Studies on Chemical Bath Deposited Semiconducting Copper Selenide and Iron Sulfide Thin Films Useful For Photovoltaic Applications

Chemical bath deposition (CBD)is one of the simplest, very convient and probably the cheapest method for thin film preparation. Photovoltaic is the cleanest and the most efficient mode of conversion of energy to electrical power. Silicon is the most popular material in this field. The present study on chemical bath deposited semiconducting copper selenide and iron sulfide thin films useful for photovoltaic applications. Semiconducting thin films prepared by chemical deposition find applications as photo detectors, solar control coatings and solar cells. Copper selenide is a p-type semiconductor that finds application in photovolitics. Several heterojunction systems such as Cu2-xSe/ZnSe (for injection electro luminescence), Cu2Se/AgInSe2 and Cu2Se/Si (for photodiodes), Cu2-xSe/CdS, Cu2-xSe/CdSe, CuxSe/InP and Cu2-xSe/Si for solar cells are reported. A maximum efficiency of 8.3% was achieved for the Cu2-xSe/Si cell, various preparation techniques are used for copper selenide like vacuum evaporation, direct reaction, electrodeposition and CBD. Instability of the as-prepared films was investigation and is accounted as mainly due to deviation from stoichiometry and the formation of iron oxide impurity. A sulphur annealing chamber was designed and fabricated for this work. These samples wee also analysed using optical absorption technique, XPS (X-ray Photoelectron Spectroscopy) and XRD.(X-Ray Diffraction).The pyrite films obtained by CBD technique showed amorphous nature and the electrical studies carried out showed the films to be of high resistive nature. Future work possible in the material of iron pyrite includes sulphur annealing of the non-stochiometric iron pyrite CBD thin films in the absence of atmospheric oxygen

Characteristics of sulfide corrosion products on 316L stainless steel surfaces in the presence of sulfate-reducing bacteria

It has been found that microbial communities play a significant role in the corrosion process of steels exposed in aquatic and soil environments. Biomineralization influenced by microorganisms is believed to be responsible for the formation of corrosion products via complicated pathways of electron transfer between microbial cells and the metal. In this study, sulfide corrosion products were investigated for 316L stainless steel exposed to media with sulfate-reducing bacteria media for 7 weeks. The species of inorganic and organic sulfides in the passive film on the stainless steel were observed by epifluorescence microscope, environmental scanning electron microscope combined with energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The transformation from metal oxides to metal sulfides influenced by sulfate-reducing bacteria is emphasized in this paper. (c) 2005 Elsevier B.V. All rights reserved.

The effects of manipulation of sedimentary iron and organic matter on sediment biogeochemistry and seagrasses in a subtropical carbonate environment

The microbial metabolism of organic matter (OM) in seagrass beds can create sulfidic conditions detrimental to seagrass growth; iron (Fe) potentially has ameliorating effects through titration of the sulfides and the precipitation of iron-sulfide minerals into the sediment. In this study, the biogeochemical effects of Fe availability and its interplay with sulfur and OM on sulfide toxicity, phosphorous (P) availability, seagrass growth and community structure were tested. The availability of Fe and OM was manipulated in a 2 × 2 factorial experiment arranged in a Latin square, with four replicates per treatment. The treatments included the addition of Fe, the addition of OM, the addition of both Fe and OM as well as no addition. The experiment was conducted in an oligotrophic, iron-deficient seagrass bed. Fe had an 84.5% retention efficiency in the sediments with the concentration of Fe increasing in the seagrass leaves over the course of the experiment. Porewater chemistry was significantly altered with a dramatic decrease in sulfide levels in Fe addition plots while sulfide levels increased in the OM addition treatments. Phosphorus increased in seagrass leaves collected in the Fe addition plots. Decreased sulfide stress was evidenced by heavier δ34S in leaves and rhizomes from plots to which Fe was added. The OM addition negatively affected seagrass growth but increased P availability; the reduced sulfide stress in Fe added plots resulted in elevated productivity. Fe availability may be an important determinant of the impact that OM has on seagrass vitality in carbonate sediments vegetated with seagrasses.

