnant polarization (30 - 40 μC/cm2). The dominant leakage current mechanisms were identified by fitting the results, showing different contributions as a function of electric field. PFM (piezoresponse force microscopy) characterizations confirmed the existence of ferroelectric domains of opposite directions. Coercive field was found to be highly dependent on work frequency. Besides, imprint properties were found to be dependent on top electrode, annealing procedure and bottom electrode thickness.

<p>Cilj&nbsp; istraživanja&nbsp; u&nbsp; okviru&nbsp; ove&nbsp; doktorske&nbsp; disertacije&nbsp; je&nbsp; utvrđivanje&nbsp; efekata&nbsp; različitih<br />oksidacionih procesa na bazi ozona, vodonik-peroksida i UV zračenja na sadržaj i reaktivnost prirodnih&nbsp; organskih&nbsp; materija&nbsp; (POM)&nbsp; u&nbsp; različitim&nbsp; vodenim&nbsp; matriksima.&nbsp; Ispitivanja&nbsp; su sprovedena&nbsp; na&nbsp; a)&nbsp; podzemnoj&nbsp; vodi&nbsp; sa&nbsp; teritorije&nbsp; Kikinde&nbsp; i&nbsp; Temerina&nbsp; (prirodni&nbsp; matriks)&nbsp; i&nbsp; b) sintetičkom&nbsp; vodenom&nbsp; matriksu&nbsp; (rastvoru&nbsp; komercijalno&nbsp; dostupne&nbsp; huminske&nbsp; kiseline),&nbsp; koji&nbsp; se među sobom razlikuju po sastavu i strukturi prisutne POM i sadržaju bromida. Za oksidacioni proces&nbsp; (ozonizacija,&nbsp; UV&nbsp; fotoliza,&nbsp; oksidacija&nbsp; sa&nbsp; H₂O₂,&nbsp; kombinovani&nbsp; O ₃/UV&nbsp; proces&nbsp; i kombinovani&nbsp; H ₂O₂<br />/UV&nbsp; proces)&nbsp; pojedinačno&nbsp; ispitan&nbsp; je&nbsp; uticaj&nbsp; različitih&nbsp; doza&nbsp; oksidanata&nbsp; i reakcionih&nbsp; uslova.Posebna&nbsp; pažnja&nbsp; posvećena&nbsp; je&nbsp; ispitivanju&nbsp; uticaja&nbsp; navedenih&nbsp; tretmana&nbsp; na<br />formiranje&nbsp; neorganskog&nbsp; bromata,&nbsp; kao&nbsp; i&nbsp; uticaja&nbsp; na&nbsp; sadržaj&nbsp; prekursora&nbsp;&nbsp; dezinfekcionih nusproizvoda nakon hlorisanja (THM, HAA, HAN, HK i CP).<br />Analiza&nbsp; hemijskih&nbsp; parametara&nbsp; sintetičkog&nbsp; matriksa&nbsp; (5,44&plusmn;0,30&nbsp; mg&nbsp; C/l; 0,255&plusmn;0,015 cm^-1 ;&nbsp; 4,68&plusmn;0,41&nbsp; lm^-1 mg ^-1)&nbsp; pokazuje&nbsp; da&nbsp; u&nbsp; njemu&nbsp; preovladavaju&nbsp; huminnske materije&nbsp; visoke&nbsp; hidrofobnosti.&nbsp; Visok&nbsp; sadržaj&nbsp; POM&nbsp; pretežno&nbsp; hidrofobnog&nbsp; karaktera&nbsp; je zabeležen i u vodi iz Kikinde (5,170,72 mg C/l; 0,2010,001 cm <span id="cke_bm_192S" style="display: none;">&nbsp;</span><span id="cke_bm_190S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_192E" style="display: none;">&nbsp;</span><span id="cke_bm_190E" style="display: none;">&nbsp;</span> ; 3,88&plusmn;0,70 lm<span id="cke_bm_193S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_193E" style="display: none;">&nbsp;</span> mg^-1 ), dok je&nbsp; sadrža<span id="cke_bm_194E" style="display: none;">&nbsp;</span>j&nbsp; POM&nbsp; u&nbsp; sirovoj&nbsp; vodi&nbsp; iz&nbsp; Temerina&nbsp; (2,060,38&nbsp; mg&nbsp; C/l;&nbsp; 0,0500,001&nbsp; cm<span id="cke_bm_203S" style="display: none;">&nbsp;</span><span