L’analyse du cycle de vie et l’évaluation du risque ont été combinées afin d’évaluer les impacts et risques potentiels de NMs de TiO2 dans l’eau, les sols et les sédiments à une échelle site-spécifique. Une approche analytique a permis de caractériser les NMs industriels dans les eaux, sols et sédiments et de déterminer leur comportement dans l’eau. Un modèle bayésien a été réalisé pour évaluer leur devenir dans les eaux et sédiments de la rivière, ainsi que leurs effets et risques associés en mésocosmes. Il a ainsi été montré que le TiO2 est présent en faible concentration dans l’eau de rivière. En mésocosmes, des risques ont été quantifiés sur deux espèces : Dreissena polymorpha et Gammarus roeseli. Il est apparu nécessaire de mieux caractériser la dimension fractale des agrégats de NMs pour comprendre leur sédimentation et de quantifier les effets des nano-TiO2 dans le milieu naturel, en dépassant l’approche par mésocosmes. / In this work, life cycle and risk assessments were combined in order to assess the potential impacts and risks of TiO2 NMs in water, soils and sediments at a site-specific scale. Two approaches were used: (1) An analytical approach allowed the analysis of waters, sediments and soils, the characterization of industrial NMs and the determination of their aggregation behavior in water; (2) A Bayesian modeling approach was used to assess their fate in the river water and sediments, as well as their potential effects and risks in mesocosms. It was thus shown that TiO2 occurs at low concentrations in the river water. Quantifying the TiO2 mass which deposits on the sediment requires characterizing more precisely their fractal dimension. Finally, nano-TiO2 were shown to induce risks to two species in mesocosms: it is consequently necessary to assess the potential effects of the nano-TiO2 produced on the study area in mesocosms, simulating realistic conditions.

Yes / To develop high deterioration resistance concrete for marine infrastructures, two types of nano TiO2 (NT) including anatase phase NT and silica surface-treated rutile phase NT were incorporated into concrete. The fabricated NT modified concrete was then put into the marine environment for 21 months in this study. The effects and mechanisms of two types of NT on the deterioration of concrete in the marine environment were investigated from three aspects, including seawater physical and biological and chemical actions on concrete with NT. Under the seawater physical action, the exposed degree of coarse sand particles on the surface of control concrete is greater than that of concrete with NT. Owing to the microorganism biodegradation property of NT, the elimination and inhibition rates of concrete with NT on microorganisms can reach up to 76.98% and 96.81%, respectively. In addition, the surface biofilm thickness of concrete can be reduced by 49.13% due to the inclusion of NT. In the aspect of seawater chemical action, NT can increase the pH value inside concrete by 0.81, increase the degree of polymerization of C-S-H gel, and improve the interfacial transition zone between cement paste and aggregate in concrete. Compared to concrete with anatase phase NT, silica surface-treated rutile phase NT is more effective in improving the deterioration resistance of concrete in the marine environment. It can be concluded that incorporating NT can inhibit the deterioration of concrete in the marine environment.

