Este trabalho descreve, sob um ponto de vista atômico, a investigação das nanopartículas magnéticas (NPMs) de magnetita (Fe3O4) e ferritas do tipo TMFe2O4 (TM = Co, Ni), que são uma classe de materiais estruturados que atualmente tem um grande interesse devido à grande variedade de suas possíveis aplicações tecnológicas e biomédicas, pela Espectroscopia de Correlação Angular γ-γ Perturbada (CAP). Para a produção das NPMs foram utilizadas duas rotas químicas: o método de co-precipitação e o método de decomposição térmica. A co-precipitação apresenta as vantagens de ter temperaturas moderadas e custos relativamente baixos, porém não se consegue ter um controle da distribuição de tamanho das partículas. Por outro lado, a decomposição térmica possibilita uma amostra monodispersa com controle de tamanho e forma, mas este método necessita de reagentes tóxicos, caros e alta temperatura de reação. Para caracterização das amostras foi usada a técnica de Difração de Raio X (DRX) e a morfologia das NPs foi estudada por meio da Microscopia Eletrônica de Transmissão (MET). A partir desta técnica foi possível avaliar a distribuição do tamanho dos grãos, pois algumas características como, elevado valor de magnetização, alta anisotropia e um alto valor de coercividade são propriedades que dependem das nanoestruturas. As propriedades magnéticas foram estudadas localmente a partir da Correlação Angular Perturbada (CAP) que utiliza como sondas núcleos atômicos das medidas, como os núcleos de prova 111In (111Cd), 140La (140Ce) e 181Hf(181Ta). Estas propriedades foram complementadas por medidas de Magnetização. / This work describes, from an atomic point of view, the investigation of magnetic nanoparticles (MNPs) of magnetite (Fe3O4) and ferrites of the type TMFe2O4 (TM = Co, Ni), which are a class of structured materials that currently have a great interest due to the great variety of its possible technological and biomedical applications by Perturbed γ-γ Angular Correlation Spectroscopy (PAC). Two chemical routes were used to produce MNPs: the co-precipitation method and the thermal decomposition method. Co-precipitation has the advantages of having moderate temperatures and relatively low costs, but particle size distribution control is not achieved. On the other hand, the thermal decomposition allows a monodisperse sample with size and shape control, but this method requires toxic reagents, expensive and high reaction temperature. The X-Ray Diffraction (XRD) technique was used to characterize the samples and the morphology of the NPs was studied by Electron Transmission Electron Microscopy (TEM). From this technique it was possible to evaluate grain size distribution, because some characteristics such as high magnetization value, high anisotropy and a high coercivity value are properties that depend on the nanostructures. The magnetic properties were studied locally from the Perturbed Angular Correlation (CAP), which uses as probe nuclei of the measurements, such as 111In (111Cd), 140La (140Ce) and 181Hf (181Ta). These properties were complemented by Magnetization measurements.

Este trabalho descreve, sob um ponto de vista atômico, a investigação das nanopartículas magnéticas (NPMs) de magnetita (Fe3O4) e ferritas do tipo TMFe2O4 (TM = Co, Ni), que são uma classe de materiais estruturados que atualmente tem um grande interesse devido à grande variedade de suas possíveis aplicações tecnológicas e biomédicas, pela Espectroscopia de Correlação Angular γ-γ Perturbada (CAP). Para a produção das NPMs foram utilizadas duas rotas químicas: o método de co-precipitação e o método de decomposição térmica. A co-precipitação apresenta as vantagens de ter temperaturas moderadas e custos relativamente baixos, porém não se consegue ter um controle da distribuição de tamanho das partículas. Por outro lado, a decomposição térmica possibilita uma amostra monodispersa com controle de tamanho e forma, mas este método necessita de reagentes tóxicos, caros e alta temperatura de reação. Para caracterização das amostras foi usada a técnica de Difração de Raio X (DRX) e a morfologia das NPs foi estudada por meio da Microscopia Eletrônica de Transmissão (MET). A partir desta técnica foi possível avaliar a distribuição do tamanho dos grãos, pois algumas características como, elevado valor de magnetização, alta anisotropia e um alto valor de coercividade são propriedades que dependem das nanoestruturas. As propriedades magnéticas foram estudadas localmente a partir da Correlação Angular Perturbada (CAP) que utiliza como sondas núcleos atômicos das medidas, como os núcleos de prova 111In (111Cd), 140La (140Ce) e 181Hf(181Ta). Estas propriedades foram complementadas por medidas de Magnetização. / This work describes, from an atomic point of view, the investigation of magnetic nanoparticles (MNPs) of magnetite (Fe3O4) and ferrites of the type TMFe2O4 (TM = Co, Ni), which