Au vu de l'omniprésence des oxydes de fer dans le milieu naturel, et en particulier la goethite et l'hématite qui sont les formes les plus stables, mais aussi de la prolifération des contaminants émergents dans l'environnement, comme les fluoroquinolones, notre objectif a été d'étudier leur réactivité et de définir les mécanismes de sorption et d'oxydoréduction à l'interface oxyde/solution dans des conditions statiques (batch) et hydrodynamiques contrôlées (colonne) en couplant une étude macroscopique (techniques chromatographiques, LC/MS, LC/UV) avec une approche microscopique (spectroscopie vibrationnelle et XPS) et de modélisation mécanistique (TPM et CD-MUSIC). Ces travaux mettent en évidence les principaux mécanismes responsables de la transformation des molécules organiques à la surface d'un oxyde de fer, et donc fournissent des informations nécessaires à la compréhension du devenir des contaminants émergents dans l'environnement. / Given the ubiquity of iron oxides in environmental settings, particularly goethite and hematite, the most stable forms, but also the proliferation of emerging contaminants, such as fluoroquinolones, in the environment, our goal was to study their reactivity and describe mechanisms of sorption and redox at oxide /solution interfaces in static batch) and hydrodynamic conditions (column) by coupling a macroscopic study (LC/MS, LC/UV) with a microscopic/molecular approach (vibrational spectroscopy and XPS) and mechanistic modeling (TPM and CD-MUSIC).. These works highlight the main mechanisms responsible of the transformation of organic molecules on iron oxide surfaces and thus provide valuable information necessary for the understanding of the fate of emerging contaminants in the environment.

Commonly used amines in power industry, including morpholine, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and DMA (dimethylallylamine) were evaluated for their effect on AISI 1018 steel at 250oF. Samples were exposed to an autoclave containing amine added aqueous solution at pH of 9.5 for 1, 2, 4, 6, 8, and 12 hours. Morphology studies were carried using scanning electron microscope (SEM), phase analysis was done utilizing Fourier transform infrared spectroscopy (FTIR), and weight loss was performed to assess kinetics of oxidation. Control samples showed the highest metal dissolution rate. DBU showed the best performance in metal protection and SEM indicated the presence of a free-crack layer formed by fine particles in that set. FTIR showed that DBU apparently favored the formation of magnetite. It is believed that fine particles impede intrusion of aggressive ions into the metal surface by forming a barrier layer. FTIR demonstrated that DMA formed more oxyhydroxides, whereas morpholine presented magnetite to hematite transformation as early as 2 hours. SEM revealed that control and DMA produced acicular particles characteristic of oxyhydroxides while morpholine and DBU presented more equiaxed particles.

Orientador: Claudia Longo / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-18T16:06:49Z (GMT). No. of bitstreams: 1 Santos_ReginaldodaSilva_D.pdf: 4843119 bytes, checksum: 3b7dd1f72628c75da40e0f76317b6cfa (MD5) Previous issue date: 2011 / Resumo: Nanopartículas de TiO2 foram preparadas por método sol-gel a partir da hidrólise de isopropóxido de titânio, tratamento hidrotérmico (200 °C, 8 h) e calcinação (450 °C, 30 min); amostras de TiO2 dopado com ferro (Fe:TiO2) foram obtidas pela mesma metodologia incluindo nitrato férrico nos precursores (razão molar Fe/Ti de 1, 3 e 5%). Para comparação, investigou-se também uma mistura de a-Fe2O3/TiO2 (Fe/Ti = 4 %). O intervalo de banda proibida, de 3,2 eV para o TiO2, diminuiu de 3,0 para 2,7 eV com o aumento do teor de Fe. Análises por difração de raios X e refinamento Rietveld revelaram que o TiO2 é constituído por anatasa (82 %) e brookita (18 %); para Fe:TiO2, observou-se 30 % de brookita e identificou-se 0,5; 1,0 e 1,2 wt % de hematita nas amostras com Fe/Ti de 1; 3 e 5%. Filmes porosos, com espessura de 1,5 mm, foram depositados em eletrodos de vidro a partir de suspensões com