Concrete deterioration due to sulfide-bearing aggregates

Dans la région de Trois-Rivières (Québec, Canada), plus de 1 000 bâtiments résidentiels et commerciaux montrent de graves problèmes de détérioration du béton. Les problèmes de détérioration sont liés à l’oxydation des sulfures de fer incorporés dans le granulat utilisé pour la confection du béton. Ce projet de doctorat vise à mieux comprendre les mécanismes responsables de la détérioration de béton incorporant des granulats contenant des sulfures de fer, et ce afin de développer une méthodologie pour évaluer efficacement la réactivité potentielle de ce type de granulats. Un examen pétrographique détaillé de carottes de béton extraites de fondations résidentielles montrant différents degré d’endommagement a été réalisé. Le granulat problématique contenant des sulfures de fer a été identifié comme un gabbro à hypersthène incorporant différentes proportions (selon les différentes localisations dans les deux carrières d’origine) de pyrrhotite, pyrite, chalcopyrite et pentlandite. Les produits de réaction secondaires observés dans les échantillons dégradés comprennent des formes minérales de "rouille", gypse, ettringite et thaumasite. Ces observations ont permis de déterminer qu’en présence d’eau et d’oxygène, la pyrrhotite s’oxyde pour former des oxyhydroxides de fer et de l’acide sulfurique qui provoquent une attaque aux sulfates dans le béton. Tout d’abord, la fiabilité de l’approche chimique proposée dans la norme européenne NF EN 12 620, qui consiste à mesurer la teneur en soufre total (ST,% en masse) dans le granulat pour détecter la présence (ou non) de sulfures de fer, a été évaluée de façon critique. Environ 50% (21/43) des granulats testés, représentant une variété de types de roches/lithologies, a montré une ST > 0,10%, montrant qu’une proportion importante de types de roches ne contient pas une quantité notable de sulfure, qui, pour la plupart d’entre eux, sont susceptibles d’être inoffensifs dans le béton. Ces types de roches/granulats nécessiteraient toutefois d’autres tests pour identifier la présence potentielle de pyrrhotite compte tenu de la limite de ST de 0,10 % proposée dans les normes européennes. Basé sur une revue exhaustive de la littérature et de nombreuses analyses de laboratoire, un test accéléré d’expansion sur barres de mortier divisé en deux phases a ensuite été développé pour reproduire, en laboratoire, les mécanismes de détérioration observés à Trois-Rivières. Le test consiste en un conditionnement de 90 jours à 80°C/80% RH, avec 2 cycles de mouillage de trois heures chacun, par semaine, dans une solution d’hypochlorite de sodium (eau de javel) à 6% (Phase I), suivi d’une période pouvant atteindre 90 jours de conditionnement à 4°C/100 % HR (Phase II). Les granulats ayant un potentiel d’oxydation ont présenté une expansion de 0,10 % au cours de la Phase I, tandis que la formation potentielle de thaumasite est détectée par le regain rapide de l’expansion suivi par la destruction des échantillons durant la Phase II. Un test de consommation d’oxygène a également été modifié à partir d’un test de Drainage Minier Acide, afin d’évaluer quantitativement le potentiel d’oxydation des sulfures de fer incorporés dans les granulats à béton. Cette technique mesure le taux de consommation d’oxygène dans la partie supérieure d’un cylindre fermé contenant une couche de matériau compacté afin de déterminer son potentiel d’oxydation. Des paramètres optimisés pour évaluer le potentiel d’oxydation des granulats comprennent une taille de particule inférieure à 150 μm, saturation à 40 %, un rapport de 10 cm d’épaisseur de granulat par 10 cm de dégagement et trois heures d’essai à 22ᵒC. Les résultats obtenus montrent que le test est capable de discriminer les granulats contenant des sulfures de fer des granulats de contrôle (sans sulfures de fer) avec un seuil limite fixé à 5% d’oxygène consommé. Finalement, un protocole d’évaluation capable d’estimer les effets néfastes potentiels des granulats à béton incorporant des sulfures de fer a été proposé. Le protocole est divisé en 3 grandes phases: (1) mesure de la teneur en soufre total, (2) évaluation de la consommation d’oxygène, et (3) un test accéléré d’expansion sur barres de mortier. Des limites provisoires sont proposées pour chaque phase du protocole, qui doivent être encore validées par la mise à l’essai d’un plus large éventail de granulats.

