In this study, the synergistic elfects of ethylene-propane and ethylene-dimethyl ester (DME) mirtures on soot formation were investigated experimentully using u coflow dilfusion flame burnen The soot volume fraction, soot particle diameter and number density were measured and compured to the homogenous mixture. Addition of DME and propane to the ethylene fuel increased soot volume fraction in the ethylene flames. The ethylene- propnne has more pronounced synergistic ffict in compsrison to the ethylene-DME flame* This is due to the fact that during the decomposition of propane some methyl radicals are generated, The reuctions related to these methyl radicals promote the formation of propargyl rodiculs and conseqaently the formation of benzene through propargyl self-reaction and finally to the soot formation. Althoagh DME decomposition produces methyl, the C-O bond in the DME removes some carbon from the reaction puth that produces soot, Hence the soot formation in ethylene-DME mixture is much slower than that in ethylene-propane mixtuFe,

The objective of this thesis is to experimentally investigate the performance of steam gasification of chars of pure coal (lignite, sub-bituminous), pure biomass (radiata pine, eucalyptus nitens) and their blends. The influences of gasification temperature, types of coal and biomass, coal-biomass blending ratio, alkali and alkaline earth metal (AAEM) in lignite, on specific gasification characteristics (producer gas composition and yield, char reactivity) were studied. In addition, synergistic effects in co-gasification of coal-biomass blend char were also investigated. This project is in accordance with objectives of the BISGAS Consortium. In this study, experiments were performed in a bench-scale gasifier at gasification temperatures of 850°C, 900°C and 950°C, respectively. Two types of coals (lignite and sub-bituminous) and two kinds of biomass (radiata pine and eucalyptus nitens) from New Zealand were selected as sample fuels. From these raw materials, the chars with coal-to-biomass blending ratios of 0:100 (pure coal), 20:80, 50:50, 80:20 and 100:0 (pure biomass), which were derived through the devolatilization at temperature of 900°C for 7 minutes, were gasified with steam as gasification agent. During the gasification tests, the producer gas composition and gas production were continuously analysed using a Micro gas chromatograph. When the gas production was undetectable, the gasification process was assumed to be completed and the gasification time was recorded. The gasification producer gas consisted of three main gas components: hydrogen (H2), carbon monoxide (CO) and carbon dioxide (CO2). The results from gasification of chars of individual solid fuels (coal or biomass) confirmed that biomass char gasification was faster than coal char gasification. The influences of gasification temperatures were shown as: when gasification temperature increased, the H2 yield increased in coal char gasification but decreased in biomass char gasification. In the meantime, CO yields increased while CO2 yields decreased in both coal char and biomass char gasification. In addition, the char reactivity of all the pure fuel samples increased with elevated gasification temperatures. The results from co-gasification of coal-biomass blend char exhibited that the syngas production rate, which is defined as the total gas production divided by the gasification completion time, was enhanced by an increase in gasification temperatures as well as an increase in the biomass proportion in the blend. The AAEM species played a significant catalytic role in both gasification of pure coal chars and co-gasification of coal-biomass blend chars. The presence of AAEM increased the producer gas yield and enhanced the char reactivity. The positive synergistic effects of the coal-biomass blending char on syngas production rate only existed in the co-gasification of lignite-eucalyptus nitens blend chars. The other blend chars showed either insignificant synergistic effects or negative effects on the syngas production rate.

