Synthesis and analysis of phase segregation of polystyrene-block-poly(methyl methacrylate) copolymer obtained by Steglich esterification from semitelechelic blocks of polystyrene and poly(methyl methacrylate)

Here, an alternative route to successfully synthesize polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is reported. Steglich esterification was used as an effective, metal free approach for coupling carboxylic terminated PS and the hydroxyl end-functionalized PMMA chains obtained by nitroxide-mediated polymerization and atom transfer radical polymerization, respectively. α-Functionalization was obtained using 4,4′-azobis(4-cyanovaleric acid) and 2,2,2-tribromoethanol as initiators. The synthesis of PS-b-PMMA was confirmed by gel permeation chromatography and nuclear magnetic resonance (NMR), while the dependence of the diffusion coefficients of the polymers (PS, PMMA, PS/PMMA blend, and PS-b-PMMA) with their corresponding molecular weights was discussed based on the results of atomic force microscopy-based infrared spectroscopy, differential scanning calorimetry, and spectra of diffusion-ordered NMR spectroscopy. Differently from PS-b-PMMA, a partial segregation was observed for the PS/PMMA blend, affecting its thermal behavior and diffusion coefficient. The study here presented provides an easier and efficient strategy for the synthesis of PS-b-PMMA and new insights into the diffusion of polymers.     

Formulation of a Biodegradable Detergent for Cleaning Oily Residues Generated during Industrial Processes

The use of toxic petroleum-based heavy oils is common in industrial processes. The cleaning of machines, equipment, and other surface covered in these oils is achieved with expensive products that are often also toxic and harmful to both the health of workers and the environment. The present paper proposes the development of a sustainable biodetergent made from plant-based materials. Tests were performed to determine the properties of the biodetergent in terms of its surfactant and emulsifying capacities, stability, toxicity, and the removal of heavy oil from glass plates and metallic surfaces. The formulation was composed of a natural solvent (cottonseed oil), a plant-based surfactant agent (saponin), and two natural stabilizers (carboxymethylcellulose and glycerine). The formulation was stable, nontoxic, and highly efficient, removing 100% of the heavy oil from glass and metallic surfaces. This solution developed in this study could be used in diverse industries with the need to clean machines and parts encrusted with oil and grease as well as the cleaning of floors covered with petroleum-based residues. A preliminary analysis of the economic feasibility of using the detergent was carried out at a Brazilian power plant. Besides the reduction in environmental impact due to the use of a nontoxic, biodegradable product as well as the reduction in health risks to workers associated with toxic cleaning products, this new product can have a considerable impact on the market as an environmentally friendly solution.     

Decision support systems in water resources in the demarcated region of Douro – case study in Pinhão river basin,Portugal

This paper puts forward the importance of decision support systems (DSS) for the planning and management of water resources. A case study of the Pinhão river basin, in Portugal, is presented. Given the importance of vineyards in the Douro region, it is important to determine if water availability will be enough to meet present and future water demands. In order to answer this question, DSS tools were used to assess different scenarios. The MIKE BASIN software was used in the hydrographical basin of Pinhão river, assisted by a geographic information system, GIS, which allowed the modelling of the basin, both temporally and spatially, facilitating the visualisation and interpretation of results. According to the attained results, it was verified that, at present, the hydrographical basin meets the considered water needs. The DSS proved to be an important tool to assist the decision‐making process in the studied river basin.     

Stress and strain distribution in demineralized enamel: A micro‐CT based finite element study

Physiological oral mechanical forces may play a role on the progression of enamel carious lesions to cavitation. Thus, the aim of this study was to describe, by 3D finite element analysis, stress, and strain patterns in sound and carious enamel after a simulated occlusal load. Micro‐CT based models were created and meshed with tetrahedral elements (based on an extracted third molar), namely: a sound (ST) and a carious tooth (CT). For the CT, enamel material properties were assigned according to the micro‐CT gray values. Below the threshold corresponding to the enamel lesion (2.5 g/cm³) lower and isotropic elastic modulus was assigned (E = 18 GPa against E₁ = 80 GPa, E₂ = E₃ = 20 GPa for sound enamel). Both models were imported into a FE solver where boundary conditions were assigned and a pressure load (500 MPa) was applied at the occlusal surface. A linear static analysis was performed, considering anisotropy in sound enamel. ST showed a more efficient transfer of maximum principal stress from enamel to the dentin layer, while for the CT, enamel layer was subjected to higher and concentrated loads. Maximum principal strain distributions were seen at the carious enamel surface, especially at the central fossa, correlating to the enamel cavity seen at the original micro‐CT model. It is possible to conclude that demineralized enamel compromises appropriate stress transfer from enamel to dentin, contributing to the odds of fracture and cavitation. Enamel fracture over a dentin lesion may happen as one of the normal pathways to caries progression and may act as a confounding factor during clinical diagnostic decisions. Microsc. Res. Tech. 78:865–872, 2015. © 2015 Wiley Periodicals, Inc.     