Estudo de corrosão em sistema simulado de retortagem para processamento de folhelhos pirobetuminosos

O aço inoxidável é amplamente utilizado em sistemas para processamento e obtenção de derivados de folhelhos pirobetuminosos. Em função dos problemas de corrosão, originários da composição química dos folhelhos e do processamento em si, são gastos anualmente valores expressivos em manutenção e paradas programadas para reparos nestes sistemas. O presente trabalho busca estudar o processo de corrosão do aço inoxidável AISI 304L em meio simulado de retortagem de folhelhos, em condições de alta temperatura e em presença de elevados teores de enxofre, orgânico e inorgânico, empregando técnicas microscópicas e eletroquímicas. Os resultados mostraram que a temperatura influencia diretamente no processo de corrosão do aço, causando modificação na camada externa de óxidos. Este processo é agravado com a presença de sulfetos no meio, havendo formação, principalmente, de sulfetos de ferro sobre a superfície do aço inoxidável AISI 304L e consequente aumento do processo de corrosão. Foi observado que o enxofre de origem orgânica promove maior destruição da camada de óxido protetor do aço e aumento na formação do filme de sulfeto aderido à superfície deste material. Verificou-se ainda que o processo corrosivo é predominantemente químico, sendo o filme formado considerado protetor, do ponto de vista eletroquímico, no meio eletrolítico estudado

3D Fe3S4 flower-like microspheres: high-yield synthesis via a biomolecule-assisted solution approach, their electrical, magnetic and electrochemical hydrogen storage properties

Well-defined 3D Fe3S4 flower-like microspheres were synthesized via a simple biomolecule-assisted hydrothermal process for the first time. On the basis of a series of contrast experiments, the probable growth mechanism and fabrication process of the products were proposed. The electrical conductivity property of the as-synthesized Fe3S4 sample exhibited a rectifying characteristic when a forward bias was applied for the bottom-contacted device. The magnetic properties of the products were studied as well and the results demonstrated that the products presented ferromagnetic properties related to the corresponding microstructure. In addition, we first verified that the Fe3S4 flower-like microspheres could store hydrogen electrochemically, and a discharge capacity of 214 mA h g(-1) was measured without any activation under normal atmospheric conditions at room temperature.

Corrosion of carbon steel influenced by anaerobic biofilm in natural seawater

The bacteria in the anaerobic biofilm on rusted carbon steel immersed in natural seawater were characterized by culturing and molecular biology techniques. Two types of anaerobic bacterium, sulfate-reducing bacteria (SRB) Desulfovibrio caledoniensis and iron-reducing bacteria Clostridium sp. uncultured were found. The compositions of the rust layer were also analyzed and we found that iron oxide and sulfate green rust were the major components. To investigate the corrosion mechanisms, electrochemical impedance spectra was obtained based on the isolated sulfate-reducing bacteria and mixed bacteria cultured from rust layer in laboratory culture conditions. We found that single species produced iron sulfide and accelerated corrosion, but mixed species produced sulfate green rust and inhibited corrosion. The anaerobic corrosion mechanism of steel was proposed and its environmental significance was discussed. (c) 2008 Elsevier Ltd. All rights reserved.

Effect of sulfate-reducing bacteria on corrosion behavior of mild steel in sea mud

Microbiologically influenced corrosion (MIC) is very severe corrosion for constructions buried under sea mud environment. Therefore it is of great importance to carry out the investigation of the corrosion behavior of marine steel in sea mud. In this paper, the effect of sulfate-reducing bacteria (SRB) on corrosion behavior of mild steel in sea mud was studied by weight loss, dual-compartment cell, electronic probe microanalysis (EPMA), transmission electron microscopy (TEM).combined with energy dispersive X-ray analysis (EDX) and electrochemical impedance spectroscopy (EIS). The results showed that corrosion rate and galvanic current were influenced by the metabolic activity of SRB. In the environment of sea mud containing SRB, the original corrosion products, ferric (oxyhydr) oxide, transformed to iron sulfide. With the excess of the dissolved H2S, the composition of the protective layer formed of FeS transformed to FeS2 or other non-stoichiometric polysulphide, which changed the state of the former layer and accelerated the corrosion process.