id="cke_bm_201S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_203E" style="display: none;">&nbsp;</span><span id="cke_bm_201E" style="display: none;">&nbsp;</span>&nbsp; ; 2,43&plusmn;0,21 lm <span id="cke_bm_204S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_204E" style="display: none;">&nbsp;</span> mg ^-1<span id="cke_bm_205E" style="display: none;">&nbsp;</span><span id="cke_bm_202E" style="display: none;">&nbsp;</span><span id="cke_bm_191E" style="display: none;">&nbsp;</span><br />) značajno niži i preovladavaju POM hidrofilnog karaktera. Veći stepen hidrofobnosti sintetičkog matriksa u poređenju sa&nbsp; prirodnim matriksima, rezultovao&nbsp; je&nbsp; i&nbsp; većom&nbsp; reaktivnosti&nbsp; organske&nbsp; materije&nbsp; sa&nbsp; hlorom,&nbsp; &scaron;to&nbsp; se&nbsp; može&nbsp; zaključiti&nbsp; na<br />osnovu visokih vrednosti PFDBP nakon hlorisanja. Vrednost PFTHM u sintetičkom matriksu iznosi&nbsp; 544&plusmn;85,9&nbsp; &micro;g/l,&nbsp; dok&nbsp; je&nbsp; PFTHM&nbsp; u&nbsp; kikindskoj&nbsp; i&nbsp; temerinskoj&nbsp; sirovoj&nbsp; vodi&nbsp; znatno&nbsp; niži (279&plusmn;32,3&nbsp; i&nbsp; 180&plusmn;44,0&nbsp; &micro;g/l,&nbsp; respektivno).&nbsp; Vrednost&nbsp; PFHAA&nbsp; u&nbsp; sintetičkom&nbsp; matriksu&nbsp; iznosi 484&plusmn;77,5 &micro;g/l, dok je PFHAA u kikindskoj 244&plusmn;11,1 &micro;g/l i u temerinskoj vodi 165&plusmn;32,5 &micro;g/l. Sadržaj&nbsp; HK&nbsp; (8,05&plusmn;3,63&nbsp; &micro;g/l&nbsp; sintetički&nbsp; matriks;&nbsp; 14,91,38&nbsp; &micro;g/l&nbsp; Kikinda;&nbsp; 7,400,25&nbsp; &micro;g/l Temerin)&nbsp; je&nbsp; znatno&nbsp; niži&nbsp; u&nbsp; poređenju&nbsp; sa&nbsp; prekursorima&nbsp; THM&nbsp; i&nbsp; HAA,&nbsp; dok&nbsp; prekursori&nbsp; HAN&nbsp; i hlorpikrina&nbsp; nisu&nbsp; detektovani&nbsp; u&nbsp; sirovoj&nbsp; vodi.&nbsp; Nusproizvodi&nbsp; koji&nbsp; se&nbsp; dominantno&nbsp; formiraju&nbsp; u svim&nbsp; ispitivanim&nbsp; vodenim&nbsp; matriksima&nbsp; su&nbsp; hlorovani&nbsp; THM&nbsp; i&nbsp; HAA,&nbsp; dok&nbsp; se&nbsp; bromovani&nbsp; DBPformiraju u znatno nižim koncentracijama. Zastupljenost bromovanih DBP u temerinskoj vodi<br />je&nbsp; znatno&nbsp; veći&nbsp; u&nbsp; poređenju&nbsp; sa&nbsp; vodom&nbsp; iz&nbsp; Kikinde,&nbsp; kao&nbsp; rezultat&nbsp; prisustva&nbsp; veće&nbsp; koncentracije bromida u sirovoj vodi (0,05&plusmn;0,01 mg Br -/l Temerin; 0,03&plusmn;0,01 mg Br<br />-/l Kikinda). Ispitivanjem&nbsp; uticaja&nbsp; oksidacionih&nbsp; procesa&nbsp; (UV&nbsp; fotolize,&nbsp; ozonizacije,&nbsp; oksidacije vodonik-peroksidom)&nbsp; na&nbsp; sadržaj&nbsp; i&nbsp; reaktivnost&nbsp; POM&nbsp; u&nbsp; ispitivanim&nbsp; vodenim&nbsp; matriksima utvrđeno&nbsp; je&nbsp; da&nbsp; tretman&nbsp; vode&nbsp; UV&nbsp; zračenjem&nbsp; i&nbsp; vodonik-peroksidom,&nbsp; kada&nbsp; se&nbsp; primenjuju&nbsp; kao samostalan&nbsp; tretman,&nbsp; ne&nbsp; pokazuju&nbsp; značajnu&nbsp; efikasnost&nbsp; u&nbsp; smanjenju&nbsp; sadržaja&nbsp; POM.Tretman vode&nbsp; ozonom&nbsp; se&nbsp; pokazao&nbsp; kao&nbsp; veoma&nbsp; efikasan&nbsp; u&nbsp; uklanjanju&nbsp; POM&nbsp; i&nbsp; u&nbsp; smanjenju&nbsp; sadržaja prekursora&nbsp; DBP&nbsp; kod&nbsp; svih&nbsp; ispitivanih&nbsp; vodenih&nbsp; matriksa,&nbsp; kao&nbsp; rezultat&nbsp; smanjenja&nbsp; reaktivnosti POM&nbsp; ka&nbsp; formiranju&nbsp; ovih&nbsp; DBP.