Structural modification of TiO2 nanorod films with an influence on the photovoltaic efficiency of a dye-sensitized solar cell (DSSC).

TiO2 nanorod films have been deposited on ITO substrates by dc reactive magnetron sputtering technique. The structures of these nanorod films were modified by the variation of the oxygen pressure during the sputtering process. Although all these TiO2 nanorod films deposited at different oxygen pressures show an anatase structure, the orientation of the nanorod films varies with the oxygen pressure. Only a very weak (101) diffraction peak can be observed for the TiO2 nanorod film prepared at low oxygen pressure. However, as the oxygen pressure is increased, the (220) diffraction peak appears and the intensity of this diffraction peak is increased with the oxygen pressure. The results of the SEM show that these TiO2 nanorods are perpendicular to the ITO substrate. At low oxygen pressure, these sputtered TiO2 nanorods stick together and have a dense structure. As the oxygen pressure is increased, these sputtered TiO2 nanorods get separated gradually and have a porous structure. The optical transmittance of these TiO2 nanorod films has been measured and then fitted by OJL model. The porosities of the TiO2 nanorod films have been calculated. The TiO2 nanorod film prepared at high oxygen pressure shows a high porosity. The dye-sensitized solar cells (DSSCs) have been assembled using these TiO2 nanorod films prepared at different oxygen pressures as photoelectrode. The optimum performance was achieved for the DSSC using the TiO2 nanorod film with the highest (220) diffraction peak and the highest porosity.

Microstructure, mechanical properties and chemical degradation of brazed AISI 316 stainless steel/alumina systems

The main aims of the present study are simultaneously to relate the brazing parameters with: (i) the correspondent interfacial microstructure, (ii) the resultant mechanical properties and (iii) the electrochemical degradation behaviour of AISI 316 stainless steel/alumina brazed joints. Filler metals on such as Ag–26.5Cu–3Ti and Ag–34.5Cu–1.5Ti were used to produce the joints. Three different brazing temperatures (850, 900 and 950 °C), keeping a constant holding time of 20 min, were tested. The objective was to understand the influence of the brazing temperature on the final microstructure and properties of the joints. The mechanical properties of the metal/ceramic (M/C) joints were assessed from bond strength tests carried out using a shear solicitation loading scheme. The fracture surfaces were studied both morphologically and structurally using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The degradation behaviour of the M/C joints was assessed by means of electrochemical techniques. It was found that using a Ag–26.5Cu–3Ti brazing alloy and a brazing temperature of 850 °C, produces the best results in terms of bond strength, 234 ± 18 MPa. The mechanical properties obtained could be explained on the basis of the different compounds identified on the fracture surfaces by XRD. On the other hand, the use of the Ag–34.5Cu–1.5Ti brazing alloy and a brazing temperature of 850 °C produces the best results in terms of corrosion rates (lower corrosion current density), 0.76 ± 0.21 μA cm−2. Nevertheless, the joints produced at 850 °C using a Ag–26.5Cu–3Ti brazing alloy present the best compromise between mechanical properties and degradation behaviour, 234 ± 18 MPa and 1.26 ± 0.58 μA cm−2, respectively. The role of Ti diffusion is fundamental in terms of the final value achieved for the M/C bond strength. On the contrary, the Ag and Cu distribution along the brazed interface seem to play the most relevant role in the metal/ceramic joints electrochemical performance.

Influence of mixtures of acenaphthylene and benzo[a] anthracene on their degradation by Pleurotus ostreatus in sandy soil

Purpose Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds commonly found as soil contaminants. Fungal degradation is considered as an environmentally friendly and cost-effective approach to remove PAHs from soil. Acenaphthylene (Ace) and Benzo[a]anthracene (BaA) are two PAHs that can coexist in soils; however, the influence of the presence of each other on their biodegradation has not been studied. The biodegradation of Ace and BaA, alone and in mixtures, by the white rot fungus Pleurotus ostreatus was studied in a sandy soil. Materials and methods Experimental microcosms containing soil spiked with different concentrations of Ace and BaAwere inoculated with P. ostreatus. Initial (t 0) and final (after 15 days of incubation) soil concentrations of Ace and BaA were determined after extraction of the PAHs. Results and discussion P. ostreatus was able to degrade 57.7% of the Ace in soil spiked at 30 mg kg−1 dry soil and 65.8% of Ace in soil spiked at 60 mg kg−1 dry soil. The degradation efficiency of BaA by P. ostreatus was 86.7 and 77.4% in soil spiked with Ace at 30 and 60 mg kg−1 dry soil, respectively. After 15 days of incubation, there were no significant differences in Ace concentration between soil spiked with Ace and soil spiked with Ace + BaA, irrespective of the initial soil concentration of both PAHs. There were also no differences in BaA concentration between soil spiked with BaA and soil spiked with BaA + Ace. Conclusions The results indicate that the fungal degradation of Ace and BaA was not influenced by the presence of each other’s PAH in sandy soil. Bioremediation of soils contaminated with Ace and BaA using P. ostreatus is a promising approach to eliminate these PAHs from the environment.