In the process of biodiesel production, glycerol is produced as a byproduct in bulk amounts. The amount of glycerol supplied is larger than its demand thus stockpiling and acting as waste. As a solution, glycerol which is a highly functionalized molecule must be converted to value-added products. Several catalytic routes were thoroughly investigated including, hydrogenolysis, dehydration, pyrolysis, transesterification, etherification, carboxylation and electro-oxidation. All of these routes produce products of high economic interests. However, electro-oxidation seems to be the most promising as it runs under milder conditions and the selectivity may be easily tuned by varying the applied potential and the catalyst type. In addition, the electrical energy required may be provided by renewable energy sources. Some of the value-added products that may be produced by electrooxidation listed from highest economic value to lowest are glyceraldehyde, dihydroxyacetone, lactate, glycerate, tartronate (C₃ products) > mesooxalate, glycolate, oxalate (C₂ products) > and formate (C₁ products). Noble metals (Pt, Pd and Au) are considered to be the best for alcohol electrooxidation reactions as they present high electrocatalytic activity and selectivity. To date, research is focused on enhancing the activity and selectivity of noble metals by changing the nanoparticles morphology and adding adatoms/promoters/supports. On the other hand, these metals are non-abundant and expensive which limits their actual use in the industry. For this reason, non-noble metals (Ni and Co) have gained interest as potential alternatives. Particularly, nickel has proved to have significant activity, high durability and anti-poisoning capability for GEOR. A few studies presented enhancement in catalytic performance by varying the nanoparticles structure and adjusting the surface with a bimetallic promoter. However, there is still so much space for further research to enhance the catalytic performance and selectivity of Ni-based materials. In this thesis, carbon supported bimetallic NiₓBi₁₀₀₋ₓ [x= 100, 95, 90, 80, and 50 at.%] and Ni₉₅Bi₅/C mixed with small amounts of metal oxides (CeO₂, SnO₂ and Sb₂O₃:SnO₂) were studied for GEOR application. All catalysts were synthesized by facile sodium borohydride reduction method which can be easily scaled up. Transmission electron microscopy (TEM) and electron dispersive x-ray spectroscopy (EDS) techniques were implemented to gather physical characterizations of the as-synthesized bimetallic NiBi/C catalyst. Different electrochemical tests such as; cyclic voltammetry, linear sweep voltammetry and chronoamperometry were conducted using a conventional three electrode electrochemical cell and a potentiostat to get insight on the electrochemical performance of all catalysts. Finally, quantitative product analysis was generated by running continuous glycerol electrolysis experiments in a 25 cm2 cell accompanied by HPLC analysis. The nanoparticles size of Ni₉₅Bi₅/C was ≥6nm as determined by TEM images. Results indicated that tuning the nanoparticles size has an impact on both activity and selectivity of bimetallic carbon supported NiBi catalyst. For instance, the NiBi/C (≥6nm NP size) synthesized herein had 40% higher selectivity to C₃ products compared to NiBi/C (≤3nm NP size) reported in literature. Additionally, the selectivity of Ni-based catalysts to C₃ products were largely enhanced by developing bimetallic carbon supported NiBi catalysts of different Ni:Bi atomic ratios and adding metal oxides (CeO₂, SnO₂ and Sb₂O₃.SnO₂) to NiBi/C catalysts. Results indicate that addition of metal oxides greatly enhanced selectivity to C₃ products in the following order; Ni₉₅Bi₅/C-ATO (100%)> Ni/C-ATO (99.17%)> Ni₉₅Bi₅/C-ceria (98.05%)> Ni/C-ceria (78.29%)> Ni₉₅Bi₅/C (41.43%)> Ni/C (34.57%). However, the activity of Ni₉₅Bi₅/C-X [X=CeO₂, SnO₂, and Sb₂O₃:SnO₂] was lower than that of Ni₉₅Bi₅/C and Ni/C which was explained by the strong metal support interactions between metal oxides and nickel.

Due to the limited number of approved antioxidants for food applications, several alternative strategies to improve antioxidant performance have been developed by focusing on synergistic antioxidant interactions. Susceptibility to lipid oxidation in food systems is the result of the summation of antioxidative and prooxidative mechanisms. Understanding the sometimes paradoxical behavior of antioxidants and prooxidants is a vital key to design synergistic antioxidant systems suitable for particular foods. This research focused on 3 main strategies to improve the performance of antioxidant activity in oil-in-water emulsions. The first part of this research has been focused on inhibition of lipid oxidation by a combination of the modification of liposomal surfaces by chitosan-coating techniques along with addition of rosmarinic acid esters of varying polarity. Repelling metal ions away from the interface of positively charged liposomes can inhibit lipid oxidation (induced by Fe2+), and also reduce antioxidant loss by Fe3+ reduction. As a result, lipid oxidation can be inhibited synergistically because of a reduction in the prooxidant activity of iron. Second, understanding non-linear antioxidant behavior (the cut-off effect) of antioxidant esters in oil-in-water (O/W) emulsions was also studied to determine how the distributions and locations of antioxidants impacted their antioxidant activity. Antioxidant activity of rosmarinic acid was improved by esterification with alkyl chain lengths between 4 to 12 carbons due to increased ability to partitioning at the interface in oil-in-water emulsions. Surfactant micelles which could increase or decreased the concentration of the antioxidants at the emulsion droplet interface altered antioxidant activity. In the last part of this research, rosmarinic acid and its esters were found to be an excellent tool for studying how antioxidant location could impact its ability to interact with α-tocopherol in O/W emulsions. Synergistic, additive, and antagonistic effects were observed in the combinations between the rosmarinate esters with α-tocopherol. Increases in alkyl chain lengths of rosmarinic acid have influenced both the partitioning of the rosmarinate esters as well as their ability to they interact with α-tocopherol at the interface of oil-in-water emulsions. Fluorescence quenching and EPR studies showed that water soluble rosmarinic acid (R0) exhibited more interactions with á-tocopherol than any of the esters (R4-R20). Synergistic antioxidant interactions between rosmarinic acid and α-tocopherol could not be explained by electron transfer mechanisms, but formation of caffeic acid from rosmarinic acid. Due to the thermodynamic infeasibility and the fact that increases in α-tocopherol degradation rates, α-tocopherol could not be regenerated efficiently by rosmarinic acid. This formation of caffeic acid was proposed to be responsible of the synergistic activity of R0 and α-tocopherol since the formation of an additional antioxidant could further increase the oxidative stability of the emulsion.