&nbsp; Smanjenje&nbsp; sadržaja&nbsp; POM&nbsp; u&nbsp; vodi&nbsp; tokom&nbsp; tretmana&nbsp; raste&nbsp; sa povećanjem&nbsp; primenjene&nbsp; doze&nbsp; ozona,&nbsp; pri&nbsp; čemu&nbsp; se&nbsp; najbolji&nbsp; rezultati&nbsp; postižu&nbsp; pri&nbsp; najvećoj primenjenoj&nbsp; dozi&nbsp; od&nbsp; 3,0&nbsp; mg&nbsp; O 3/mg&nbsp; DOC&nbsp; (do&nbsp; 32%&nbsp; DOC,&nbsp; 92%&nbsp; UV254 sintetički&nbsp; matriks;&nbsp; do 17%&nbsp; DOC,&nbsp; 76%&nbsp; UV 254&nbsp; Kikinda;&nbsp; do&nbsp; 15%&nbsp; DOC&nbsp; i&nbsp; 66%&nbsp; UV254&nbsp;&nbsp;&nbsp; Temerin).&nbsp; U&nbsp; sintetičkom matriksu&nbsp; najveće&nbsp; smanjenje&nbsp; PFTHM&nbsp; (za&nbsp; 76%)&nbsp; i&nbsp; PFHAA&nbsp; (za&nbsp; 80%)&nbsp; u&nbsp; odnosu&nbsp; na&nbsp; sadržaj&nbsp; u sirovoj vodi se postiže pri dozi od 1,0&nbsp; mg O₃/mg DOC. Najveće smanjenje PFTHM (za 38%)<br />i PFHAA (za 42%) u vodi iz Kikinde postiže se pri dozi od 3,0 mg O ₃/mg DOC. U vodi iz Temerina najveće smanjenje PFTHM (za&nbsp; 27%) je pri dozi od 3,0 mg O ₃ /mg DOC, dok se za smnjenje&nbsp; PFHAA&nbsp; (za&nbsp; 54%)&nbsp; najbolje&nbsp; pokazala&nbsp; doza&nbsp; od&nbsp; 1,0&nbsp; mg&nbsp; O<br />3 /mg&nbsp; DOC.&nbsp; Sadržaj prekursora&nbsp; HK&nbsp; i&nbsp; HAN&nbsp; (temerinska&nbsp; voda)&nbsp; je&nbsp; veoma&nbsp; nizak&nbsp; nakon&nbsp; tretmana.&nbsp; Tretman&nbsp; vode ozonom&nbsp; vodi&nbsp; ka&nbsp; formiranju&nbsp; DBP&nbsp; sa&nbsp; vi&scaron;e&nbsp;&nbsp; supstituisanih&nbsp; atoma&nbsp; broma,&nbsp; dok&nbsp; u&nbsp; vodama&nbsp; sa srednjim sadržajem bromida (50 &micro;g Br -/l) dovodi do formiranja bromata. Kombinacijom&nbsp; ozonizacije&nbsp; sa&nbsp; UV&nbsp; zračenjem&nbsp; se&nbsp; značajno&nbsp; može&nbsp; pospe&scaron;iti&nbsp; efiksnost uklanjanja&nbsp; POM&nbsp; postignuta&nbsp; primenom&nbsp; samostalne&nbsp; ozonizacije.&nbsp; Najveće&nbsp; smanjenje&nbsp; sadržaja POM u&nbsp; sintetičkom matriksu (za 85% DOC, 98% UV254 i 87% SUVA), u vodi iz Kikinde (za<br />23% DOC, 83% UV 254, 77% SUVA), i vodi iz Temerina (za 15% DOC, 80% UV<br />254 i 75% SUVA), u odnosu na vrednosti u netretiranoj vodi postignuto je pri najvećoj primenjenoj dozi od&nbsp; 3,0&nbsp; mg&nbsp; O₃ /mg&nbsp; DOC&nbsp; i&nbsp; 6000&nbsp; mJ/cm 2 .&nbsp; Efikasnost&nbsp; procesa&nbsp; raste&nbsp; u&nbsp; vodama&nbsp; u&nbsp; kojima preovladavaju&nbsp; POM&nbsp; veće&nbsp; hidrofobnosti.&nbsp; MeĎutim,&nbsp; iako&nbsp; se&nbsp; O₃ /UV&nbsp; procesom&nbsp; postiže&nbsp; visok stepen&nbsp; smanjenja&nbsp; PFTHM&nbsp; u&nbsp; sintetičkom&nbsp; matriksu&nbsp; se&nbsp; najbolje&nbsp; pokazao&nbsp; tretman&nbsp; ozonom (1,0 mg&nbsp; O3/mg&nbsp; DOC),&nbsp; dok&nbsp; se&nbsp; najveće&nbsp; smanjenje&nbsp; PFHAA&nbsp; (82%)&nbsp; postiže&nbsp; pri&nbsp; dozi&nbsp; ozona&nbsp; od 1,0 mg O_3/mg DOC i UV zračenja od 6000 mJ/cm ^{2 .