Anticorrosive painting for a wide spectrum of marine atmospheres: Environmental-friendly versus traditional paint systems

This work presents some of the main results obtained in different marine atmospheres by Working Groups 1 and 2 (dedicated to anticorrosive protection of steel by paint coatings) of the Ibero-American PATINA network, developed in the context of the CYTED Programme. As marine atmospheres it includes natural atmospheres with a salinity level above S1 classification of ISO standard 9223 (>3 mg Cl⁻ m⁻² day⁻¹), and sulphur dioxide contamination only up to classification P1 of the same standard (maximum of 35 mg SO₂ m⁻² day⁻¹). Consideration is also made of accelerated tests traditionally used to assess the anticorrosive behaviour of the substrate/paint coatings contemplated in the study, namely salt spray, artificial weathering and different cycles involving ultraviolet radiation, humidity, temperature and different contamination conditions. The substrates were steel, hot-dip galvanised steel and electrogalvanised steel (Zincorr^® sheet). The paint systems applied on these substrates, with or without pretreatments, were solventborne, waterborne, high solid and powder paint systems. As a result it has been possible to conclude which of the studied anticorrosive coating types were the most suitable for each of the different types of marine atmospheres considered in the study.     

Microbiological characterization of randomly selected Portuguese raw milk cheeses with reference to food safety

Seventy raw milk cheeses made in different regions of Portugal, both hard and soft varieties, made with cow's, ewe's, or goat's milk or combinations of these, were sampled within their quoted shelf lives for microbiological safety. On the basis of the presence or numbers of Escherichia coli, E. coli O157, Staphylococcus aureus, Salmonella, and Listeria monocytogenes, cheeses were categorized as satisfactory, acceptable, unsatisfactory, or unacceptable and potentially hazardous. Twenty-two of the 70 cheeses were classified as satisfactory or acceptable. Thirty-seven of the cheeses were considered unsatisfactory because of the presence of E. coli, S. aureus, or both, while 11 of the cheeses were graded as unacceptable and potentially hazardous because of the presence of excessive numbers of S. aureus, E. coli, or L. monocytogenes and the presence of Salmonella in three of these. All cheeses graded as unacceptable and potentially hazardous were soft or semisoft cheeses made with ewe's and goat's milk, with the exception of two hard cheeses made with cow's milk. E. coli O157 was not detected in any of the cheeses. According to the present results, it seems that the presence or counts of pathogenic or indicator organisms in raw milk cheeses cannot be related to the processing conditions, milk type, or region of production.     

Understanding the Evolution of CdTe Buffer Layer Surfaces on ZnTe/Si(211) and GaAs(211)B During Cyclic Annealing

We present the results of a detailed study of the changes that occur on CdTe buffer layer surfaces grown on ZnTe/Si(211) and GaAs(211)B during the routine thermal cyclic annealing (TCA) process. Observations indicate that CdTe buffer layer surfaces are Te saturated when the TCA is performed under Te overpressure. In the absence of Te flux during the TCA step, the CdTe surface loses CdTe congruently and the typical CdTe nanowires show the presence of nodules on their surfaces. The observed changes in reflection high-energy electron diffraction patterns during TCA are explained in terms of surface chemistry and topography observations. Overall, the Te overpressure is necessary to maintain a smoother and pristine surface to continue the molecular beam epitaxy (MBE) growth.     

Impact of Tellurium Precipitates in CdZnTe Substrates on MBE HgCdTe Deposition

State-of-the-art (112)B CdZnTe substrates were examined for near-surface tellurium precipitate-related defects. The Te precipitate density was observed to be fairly uniform throughout the bulk of the wafer, including the near-surface region. After a molecular beam epitaxy (MBE) preparation etch, exposed Te precipitates, small pits, and bumps on the (112)B surface of the CdZnTe wafer were observed. From near-infrared and dark field microscopy, the bumps and small pits on the CdZnTe surface are associated with strings of Te precipitates. Raised bumps are Te precipitates near the surface of the (112)B CdZnTe where the MBE preparation etch has not yet exposed the Te precipitate(s). An exposed Te precipitate sticking above the etched CdZnTe surface plane occurs when the MBE preparation etch rapidly undercuts a Te precipitate. Shallow surface pits are formed when the Te precipitate is completely undercut from the surrounding (112)B surface plane. The Te precipitate that was previously located at the center of the pit is liberated by the MBE preparation etch process.     

Life cycle assessment of Jatropha biodiesel as transportation fuel in rural India

Since 2003 India has been actively promoting the cultivation of Jatropha on unproductive and degraded lands (wastelands) for the production of biodiesel suitable as transportation fuel. In this paper the life cycle energy balance, global warming potential, acidification potential, eutrophication potential and land use impact on ecosystem quality is evaluated for a small scale, low-input Jatropha biodiesel system established on wasteland in rural India. In addition to the life cycle assessment of the case at hand, the environmental performance of the same system expanded with a biogas installation digesting seed cake was quantified. The environmental impacts were compared to the life cycle impacts of a fossil fuel reference system delivering the same amount of products and functions as the Jatropha biodiesel system under research. The results show that the production and use of Jatropha biodiesel triggers an 82% decrease in non-renewable energy requirement (Net Energy Ratio, NER = 1.85) and a 55% reduction in global warming potential (GWP) compared to the reference fossil-fuel based system. However, there is an increase in acidification (49%) and eutrophication (430%) from the Jatropha system relative to the reference case. Although adding biogas production to the system boosts the energy efficiency of the system (NER = 3.40), the GWP reduction would not increase (51%) due to additional CH₄ emissions. For the land use impact, Jatropha improved the structural ecosystem quality when planted on wasteland, but reduced the functional ecosystem quality. Fertilizer application (mainly N) is an important contributor to most negative impact categories. Optimizing fertilization, agronomic practices and genetics are the major system improvement options.