Application of green zero-valent iron nanoparticles to the remediation of soils contaminated with ibuprofen

Zero-valent iron nanoparticles (nZVIs) are often used in environmental remediation. Their high surface area that is associated with their high reactivity makes them an excellent agent capable of transforming/degrading contaminants in soils and waters. Due to the recent development of green methods for the production of nZVIs, the use of this material became even more attractive. However, the knowledge of its capacity to degrade distinct types of contaminants is still scarce. The present work describes the study of the application of green nZVIs to the remediation of soils contaminated with a common anti-inflammatory drug, ibuprofen. The main objectives of this work were to produce nZVIs using extracts of grape marc, black tea and vine leaves, to verify the degradation of ibuprofen in aqueous solutions by the nZVIs, to study the remediation process of a sandy soil contaminated with ibuprofen using the nZVIs, and to compare the experiments with other common chemical oxidants. The produced nZVIs had nanometric sizes and were able to degrade ibuprofen (54 to 66% of the initial amount) in aqueous solutions. Similar remediation efficiencies were obtained in sandy soils. In this case the remediation could be enhanced (achieving degradation efficiencies above 95%) through the complementation of the process with a catalyzed nZVI Fenton-like reaction. These results indicate that this remediation technology represents a good alternative to traditional and more aggressive technologies.

Accounting for the dissociating properties of organic chemicals in LCIA: an uncertainty analysis applied to micropollutants in the assessment of freshwater ecotoxicity

In life cycle impact assessment (LCIA) models, the sorption of the ionic fraction of dissociating organic chemicals is not adequately modeled because conventional non-polar partitioning models are applied. Therefore, high uncertainties are expected when modeling the mobility, as well as the bioavailability for uptake by exposed biota and degradation, of dissociating organic chemicals. Alternative regressions that account for the ionized fraction of a molecule to estimate fate parameters were applied to the USEtox model. The most sensitive model parameters in the estimation of ecotoxicological characterization factors (CFs) of micropollutants were evaluated by Monte Carlo analysis in both the default USEtox model and the alternative approach. Negligible differences of CFs values and 95% confidence limits between the two approaches were estimated for direct emissions to the freshwater compartment; however the default USEtox model overestimates CFs and the 95% confidence limits of basic compounds up to three orders and four orders of magnitude, respectively, relatively to the alternative approach for emissions to the agricultural soil compartment. For three emission scenarios, LCIA results show that the default USEtox model overestimates freshwater ecotoxicity impacts for the emission scenarios to agricultural soil by one order of magnitude, and larger confidence limits were estimated, relatively to the alternative approach.

Photostabilization of phenoxyacetic acid herbicides MCPA and mecoprop by hydroxypropyl-β-cyclodextrin

New strategies to reduce the environmental and economic costs of pesticides use are currently under study. Microencapsulation has been used as a versatile tool for the production of controlled release agricultural formulations. In this study, the photochemical degradation of the herbicides MCPA and mecoprop has been investigated in different aqueous media such as ultrapure and river water under simulated solar irradiation. To explore the possibility of introducing cyclodextrins in the herbicide formulations, the photodegradation study of the inclusion complexes of MCPA and mecoprop with (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was also performed. The half-lives of MCPA and mecoprop inclusion complexes were increased approximately by a factor of three related to the free molecules. Additionally, it has been shown that the photodegradation of MCPA and mecoprop is influenced by their structural features. The additional methyl group existing in mecoprop molecular structure has a positive influence on the stabilization of the radical intermediate formed in the first stage of photodegradation of both herbicides. The results found indicated that MCPA and mecoprop form inclusion complexes with HP-β-CD showing higher photostability compared to free herbicides indicating that HP-β-CD may serve as ingredient in these herbicide formulations.

Novos processos e produtos para o couro de base vegetal

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química

Acqusition and data analysis of the eco-efficiency for the establishment of indicators parameters for industrial environmental sustainability

The industrial activity is inevitably associated with a certain degradation of the environmental quality, because is not possible to guarantee that a manufacturing process can be totally innocuous. The eco-efficiency concept is globally accepted as a philosophy of entreprise management, that encourages the companies to become more competitive, innovative and environmentally responsible by promoting the link between its companies objectives for excellence and its objectives of environmental excellence issues. This link imposes the creation of an organizational methodology where the performance of the company is concordant with the sustainable development. The main propose of this project is to apply the concept of eco-efficiency to the particular case of the metallurgical and metal workshop industries through the development of the particular indicators needed and to produce a manual of procedures for implementation of the accurate solution.

Influence of Hydroxypropyl- β -Cyclodextrin on the Photostability of Fungicide Pyrimethanil

Pesticides continue to play an important role in pest management. However, the intensive pesticide application has triggered several environment negative effects that cannot be disregarded. In this study, the inclusion complex of pyrimethanil with HP- β -CD has been prepared and characterized by proton nuclear magnetic resonance spectroscopy. The formation of the pyrimethanil/HP- β -CD inclusion complex increased the aqueous solubility of this fungicide around five times. To assess the influence of microencapsulation on the environmental photostability of the fungicide, the photochemical degradation of pyrimethanil and pyrimethanil/HP- β -CD inclusion complex has been investigated in different aqueous media such as ultrapure and river water under simulated solar irradiation. The studies allow concluding that pyrimethanil/HP- β -CD inclusion complex increases significantly the photostability of the fungicide in aqueous solutions, especially in natural water. Actually, the half-life of pyrimethanil/HP- β -CD inclusion complex was increased approximately by a factor of four when compared to the free fungicide. The overall results point out that pyrimethanil can be successfully encapsulated by HP- β -CD, a process that can improve its solubility and photostability properties.