} U vodi iz Kikinde se PFTHM smanjuje za 50% pri dozi od 3,0 mg O ₃/mg DOC i 6000 mJ/cm 2 , dok se u slučaju uklanjanja prekursora<br />HAA&nbsp; ozonizacija&nbsp; pokazala&nbsp; kao&nbsp; superiorniji&nbsp; proces.&nbsp; U&nbsp; vodi&nbsp; iz&nbsp; Temerina&nbsp; se&nbsp; u&nbsp; pogledu uklanjanja&nbsp; prekursora&nbsp; THM&nbsp; i&nbsp; HAA&nbsp; ozonizacija&nbsp; pokazala&nbsp; kao&nbsp; optimalan&nbsp; proces.&nbsp; Visok alkalitet&nbsp; prirodnih&nbsp; voda&nbsp; inhibira&nbsp; radikalski&nbsp; mehanizam&nbsp; u&nbsp; toku&nbsp; AOP&nbsp; i&nbsp; favorizuje&nbsp; oksidaciju POM molekulskim ozonom.&nbsp; Prekursori HK se formiraju u&nbsp; veoma niskim koncentracijama i njihov sadržaj ne varira značajno tokom tretmana. U prirodnim matriksima tokom AOP pri dozi&nbsp; ozona&nbsp; od&nbsp; 3,0 mg&nbsp; O₃ /mg&nbsp; DOC&nbsp; dolazi&nbsp; do&nbsp; formiranja&nbsp; HAN,&nbsp; međutim,&nbsp; nije&nbsp; uočen&nbsp; jasan trend&nbsp; sa&nbsp; povećanjem&nbsp; doze&nbsp; UV&nbsp; zračenja.&nbsp; Tretman&nbsp; doprinosi&nbsp; formiranju&nbsp; bromovanih&nbsp; vrsta THM,&nbsp; dok&nbsp; se&nbsp; tokom&nbsp; AOP&nbsp; pri&nbsp; najvećoj&nbsp; dozi&nbsp; ozona&nbsp; od&nbsp; 3,0 mg&nbsp; O₃ /mg&nbsp; DOC&nbsp; formiraju bromovani HAN.<br />Najveće&nbsp; smanjenje&nbsp; sadržaja&nbsp; POM&nbsp; primenom&nbsp; kombinacije&nbsp; oksidacije&nbsp; sa&nbsp; H ₂O₂<br />i&nbsp; UV zračenja u sintetičkom matriksu (za do 17% DOC, 70% UV 254 ), u vodi iz Kikinde (za do 22% DOC, 53% UV₂₅₄), i vodi iz Temerina (za do 7% DOC, 68% UV<br />₂₅₄), u odnosu na vrednosti u sirovoj vodi, se postižu pri dozi H ₂O₂ i UV zračenja od 3,0 mg H₂O₂/mg DOC i 6000 mJ/cm ² .<br />Najveće&nbsp; smanjenje&nbsp; PFTHM&nbsp; od&nbsp; 54%&nbsp; u&nbsp; sintetičkom&nbsp; matriksu&nbsp; se&nbsp; postiže&nbsp; pri&nbsp; dozi&nbsp; od 0 mg H₂O₂/mg DOC i 6000 mJ/cm ² ,&nbsp; dok se smanjenje PFHAA (za 35%)&nbsp; postiže primenom doze vodonik-peroksida i UV zračenja od 1,0 mg H ₂O₂ /mg&nbsp; DOC i 3000 mJ/cm ² . U vodi izKikinde&nbsp; H₂O₂ /UV&nbsp; proces&nbsp; ne&nbsp; utiče&nbsp; značajno&nbsp; na&nbsp; sadržaj&nbsp; prekursora&nbsp; THM,&nbsp; dok&nbsp; se&nbsp; najveće smanjenje&nbsp; PFHAA&nbsp; (za&nbsp; 35%)&nbsp; postiže&nbsp; pri&nbsp; dozi&nbsp; od&nbsp; 3,0&nbsp; mg&nbsp; H_{<span id="cke_bm_235S" style="display: none;">&nbsp;</span>2<span id="cke_bm_235E" style="display: none;">&nbsp;</span>}O₂/mg&nbsp; DOC&nbsp; i&nbsp; 600&nbsp; mJ/cm ² .H<span id="cke_bm_184S" style="display: none;">&nbsp;</span>₂<span id="cke_bm_184E" style="display: none;">&nbsp;</span>O₂<span id="cke_bm_185E" style="display: none;">&nbsp;</span>/UV&nbsp; proces&nbsp; dovodi&nbsp; do&nbsp; smanjenja&nbsp; PFTHM&nbsp; u&nbsp; Temerinskoj&nbsp; vodi&nbsp; za&nbsp; 74%&nbsp; pri&nbsp; dozi&nbsp; od 3,0 mg H₂O₂/mg DOC i 600 mJ/c<span id="cke_bm_236E" style="display: none;">&nbsp;</span>m ² ,&nbsp; dok primenjeni tretman ne pokazuje značajan uticaj na<br />PFHAA.&nbsp; Prekursori HK su detektovani u sintetičkom matriksu i temerinskoj vodi u niskim koncentracijama.