Chemical characterization and anticorrosion properties of corrosion products formed on pure copper in synthetic rainwater of Rio de Janeiro and Sao Paulo

This work aims to characterize corrosion products formed on copper samples exposed to synthetic rainwater of Rio Janeiro and Sao Paulo. XRD and XPS were employed to determine their composition, while electrochemical techniques were used to evaluate their protective properties. XRD and XPS indicated the thickening of the corrosion layer with time. Electrochemical results showed that the protectiveness of the corrosion layer depends on the solution composition. Based on our findings a corrosion mechanism for copper in simulated rainwater is proposed where the role of NH(4)(+) ions in the cuprite layer partial regeneration is taken into account. (C) 2009 Elsevier Ltd. All rights reserved.

The chemistry of copper patination

The chemistry of copper patination was investigated by two series of experiments. The chemistry of an aqueous copper-sulphate solution was studied at concentrations and pH values near those predicted in an electrolyte on copper exposed to the atmosphere. The electrochemical reactions in an electrolyte in contact with cuprite were investigated in a reaction vessel which used cuprite powder in artificial rainwater to study the electrochemistry of the atmospheric corrosion and patination of copper. Typical sulphate concentrations in rainwater are sufficient to precipitate posnjakite (Cu4SO4(OH)(6)2H(2)O)), a possible precursor to brochantite, within an hour of wetting a cuprite surface. Brochantite (Cu4SO4(OH)(6)), the most commonly found copper salt in natural patinas is responsible for their green appearance. Precipitation of brochantite from the electrolyte resulted from an increase in pH due to the cathodic reduction of oxygen and an increase in cupric ion concentrations by cuprite oxidation. (C) 1998 Elsevier Science Ltd. All rights reserved.

Atmospheric corrosion of copper at Heron Island

Atmospheric corrosion tests have been conducted at Heron Island, Queensland, a low SO2 marine environment. The corrosion rates for copper followed the linear bi-logarithmic law. X-ray diffraction identified atacamite (basic copper chloride) and cuprite (cuprous oxide) as the predominant corrosion products. Biogenic and anthropogenic sources of pollution did not have a measurable influence.

Unsupervised hyperspectral signal subspace identification

Hyperspectral imaging sensors provide image data containing both spectral and spatial information from the Earth surface. The huge data volumes produced by these sensors put stringent requirements on communications, storage, and processing. This paper presents a method, termed hyperspectral signal subspace identification by minimum error (HySime), that infer the signal subspace and determines its dimensionality without any prior knowledge. The identification of this subspace enables a correct dimensionality reduction yielding gains in algorithm performance and complexity and in data storage. HySime method is unsupervised and fully-automatic, i.e., it does not depend on any tuning parameters. The effectiveness of the proposed method is illustrated using simulated data based on U.S.G.S. laboratory spectra and real hyperspectral data collected by the AVIRIS sensor over Cuprite, Nevada.

Hyperspectral signal subspace estimation

Given an hyperspectral image, the determination of the number of endmembers and the subspace where they live without any prior knowledge is crucial to the success of hyperspectral image analysis. This paper introduces a new minimum mean squared error based approach to infer the signal subspace in hyperspectral imagery. The method, termed hyperspectral signal identification by minimum error (HySime), is eigendecomposition based and it does not depend on any tuning parameters. It first estimates the signal and noise correlation matrices and then selects the subset of eigenvalues that best represents the signal subspace in the least squared error sense. The effectiveness of the proposed method is illustrated using simulated data based on U.S.G.S. laboratory spectra and real hyperspectral data collected by the AVIRIS sensor over Cuprite, Nevada.

Hyperspectral unmixing algorithm via dependent component analysis

This paper introduces a new method to blindly unmix hyperspectral data, termed dependent component analysis (DECA). This method decomposes a hyperspectral images into a collection of reflectance (or radiance) spectra of the materials present in the scene (endmember signatures) and the corresponding abundance fractions at each pixel. DECA assumes that each pixel is a linear mixture of the endmembers signatures weighted by the correspondent abundance fractions. These abudances are modeled as mixtures of Dirichlet densities, thus enforcing the constraints on abundance fractions imposed by the acquisition process, namely non-negativity and constant sum. The mixing matrix is inferred by a generalized expectation-maximization (GEM) type algorithm. This method overcomes the limitations of unmixing methods based on Independent Component Analysis (ICA) and on geometrical based approaches. The effectiveness of the proposed method is illustrated using simulated data based on U.S.G.S. laboratory spectra and real hyperspectral data collected by the AVIRIS sensor over Cuprite, Nevada.