We use different methods to deposit Ti thin film on the ITO glass substrate. Under the circumstances of using fixed concentration of electrolyte, changing anodic time, and applying voltage, we are able to use anodic method to make ordered nano TiO2 thin film,of which the smallest pore size is 18nm and the thickness is 4500

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No. of bitstreams: 1 DissGML.pdf: 3541713 bytes, checksum: 0c6f05408f457af46db02eef2c8ca598 (MD5) Previous issue date: 2016-06-10 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / In recent years, increased use of titanium dioxide nanoparticles (TiO 2 NPs) in consumer products and technological devices has raised concerns regarding their environmental impacts and their risks to human health. Ecotoxicological studies have been used as a tool to analyze the toxic potential of TiO 2 NP S in different trophic levels, such as primary producers (algae) and first order consumers (cladocerans). In the present study, the chronic effects of TiO2 NPS on the population growth of the microalgae chlorophycean Pseudokirchneriella subcapitata was evaluated during an exposure period of 96 hours, under conditions of temperature and photoperiod similar to those found in tropical ecosystems. New methods were developed for the separation of the aggregates between the algae cells and TiO2 NPS, whose formation was observed at above 0.01 mg L-1 concentrations after a period of 96 hours’ exposure. The only effective method was the one in which the cells were washed three times with a metal chelator (EDTA), with duration of 1 minute for each wash. In the toxicity chronic test, there was obtained a significant inhibition of algal growth from the concentration of 64 mg L-1 of TiO2 NPs, with a concentration of 50% inhibition of algal cells (96 h - IC50) of 201.22 mg L -1 in 96 h of exposure. Then, it was evaluated the acute effects of exposure by contact and the chronic effects of TiO2 NPs for the cladoceran Ceriodaphnia silvestrii, using contaminated food (Pseudokirchneriella subcapitata) as a route of exposure. In acute toxicity tests was obtained the average value of EC50 - 48 h of 77.57 mg L-1. In chronic toxicity tests, it was observed significant differences in survival from the concentration of 0.01 mg L-1, while for the body length, the number of eggs and neonates produced, toxic effects were observed from the concentration of 1 mg L-1. These results indicate that the nano-TiO2 NPS had a deleterious effect on the growth of Pseudokirchneriella subcapitata only at concentrations above those normally found in natural aquatic environments. For the cladoceran Ceriodaphnia silvestrii, the route of dietary exposure indicated a greater toxic effect. / Nos últimos anos, o aumento do uso das nanopartículas de dióxido de titânio (nano-TiO2) em produtos de consumo e em dispositivos tecnológicos tem gerado preocupações relativas aos seus impactos ambientais e seus riscos à saúde humana. Estudos ecotoxicológicos têm sido utilizados como uma ferramenta para analisar o potencial tóxico das nano-TiO2 em diversos níveis tróficos, tais como produtores primários (algas) e consumidores de primeira ordem (cladóceros). No presente estudo, os efeitos crônicos das nano-TiO2 sobre o crescimento populacional da microalga clorofícea Pseudokirchneriella subcapitata foi avaliado durante um período de exposição de 96 horas, sob condições de temperatura e de fotoperíodo semelhantes às encontradas em ecossistemas de regiões tropicais. Foram desenvolvidas novas metodologias para separação dos agregados entre as células algais e as nano-TiO2, cuja formação foi observada nas concentrações acima de 0,01 mg L -1 após um período de exposição de 96 horas. O único método eficiente foi aquele em que as células foram lavadas três vezes com um quelante de metal (EDTA), com duração de 1 minuto para cada lavagem. No teste de toxicidade crônico obteve-se inibição significativa do crescimento algal a partir da concentração de 64 mg L-1 de nano-TiO2, com uma concentração de inibição a 50% das células algais (CI 50 - 96h) de 201,22 mg L-1 em 96 h de exposição. Em seguida, foram avaliados os efeitos agudos via exposição por contato e os efeitos crônicos das nano-TiO2 para o cladócero Ceriodaphnia silvestrii, utilizando o alimento (Pseudokirchneriella subcapitata) contaminado como via de exposição. Nos testes de toxicidade aguda foi obtido o valor médio de CE50 - 48 h de 77,57 mg L-1. Nos ensaios de toxicidade crônica, diferenças significativas foram observadas na sobrevivência a partir da concentração de 0,01 mg L -1, enquanto que para o comprimento corporal, o número de ovos e o número de neonatas produzidos, os efeitos tóxicos foram observados a partir da concentração de 1 mg L-1. Tais resultados indicam que as nano-TiO2 possuíram um efeito deletério sobre o crescimento de Pseudokirchneriella subcapitata somente em concentrações acima daquelas normalmente encontradas em ambientes aquáticos naturais. Para o cladócero Ceriodaphnia silvestrii, a via de exposição alimentar indicou um maior efeito tóxico. / CNPq: 305698/2013-30 / FAPESP: 2014/14139-3 e 2016/00753-7