&nbsp; U&nbsp; temerinskoj&nbsp; vodi&nbsp; nakon&nbsp; AOP&nbsp; pri&nbsp; dozi&nbsp; vodonik-peroksida&nbsp; od 3,0 mg H₂O₂ /mg DOC dolazi&nbsp; do formiranja HAN i hlorpikrina. Primenjeni tretman vodi ka formiranju bromovanih DBP. Svi rezultati dobijeni u toku istraživanja ukazuju na neophodnost optimizacije procesa u&nbsp; tretmanu&nbsp; ispitivanih&nbsp; vodenih&nbsp; matriksa&nbsp; i&nbsp; određivanja&nbsp; optimalnog&nbsp; procesa uzimajući&nbsp; u&nbsp; obzir<br />karakteristika&nbsp; sirove&nbsp; vode&nbsp; i&nbsp; efikasnost&nbsp; koja&nbsp; se&nbsp; želi&nbsp; postići.Kombinacijom&nbsp; dva&nbsp; i&nbsp; vi&scaron;e konvencionalnih&nbsp; tretmana&nbsp; i&nbsp; optimizacijom&nbsp; reakcionih&nbsp; uslova&nbsp; može&nbsp; se&nbsp; postići&nbsp; visoka efikasnost uklanjanja POM, kao i ciljano uklanjanje prekursorskog materijala odabranih DBP, međutim&nbsp; tretman&nbsp; vode&nbsp; ozonom&nbsp; pri&nbsp; dozi&nbsp; od&nbsp; 1,0 mg&nbsp; O₃<br />/mg&nbsp; DOC&nbsp; se&nbsp; pokazao&nbsp; kao&nbsp; optimalan proces.</p> / <p>The aim of the research&nbsp; of&nbsp; this&nbsp; PhD thesis&nbsp; was&nbsp; to determine the effects of various oxidation processes based on ozone, hydrogen peroxide and UV irradiation on the content and reactivity of natural organic matter&nbsp; (NOM)&nbsp; in different water matrices. The&nbsp; tests were carried out&nbsp; on&nbsp; a)&nbsp; groundwater&nbsp; from&nbsp; the&nbsp; territory&nbsp; of&nbsp; Kikinda&nbsp; and&nbsp; Temerin&nbsp; (natural&nbsp; matrix)&nbsp; and&nbsp; b) synthetic aqueous matrix (solution of commercially available humic&nbsp; acid), which differ in the composition&nbsp; and&nbsp; structure&nbsp; of&nbsp; NOM&nbsp; present&nbsp; and&nbsp; the&nbsp; content&nbsp; of&nbsp; bromide.&nbsp; For&nbsp; the&nbsp; oxidation process&nbsp; (ozonation,&nbsp; UV&nbsp; photolysis,&nbsp; oxidation&nbsp; with&nbsp; H 2O2 ,&nbsp; combined&nbsp; O 3 /UV&nbsp; process&nbsp; and combined&nbsp; H 2O2 /UV&nbsp; process),&nbsp; the&nbsp; influence&nbsp; of&nbsp; different&nbsp; doses&nbsp; of&nbsp; oxidants&nbsp; and&nbsp; reaction conditions&nbsp; was&nbsp; examined&nbsp; individually.&nbsp; Particular&nbsp; attention&nbsp; was&nbsp; paid&nbsp; to&nbsp; the&nbsp; influence&nbsp; of&nbsp; the above treatment on the formation of inorganic bromate, as well as the effect on the content of precursors of disinfectant by-products after chlorination (THM, HAA, HAN, HK and CP).Analysis&nbsp; of&nbsp; the&nbsp; chemical&nbsp; parameters&nbsp; of&nbsp; the&nbsp; synthetic&nbsp; matrix&nbsp; (5.44&plusmn;0.30&nbsp; mg&nbsp; C/L; 0.255&plusmn;0.015 cm -1 ;&nbsp; 4.68&plusmn;0.41&nbsp; lm -1 mg -1 )&nbsp; shows&nbsp; that&nbsp; the&nbsp; high-hydrophobic&nbsp; humic&nbsp; compounds predominate in this water. Also, high NOM content of predominantly hydrophobic character was recorded in Kikinda water (5.170.72 mg C/L; 0.2010.001 cm -1 ;&nbsp; 3.88&plusmn;0.70 lm -1 mg -1 ), while&nbsp; NOM&nbsp; content&nbsp; in&nbsp; raw&nbsp; water&nbsp; from&nbsp; Temerin&nbsp; (2.060.38&nbsp; mg&nbsp; C/L;&nbsp; 0.0500.001&nbsp; cm -1 ; 2.43&plusmn;0.21 lm -1 mg -1 ) significantly lower and predominate NOM of hydrophilic character. A higher degree of hydrophobicity of the synthetic matrix in comparison with&nbsp; natural matrices, resulted in higher reactivity of organic matter with chlorine, which can be concluded on&nbsp; the&nbsp; basis&nbsp; of&nbsp; high&nbsp; PFDBP&nbsp; values&nbsp; after&nbsp; chlorination.