polietilenoglicol e calcinação. Em solução aquosa, irradiados com um simulador solar, os eletrodos apresentaram comportamento de semicondutor tipo-n: para o TiO2, fotopotencial de -0,95 V em circuito aberto e fotocorrente de 0,34 mA cm em 0,8 V; valores muito menores foram observados para Fe:TiO2 e a-Fe2O3/TiO2. O TiO2 também apresentou maior atividade fotocatalítica para degradação de fenol e, quando utilizado como foto-anodo em célula de dois compartimentos, polarizado a + 0,7 V por 4 h, promoveu a oxidação de formiato e a produção de 18 mmol de H2 sobre contra-eletrodo de Pt. Os eletrodos de Fe:TiO2 e a-Fe2O3/TiO2 apresentaram valores menores de corrente, impossibilitando a obtenção de H2 no catodo. Embora as amostras de Fe:TiO2 tenham apresentado maior aproveitamento da luz visível, a inserção do ferro como dopante e a hematita segregada podem dificultar a separação das cargas fotogeradas e o transporte de elétrons através dos contornos de grãos, resultando em menor atividade fotocatalítica nas aplicações decorrentes da conversão de energia solar / Abstract: TiO2 nanoparticles were synthesized by sol-gel method from hydrolysis of titanium isopropoxide followed by hydrothermal treatment (200 °C, 8 h) and annealing (450 °C, 30 min). Fe doped TiO2 (Fe:TiO2) samples were synthesized by similar methodology adding ferric nitrate, with Fe/Ti atomic ratio corresponding to 1, 3 and 5 %. A mixture of a-Fe2O3/TiO2 (with Fe/Ti = 4 at %) was also investigated. The band gap energy, estimated as 3.2 eV for TiO2, gradually ranged from 3.0 to 2.7 eV with increasing iron content. Rietveld refinement of X ray diffraction data revealed that TiO2 consisted of 82 % anatase and 18 % brookite; for Fe:TiO2, brookite increased to 30 % and hematite was also identified (0.5; 1.0 and 1.2 wt % for samples prepared with 1; 3 and 5 % of Fe/Ti). Porous films, 1.5 mm thick, were deposited on transparent electrodes from aqueous suspension with polyethylene glycol and annealing. In aqueous solution, irradiated by a solar simulator, the electrodes exhibited n-type semiconductor behavior: for TiO2 electrode, -0,95 V of photo-potential at open circuit condition and 0,34 mA cm of photocurrent when biased at 0.8 V; much lower values were observed for Fe:TiO2 and a-Fe2O3/TiO2 electrodes. TiO2 film also exhibited higher photocatalytic activity for phenol oxidation than other samples. The electrodes were also used as photo-anodes in a two-compartment electrochemical cell with Pt counter-electrode and HCOONa as hole scavenger. The cell assembled with irradiated TiO2 anode biased at + 0.7 V for 4 h produced 18 mmol of H2 at the cathodic compartment. H2 evolution was not detected and very low currents were observed for Fe:TiO2 or a-Fe2O3/TiO2 photo- anodes. Although Fe:TiO2 samples exhibited higher sunlight harvesting, inserted iron and segregated hematite can hinder the separation of photogenerated charges, as well as the electron transport across the grain boundaries, resulting in lower photocatalytic activity for solar energy conversion / Doutorado / Físico-Química / Doutor em Ciências

[pt] O presente trabalho visou avaliar o processo de eletroflotação de partículas finas e ultrafinas de minério de ferro com o uso de um biossurfactante extraído da bactéria Rhodococcus Opacus. Foram realizados estudos de caracterização de um minério de ferro (análise granulométrica, difração de raios - X e fluorescência de raios - X). Através das medições de espectroscopia no infravermelho foi possível identificar uma provável interação do biossurfactante com a hematita, o espectro após a interação mostrou grupos funcionais característicos do biossurfactante (NH, CH2, C=O, COO-e PO2-). As medidas de potencial zeta mostraramuma possível interação eletrostática entre a hematita e o biossurfactante, a reversão de carga mudou do pH 5,3 para 3,5 após a interação. As medidas de ângulo de contato sugeremque após a interação, a hematita pode ter se tornado mais hidrofóbica, alterando o ângulo de contato de 40 graus para 60 graus. As medidas de tensão superficial foram realizadas para determinar as propriedades físico-químicas do