黄铁矿热转变过程的岩石磁学研究

Pyrite is the most stable iron-sulfide in reduced environment, and plays an important role in geochemical iron-sulfur cycling of sediments. Thus, the presence of pyrite in sediments and rocks is an important indicator of sedimentary environments. Previous studies on the thermal products of pyrite showed that all of the products (e.g., pyrrhotite, magnetite, hematite) have strong capability of carrying remanence. To deepen our understanding of the environmental and paleomagnetic significances of pyrite, the mineral transformation processes of pyrite upon heating were systematically investigated in this study using intergrated rock magnetic experiments (in both argon and air atmospheres) and X-ray diffraction analysis. The room temperature susceptibility of the paramagnetic pyrite is about 2.68×10-5 SI. In argon atmosphere (reducing environment), pyrite was transformed into monoclinic stable single domain (SD) pyrrhotite above 440 C. The corresponding coercive force and remanence coercivity are about 20 mT and 30 mT, respectively. In contrast, in air atmosphere (oxidation environment), the intermediate thermal products of pyrite are magnetite and pyrrhotite, which were quickly further oxidated to SD hematite, which has coercivity of about 1400 mT. In addition, the hematite particles gradually grow from SD to PSD grain size region by multiple heating runs. The transformation processes of pyrite in oxidation atomosphere can be interpreted by three possible pathways: (1) pyrite→magnetite→hematite; (2) pyrite→pyrrhotite→magnetite→hematite; and (3) pyrite→pyrrhotite→hematite. Low-temperature magnetic experiments show no transitions for pyrite. Despite that low-temperature magnetic method is not suitable for identification of pyrite, it is clear in this study that the high-temperature thermomagnetic measurements (e.g.,  -T and J-T curves) are very sensitive to the presence of pyrite in sediments and rocks. Nevertheless, for the thermal treatment products, low-temperature magnetic measurements showed the 34 K transition of pyrrhotite and the 250 K Morine transition of hematite. Iron-sulfide has also been found on Martian meteorolites by other workers. Therefore, systematic study of rock magnetism of pyrite (and other iron-sulfides) and their products will have great significances for both paleomagnetism and planetary magnetism.

Biodeposition and Biogeochemical Processes in Shallow, Mesohaline Sediments of Chesapeake Bay

Stocks of the eastern oyster, Crassostrea virginica, have been declining in Chesapeake Bay since the late 19th century, and current strategies involve restoring culture of Crassostrea virginica on-bottom and in devices suspended within the water column. Sub-tidal suspension culture of Crassostrea virginica in Chesapeake Bay occurs mostly in sheltered inlets and tidal creeks and, thereby, has the potential to influence shallow water biogeochemical processes. To assess the influence of Crassostrea virginica biodeposits and benthic microalgae on sediment nitrogen and phosphorus exchange, field studies with Crassostrea virginica held in aquaculture floats and laboratory experiments were conducted. Enhanced organic nitrogen deposition from Crassostrea virginica biodeposits led to gradual increases in surface sediment nitrogen and pore water ammonium concentrations; however, modifications to pore water concentrations were not always expressed at the sediment-water interface. Benthic microalgae often modulated the influence of biodeposits on sediment nitrogen exchange but, as observed in laboratory experiments, the supply of nitrogen from Crassostrea virginica biodeposits may exceed their biological demand. Organic carbon from biodeposits had varying influences on aerobic respiration but consistently stimulated anaerobic metabolism. Shifts in net phosphorus exchange were driven by this anaerobic remineralization and concentrations of iron and manganese oxy(hydr)oxides, with transitions in fluxes coinciding with changes in benthic photosynthesis and oxidation of surface sediments. Manganese and iron oxy(hydr)oxides from biodeposits supported incorporation of added phosphorus and prevented exchange at the sediment-water interface in the absence of iron-sulfide mineral formation. Differences in the response of shallow water sediments to Crassostrea virginica biodeposits were due to the quality and quantity of biodeposits supplied, as well as the spatial and temporal variability within these sediments. Initial conditions and corresponding reference sediments illustrated the potential for sediment biogeochemistry and nutrient exchange from tidal creek sediments to vary spatially and temporally on relatively small scales. Factors influencing variability within tidal creek sediments were related to shifts in riverine freshwater inputs, macroalgal blooms, nutrient concentrations in overlying waters, and bioirrigation from the clam, Macoma balthica.