&nbsp; The&nbsp; PFTHM&nbsp; value&nbsp; in&nbsp; the&nbsp; synthetic matrix&nbsp; was&nbsp; 544&plusmn;85.9 &micro;g/L, while the PFTHM in the raw waters from Kikinda and Temerin was&nbsp; significantly&nbsp; lower&nbsp; (279&plusmn;32.3&nbsp; and&nbsp; 180&plusmn;44.0&nbsp; &micro;g/L,&nbsp; respectively).&nbsp; The&nbsp; PFHAA&nbsp; value&nbsp; in the&nbsp; synthetic&nbsp; matrix&nbsp; was&nbsp; 484&plusmn;77.5&nbsp; &micro;g/L,&nbsp; while&nbsp; PFHAA&nbsp; in&nbsp; the&nbsp; Kikinda&nbsp; water&nbsp; was 223 244&plusmn;11.1 &micro;g/L&nbsp; and in&nbsp; the&nbsp; Temerin&nbsp; water&nbsp; was&nbsp; 165&plusmn;32.5 &micro;g/L.&nbsp; The content of&nbsp; precursors of HK&nbsp; (8.05&plusmn;3.63&nbsp; &micro;g/L&nbsp; synthetic&nbsp; matrix;&nbsp; 14.91.38&nbsp; &micro;g/L&nbsp; Kikinda;&nbsp; 7.400.25&nbsp; &micro;g/L&nbsp; Temerin) was&nbsp; significantly&nbsp; lower&nbsp; compared&nbsp; to&nbsp; precursors&nbsp; of&nbsp; THMs&nbsp; and&nbsp; HAAs,&nbsp; while&nbsp; precursors&nbsp; of HANs&nbsp; and&nbsp; chloropicrin&nbsp; were&nbsp; not&nbsp; detected&nbsp; in&nbsp; raw&nbsp; water.&nbsp; The&nbsp; by- products&nbsp; that&nbsp; were predominantly&nbsp; formed&nbsp; in&nbsp; all&nbsp; the&nbsp; tested&nbsp; water&nbsp; matrices&nbsp; were&nbsp; chlorinated&nbsp; THMs&nbsp; and&nbsp; HAAs, while the brominated DBPs&nbsp; were&nbsp; formed at substantially lower concentrations. The presence of&nbsp; brominated DBPs&nbsp; in&nbsp; Temerine&nbsp; water&nbsp; were&nbsp; significantly higher compared to Kikinda water as&nbsp; a&nbsp; result&nbsp; of&nbsp; the&nbsp; presence&nbsp; of&nbsp; higher&nbsp; bromide&nbsp; content&nbsp; in&nbsp; raw&nbsp; water&nbsp; (0.05&plusmn;0.01&nbsp; mg&nbsp; Br -/L Temerin; 0.03&plusmn;0.01 mg Br -/L Kikinda). By&nbsp; examining&nbsp; the&nbsp; influence&nbsp; of&nbsp; oxidation&nbsp; processes&nbsp; (UV&nbsp; photolysis,&nbsp; ozonation,hydrogen&nbsp; peroxide&nbsp; oxidation)&nbsp; on&nbsp; the&nbsp; content&nbsp; and&nbsp; reactivity&nbsp; of&nbsp; NOM&nbsp; in&nbsp; the&nbsp; tested&nbsp; water matrix, it was&nbsp; found that the UV&nbsp; irradiation and&nbsp; treatment by&nbsp; hydrogen peroxide, when used as an independent treatment, did&nbsp; not show significant efficacy in reducing the&nbsp; NOM content. Water treatment by ozone&nbsp; proved to be very effective in eliminating&nbsp; NOM and reducing the content of DBP precursors in all tested water&nbsp; matrices, as a result of the reduction of&nbsp; NOM reactivity &nbsp; to&nbsp; the&nbsp; formation&nbsp; of&nbsp; these&nbsp; DBPs.