are a class of structured materials that currently have a great interest due to the great variety of its possible technological and biomedical applications by Perturbed γ-γ Angular Correlation Spectroscopy (PAC). Two chemical routes were used to produce MNPs: the co-precipitation method and the thermal decomposition method. Co-precipitation has the advantages of having moderate temperatures and relatively low costs, but particle size distribution control is not achieved. On the other hand, the thermal decomposition allows a monodisperse sample with size and shape control, but this method requires toxic reagents, expensive and high reaction temperature. The X-Ray Diffraction (XRD) technique was used to characterize the samples and the morphology of the NPs was studied by Electron Transmission Electron Microscopy (TEM). From this technique it was possible to evaluate grain size distribution, because some characteristics such as high magnetization value, high anisotropy and a high coercivity value are properties that depend on the nanostructures. The magnetic properties were studied locally from the Perturbed Angular Correlation (CAP), which uses as probe nuclei of the measurements, such as 111In (111Cd), 140La (140Ce) and 181Hf (181Ta). These properties were complemented by Magnetization measurements.

Supercapacitors (SCs) have generated significant interest due to their advantages including lightweight, rapid charge-discharge, good rate capability and high cyclic stability. Electrodes are one of the most important factors influencing the performance of SCs. MXene is a promising candidate for supercapacitor electrodes, which is a relatively new material with formula Mn+1XnTx, where M is a transitional metal, X stands for C or N, and Tx is surface terminations. Due to its multi-layered structure, high surface area and rich redox chemistry, good electrochemical performance can be expected. To further enhance the conductivity of the MXene electrodes, multi-walled carbon nanotubes (MCNT) were applied as the conducting additive. The as-fabricated composite electrodes showed reduced resistance and enhanced electrochemical performance. Advanced co-dispersants such as cationic celestine blue (CCB) and anionic catechol violet (ACV) were employed to improve the dispersion of components. CCB and ACV can adsorb strongly on the MXene and MCNT surface to form a homogenous suspension and thus improve the mixing between them. Another advanced dispersant 3,4,5-trihydroxybenzamide (THB) also showed adsorption on both MXene and MCNT particles, favored their dispersive mixing and improved electrochemical performance. Iron oxides are promising materials for negative electrodes for supercapacitors. The attempt to combine highly capacitive Fe3O4 with MXene-MCNT composites proved the synergistic effect of individual components. Investigation of Zn-doped FeOOH as high active mass loading anode with MCNT as conducting additive allowed for enhanced performance. Zn-Fe double hydroxide materials are promising for the fabrication of advanced supercapacitor electrodes. A safe and neutral Na2SO4 electrolyte was was beneficial for the development of asymmetric devices with enlarged voltage window. For cathodes working in an overlapping window with Zn-FeOOH anode, polypyrrole coated carbon nanotube electrode was fabricated with a comparable capacitance. The advanced dopant eriochrome cyanine R (ECR) allowed for the uniform thickness of PPy coating on MCNT and enhanced charge transfer between PPy and MCNT was achieved. Enhanced capacitive properties of cathodes and anodes at high active mass loading working in complimentary voltage windows allowed for fabrication of high-performance supercapacitor, which was a promising device for practical applications. / Thesis / Doctor of Philosophy (PhD) / To reduce the consumption of fossil fuel and meet the surging demand of electric energy, intensive attention has been drawn to new energy storage device, such as capacitors, batteries and supercapacitors. Owing to their higher energy density compared with conventional capacitors and higher power density compared with batteries, supercapacitors are attracting tremendous research interest. The advantages of supercapacitors are fast charge-discharge rate, high power and energy density and excellent cyclic stability. The objective of this work was to fabricate high-performance supercapacitor devices based on the development of advanced electrode materials. MXene and Fe-based composite materials were synthesized by conceptually new colloidal approach and some efficient dispersants were developed during the process. The enlarged voltage window and superior performance were recorded for asymmetric supercapacitors. The results presented in this work showed much more promising performance compared with that reported in the literature and paved the way for future research.