A Capela de S. João Baptista: o esplendor do mosaico vítreo - Caracterização dos elementos colorantes

Dissertação para obtenção do Grau de Mestre em Conservação e Restauro

Electronic structure and properties of Cu2O

The structural and electronic properties of Cu2O have been investigated using the periodic Hartree-Fock method and a posteriori density-functional corrections. The lattice parameter, bulk modulus, and elastic constants have been calculated. The electronic structure of and bonding in Cu2O are analyzed and compared with x-ray photoelectron spectroscopy spectra, showing a good agreement for the valence-band states. To check the quality of the calculated electron density, static structure factors and Compton profiles have been calculated, showing a good agreement with the available experimental data. The effective electron and hole masses have been evaluated for Cu2O at the center of the Brillouin zone. The calculated interaction energy between the two interpenetrated frameworks in the cuprite structure is estimated to be around -6.0 kcal/mol per Cu2O formula. The bonding between the two independent frameworks has been analyzed using a bimolecular model and the results indicate an important role of d10-d10 type interactions between copper atoms.

Electronic structure and properties of Cu2O

The structural and electronic properties of Cu2O have been investigated using the periodic Hartree-Fock method and a posteriori density-functional corrections. The lattice parameter, bulk modulus, and elastic constants have been calculated. The electronic structure of and bonding in Cu2O are analyzed and compared with x-ray photoelectron spectroscopy spectra, showing a good agreement for the valence-band states. To check the quality of the calculated electron density, static structure factors and Compton profiles have been calculated, showing a good agreement with the available experimental data. The effective electron and hole masses have been evaluated for Cu2O at the center of the Brillouin zone. The calculated interaction energy between the two interpenetrated frameworks in the cuprite structure is estimated to be around -6.0 kcal/mol per Cu2O formula. The bonding between the two independent frameworks has been analyzed using a bimolecular model and the results indicate an important role of d10-d10 type interactions between copper atoms.

Hyperspectral Mineral Identification using SVM and SOM

Remote sensing techniques involving hyperspectral imagery have applications in a number of sciences that study some aspects of the surface of the planet. The analysis of hyperspectral images is complex because of the large amount of information involved and the noise within that data. Investigating images with regard to identify minerals, rocks, vegetation and other materials is an application of hyperspectral remote sensing in the earth sciences. This thesis evaluates the performance of two classification and clustering techniques on hyperspectral images for mineral identification. Support Vector Machines (SVM) and Self-Organizing Maps (SOM) are applied as classification and clustering techniques, respectively. Principal Component Analysis (PCA) is used to prepare the data to be analyzed. The purpose of using PCA is to reduce the amount of data that needs to be processed by identifying the most important components within the data. A well-studied dataset from Cuprite, Nevada and a dataset of more complex data from Baffin Island were used to assess the performance of these techniques. The main goal of this research study is to evaluate the advantage of training a classifier based on a small amount of data compared to an unsupervised method. Determining the effect of feature extraction on the accuracy of the clustering and classification method is another goal of this research. This thesis concludes that using PCA increases the learning accuracy, and especially so in classification. SVM classifies Cuprite data with a high precision and the SOM challenges SVM on datasets with high level of noise (like Baffin Island).

Electronic structure and properties of Cu2O

The structural and electronic properties of Cu2O have been investigated using the periodic Hartree-Fock method and a posteriori density-functional corrections. The lattice parameter, bulk modulus, and elastic constants have been calculated. The electronic structure of and bonding in Cu2O are analyzed and compared with x-ray photoelectron spectroscopy spectra, showing a good agreement for the valence-band states. To check the quality of the calculated electron density, static structure factors and Compton profiles have been calculated, showing a good agreement with the available experimental data. The effective electron and hole masses have been evaluated for Cu2O at the center of the Brillouin zone. The calculated interaction energy between the two interpenetrated frameworks in the cuprite structure is estimated to be around -6.0 kcal/mol per Cu2O formula. The bonding between the two independent frameworks has been analyzed using a bimolecular model and the results indicate an important role of d10-d10 type interactions between copper atoms.