&nbsp; Reduction&nbsp; of&nbsp; NOM&nbsp; content&nbsp; in&nbsp; water&nbsp; during treatment increased&nbsp; with increasing the applied dose of ozone, with the best results achieved at the highest dosage of&nbsp; 3.0 mg O 3/mg DOC&nbsp; (up to 32% DOC, 92% UV 254&nbsp; synthetic matrix, up&nbsp; to&nbsp; 17%&nbsp; DOC,&nbsp; 76%&nbsp; UV 254 Kikinda,&nbsp; up&nbsp; to&nbsp; 15%&nbsp; DOC&nbsp; and&nbsp; 66%&nbsp; UV254 Temerin).&nbsp; In&nbsp; the synthetic&nbsp; matrix the highest reduction&nbsp; in&nbsp; PFTHM (76%) and PFHAA (by 80%)&nbsp; compared to raw water content&nbsp; was&nbsp; achieved at a dosage&nbsp; of 1.0 mg O 3/mg DOC. The highest reduction in PFTHM&nbsp; (38%)&nbsp; and&nbsp; PFHAA&nbsp; (42%)&nbsp; in&nbsp; Kikinda&nbsp; water&nbsp; was&nbsp; achieved&nbsp; at&nbsp; a&nbsp; dose&nbsp; of 3.0 mg O3 /mg DOC. In Temerin water, the highest reduction in PFTHM (27%) was at a dose of&nbsp; 3.0 mg O 3/mg DOC, while the dose of 1.0&nbsp; mg O3 /mg&nbsp; DOC&nbsp; was best shown for removing PFHAA (by 54%). The content of the precursors of HKs and HANs (Temerin water) was very low&nbsp; after&nbsp; treatment.&nbsp; Water&nbsp; treatment&nbsp; by&nbsp; ozone&nbsp; led&nbsp; to&nbsp; the&nbsp; formation&nbsp; of&nbsp; DBPs&nbsp; with&nbsp; more substituted bromine atoms, while in waters with a mean bromide content (50 &mu;g Br -/L) led&nbsp; to bromate formation.Combination of ozonation with UV irradiation can greatly accelerate the effectiveness of&nbsp; NOM&nbsp; removal&nbsp; achieved&nbsp; by&nbsp; the&nbsp; use&nbsp; of&nbsp; ozonation&nbsp; alone.&nbsp; The&nbsp; highest&nbsp; reduction&nbsp; in&nbsp; NOM content in the synthetic matrix (by 85% DOC, 98% UV 254 and 87% SUVA), in Kikinda water (by 23%&nbsp; DOC, 83% UV 254 , 77% SUVA) and water from Temerin (by 15% DOC, 80% UV 254 and 75% SUVA), compared to the values in&nbsp; raw&nbsp; water, was achieved at the highest&nbsp; dose of 3.0&nbsp; mg&nbsp; O 3 /mg&nbsp; DOC&nbsp; and&nbsp; 6000&nbsp; mJ/cm 2 .&nbsp; The&nbsp; efficiency&nbsp; of&nbsp; the&nbsp; process&nbsp; was&nbsp; growing&nbsp; in&nbsp; the waters where NOM predominates of hydrophobicity. Although the O 3 /UV process achieved a high&nbsp; degree&nbsp; of&nbsp; reduction&nbsp; in&nbsp; PFTHM&nbsp; in&nbsp; the&nbsp; synthetic&nbsp; matrix&nbsp; the&nbsp; ozonation (1.0 mg O3 /mg DOC)&nbsp; was&nbsp; proved&nbsp; as&nbsp; more&nbsp; efficient,&nbsp; while&nbsp; the&nbsp; highest&nbsp; reduction&nbsp; in&nbsp; PFHAA (82%)&nbsp; was&nbsp; achieved&nbsp; at&nbsp; a&nbsp; ozone&nbsp; dose&nbsp; of&nbsp; 1.0&nbsp; mg&nbsp; O 3/mg&nbsp; DOC&nbsp; and&nbsp; UV&nbsp; irradiation&nbsp; of 6000 mJ/cm 2 . In the water from Temerin,&nbsp; in case to removal of precursors of THM and HAA, ozonation&nbsp; was proved&nbsp; to be an optimal process. High alkalinity of natural waters&nbsp; inhibits the radical &nbsp; mechanism&nbsp; during&nbsp; AOP&nbsp; and&nbsp; favors&nbsp; NOM&nbsp; oxidation&nbsp; with&nbsp; molecular&nbsp; ozone.&nbsp; HKs precursors were formed at very low concentrations and their content did not vary significantly during&nbsp; the&nbsp; treatment.