Electrochemical behaviour of heat-treated AlZnMg alloys in chloride solutions containing sulphate

The electrochemical corrosion and passivation of Al5Zn1.7Mg0.23Cu0.053Nb alloys, submitted to different heat treatments (cold-rolled, annealed, quenched and aged, and quenched in two steps and aged), in sulphate-containing chloride solutions, has been studied by means of cyclic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The cyclic polarization curves showed that sulphate addition to the chloride solution produced a poor reproducible shift of the breakdown potential to more positive potentials. The repassivation potentials, much more reproducible, and practically separating the passive from the pitting potential region, were slightly displaced in the negative direction with that addition. When the alloys were potentiodynamically polarized in the passive potential region, sulphate was incorporated in the oxide film, thus precluding chloride ingress. In addition, Zn depletion was favoured, whereas Mg losses were avoided. Different equivalent circuits corresponding to different alloys and potentials in the passive and pitting regions were employed to account for the electrochemical processes taking place in each condition. This work shows that sulphate makes these alloys more sensitive to corrosion, increasing the fracture properties of the surface layer and favouring the pitting attack over greater areas than chloride alone.     

Very long chain PUFA in murine testicular triglycerides and cholesterol esters

Very long chain (VLC) PUFA of the n−6 and n−3 series are known to occur in mammalian testis. The aim of this work was to characterize further two testicular lipid classes with VLCPUFA, cholesterol esters (CE) and total triglycerides (TG) in rat and mouse testis. The VLCPUFA predominating in these lipids were a series of n−6 pentaenes and tetraenes with 24 to 32 carbons, including small amounts of odd-chain PUFA, 28∶5n−6 and 24∶5n−6 prevailing in CE and TG, respectively. Most of the VLCPUFA of TG were concentrated in a small fraction of TG, made up by 1-O-alkyl-2,3-DAG. This TG subclass was absent altogether from the TG of sexually immature testis. The TG and the CE with VLCPUFA only occurred in testis of adult fertile animals. The proportion of VLCPUFA in total TG and CE was higher in rodents than in other mammals. In the n−6 PUFA-rich adult mouse testis, the amounts of testicular triacylglycerols decreased significantly after consumption of fish oil for 2 wk. Whereas 18∶2n−6 was significantly reduced, the amounts of 22∶5n−6 and longer n−6 PUFA were less affected in all mamor testicular lipids including PC and PE, where they were unchanged. The 1-O-alkyl-2,3-DAG and their n−6 VLCPUFA were virtually unaffected by the diet. The VLCPUFA-containing molecular species of CE and TG may represent a form of storage of cholesterol and polyenoic FA required to sustain spermatogenesis. Via chain-shortening, VLCPUFA stored in the neutral lipids may serve as precursors of the major C₂₂ PUFA typical of cell membrane glycerophospholipids, protecting testicular cells against shifts in FA composition induced by dietary changes.     

Effect of the addition of Cr and Nb on the microstructure and electrochemical corrosion of heat-treatable Al-Zn-Mg alloys

The effect of the addition of Cr and Nb on the microstructure and the electrochemical corrosion of the weldable, high-strength and stress corrosion cracking (SCC) resistant Al-5%Zn–1.67%Mg–0.23%Cu alloy (H) has been studied. Combined additions of the alloying elements, J (with Nb), L (with Cr) and O (with Cr and Nb) and different heat treatments, ST (cold-rolled), A (annealed), F (quenched), B (quenched and aged) and C (quenched in two steps and aged), to obtain different microstructures and hardness have been performed. To correlate the electrochemical corrosion with the microstructure of the specimens, corrosion potential (E _cor) measurements in different chloride solutions were performed and optical microscopy, SEM, TEM and EDX were applied. In chloride solutions containing dissolved O₂ or H₂O₂, the present alloys were polarized up to the pitting attack. It was shown that theE _cor measurements were very sensitive to the alloy composition and heat treatment, increasing in the order H < J < L < O < Al (for a given heat treatment) and F < A ST < B < C (for a given alloy). The MgZn₂ precipitates of the annealed (A) and cold-rolled (ST) specimens were dissolved in chloride solutions containing oxidizing agents and pitting attack was shown to develop in the cavities where the precipitates were present. In the specimens B and C, the compositions of the precipitate free zones was found to be equal to that of the matrix solid solution and preferential intergranular attack was not evident, this being in agreement with their SCC resistance. The addition of Cr and Nb increased the pitting corrosion resistance. The effects of Cr and Nb were additive, that of Cr being predominant, either, in theE _cor shift or in the increase in the pitting corrosion resistance.     