No description available.

Tout composant envoyé dans l'espace est soumis à de nombreuses contraintes (radiations, température) qui peuvent conduire à une défaillance de l'ensemble du système. Dans un avenir proche, ces contraintes deviendront de plus en plus critiques à mesure que les agences spatiales développeront des missions visant d'autres planètes, telles que Jupiter, pour lesquelles la contrainte radiative est extrême. Dans ce travail, deux types d'effets dus aux radiations sont étudiés : les effets cumulatifs et les effets transitoires. L'un correspond à la dégradation induite par les radiations au cours du temps, tandis que l'autre correspond à un événement ponctuel qui peut se produire à tout moment lorsque le système est dans l'espace. Pour garantir le bon fonctionnement en vol, des normes de qualification des composants électroniques ont été élaborées par différentes agences spatiales. Toutes ces normes précisent que les effets cumulatifs et transitoires doivent être vérifiés à l'aide de composants intacts pour chaque essai. Par conséquent, les effets cumulatifs sont traités séparément des effets transitoires, alors qu'il y a une forte probabilité qu'ils apparaissent simultanément pendant une mission spatiale. L'étude des effets de synergie est alors le thème principal de cette thèse.Sur un amplificateur opérationnel bipolaire, la réponse de sortie du composant due à un événement transitoire est directement liée aux paramètres internes du composant, qui varient sous l’effet des radiations. A l’aide d’une comparaison entre trois amplificateurs opérationnels différents partageant la même référence, l'impact du design sur la dégradation due aux radiation est étudié.Récemment, des défaillances imprévues ont été reportées pour lesquelles le mode de défaillance semblait indiquer qu'une structure de protection contre les décharges électrostatiques (ESD) était en cause. Par conséquent, pour comprendre si ces protections peuvent causer des défaillances inattendues, la dégradation des « Gate Grounded n-MOSFET » (GGnMOS) est également étudiée. / Any system sent to space is submitted to many constraints (radiations, temperature) which may lead to a failure of the whole system. In a close future, these constraints will become more and more critical as the space agencies are developing missions aiming at others planets such as Jupiter for which the radiative constraint is extremely harsh. In this work, two types of radiation effects are studied: the cumulative effects and the transient effects. One corresponds to the radiation-induced degradation over time, while the other corresponds to a punctual event that can happen at any time when the system is in space. To ensure a proper functioning of a system sent to space, qualifications standards for electronic components have been developed by different space agencies. All of these standards specify that the components must be tested for cumulative and transient effects, using pristine components for each test. Therefore, cumulative effects are treated separately from transient effects, while there is a significant probability that they will appear simultaneously during a space mission. The study of the synergistic effects is then the main frame of this thesis.On a bipolar operational amplifier, the output response of the component due to a transient event is directly related to the internal parameters of the component, which vary over time once in space. Through a comparison between three different operational amplifier sharing the same reference, the impact of the design over the degradation is explained.Lately, some unexpected failures were reported for which the failure mode seemed to indicate that an Electrostatic Discharge (ESD) protection structure was involved. Therefore, to understand if those protections may cause some unexpected failures, the degradation of gate grounded n-MOSFET (GGnMOS) will be investigated next.