biossurfactante. De acordo com os resultados, o biossurfactante apresentou características tensoativas, reduzindo a tensão superficial de 71 mN/m para 40 mN/m em 25 mg/L de biossurfactante.Finalmente, foram realizados testes de eletroflotação com duas frações granulométricas de minério de ferro (-38+20micrometro e -20 micrometro) para avaliar o pH (3-11), a concentração do biossurfactante (50-800 mg/L), a densidade de corrente (5,28-16mA/cm2) e a agitação da solução (300-700 rpm). Segundo os resultados obtidos, o aumento do pH prejudicou a recuperação metalúrgica e o teor de ferro. Os melhores resultados ocorreram em pH 3, esse comportamento pode ser atribuído a interações eletrostáticas que ocorrem nessa faixa de pH. O aumento da concentração do biossurfactante favoreceu a recuperação metalúrgica e o teor de ferro, este comportamento se manteve até 300 mg/L, acima deste valor ocorreu um declínio provocado provavelmente pela formação de micelas. O aumento da densidade de corrente também favoreceu a recuperação metalúrgica e o teor de ferro. Para a amostra com faixa granulométrica de -38+20 micrometro a recuperação metalúrgica máxima foi em torno de 83 porcento e teor de ferro de 59 porcento, e a amostra com granulometria inferior a 20 μmapresentou uma recuperação metalúrgica e teor de Fe máxima de aproximadamente de 98 porcento e 64 porcento respectivamente. Dessa forma, os resultados obtidos mostram um potencial uso da técnica de eletroflotação na recuperação de partículas finas e ultrafinas de minério de ferro, utilizando o biossurfactante extraído da bactéria Rhodococcus opacus. / [en] This work aimed to evaluate the electroflotation process of fine and ultrafine iron ore particles using biosurfactant extracted from Rhodococcus Opacus bacteria. Characterization studies of iron ore were carried out (particle size analysis, X-ray diffraction and X-ray fluorescence). Through infrared spectroscopy measurements it was possible to identify a possible interaction of the biosurfactant with the mineral, the hematite spectrum after the interaction showed characteristic functional groups of the biosurfactant (NH, CH2, C=O, COO-e PO2-).The measurements of zeta potential suggest a possible electrostatic interaction between the hematite and the biosurfactant, by shifting the isoelectric point from 5.3 to 3.5.Contact angle measurements suggest that after interaction, hematite may have become more hydrophobic, changing the contact angle from 40 degrees to 60 degrees.Surface tension measurements were performed to determine the physico-chemical properties of the biosurfactant. According to the results, the biosurfactant showed tensioactive characteristics, reducing the surface tension from 71 mN/m to 40 mN/m in 25 mg/L of biosurfactant, the formation of micelles occurred from 300mg/L of biosurfactant. Finally, electroflotation tests were performed with two size fractions of iron ore (-38+20 micrometre and -20 micrometre) to evaluate the pH (3-11), biosurfactant concentration (50-800 mg/L), current density (5.28-16mA/cm2) and solution agitation (300-700 rpm). According to the results obtained, the increase in the pH impaired the metallurgical recovery and iron grade. The best results occurred at pH 3, this behavior can be attributed to electrostatic interactions that occur in this pH range. The increase of the biosurfactant concentration favored metallurgical recovery and the iron grade, this behavior remained up to 300 mg/L, above this value occurred a decline probably caused by the formation of micelles. The increase in current density also favored metallurgical recovery and iron content. For the sample with particle size range from -38+20 micrometre the maximum metallurgical recovery was around 76 percent and 59 percent iron grade and the sample with particle size from -20 micrometre the maximum metallurgical recovery and grade of Fe were around 90 percent and 64 percent, respectively. The results obtained show a potential use of the electroflotation technique in the recovery of fine and ultrafine iron ore particles, using the biosurfactant extracted from the Rhodococcus opacus bacterium.