The heart of a dragon: 3D anatomical reconstruction of the 'scaly-foot gastropod' (Mollusca: Gastropoda: Neomphalina) reveals its extraordinary circulatory system

Introduction: The 'scaly-foot gastropod' (Chrysomallon squamiferum Chen et al., 2015) from deep-sea hydrothermal vent ecosystems of the Indian Ocean is an active mobile gastropod occurring in locally high densities, and it is distinctive for the dermal scales covering the exterior surface of its foot. These iron-sulfide coated sclerites, and its nutritional dependence on endosymbiotic bacteria, are both noted as adaptations to the extreme environment in the flow of hydrogen sulfide. We present evidence for other adaptations of the 'scaly-foot gastropod' to life in an extreme environment, investigated through dissection and 3D tomographic reconstruction of the internal anatomy.

Results: Our anatomical investigations of juvenile and adult specimens reveal a large unganglionated nervous system, a simple and reduced digestive system, and that the animal is a simultaneous hermaphrodite. We show that Chrysomallon squamiferum relies on endosymbiotic bacteria throughout post-larval life. Of particular interest is the circulatory system: Chrysomallon has a very large ctenidium supported by extensive blood sinuses filled with haemocoel. The ctenidium provides oxygen for the host but the circulatory system is enlarged beyond the scope of other similar vent gastropods. At the posterior of the ctenidium is a remarkably large and well-developed heart. Based on the volume of the auricle and ventricle, the heart complex represents approximately 4 % of the body volume. This proportionally giant heart primarily sucks blood through the ctenidium and supplies the highly vascularised oesophageal gland. Thus we infer the elaborate cardiovascular system most likely evolved to oxygenate the endosymbionts in an oxygen poor environment and/or to supply hydrogen sulfide to the endosymbionts.

Conclusions: This study exemplifies how understanding the autecology of an organism can be enhanced by detailed investigation of internal anatomy. This gastropod is a large and active species that is abundant in its hydrothermal vent field ecosystem. Yet all of its remarkable features-protective dermal sclerites, circulatory system, high fecundity-can be viewed as adaptations beneficial to its endosymbiont microbes. We interpret these results to show that, as a result of specialisation to resolve energetic needs in an extreme chemosynthetic environment, this dramatic dragon-like species has become a carrying vessel for its bacteria.

Avaliação da corrosão em dutos por técnica gravimétrica e de resistência elétrica

With the increasing of demand for natural gas and the consequent growth of the pipeline networks, besides the importance of transport and transfer of oil products by pipeline, and when it comes to product quality and integrity of the pipeline there is an important role regarding to the monitoring internal corrosion of the pipe. This study aims to assess corrosion in three pipeline that operate with different products, using gravimetric techniques and electrical resistance. Chemical analysis of residues originated in the pipeline helps to identify the mechanism corrosive process. The internal monitoring of the corrosion in the pipelines was carried out between 2009 and 2010 using coupon weight loss and electrical resistance probe. Physico-chemical techniques of diffraction and fluorescence X-rays were used to characterize the products of corrosion of the pipelines. The corrosion rate by weight loss was analyzed for every pipeline, only those ones that has revealed corrosive attack were analyzed located corrosion rate. The corrosion potential was classified as low to pipeline gas and ranged from low to severe for oil pipelines and the pipeline derivatives. Corrosion products were identified as iron carbonate, iron oxide and iron sulfide