Thesis (M. Sc. (Microbiology)) --University of Limpopo, 2019 / Informal street traders and traditional health practitioners at Ga Maja (Limpopo Province) primarily offer consumers semi-processed herbal concoctions that are indicated to have blood-cleansing, immune-boosting, detoxifying, antidiarrheal, antiHIV/AIDS and pain-relieving therapeutic properties. The focus of this study was to validate the pharmacological effects and safety of these herbal concoctions as indicated by the traders. Five herbal concoctions and their medicinal plant recipies used for their preparation were purchased from five independent traders. A laboratory concoction was prepared according to the traders’ instructions. Possible microbial contaminants were identified using Matrix-assisted laser desorption/ionisation time-offlight mass spectrometry and VITEK 2. Nutritional content of the concoctions was determined by a plasma atomic emission spectrophotometer. Qualitative phytochemical analysis was determined using standard chemical tests and thin layer chromatography. Total polyphenol content was quantified calorimetrically. Antioxidant activity was quantified using 2, 2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing power assays. Antimicrobial activities were determined using a broth micro-dilution assay and bioautography. Anti-HIV-1 reverse transcriptase activity was used to determine the antiviral potential of the concoctions. Anti-inflammatory activity was determined using the cyclooxygenase inhibition assays and possible cytotoxic effects of the concoctions were evaluated using MTT cell viability assay. Growth on potato dextrose and nutrient agar plates indicated heavy microbial contamination. Sodium, potassium and zinc were most abundant in the concoctions. The concoctions had similar phytochemical profiles, and together with plant decoctions consisted primarily of polyphenolic constituents. Generally, some plant decoctions had higher antioxidant (EC50: 15.71 – 40.87 µg/mL) and antibacterial (MIC: 0.04 – 0.63 mg/mL) activities. The antimicrobial activities of the concoctions were as a result of synergistic effects of the compounds because no single compound was observed to have antimicrobial activities on the bioautograms. Combination studies showed that the combination of crude decoctions from different plant species resulted in reduced antioxidant, antibacterial and antifungal activities. The laboratory concoction had higher anti-HIV reverse transcriptase activity (EC50: 2.90 µg/mL) than the positive controls used (EC50: 36.65 – 40.90 µg/mL). The concoctions also demonstrated considerable antiinflammatory activity. The lack of standardisation of phytomedicines reduces their xxi pharmacological potential and consistency. However, this study validated the ethnopharmacological use of the different plant species and herbal concoctions towards the treatment of human immune-deficiency virus, pain caused by inflammation, infectious diarrhoea and for immune-boosting. This study also highlighted the complexities associated with combinations of aqueous extracts and the importance of appropriate knowledge on which plant species are to be mixed to enhance their therapeutic properties. Although the concoctions did not exhibit cyctotoxic effects, toxicities may arise from endotoxins produced by the microbial contaminants. Hygienic processing and packaging are essential to ensure that consumers receive quality products that are safe to consume.