<p>The study focused on examining the effects of using nanoadditives (nano-TiO2 and colloidal silica) on the hydration kinetics, microstructure, mechanical properties, and durability of concretes, especially those containing fly ash and slag and cured at low (4°C) temperature. </p> <p>The results of the Vicat and isothermal calorimetery (IC) tests suggest that the addition of nano-TiO2 accelerates the hydration process of pastes. In addition, the results of the thermogravimetric analysis (TGA) indicated that the addition of nano-TiO2 increased the amount of hydration products in the pastes, with more notable increases observed in fly ash pastes. Moreover, X-ray diffraction (XRD) results revealed that the addition of nano-TiO2 reduced the mean size of calcium hydroxide (CH) crystals.  </p> <p>The interfacial transition zone (ITZ) of concretes with nano-TiO2 was found to be less cracked and less porous when compared to that of concrete without nano-TiO2. Furthermore, the energy dispersive X-ray (EDX) analyses of the outer hydration products around partially hydrated cement particles in fly ash concretes with nano-TiO2 revealed reduction in the values of Ca/Si atomic ratios when compared to the reference fly ash concrete. The image analysis results of the concrete air void system indicated slightly reduced air content, increased specific surface area (SSA), and decreased spacing factor (SF) in concretes with added nano-TiO2. </p> <p>The addition of nano-TiO2 was also found to enhance the compressive and flexural strengths of mortars and concretes. Nano-TiO2 also improved the resistivity and formation factor values of concretes containing fly ash. Moreover, the total volume of pores, as well as the values of water absorption, were also reduced as a result of addition of nano-TiO2. This was true for all types of concretes (i.e., with or without SCMs). Finally, the use of nano-TiO2 seemed to be more beneficial with respect to improving the scaling and freeze-thaw resistance of fly ash concretes compared to cement-only and slag concretes. </p> <p>Concretes with added nanosilica (colloidal silica) also developed higher compressive and flexural strengths when compared to reference concrete. Moreover, the total pores and permeability of concretes decreased due to the addition of nanosilica while the improvement in scaling resistance of these concretes was only slight. Furthermore, concretes with nanosilica were found to have higher percentage of finer air voids compared to reference concretes. Finally, the ITZ of concretes with nanosilica was found to have fewer defects and cracks compared to the reference concrete. </p> <p>In summary, this dissertation presents the results of a study on the multi-scale behavior of nanomodified concretes with and without SCMs cured at both room and low temperatures. Knowledge gained from this study would be helpful in developing concretes with denser and less porous microstructure, a more refined and better-distributed air void system, improved strength, reduced permeability, and enhanced scaling and freeze-thaw resistance, especially in cases when involving the use of SCMs and exposure to low early-age temperatures.</p>

Photo-initiated reactions involve the use of ultraviolet (UV) or visible light radiation to effect chemical transformations. Some of the advantages of photo-initiated reactions over thermal or high pressure reactions include mild reaction conditions like ambient temperature and pressure, good control over the reaction by the simple switching on/off the light source, and faster reaction kinetics. Usually, semiconductor photocatalysts or oxidizing agents are used to enhance the rate of photo reactions. “Photocatalysis” involves the generation of valence band holes and conduction band electrons by the band gap excitation of a semiconductor photocatalyst. These charge carriers produce reactive hydroxyl and superoxide radicals, which mediate oxidation and reduction reactions. However, the oxidizing agents are decomposed by the incident radiation to generate reactive radicals, which accelerate the photo reaction. Today, photocatalysis and photo-oxidative reactions are widely being practiced for environmental pollution abatement, synthesis of fine chemicals, synthesis of polymers, generation of hydrogen as a clean energy carrier, and in anti-fogging and self-cleaning surface