Com o desenvolvimento de novos nanomateriais têm-se descoberto propriedades eletrônicas, elétricas, ópticas e catalíticas únicas para aplicações nanotecnológicas. Entre estes nanomateriais com caraterísticas singulares, estão as nanopartículas (Np) CoreαShell, as quais combinam propriedades físico-químicas de dois materiais diferentes, provendo maior eficiência em aplicações como nanoeletrônica, sensoreamento, biossensoreamento e biomédicas. Neste trabalho, Np CoreαShell são sintetizada com núcleo (Core) de Np Fe₃O₄ e com casca (Shell) de Np Au, formando as Nps Fe₃O₄αAu na presença do dendrímero poli(amidoamina) geração 4.0 (Pamam G4). As propriedades físico-químicas do nanomaterial core-shell são estudadas através de análises espectroscópicas, microscopias e eletroquímicas, além de medidas de magnetização. Essas técnicas revelam a formação das Nps Au nas cavidades do Pamam G4 e as interações eletrostáticas entre os grupos funcionais do Pamam G4 e os grupos OH ⁻ e H ⁺ da superfície das Nps magnéticas, as quais dão uma forte estabilidade na configuração da Np Fe₃O₄αAu. Evidencia-se propriedades óticas da Np Au e propriedades superparamagnéticas da Np Fe ₃ O ₄, as quais podem ser usadas para aplicações em nanomedicina. As propriedades electrocatalíticas das Nps são utilizadas na detecção de dopamina (DA). Foram fabricados sensores eletroquímicos das Nps Fe₃O₄αAu, Nps Fe₃O₄ e Nps Au, e caracterizados por técnicas de voltametria cíclica e voltametria de pulso diferencial. A fabricação dos sensores consistiu na deposição de camadas alternadas entre as nanopartículas com o poliânion poly(ácido vinil sulfônico) (PVS) no eletrodo de ITO, levando à configuração de três arquiteturas; ITO - (Fe₃O₄αAu ⁄ PV S), ITO - (Fe₃O₄ ⁄ PV S) e ITO - (Au ⁄ PV S). Um problema encontrado na detecção de DA é que esta tem potenciais de oxidação aproximadamente iguais ao ácido ascórbico (AA) e ao ácido úrico (AU). Portanto, os sensores utilizados na detecção de DA, devem ser altamente seletivos a DA em relação a seus interferentes. Os sensores desenvolvidos aqui mostraram uma boa seletividade e velocidade de resposta na detecção de DA, sendo o sensor ITO - (Fe₃O₄αAu ⁄ PV S) o mais eficiente. As Nps Fe₃O₄αAu revelam maior citotoxicidade nas células cancerígenas comparadas com as células saudáveis, já que as células cancerígenas são mais sensíveis ao estresse oxidativo produzido pelas nanopartículas no interior da célula. / Along with the development of nanomaterials came the knowledge and design of their unique eletronic, optical and catalitycal properties which may be used for a variety of nanotecnological applications. A special class of nanomaterials with interesting characteristics is represented by the CoreαShell nanoparticles, which combine the physicochemical properties of two differerent nanomaterials (including oxides, metals, semiconductors or polymers). This combination provides greater efficiency in applications such as nanoelectronics, sensing, biosensing and biomedical areas. This study reports the synthesis of Fe₃O₄ Np, which in the presence of the polyamido amine generation 4.0 (Pamam G4), is covered with Au Np forming the Fe₃O₄αAu Nps. The nanomaterials had been characterized using spectroscopic, microscopic and electrochemical techniques. The results revealed the formation of Au Nps in the cavities of PAMAM G4 and showed that the electrostatic interactions between the PAMAM functional groups and the OH ⁻ and H ⁺ groups on the surface of the magnetic nanoparticles lead to a strong stability in the configuration of Fe₃O₄αAu Nps. The optical properties of the Au Np (namely the Plasmon resonance band at 542 nm) as well as the superparamagnetic properties of the Fe₃O₄ Np were present in the core-shell nanostrutures. Due to their electrocatalytical properties, the core-shell nanoparticles were employed as active elements for dopamine (DA) detection. The fabrication of the modified electrodes for DA detection consisted in the deposition by LbL technique of alternating layers of nanoparticles and poly(vinyl sulfonic acid) (PVS) on the ITO eletrode, in three distinct architectures: ITO - (Fe₃O₄αAu Fe₃O₄ PV S), ITO - (Fe₃O₄ ⁄ PV S) and ITO - (Au ⁄ PV S). We found a good selectivity and rapid response toward the detection of DA, being the sensor ITO - (Fe₃O₄αAu ⁄ PV S) the most efficient. The effect of Fe₃O₄αAu Nps showed a higher cytotoxicity in cancer cells compared to healthy cells, because cancer cells are more sensitive to oxidative stress produced by the nanoparticles.