[pt] O uso de biossurfactantes derivados de matérias-primas de base biológica apresentam diversas vantagens sobre surfactantes convencionais como por exemplo: baixa toxicidade, alta cinética de degradação, versatilidade na flotação mineral podendo atuar como coletor ou espumante. O presente trabalho tem como objetivo avaliar o uso de biossurfactante extraído da bactéria Rhodococcus opacus na concentração da hematita do rejeito de minério de Ferro. Primeiramente, foram realizados estudos de caracterização da amostra (Análise granulométrica, química e mineralógica). Também foram feitas medições do Potencial zeta, espectroscopia no infravermelho com transformada de Fourier (FTIR) com o intuito de avaliar a interação do biossurfactante e do silicato de sódio na superfície mineral (hematita). As propriedades físico-químicas do biosurfactante foram determinadas pela tensão superficial. Diferentes estudos de microflotação (célula Patridge-Smith) e flotação em bancada (célula mecânica CDC) foram realizados para avaliar o pH (2, 3, 5, 7, 9, 11), a concentração de biossurfactante (1000, 2000, 4000, 6000 e 8000 g/t), e a concentração de depressor (100, 300, 600, 900 e 1200 g/t) na recuperação e teor de Fe. Além disso, foram realizados testes de flotação em circuito (rougher, cleaner, scavenger) visando aumentar a recuperação e teor de Fe. A concentração micelar crítica (CMC) do biossurfactante foi alcançada na concentração de 1 g/L. A recuperação de hematita foi possível em pH 3. De acordo com os estudos de espectroscopia no infravermelho e o potencial zeta houve interação entre o biossurfactante, e o silicato de sódio na superfície da hematita. A recuperação e teor de Fe na microflotação foi em torno de 37 porcento para uma concentração de biosurfactante de 6000 g/t em pH 3. A recuperação e teor de Fe na flotação em bancada (rougher) foi de aproximadamente 28,50 porcento e 44 porcento respectivamente, para uma concentração de biosurfactante de 2000 g/t em pH 3, também foram realizados testes em presença de silicato de sódio (600 g/t) obtendo aproximadamente 50,5 porcento de recuperação metalúrgica e 58 porcento de teor de Fe. Além disso, foram feitos ensaios em circuito de flotação (rougher, cleaner e scavenger) alcançando uma recuperação e teor de Fe em torno de 44 porcento e 65 porcento, respectivamente. Os resultados obtidos mostraram o potencial uso do biossurfactante como coletor na flotação da hematita do rejeito de minério de ferro, podendo futuramente ser aplicado na indústria mineral substituindo os coletores convencionais com o avanço dos estudos. / [en] The use of biosurfactants derived from bio-based feedstocks which present several advantages over conventional surfactants such as low toxicity, high degradation kinetics, versatility in mineral flotation, it can act as a collector or frother agent. The present work aims to evaluate the use of biosurfactant extracted from bacteria Rhodococcus opacus in the hematite concentration of the iron ore tailings. Firstly, characterization studies of the samples were carried out (granulometric, chemical and mineralogical analysis). Measurements of Zeta Potential, Fourier Transform Infrared Spectroscopy (FTIR) were also carried out to evaluate the interaction of the biosurfactant and sodium silicate on the mineral surface (hematite). The physicochemical properties of biosurfactant were determined by surface tension. Different microflotation studies (Patridge-Smith cell) and batch (CDC mechanical cell) were carried out to evaluate the pH (2, 3, 7, 9, 11), the biosurfactant concentration (1000, 2000, 4000, 6000 and 8000g/t), and the depressor concentration (100, 300, 600, 900 and 1200 g/t) on recovery and Fe grade. In addition, flotation circuit tests (rougher, cleaner, scavenger) were carried out aiming to increase recovery and Fe grade. The critical micellar concentration (CMC) of the biosurfactant was reached at a concentration of 1 g/L. Hematite recovery was possible at pH 3. According to the studies of infrared spectroscopy and zeta potential, there was interaction between the biosurfactant, the sodium silicate on the hematite surface. The Fe recovery and Fe grade in the microflotation was around 37 percent for 6000 g/t biosurfactant concentration at pH 3. The Fe recovery and Fe grade in the batch flotation (Rougher) was approximately 28.50 percent and 44 percent, respectively for 2000 g/t biosurfactant concentration at pH 3, tests were also performed in the presence of sodium silicate (600 g/t) obtaining around 50.50 percent Fe recovery and 58 percent Fe grade. Furthermore, flotation circuit tests (rougher, cleaner and scavenger) were carried out, achieving a Fe recovery and Fe grade around 44 percent and 64.8 percent, respectively. Therefore, the results showed the potential use of the biosurfactant as a collector in the hematite flotation from the iron ore tailings, it may be applied in the mining industry in the future, replacing conventional collectors with the advancement of the studies.