treatments. The present investigation focuses on elucidating the mechanism and kinetics of environmentally and synthetically relevant photo-initiated reactions for a better understanding of the fundamental aspects of the photo processes. The different photo-initiated reactions studied in this dissertation can be grouped under the broad categories of (i) photocatalytic degradation of organic compounds like dyes and phenols, and reduction of metal ions, (ii) photocatalytic degradation of polymers, (iii) selective photocatalytic oxidation of cyclohexane, (iv) sonophotocatalytic degradation of dyes, (v) photopolymerization, and (vi) sonophotooxidative degradation of polymers. Nano-sized TiO2, synthesized by solution combustion technique (henceforth denoted as CS TiO2), was used as the photocatalyst for most of the above reactions, except for the last two polymer reactions, where organic initiators were used. Invariably, the photocatalytic activity of CS TiO2 was compared with the commercially available Degussa P-25 TiO2 (DP25). Based on the experimental results, detailed mechanisms were proposed for the different reactions, kinetic models were derived, and the rate coefficients signifying the importance of the underlying reaction steps were evaluated. Pd2+ substituted and Pd0 impregnated TiO2 were synthesized by solution combustion and reduction techniques, respectively, and characterized by powder XRD, XPS, TEM, BET surface area, UV/visible, TGA, FT-IR and photoluminescence measurements. While the above catalysts are known to be more active compared to CS TiO2 for the gas phase NO reduction and NO decomposition reactions, it was found in this study, that these catalysts exhibit lower activity for the degradation of organic compounds like dyes, phenol and 4-chlorophenol, in the aqueous phase. The decrease in activity was correlated with a reduction in surface area and photoluminescence intensity of these catalysts, compared to CS TiO2. Ag+ substituted (Ag sub) and Ag0 impregnated (Ag imp) nano-TiO2 were synthesized by solution combustion and reduction techniques, respectively, and characterized by the above standard measurements. These catalysts were used for the photodegradation of dyes, and the selective photooxidation of cyclohexane to cyclohexanone. For the photocatalytic degradation of dyes, unsubstituted CS TiO2 exhibited the highest activity, followed by 1% Ag imp and 1% Ag sub. However, for the photooxidation of cyclohexane, the total conversion of cyclohexane and the selectivity of cyclohexanone followed the order: 1% Ag sub > DP-25 > CS TiO2 > 1% Ag imp. The kinetics of photodegradation of the dyes and the photooxidation of cyclohexane was modeled using Langmuir-Hinshelwood rate equation, and a free radical mechanism, respectively. This study proves that the photoactivity of a catalyst is not solely determined by a single physical property, but rather by a number of variables including the surface area, band gap, surface hydroxyl content, oxide ion vacancy and surface charge of the catalyst. The photocatalytic degradation of five anionic, eight cationic and three solvent dyes, containing different functional groups, was evaluated. The degradation of the dyes was quantified using the initial rate of decolorization and overall percent mineralization. The decolorization of the anionic dyes with CS TiO2 followed the order: Indigo Carmine > Eosin Y > Amido Black 10B > Alizarin Cyanine Green > Orange G. The decolorization of the cationic dyes with DP-25 followed the order: Malachite Green > Pyronin Y > Rhodamine 6G > Azure B > Nile Blue Sulfate > Auramine O ≈ Acriflavine ≈ Safranin O. CS TiO2 exhibited higher rates of decolorization and mineralization for all the anionic dyes, while DP-25 was better in terms of decolorization for most of the cationic dyes. The solvent dyes exhibited adsorption dependent decolorization. The observed results were rationalized based on the molecular structure and degradation pathway of the dyes. The simultaneous photocatalytic degradation of phenolic compounds like phenol and 4-nitrophenol, and the reduction of metal ions like copper (Cu2+) and chromium (Cr6+) were studied. It was found that the presence of phenol accelerated the reduction of Cu2+ to Cu+, and the presence of phenol and 4-nitrophenol accelerated the adsorption of Cr6+ onto CS TiO2. A detailed dual-cycle, multi-step reaction mechanism was proposed for the simultaneous degradation and reduction, and a model was developed using the network reduction technique. The kinetic rate constants in the model were evaluated for the systems studied. The simultaneous UV and ultrasound (US) degradation of anionic dyes was carried out in presence of CS TiO2. The rates of degradation and mineralization of the