Com o desenvolvimento de novos nanomateriais têm-se descoberto propriedades eletrônicas, elétricas, ópticas e catalíticas únicas para aplicações nanotecnológicas. Entre estes nanomateriais com caraterísticas singulares, estão as nanopartículas (Np) CoreαShell, as quais combinam propriedades físico-químicas de dois materiais diferentes, provendo maior eficiência em aplicações como nanoeletrônica, sensoreamento, biossensoreamento e biomédicas. Neste trabalho, Np CoreαShell são sintetizada com núcleo (Core) de Np Fe₃O₄ e com casca (Shell) de Np Au, formando as Nps Fe₃O₄αAu na presença do dendrímero poli(amidoamina) geração 4.0 (Pamam G4). As propriedades físico-químicas do nanomaterial core-shell são estudadas através de análises espectroscópicas, microscopias e eletroquímicas, além de medidas de magnetização. Essas técnicas revelam a formação das Nps Au nas cavidades do Pamam G4 e as interações eletrostáticas entre os grupos funcionais do Pamam G4 e os grupos OH ⁻ e H ⁺ da superfície das Nps magnéticas, as quais dão uma forte estabilidade na configuração da Np Fe₃O₄αAu. Evidencia-se propriedades óticas da Np Au e propriedades superparamagnéticas da Np Fe ₃ O ₄, as quais podem ser usadas para aplicações em nanomedicina. As propriedades electrocatalíticas das Nps são utilizadas na detecção de dopamina (DA). Foram fabricados sensores eletroquímicos das Nps Fe₃O₄αAu, Nps Fe₃O₄ e Nps Au, e caracterizados por técnicas de voltametria cíclica e voltametria de pulso diferencial. A fabricação dos sensores consistiu na deposição de camadas alternadas entre as nanopartículas com o poliânion poly(ácido vinil sulfônico) (PVS) no eletrodo de ITO, levando à configuração de três arquiteturas; ITO - (Fe₃O₄αAu ⁄ PV S), ITO - (Fe₃O₄ ⁄ PV S) e ITO - (Au ⁄ PV S). Um problema encontrado na detecção de DA é que esta tem potenciais de oxidação aproximadamente iguais ao ácido ascórbico (AA) e ao ácido úrico (AU). Portanto, os sensores utilizados na detecção de DA, devem ser altamente seletivos a DA em relação a seus interferentes. Os sensores desenvolvidos aqui mostraram uma boa seletividade e velocidade de resposta na detecção de DA, sendo o sensor ITO - (Fe₃O₄αAu ⁄ PV S) o mais eficiente. As Nps Fe₃O₄αAu revelam maior citotoxicidade nas células cancerígenas comparadas com as células saudáveis, já que as células cancerígenas são mais sensíveis ao estresse oxidativo produzido pelas nanopartículas no interior da célula. / Along with the development of nanomaterials came the knowledge and design of their unique eletronic, optical and catalitycal properties which may be used for a variety of nanotecnological applications. A special class of nanomaterials with interesting characteristics is represented by the CoreαShell nanoparticles, which combine the physicochemical properties of two differerent nanomaterials (including oxides, metals, semiconductors or polymers). This combination provides greater efficiency in applications such as nanoelectronics, sensing, biosensing and biomedical areas. This study reports the synthesis of Fe₃O₄ Np, which in the presence of the polyamido amine generation 4.0 (Pamam G4), is covered with Au Np forming the Fe₃O₄αAu Nps. The nanomaterials had been characterized using spectroscopic, microscopic and electrochemical techniques. The results revealed the formation of Au Nps in the cavities of PAMAM G4 and showed that the electrostatic interactions between the PAMAM functional groups and the OH ⁻ and H ⁺ groups on the surface of the magnetic nanoparticles lead to a strong stability in the configuration of Fe₃O₄αAu Nps. The optical properties of the Au Np (namely the Plasmon resonance band at 542 nm) as well as the superparamagnetic properties of the Fe₃O₄ Np were present in the core-shell nanostrutures. Due to their electrocatalytical properties, the core-shell nanoparticles were employed as active elements for dopamine (DA) detection. The fabrication of the modified electrodes for DA detection consisted in the deposition by LbL technique of alternating layers of nanoparticles and poly(vinyl sulfonic acid) (PVS) on the ITO eletrode, in three distinct architectures: ITO - (Fe₃O₄αAu Fe₃O₄ PV S), ITO - (Fe₃O₄ ⁄ PV S) and ITO - (Au ⁄ PV S). We found a good selectivity and rapid response toward the detection of DA, being the sensor ITO - (Fe₃O₄αAu ⁄ PV S) the most efficient. The effect of Fe₃O₄αAu Nps showed a higher cytotoxicity in cancer cells compared to healthy cells, because cancer cells are more sensitive to oxidative stress produced by the nanoparticles.