A expansão das atividades humanas está associada a várias ameaças antrópicas que afetam a biodiversidade tropical, especialmente a perda e fragmentação de habitat, o continuado crescimento populacional humano e a expansão de infraestrutura, como estradas e rodovias. Embora seja esperado que as ameaças antrópicas interajam e criem mosaicos de manchas de habitat de diferentes qualidades, há ainda poucos estudos sobre os efeitos aditivos e interativos de diferentes ameaças sobre a biodiversidade ou sobre a capacidade de espécies nativas de usar remanescentes de diferentes qualidades. De fato, a maioria dos estudos focaram em apenas uma ou poucas ameaças isoladas, na escala do fragmento em vez da escala da paisagem e não consideraram as variações na qualidade dos remanescentes. Mamíferos de maior porte são um bom modelo de estudo porque possuem um conjunto de características que os tornam particularmente vulneráveis a várias ameaças antrópicas. Dada a dificuldade de obter dados sobre estas espécies elusivas em escalas espaciais adequadas, entrevistas com moradores locais vêm sendo cada vez mais usadas para acessar a distribuição de mamíferos de maior porte, e podem fornecer informações confiáveis. Através da estimativa da ocorrência de 15 espécies de mamíferos de maior porte por meio de entrevistas com o chefe de 12 unidades domésticas em cada uma de 20 paisagens em uma região de pós-fronteira de 1 milhão ha na Amazônia, investigamos: (i) que tipo de habitat e em qual escala espacial está associado com a ocorrência das espécies, e (ii) os efeitos, a importância relativa e as interações de quatro ameaças antrópicas - cobertura de habitat, fragmentação de habitat, densidade populacional humana e densidade de estrada - sobre a persistência das espécies. Dados de presença/ausência nos arredores de 227 unidades domésticas foram analisados usando modelos lineares generalizados mistos e seleção de modelos baseada no Critério de Informação de Akaike em duas etapas. A persistência das espécies maiores e ameaçadas não foi necessariamente afetada pela qualidade do habitat, mas elas responderam majoritariamente a cobertura de habitat em escalas maiores. A chance de persistência de todas as espécies - mesmo das duas menores, que não responderam à perda de habitat isoladamente - foi afetada por alguma combinação das quatro ameaças antrópicas. Efeitos aditivos entre as ameaças antrópicas foram mais importantes do que as interações entre elas na determinação da ocorrência de mamíferos de maior porte. Enquanto os efeitos da perda de habitat foram mais fortes do que os efeitos da fragmentação de habitat per se, a densidade de estradas foi tão importante quanto à perda de habitat para a ocorrência das espécies. Por último, não houve um padrão claro em termos do grau de ameaça e do tamanho corpóreo por trás da reposta dos mamíferos de maior porte a ameaças antrópicas combinadas. Nosso estudo sugere que áreas protegidas em terras públicas ou privadas na Amazônia devem ser grandes para assegurar a persistência de mamíferos de maior porte, mas podem incluir mosaicos de florestas primárias e secundárias. Os resultados também ressaltam a necessidade de considerar os impactos acumulados de múltiplas ameaças simultaneamente - em especial, as consequências da expansão da malha viária - em planejamentos e manejos, de maneira a evitar subestimar a chance de extinções. Evitar que paisagens na Amazônia se tornem muito desmatadas e alteradas é fundamental, dado que a persistência até mesmo das espécies mais comuns pode ser prejudicada, afetando um dos serviços ecossistêmicos mais importantes para moradores locais - a carne de caça - e potencialmente erodindo o valor que estes atribuem às florestas / The expansion of human activities is associated to a myriad of anthropogenic threats that affect tropical biodiversity, especially habitat loss and fragmentation, the continued human population growth and the expansion of infrastructure, as roads and highways. Although anthropogenic threats are expected to interact and to create mosaics of patches of varying quality, their additive and interaction effects on biodiversity, as well as the extent native species are able to use remnants of distinct quality, have yet been poorly studied. Indeed most studies focused on only one or few threats in isolation, on the patch rather than the landscape scale and did not considered the varying quality of remnants. Large mammals are a good study model as they have a set of traits that make them particularly vulnerable to several anthropogenic threats. Due to the difficulties in gathering data on these elusive species at adequate spatial scales, interviews with local residents have increasingly being used to access their distribution and can provide reliable information. By estimating the occurrence of 15 large mammal species through interviews with the head of 12 households within each of 20 landscapes across a 1-million ha post-frontier region in Amazonia, we investigated: (i) which habitat type at which spatial scale is associated with species occurrence, and (ii) the effects, relative importance and interactions of four anthropogenic threats - habitat cover, habitat fragmentation, human population density and road density - on species persistence. Presence/absence data across the surroundings of 227 households was analyzed using generalized linear mixed-effects models, and a two-step model selection based on Akaike’s Information Criteria. The persistence of larger and endangered species was not necessarily affected by habitat quality, but they responded to habitat cover mostly at larger spatial scales. The chance of persistence of all species - even the two smallest that were not affected by habitat loss alone - was disrupted by some combination of the four anthropogenic threats. Additive effects between anthropogenic threats were more important than their interaction in determining the occurrence of large mammals. While the effects of habitat loss were stronger than the effects of habitat fragmentation per se, road density was as important as habitat loss to species occurrence. Finally, there was no clear pattern in threat status or body size underlying the response of large mammals to combined anthropogenic threats. Our study suggest that protected areas in public or private lands in Amazonia should be large to secure the persistence of large mammals, but may include mosaics of primary and secondary forest. The findings also highlight the need to take into account the accumulated impacts of multiple threats simultaneously - particularly, the consequences of the expansion of the road network - in planning and management, as a way to avoid underestimating the chance of extinctions. Preventing Amazonian landscapes to become heavily deforested and altered is critical, as the persistence of even common species can be impaired, affecting one of the most important ecosystem services provided to local residents - bushmeat - and potentially eroding the value people attribute to forests

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.

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.