dyes were higher for the sonophotocatalytic process compared to the individual photo-and sonocatalytic processes. The effect of dissolved gases and US intensity on the sonophotocatalytic degradation of the dyes was evaluated. A dual-pathway network mechanism of sonophotocatalytic degradation was proposed for the first time, and the rate equations were modeled using the network reduction technique. The kinetic rate coefficients of the individual steps were evaluated for all the systems by fitting the model with the experimental data. Eosin Y and Fluorescein dye sensitized visible light degradation of phenol, 4chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol was studied. A detailed mechanism of sensitized degradation was proposed, and a mechanistic model for the rate of degradation of the phenolic compound was derived by using the pyramidal network reduction technique to evaluate the rate coefficients. An important conclusion of this study indicates that at low initial dye concentrations, the rate of degradation of the phenolic compound is first order in the concentration of the dye, while at high initial dye concentrations, the rate is first order in the concentration of the phenolic compound. The different phenolic and dye intermediates that were formed during degradation were identified by mass spectrometry, and a most probable pathway of degradation was proposed. The solution photopolymerization of methyl-, ethyl-, butyl-and hexylmethacrylates in presence of benzoyl peroxide as the initiator was studied. The effect of initiator and monomer concentrations on the time evolution of polymer concentration, number average molecular weight (Mn) and polydispersity (PDI) was examined. The reversible chain addition and β-scission, and primary radical termination steps were included in the mechanism along with the classical initiation, propagation and termination steps. The rate equations were derived using continuous distribution kinetics and solved numerically to fit the experimental data. The model predicted the instantaneous increase of Mn and PDI of the polymers to steady state values. The rate coefficients exhibited a linear increase with the size of the alkyl chain of the alkyl methacrylates. Poly(acrylamide-co-acrylic acid) copolymers of different compositions were synthesized and characterized. The copolymers were statistical with a relatively high percentage of acrylamide units, as determined by 13C-NMR. The aqueous phase photolytic and photocatalytic degradation of the copolymers and the homopolymers was conducted. The degradation was modeled using continuous distribution kinetics. The degradation followed a two step mechanism, wherein the rapid first step comprised of the scission of weak acrylic acid units along the chain, which was followed by the breakage of the relatively strong acrylamide units. The rate constants for the weak and strong links followed a linear trend with the percentage of acrylic acid and acrylamide in the copolymer, respectively. The photocatalytic degradation of the copolymers of methyl methacrylate with butyl methacrylate (MMA-BMA), ethyl acrylate (MMA-EA) and methacrylic acid (MMA-MAA) was carried out in toluene. The copolymers and the corresponding homopolymers degraded randomly along the chain. The degradation rate coefficient was determined using continuous distribution kinetics. The time evolution of the hydroxyl and hydroperoxide stretching vibration in the FT-IR spectra of the copolymers indicated that the degradation rate follows the order: MMA-MAA > MMA-EA > MMA-BMA. The photodegradation rate coefficients were compared with the activation energy of pyrolytic degradation. The observed contrast in the order of thermal stability compared to the photostability of these copolymers was attributed to the two different mechanisms governing the scission of the polymers and the evolution of the products. The mechano-chemical degradation of poly(methyl methacrylate), poly(ethyl methacrylate) and poly(n-butyl methacrylate) using US and UV radiation, in presence of benzoin as the photoinitiator, was carried out. A degradation mechanism that included the decomposition of the initiator, generation of polymer radicals by hydrogen abstraction of the initiator radicals, and reversible chain transfer between the stable polymer and the polymer radicals, was proposed. The mechanism assumed mid-point chain scission due to US and random chain scission due to UV radiation. The steady state evolution of PDI was successfully predicted by the continuous distribution kinetics model. The rate coefficients of polymer scission due to US and UV radiation exhibited a linear increase and decrease with the size of the alkyl group of the poly(alkyl methacrylate)s, respectively.