Nanopartículas de Fe3O4 e Fe2O3 foram sintetizadas a partir da rota de coprecipitação, em atmosfera de N2, mantendo-se o pH entre 9 e 14 na temperatura ambiente e utilizando como precursores o FeCl2 e FeCl3. Após a síntese, as nanopartículas foram tratadas termicamente a 250, 500 e 800 oC. Para obtenção de um sistema híbrido, foram sintetizadas nanopartículas de ouro sobre as nanopartículas de óxido previamente tratadas em diferentes temperaturas. As amostras foram caracterizadas por UV-Vis, difratometria de Raios-X (DRX), microscopia eletrônica de transmissão (MET), microscopia eletrônica de transmissão de alta resolução (MET-AR), espectroscopia no na região do infravermelho (FTIR), magnometria de amostra vibrante (VSM) e espectroscopia Mossbauer (EM), e aplicadas para produção de hidrogênio promovendo a decomposição da hidrazina. Os resultados mostram a síntese de nanopartículas de óxido de ferro com diâmetro médio de cerca de 7 nm. Quando aquecidas a 250 oC o tamanho médio aumentou para ca. de 11 nm e foi observado uma pequena mudança no comportamento óptico e estrutural, mantendo o comportamento superparamagnetico. Quando aquecidas a 500 oC o tamanho médio aumenta para ca. de 50nm e são observadas mudanças significativas nas propriedades ópticas, morfológicas, estruturais. Adicionalmente observa-se transição de comportamento superparamagnetico para paramagnético. Quando aquecidas a 800 oC os efeitos nas propriedades dos materiais são ainda mais significativos; as partículas apresentam tamanho médio de 200 nm, o espectro de absorção no UV-Vis muda significativamente e as partículas passam a ter comportamento pagamagnético. Os resultados obtidos pelas diferentes técnicas e somadas ao Mossbauer sugerem que as amostras sintetizadas são uma mistura de Fe3O4 e -Fe2O3, quando aquecido a 250 e 500 oC uma mistura de -Fe2O3 e -Fe2O3 e a 800 oC somente -Fe2O3. As nanopartículas de ouro sintetizadas sobre as amostras de oxido de ferro apresentaram tamanho médio de 6,0 nm e não afetaram as propriedades magnéticas dos oxidos. As amostras de óxido com nanopartículas de ouro promoveram a decomposição da hidrazina por rota completa, levando a formação de hidrogênio com seletividade de até 33%. / Fe3O4 and Fe2O3 nanoparticles were synthesized by coprecipitation route carried out under N2 atmosphere, maintaining the pH between 9 and 14 at room temperature and using FeCl2 and FeCl3 as precursors. After synthesis the iron oxide nanoparticles were thermally treated at 250, 500 and 800 oC. To obtain a hybrid system, gold nanoparticles were synthesized on the thermally treated oxide nanoparticles. The samples were analyzed by UV-Vis, X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (MET-AR), spectroscopy in the region of Infrared (FTIR), vibrating sample magnitude (VSM) and Mossbauer, and applied to produce H2 through hydrazine decomposition. The results show the synthesis of Fe3O4 nanoparticles with average diameter of about 7 nm. When heated to 250 oC the average size increased to about 11 nm and a small change in the optical and structural behavior was observed, while the superparamegnetic behaviour was maintained. When heated to 500 °C, the average particle size increase to ca 51nm, significant changes in the optical, morphological and structural properties are observed, in addition to a transition from superparamegnetic to paramagnetic behaviour. When heated to 800 oC the effects on the properties are even more significant; the nanoparticles increase to ca. 200 nm, the absorption spectrum in UV-Vis changes significantly and the particles present paramagnetic behaviour. The results suggest that when heated to 250 and 500 oC a mixture of -Fe2O3 e -Fe2O3 is obtained, after heating at 800 oC only -Fe2O3 is observed. The gold nanoparticles synthesized on the iron oxides present average size of 6.0 nm, and did not affect the magnetic properties of the oxides. The iron oxides/gold nanoparticle samples were efficiently applied to produce hydrogen, promoting the decomposition of hydrazin. The selectivity to hydrogen reached up to 33%.