Red ochre, an iron-oxide mineral has been found in prehistoric sites worldwide, in many types of sites. It has been noted as being present, but has not been afforded the status of artifact with the same level of analysis as other artifacts such as ceramics or lithics. McCullough’s Run, a multi-component prehistoric cemetery in Indiana contained red ochre with cremation burials. By treating red ochre as more than incidental to the site, but as an artifact, new information about mortuary behavior was learned. The red ochre was from locally or regionally available materials, and was placed with the deceased during cremation. Therefore, red ochre must be treated as an artifact for comparing, contrasting information intraand inter-site. / Red ochre as an artifact -- What exactly is red ochre? -- Setting the stage -- The site : McCullough's Run, Bartholomew County, Indiana, 12B1036 -- Red ochre : the artifact. / Department of Anthropology

Although concentrated solar power can be used to produce power using traditional electricity generation, energy storage has become a problem due to the intermittent supply of solar energy. By using solar energy in chemical production processes, the solar energy can be stored in a useful chemical product. The purpose of this thesis will be to examine the possibilities of a new solar chemical cycle the produces iron and ethylene from hematite (a form of iron oxide) and ethane using concentrated solar power. These two products are important stepping stones in the production of steel and polymers. This process could allow for the current process of steel production to move away from processes using coal and towards a more sustainable process using the hydrogen formed from the ethane cracking process and solar energy. The thesis will include: (1) the development of a new solar powered iron and ethylene combined cycle, (2) a feasibility study of a Concentrated Solar Heat Supply System (CSHSS) being developed at Georgia Tech, and (3) an assessment of the proposed cycle. The assessment will include an estimate of production including a thermodynamic ASPEN model, assessment of research to realize actualization of the theoretical cycle, an exergy analysis, and a heat exchanger analysis for the exchange of heat between the CSHSS and the chemical process.

Pour mieux comprendre leurs propriétés, diverses nanostructures individuelles ont été étudiées à l’aide d’une technique couplant microscopie à force atomique et spectroscopie Raman confocale. Sous excitation lumineuse polarisée, la composition chimique, la structure et la présence de défauts a pu être précisée dans des nanobâtonnets d’oxydes métalliques (ZnO et α-Fe2O3). Sous irradiation laser résonnante, les spectres de nanotubes de carbone monoparoi enrobés de polymères ont révélé notamment l’absence de transfert de charge polymère-nanotube et un effet de désolvatation. Finalement, des feuillets de graphène oxydé et des ADNs double-brin peignés ont pu être préparés et caractérisés par spectroscopie Raman exaltée par effet de pointe en atteignant une résolution spatiale latérale voisine du rayon de courbure de l’apex de la pointe utilisée (12 nm), bien plus faible que la limite de diffraction, ce qui ouvre la voie à de nouveaux travaux spectroscopiques à l’échelle nanométrique. / To better understand their properties, various nanostructures have been studied using a technique combining atomic force microscopy and confocal Raman spectroscopy. Under polarized light excitation, the chemical composition, the structure and the presence of defects has been described in metal oxides nanorods (ZnO et α-Fe2O3). Under resonant laser excitation, Raman spectra of polymer-wrapped single-walled carbon nanotubes have revealed the absence of polymer-nanotube charge transfer and an effect due to desolvation. Finally, graphene oxide sheets and combed double-stranded DNAs have been prepared and characterized using tip-enhanced Raman spectroscopy with a lateral spatial resolution down to the curvature radius of the apex of the used tip (12 nm), well below the diffraction limit, which opens new opportunities for spectroscopic works at the nanometer scale.