Effect of elemental sulfur in the crosslinking reaction of poly(vinyl chloride) with tetramethyl thiuram disulfide

The effect of elemental sulfur (S₈) and tetramethyl thiuram disulfide (TMTD) on the chemical crosslinking of PVC is studied. The tensile strength, elongation at break, and gel content of crosslinked and uncrosslinked PVC molded samples, cured at different times in hot air, are evaluated. It was found that crosslinking PVC with TMTD improves its mechanical properties, and adding S₈ produces a slight improvement. Also, the S₈ presence accelerated the PVC/TMTD crosslinking reaction when the crosslinking reaction was carried out under shear forces, but not when the curing was done in hot air, where the S₈ retards the process.     

XPS Characterization of reduced LaCoO3 perovskite

Three samples of LaCoO₃ were prepared by two different methods and calcined at 800 or 1000 °C. They had BET areas of 1, 12, and 16 m²/g and all of them showed pure perovskite X-ray diffraction patterns with identical unit cell dimensions. In a series of experiments the oxide, having larger surface area, was stepwise reduced in hydrogen at temperatures between 60 and 500 °C. The XPS spectra, taken at room temperature after evacuation at 400 °C at each reduction level, showed that the surface concentration of Co° was very low up to 300 °C but increased sharply between 300 and 350 °C (9–75%). This concentration further increased to 100% after 10 min reduction at 450 °C, but upon heating in hydrogen for an additional 10 min at 500 °C it decreased again to 75%. In another series of experiments the mixed oxide was reoxidized after each reduction. A fresh sample was reduced to 350 and 400 °C by contacting with hydrogen for 1 hr and evacuated at temperatures between 400 and 500 °C. Both high evacuation temperatures and reduction at 400 °C during 1 hr produced a sharp decrease in Co° surface concentration. These results are consistent with the catalytic behavior of this perovskite reported earlier by E. A. Lombardo et al. (4–7). A model is proposed to interpret the reduction of LaCoO₃.     

Fabrication of hybrid proton-exchange membranes using a brandnew high temperature ionic liquid as charge transporting and clay modifier

The search for more compatibility between ionic liquids (ILs) and polymer matrices in proton-exchange membrane fuel cells (PEMFCs) is one of the ways in which IL leaking from proton-exchange membranes could be minimized. In this work, it is presented the synthesis of an aromatic high temperature ionic liquid (HTIL), which, incorporated into an aromatic matrix such as sulfonated polyether ether ketone (sPEEK), is expected to diminish the IL leaking that normally affects PEMFC. Phenylethylammonium trifluoromethane sulfonate (PhetaTfO) was successfully synthesized and characterized. Its melting point of 88°C makes it to classify as a HTIL and it was employed as modifier of natural Montmorillonite, forming the phenylethylammonium intercalated montmorillonite (MmtPheta) and thus, ternary membranes containing PhetaTfO, MmtPheta, and sPEEK were prepared and characterized. Immersion tests demonstrated a higher compatibility of PhetaTfO with matrix when compared to the reference DemaTfO, which was reflected in up to 30% lower IL loss by the synthesized IL than the DemaTfO; X-rays diffraction (XRD) patterns demonstrated that the modified clay was properly dispersed inside the membranes, while dynamic mechanical analyses (DMA) results indicated a strong plasticizer effect along the increase of PhetaTfO content inside the membrane, while at the same time, the conductivity increased in an exponential manner, which permitted to identify an empiric exponential equation to evaluate the effect of concentration on ionic conductivity. The maximum conductivity obtained at IL concentrations of around 38 wt% was 0.2 mS/cm. It could expect high ionic conductivities of 10 mS/cm when the concentration of this IL is 60%; nevertheless, in order to achieve that, crosslinking treatments should be done to give the membranes enough mechanical resistance.     