Submitted by Caroline Xavier (caroline.xavier@pucrs.br) on 2017-08-07T12:45:10Z No. of bitstreams: 1 TES_LEONARDO_MOREIRA_DOS_SANTOS_COMPLETO.pdf: 6572783 bytes, checksum: e8d5d3a0189ac032e86a93f6776a8ad0 (MD5) / Made available in DSpace on 2017-08-07T12:45:10Z (GMT). No. of bitstreams: 1 TES_LEONARDO_MOREIRA_DOS_SANTOS_COMPLETO.pdf: 6572783 bytes, checksum: e8d5d3a0189ac032e86a93f6776a8ad0 (MD5) Previous issue date: 2017-03-24 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The obtaining of materials with different and superior properties when compared to existing materials is one of the main research focuses in polymeric materials field. Nanocomposites are important in this sector because they combine materials with good performance in order to obtain new features that can be used in different niches in the market. Polyurethane based materials finds a wide application and is widely used in industry. The insertion of an alternative inorganic filler is often used to obtain better properties of these polymeric materials. Thus, this work aims to incorporate different proportions of a new filler Fe3O4-synthetic talc, in powder and gel form, in solvent and waterborne polyurethane matrix. Nanocomposites PU solvent/ Fe3O4-synthetic talc obtained by physical mixture presented a good filler dispersion/exfoliation even at higher filler contents of 10% as corroborated by XRD and TEM techniques. M?ssbauer and magnetic measurements confirmed the magnetic behavior of nanocomposites, being ferromagnetic in all tested temperatures. The use of synthetic talc to obtain magnetic nanocomposites produced materials with higher crystallization temperature and thermal stability compared with the polymeric matrix. This method is efficient to avoid attracting dipolar magnetite and therefore the charge aggregation. Nanocomposites WPU/ Fe3O4-synthetic talc presented better mechanical properties with higher filler contents compared to the pure polymer. The XRD analysis evidenced a formation of an intercalated structure between the polymer matrix and nanoparticles. Nuclear Magnetic Resonance (NMR) measurements evidenced the interaction filler/WPU corroborating the AFM analyses. M?ssbauer and magnetization curves highlighted that the magnetic properties are temperature dependent unlike for nanocomposites obtained with solvent based PU. / A obten??o de materiais com propriedades distintas e superiores quando comparados aos materiais existentes ? um dos focos das pesquisas na ?rea de materiais polim?ricos. Os nanocomp?sitos v?m se destacando neste setor, pois utilizam a combina??o de materiais que j? tenham um bom desempenho visando obter novas caracter?sticas que possam ser utilizadas em diferentes nichos no mercado. Um pol?mero que tem uma ampla aplica??o e ? muito utilizado no meio industrial ? o poliuretano. A inser??o de cargas inorg?nicas ? uma alternativa muito usada para obter melhores propriedades destes materiais polim?ricos. Desta forma, este trabalho tem como objetivo a incorpora??o de uma nova carga de Fe3O4-talco-sint?tico, em forma de p? e gel, em diferentes quantidades em rela??o a massa de poliuretano base solvente e base ?gua. Nas amostras de nanocomp?sitos obtidos por mistura f?sica com PU base solvente a carga ficou esfoliada/bem dispersa na matriz polim?rica mesmo com altos teores de carga de 10% como mostrado pelas t?cnicas de DRX e MET. O comportamento magn?tico dos nanocomp?sitos foi confirmado por M?ssbauer e medidas magn?ticas, apresentando comportamento de ferromagn?tico em todas as temperaturas testadas. O uso do talco sint?tico para obter nanocomp?sitos magn?ticos, produziu materiais com temperatura de cristaliza??o e estabilidade t?rmica superior quando comparado com a matriz polim?rica. O m?todo se mostrou eficiente para evitar a atra??o dipolar da magnetita e, consequentemente a agrega??o