&nbsp; In&nbsp; natural&nbsp; matrices&nbsp; during&nbsp; the&nbsp; AOP&nbsp; at&nbsp; a&nbsp; ozone&nbsp;&nbsp; dose&nbsp; of 3.0 mg O3 /mgDOC, HANs&nbsp; were&nbsp; formed, however, there&nbsp; was&nbsp; no clear trend with increasing UV irradiation. The treatment contributed to the formation of brominated THM species, while during&nbsp; the&nbsp; AOPs,&nbsp; brominated&nbsp; HANs&nbsp; were&nbsp; formed&nbsp; at&nbsp; the&nbsp; maximum&nbsp; dose&nbsp; of&nbsp; ozone&nbsp; of 3.0 mg O3/mg DOC. 224 The largest decrease in&nbsp; NOM content by the combination of oxidation with H2O2 and UV irradiation in the synthetic matrix (for up to 17% DOC, 70% UV 254 ), in Kikinda water (up to 22% DOC, 53% UV 254), and water from Temerin&nbsp; (7% DOC, 68% UV 254 ), compared&nbsp; to the values&nbsp; in&nbsp; raw&nbsp; water,&nbsp; were&nbsp; obtained&nbsp; at&nbsp; a&nbsp; dose&nbsp; of&nbsp; H 2O2 and&nbsp; UV&nbsp; irradiation&nbsp; of 3.0 mg O3 /mg DOC&nbsp; and 6000 mJ/cm 2 . The highest PFTHM reduction of 54% in the&nbsp; synthetic matrix was achieved at a dosage of 1.0 mg H2O2/mg DOC and 6000 mJ/cm 2 , while a decrease in&nbsp; PFHAA&nbsp; (35%)&nbsp; was&nbsp; achieved&nbsp; using&nbsp; a&nbsp; dose&nbsp; of&nbsp; hydrogen&nbsp; peroxide&nbsp; and&nbsp; UV&nbsp; irradiation&nbsp; of 1.0 mg H2O2/mg DOC and 3000 mJ/cm 2 . In the water from Kikinda, the H2O2 /UV process did not significantly affect on the THM precursors content, while the highest reduction in PFHAA (35%)&nbsp; was&nbsp; achieved&nbsp; at&nbsp; a&nbsp; dose&nbsp; of&nbsp; 3.0&nbsp; mg&nbsp; H2O2/mg&nbsp; DOC&nbsp; and&nbsp; 600&nbsp; mJ/cm 2 .&nbsp; The&nbsp; H 2O2 /UV process&nbsp; led&nbsp; to&nbsp; a&nbsp; decrease&nbsp; in&nbsp; PFTHM&nbsp; in&nbsp; the&nbsp; Temerin&nbsp; water&nbsp; by&nbsp; 74%&nbsp; at&nbsp; a&nbsp; dose&nbsp; of 3.0 mg&nbsp; 2O2 /mg&nbsp; DOC&nbsp; and&nbsp; 600&nbsp; mJ/cm 2 ,&nbsp; whereas&nbsp; the&nbsp; treatment&nbsp; applied&nbsp; had&nbsp; no&nbsp; significant effect on PFHAA. HKs precursors were detected in synthetic matrix and the Temerin water at low&nbsp; concentrations.&nbsp; In&nbsp; the&nbsp; water&nbsp; after&nbsp; the&nbsp; AOP&nbsp; at&nbsp; a&nbsp; dose&nbsp; of&nbsp; 3.0&nbsp; mg&nbsp; H 2O2 /mg&nbsp; DOC&nbsp; of hydrogen&nbsp; peroxide,&nbsp; HANs&nbsp; and&nbsp; chloropicrin&nbsp; were&nbsp; formed.&nbsp; The&nbsp; applied&nbsp; treatment&nbsp; led&nbsp; to&nbsp; the formation of brominated DBPs.<br />All the results obtained during the research indicate the necessity of optimization&nbsp; the process&nbsp; in&nbsp; the&nbsp; treatment&nbsp; of&nbsp; the&nbsp; examined&nbsp; water&nbsp; matrices&nbsp; and&nbsp; determination&nbsp; of&nbsp; the&nbsp; optimal process taking into account the characteristics of&nbsp; raw water and the efficiency to be achieved. By combining two or more conventional treatments and optimizing the reaction conditions, high&nbsp; NOM removal efficiency can be achieved, as well as removal of the&nbsp; targeted&nbsp; precursor material&nbsp; of&nbsp; the&nbsp; selected&nbsp; DBPs,&nbsp; but&nbsp; the&nbsp; treatment&nbsp; of&nbsp; ozone&nbsp; water&nbsp; at&nbsp; a&nbsp; dose&nbsp; of 1.0 mg O3 /mg DOC was proved to be an optimal process.</p>