When a Tritrophic Interaction Goes Wrong to the Third Level: Xanthoxylin From Trees Causes the Honeybee Larval Mortality in Colonies Affected by the River Disease

The “River Disease” (RD), a disorder impacting honeybee colonies located close to waterways with abundant riparian vegetation (including Sebastiania schottiana, Euphorbiaceae), kills newly hatched larvae. Forager bees from RD-affected colonies collect honeydew excretions from Epormenis cestri (Hemiptera: Flatidae), a planthopper feeding on trees of S. schottiana. First-instar honeybee larvae fed with this honeydew died. Thus, we postulated that the nectars of RD-affected colonies had a natural toxin coming from either E. cestri or S. schottiana. An untargeted metabolomics characterization of fresh nectars extracts from colonies with and without RD allowed to pinpoint xanthoxylin as one of the chemicals present in higher amounts in nectar from RD-affected colonies than in nectars from healthy colonies. Besides, xanthoxylin was also found in the aerial parts of S. schottiana and the honeydew excreted by E. cestri feeding on this tree. A larva feeding assay where xanthoxylin-enriched diets were offered to 1^st instar larvae showed that larvae died in the same proportion as larvae did when offered enriched diets with nectars from RD-colonies. These findings demonstrate that a xenobiotic can mimic the RD syndrome in honeybee larvae and provide evidence of an interspecific flow of xanthoxylin among three trophic levels. Further, our results give information that can be considered when implementing measures to control this honeybee disease.

     

Analysis of surface integrity for minimum quantity lubricant—MQL in grinding

The quality of machined components is currently of high interest, for the market demands mechanical components of increasingly high performance, not only from the standpoint of functionality but also from that of safety. Components produced through operations involving the removal of material display surface irregularities resulting not only from the action of the tool itself, but also from other factors that contribute to their superficial texture. This texture can exert a decisive influence on the application and performance of the machined component. This article analyzes the behavior of the minimum quantity lubricant (MQL) technique and compares it with the conventional cooling method. To this end, an optimized fluid application method was devised using a specially designed nozzle, by the authors, through which a minimum amount of oil is sprayed in a compressed air flow, thus meeting environmental requirements. This paper, therefore, explores and discusses the concept of the MQL in the grinding process. The performance of the MQL technique in the grinding process was evaluated based on an analysis of the surface integrity (roughness, residual stress, microstructure and microhardness). The results presented here are expected to lead to technological and ecological gains in the grinding process using MQL.     

Optimizing the use of dry cutting in rough turning steel operations

The main objective of using cutting fluids in machining operations is the reduction of temperature in the cutting region to increase tool life. However, the advantages offered by cutting fluids have been strongly debated because of their negative effects on the economic aspect, the environment and the health of workers using them. A trend to solve these problems is cutting without fluid, a method named dry cutting, which has been made possible due to technological innovations. This work aims to seek conditions in which dry cutting is satisfactory compared with the flood of fluid (called here wet cutting) usually used. Aiming at this goal, several experiments were carried out varying parameters such as cutting speed, feed, depth of cut and tool material in rough turning of ABNT 1045 steel in dry and wet cutting. The analysis of the results showed that wet turning is, as expected, better for tool life. The second conclusion is that dry cutting cannot be used with large depth of cut. But the main conclusion is that, if the tool material is changed to a more wear resistant one, dry cutting can be used with results very similar to those obtained with a flood of fluid.