da carga. Os nanocomp?sitos PUBA (poliuretano base ?gua/Fe3O4-talco sint?tico) mostraram melhores propriedades no ensaio de tra??o quando comparados ao pol?mero puro. Por exemplo, o pol?mero puro apresentou um M?dulo de Young de 29,3 MPa e passou para 70 MPa na amostra PUBA/ 40% Fe3O4-talco-sint?tico, mostrando que a adi??o de carga tende aumentar a resist?ncia mec?nica do material. As an?lises de DRX mostraram que h? forma??o de uma estrutura intercalada entre a matriz polim?rica e as nanopart?culas. An?lises de Resson?ncia Magn?tica Nuclear (RMN) mostraram que a carga interage com a matriz polim?rica, corroborando os resultados de AFM. Mossbauer e curvas de magnetiza??o, mostraram que as propriedades magn?ticas variam com a temperatura, diferentemente ao observado nos nanocomp?sitos obtidos com PU base solvente.

The aim of this study was to investigate the reaction behaviors of nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the electrokinectic (EK) process for remediation of NO3− and Cr6+ in saturated soil. To assure the above-mentioned nanomaterials were capable of reductively adsorbing inorganic pollutants (e.g., NO3− and Cr6+) in the acidic environment in the anode reservoir of the ek remediation system, an investigation on transformation of the concerned nanomaterials in different aqueous solutions (de-ionized water and simulated groundwater ) of different initial pHs (2 and 3.5) was conducted. Due to a high dose of nanoscale Fe3O4 and a resulting serious agglomeration while adsorbing NO3− and Cr6+, the characteristic peaks of the X-ray diffraction (XRD) analysis for nanoscale Fe3O4 remained the same after adsorption experiments. But the situations were quite different in the case of nanoscale H1/10-[Fe3O4]MgO, the characteristic peaks of £\-Fe2O3 in the XRD pattern were detected, confirming that this nanomaterial could reductively adsorb NO3− and Cr6+ in the acidic environment. The effectiveness of using polyacrylic acid (PAA) and soluble starch (SS) to stabilize nanoscale Fe3O4 and H1/10-[Fe3O4]MgO in different aqueous solutions containing humic acid was compared. It was found the former yielded a better stability. Therefore, PAA was chosen to prepare the slurries of target nanomaterials. Then slurry injection coupled with the EK process was tested for remediation of NO3- and Cr6+ in saturated soil. The results showed that the removal efficiency of NO3− was more than 90%, and the NO3− concentration in the anode reservoir was below Taiwan¡¦s Pollution Control Standards of type¢¹Groundwater for NO3−-N. Under the same test conditions, however, the removal efficiency of Cr6+ was unsatisfactory. This might be ascribed to acidification of soil near the anode resulting in high adsorption of Cr2O72− by soil. Thus, a solution to solve this problem has to seeked. The solution lies in how to enhance the contact of the above-mentioned nanomaterials with Cr6+ in the anode reservoir. One possibility is to use the nature of SS would hydrolyze in the acidic environment. Therefore, SS-stabilized nanomaterials in the acidic environment would hydrolyze resulting in the exposure of the soil nanomaterials therein. To this end, SS was used to replace PAA for nanomaterial slurry preparation for remediation of Cr6+. In addition, polarity reversal was practiced in the EK system to maintain a neutral ph of soil and increase the mobility of Cr6+ in soil. Finally, the result showed that nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the polarity reversal electrokinetic system could really enhance the removal efficiency of Cr6+ in the saturated soil. In summary, nanoscale Fe3O4 and H1/10-[Fe3O4]MgO slurry injection coupled with the EK process has been proven to be capable of remedying NO3− and Cr6+ in saturated soil. Meanwhile, the concept of reductive adsorption was realized in this work as well.