En Afrique Australe, plusieurs sites attribués au Middle Stone Age (MSA) ont livré de grandes quantités de blocs « d’ocre », suggérant une longue tradition d’exploitation, bien avant l’occurrence des premières peintures rupestres. Les indices sur la fonction de ce matériau et le but pour lequel il a été utilisé sont rares, ce qui a conduit à plusieurs hypothèses. Certains auteurs leur ont associé des comportements symboliques tandis que d’autres ont montré qu’une utilisation « utilitaire » était possible. La question de la fonction et du rôle qu’occupait l’ocre est par ailleurs centrale dans le contexte du MSA, étant donnée l’émergence de plusieurs innovations, production de perles, de motifs gravés et technologies de taille spécifiques. Le site de Diepkloof Rock Shelter apparait particulièrement propice pour tenter de comprendre les comportements associés à l’exploitation de l’ocre, du fait de sa longue séquence fouillée récemment. Ce travail propose d’aborder les différentes étapes de l’exploitation de l’ocre, de la collecte des matières premières à l’utilisation, à partir de l’étude des blocs. Plusieurs méthodes d’observations et d’analyse physico-chimique (MEB-EDS, DRX, ICP-MS, TL, TEM et PIXE) ont été mises en œuvre pour identifier les matières premières, leur provenance, et les transformations opérées. Des prospections et une comparaison avec un corpus géologique ont permis de déterminer l’origine géologique des objets. Des expérimentations et une étude des traces d’usure ont permis d’identifier les transformations. Les résultats obtenus indiquent que des distances supérieures à 20 km ont été parcourues pour l’acquisition de certaines matières premières, dont on constate qu’elles sont plus riches en fer que celles accessibles localement. Les matières premières ont été presque systématiquement abrasées pour produire de la poudre. Ces résultats sont compatibles avec une fonction comme agent siccatif, couvrant ou colorant. Enfin, la continuité avec laquelle l’ocre est exploitée à Diepkloof malgré les changements survenus dans les techno-complexes, ainsi qu’un usage différent par rapport à d’autres sites, suggère que l’ocre a pu jouer un rôle dans les relations sociales inter et intra-groupes. / During the Middle Stone Age hundreds of ochre pieces were discovered on numerous southern Africansites long before the first occurrences of rock paintings, suggesting an important tradition of ochreexploitation. How this material was used remains however uncertain: while symbolic uses are often assumed,archaeological evidence also suggest utilitarian functions. The function and the value attributed to ochrematerials are of high interest for an overall perspective of the Middle Stone Age context, associated with theemergence of different innovations such as new lithic technology, bead production and geometric engravings.The site of Diepkloof Rock Shelter offers a unique opportunity to discuss these questions over a long recentlyexcavated MSA sequence. In this work the modalities of selection and transformation were investigated bystudying the main witnesses of ochre exploitation, the raw and processed pieces. The nature of the rawmaterials, their geological origin and the processing steps were determined by using macroscopic observationand different analytical methods (SEM‐EDXS, XRD, ICP‐MS, PIXE, TL and TEM). Surveys were carried out andarchaeological pieces were compared with geological materials in order to define where they come from.Experimentations have been performed in order to identify mechanical and chemical transformation. Theresults obtained show that some raw materials come from relative long distance, and that they are richer iniron oxide than more local sources. Wear traces indicate that ochre were ground to produce powder, whichcould function as drying agent, protective coating, or pigment. The continuity of this material’s exploitation allover the sequence, and regional uses of this material suggested by the comparison of Diepkloof with othersites, led us to assume that ochre may have favoured intra and inter‐group socials relationships at this time.

Esta Tese trata da investigação do efeito da nanoestruturação sobre algumas propriedades espectroscópicas de óxido de ferro(III), um dos mais importantes pigmentos vermelhos usados em bens culturais, o que foi conduzido por meio do estudo da cor de pigmentos de hematita (α-Fe2O3). A formação de eflorescências em duas pinturas (têmpera sobre tela e mural) foi também investigada visando compreender o papel da composição química e de fatores ambientais no desencadeamento de processos de degradação. Pigmentos naturais e sintéticos (cores de vermelho à púrpura) com morfologia definida foram caracterizados por espectroscopia de reflectância difusa (RD) no UVVIS-NIR, espectroscopia Raman (radiações excitantes em 532 nm, 632,8 nm, 785 nm e 1064 nm) e SEM-EDS. Alterações nas propriedades ópticas de hematitas com morfologias diferentes e após tratamento térmico foram correlacionadas com as alterações observadas nos espectros de RD no UV-VIS-NIR (principalmente abaixo de 500 nm e acima de 800 nm) e nos espectros Raman. Os resultados obtidos permitiram excluir o tamanho de partícula como fator determinante da cor de pigmentos de hematita, um argumento bastante usado na literatura ainda atualmente. Com o objetivo de avaliar o desempenho de equipamentos Raman miniaturizados, frequentemente empregados em investigações de bens culturais, espectros