Mineralizações auríferas hospedadas na faixa metavulcano-sedimentar Jacuí-Bom Jesus da Penha - Sudoeste de Minas Gerais

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On the degradation mechanisms under the influence of pedological factors through the study of archeological bronze patina

This experimental thesis concerns the study of the long-term behaviour of ancient bronzes recently excavated from burial conditions. The scientific interest is to clarify the effect of soil parameters on the degradation mechanisms of ancient bronze alloy. The work took into consideration bronzes recovered from the archaeological sites in the region of Dobrudja, Romania. The first part of research work was dedicated to the characterization of bronze artefacts using non destructive (micro-FTIR, reflectance mode) and micro-destructive (based on sampling and analysis of a stratigraphical section by OM and SEM-EDX) methods. Burial soils were geologically classified and analyzed by chemical methods (pH, conductivity, anions content). Most of objects analyzed showed a coarse and inhomogeneous corroded structure, often made up of several corrosion layers. This has been explained by the silt nature of soils, which contain low amount of clay and are, therefore, quite accessible to water and air. The main cause of a high dissolution rate of bronze alloys is the alternate water saturation and instauration of the soil, for example on a seasonal scale. Moreover, due to the vicinity of the Black Sea, the detrimental effect of chlorine has been evidenced for few objects, which were affected by the bronze disease. A general classification of corrosion layers was achieved by comparing values of the ratio Cu/Sn in the alloy and in the patina. Decuprification is a general trend, and enrichment of copper within the corrosion layers, due to the formation of thick layers of cuprite (Cu2O), is pointed out as well. Uncommon corrosion products and degradation patterns were presented as well, and they are probably due to peculiar local conditions taking place during the burial time, such as anaerobic conditions or fluctuating environmental conditions. In order to acquire a better insight into the corrosion mechanisms, the second part of the thesis has regarded simulation experiments, which were conducted on commercial Cu-Sn alloys, whose composition resembles those of ancient artefacts one. Electrochemical measurements were conducted in natural electrolytes, such as solutions extracted from natural soil (sampled at the archaeological sites) and seawater. Cyclic potentiodynamic experiments allowed appreciating the mechanism of corrosion in both cases. Soil extract’s electrolyte has been evaluated being a non aggressive medium, while artificial solution prepared by increasing the concentration of anions caused the pitting corrosion of the alloy, which is demonstrated by optical observations. In particular, electrochemical impedance spectroscopy allows assessing qualitatively the nature of corroded structures formed in soil and seawater. A double-structured layer is proposed, which differ, in the two cases, for the nature of the internal passive layer, which result defectiveness and porous in case of seawater.

Geochemistry of rocks from Palmer Archipel

During the antarctic summer season in 1984 and 1986 field studies and laboratory investigations of the Mesozoic Intrusive Suite of the Palmer Archipel were carried out in cooperation with the Chilean Antarctic Institute and the University of Concepcion, Volcanic formations and intrusive series are the dominant exposed rocks together with very subordinate metasediments. Different petrological and isotopic data allow to divide the Antarctic Intrusive Suite into two intrusive types: a) Palmer Batholith (Lower Cenozoic) b) Costa Danco intrusive rocks (Upper Cretaceous). Both types belong to a calc-alkaline series. The granitoid rocks show an I-type-affinity. Ore minerals (pyrite, chalcopyrite, bornite, covellite, cuprite, pyrrhotite, magnetite and ilmenite) are mainly restricted to the intermediate rock types (e. g. granodiorites}. Propylitisation and kaolinisation are the observed alteration types, which suggest, together with the disseminated and vein-like ore fabrics the comparison with the andean Porphyry-Copper- and vein-type-deposits. The volcanic formations are subdivided into a) the Upper Cretaceous Wiencke Formation, which is composed of andesites and andesitic breccias, and b) into the Jurassic Lautaro Formation with basaltic, andesitic, dacitic and some rhyolitic rocks together with volcanic breccias. These calc-alkaline volcanic rocks apparently are part of an island are. A strong alteration of primary minerals is very common; however, the low ore mineral content does not change significantly within the different alteration types.