The purpose of this work was to investigate the use of nanoscale Fe3O4 as a catalytst for destruction of trichloroethylene (TCE) and 1,2-dichloroethane (1,2-DCA) by persulfate in spiked water and soil. First, nanoscale Fe3O4 was prepared by chemical coprecipitation. X-ray powder diffraction (XRD) was used to confirm the crystal structure; And size identification was performed using the scanning electron microscopy (SEM). The effectiveness of using 3 wt% soluble starch (SS) to stabilize nanoscale Fe3O4 was also studied. It was found that SS could effectively disperse the nanoparticles for more than one month. Therefore, SS was chosen to prepare the nanoscale Fe3O4 slurry. The efficiency of nanoscale Fe3O4 as an activator for persulfate remediation of TCE and 1,2-DCA in aqueous solutions (DI water, simulated groundwater, and actual groundwater) was then investigated. The results showed that all test removal efficiency of TCE and 1,2-DCA was more than 95%. Use of the persulfate for destruction of TCE and 1,2-DCA produced some by-products. The primary reaction products were cis-1,2-Dichloroethylene (cis-1,2-DCE) and trans-1,2-Dichloroethylene (trans-1,2-DCE)¡F The secondary daughter prodnct was vinyl chloride (VC). The VC produced is gradually degraded to safer substances (ethene, ethane, and methane). The nanoscale Fe3O4 slurry and the persulfate injection coupled with the electrokinetic (EK) process was tested for remediation of TCE and 1,2-DCA in saturated soil. The results showed that injection of persulfate into the EK reservoir could decrease the electrode polarization, and increase the electroosmotic flow and current density. When persulfate was injected into the cathode reservoir, the derived sulfate radicals would transfer into the soil compartment by ion migration. The injection of persulfate into the cathode reservoir was more efficient than injection of persulfate into the anode reservoir. The removal efficiency for TCE and 1,2-DCA was more than 96% in all tests. The remediation system was assessed for potential application in-situ. Soil was spiked with high TCE and 1,2-DCA and aged for a week. The injection of persulfate and nanoscale Fe3O4 slurry coupled with the EK process was tested for remediation of the aged contaminated soil. The results showed that the target contaminants (TCE and 1,2-DCA) met the Taiwan¡¦s EPA¡¦s control standard. After 30 d of remediation, the by-products (cis-1,2-DCE, trans-1,2-DCE, and VC) had also been removed to below the action limit. A cost analysis was performed in order to demonstrate the economic feasibility of the remediation method in this study. Operating costs (chemicals + electricity bill) of all tests were assessed. The results showed that the costs were 8000-17000 NT$/m3, which is economically reasonable.

This study was to investigate the reaction behavior of nanoscale [Fe3O4]MgO and trichlorothylene (TCE) in aqueous solutions. In addition, effects of environmental variables on TCE removal from a simulated groundwater system were investigated. At first, two types of metal oxide composites containing both nanoscale Fe3O4 and MgO (designated H-[Fe3O4]MgO and S-[Fe3O4]MgO, respectively) were prepared. Then they were characterized and verified by various apparatuses and methods including X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, specific surface area measurements. Since the substrate of S-[Fe3O4]MgO with a molar ratio of Fe3O4/MgO = 1/5 (designated S1/5-[Fe3O4]MgO) had a much greater specific surface area than that of the substrate of S-[Fe3O4]MgO with a molar ratio of Fe3O4/MgO = 5/5 (designated S5/5-[Fe3O4]MgO), S1/5-[Fe3O4]MgO was selected as the model composite for the treatment of TCE in this study. Results of batch tests showed that S1/5-[Fe3O4]MgO had the best treatment performance among various metal oxides and their composites. For an initial TCE concentration of 10 mg/L, however, only 45% removal could be achieved by 5.0 g/L of dispersed S1/5-[Fe3O4]MgO. Nevertheless, a greater removal efficiency could be obtained for a higher initial TCE concentration in a simulated groundwater system. Test results also showed that a lower temperature and higher pH would retard the relevant reaction rates in TCE removal. In the simulated groundwater system employed in this work, the existence of humic acid (< 10 mg/L) played an insignificant role in affecting the TCE removal. Analysis of TCE adsorption on S1/5-[Fe3O4]MgO in aqueous solution indicated that a Langmuir-type of chemical adsorption would have a better fit. Results of gas chromatography further showed the existence of small to trace amounts of TCE degradation products including cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, vinyl chloride, ethene and methane, etc. Thus, the relevant reaction mechanisms and pathways for the destructive adsorption were proposed.