Raman de Fe2O3 amorfo obtidos em equipamento Raman portátil foram comparados com resultados obtidos em equipamentos de bancada. A necessidade do uso de maior potência de laser para compensar o pior desempenho desses equipamentos foi considerada como um fator importante para as alterações observadas nos espectros registrados. Esse fato é mais grave quando se emprega radiação de maior energia (532 nm), que pode afetar o espectro mesmo com potências mais baixas. A pintura Barco com bandeirinhas e pássaros (têmpera, 1955) de Alfredo Volpi, pertencente ao Museu de Arte Contemporânea da Universidade de São Paulo (MAC-USP), que apresentava sinais de eflorescências em sua superfície, foi analisada dentro do período de 3 anos em diferentes campanhas de amostragem. Os materiais coletados foram analisados por microscopia Raman, SEM-EDS e microscopia óptica. Os resultados indicaram que o material eflorescente apresentava natureza proteica, provavelmente proveniente da camada pictórica (têmpera), da camada de preparação (gelatina) ou de proteínas associadas a microorganismos (biodeterioração). Foi ainda considerada a hipótese da migração de aglutinante proteico da base de preparação da pintura para sua superfície como um fator inicial que poderia ter levado ao posterior surgimento de microorganismos na superfície da obra. As eflorescências salinas presentes na pintura mural da Sala do Trono do Palácio Nacional de Mafra, Portugal (séc. XVIII XIX) foram analisadas por microscopia Raman, µ-FTIR, µ-XRD, microscopia óptica, análise microbiológica, e identificadas como CaCO3, provavelmente formados devido à alta umidade verificada na região degradada da pintura. Fungos do gênero Cladosporium e Penicillium, usualmente associados à presença de fissuras e destacamentos, foram identificados nesta mesma região da pintura.Os resultados obtidos a partir dos estudos de casos das pinturas demonstraram a importância da parceria entre museus e órgãos públicos com laboratórios de pesquisa para a implementação de tecnologia dedicada ao monitoramento ambiental e detecção de processos de degradação em estágios iniciais. / This thesis presents the investigation of nanostructuration effects on some spectroscopic properties of iron oxides, one of the most important red pigments found in cultural heritage objects, which was conducted by studying the color of hematite pigments (α-Fe2O3). Two different paintings (tempera on canvas and mural painting) showing signs of efflorescence were investigated aiming to contribute to the understanding of the role played by microenvironment chemical composition and environment factors in triggering degradation processes. Natural and synthetic pigments (red to purple colors) with a defined morphology, were characterized by UV-VIS-NIR diffuse reflectance spectroscopy, Raman spectroscopy (532 nm, 632.8 nm, 785 nm and 1064 nm) and SEM-EDS. Changes in the optical properties of hematite with different morphologies and after heat treatment were correlated with the changes observed in the diffuse reflectance spectra (observed below 500 nm and above 800 nm) and in the Raman spectra. This allowed the particle size to be excluded as the main factor to affect the color of hematite pigments. In order to evaluate the performance of miniaturized Raman equipment, frequently used in cultural property investigations, amorphous Fe2O3 Raman spectra obtained with portable Raman equipment were compared with results from benchtop equipment. The need to use higher laser power to compensate for the poorer performance of these devices was considered as an important factor for the changes observed in the recorded spectra. This fact is more significant when using higher energy radiation (532 nm), which can affect the spectrum even at lower powers. The painting \"Barco com banderinhas e pássaros\" (tempera, 1955) by Alfredo Volpi, belonging to the Museum of Contemporary Art of the University of São Paulo (MACUSP), which showed signs of efflorescence on its surface, was analyzed during 3 years in different campaigns to sampling efflorescent material. The collected materials were analyzed using Raman microscopy, SEM-EDS and optical microscopy. The results indicated that the efflorescent material had a protein nature, probably from the pictorial layer (tempering), the preparation layer (gelatin) or proteins associated with microorganisms (biodeterioration). Nevertheless the results suggest that protein binder migration from the paint preparation layer to the surface may have occurred, which could possibly have led to the subsequent proliferation of microorganisms. The saline efflorescence presented in the mural painting of the Throne Room of the National Palace of Mafra, Portugal (18th-19th century) was analyzed using Raman microscopy, µ-FTIR, µ-XRD, UV-VIS optical microscopy and microbiological analysis. Saline efflorescence was identified as calcium carbonate, which was probably formed due to the moisture in the microenvironment of the degraded region. Fungi of the genus Cladosporium and Penicillium, usually associated to the presence of fissures and detachments, were identified in the same region of the painting. The results obtained from the case studies of the paintings demonstrated the importance of collaborations between museums and public agencies with research laboratories for the implementation of technology dedicated to environmental monitoring and detection of early stages of degradation processes.