Micelle-hosted palladium nanoparticles catalyze citral molecule hydrogenation in supercritical carbon dioxide

A new approach of employing metal particles in micelles for the hydrogenation of organic molecules in the presence of fluorinated surfactant and water in supercritical carbon dioxide has very recently been introduced. This is allegedly to deliver many advantages for carrying out catalysis including the use of supercritical carbon dioxide (scCO(2)) as a greener solvent. Following this preliminary account, the present work aims to provide direct visual evidence on the formation of metal microemulsions and to investigate whether metal located in the soft micellar assemblies could affect reaction selectivity. Synthesis of Pd nanoparticles in perfluorohydrocarboxylate anionic micelles in scCO(2) is therefore carried out in a stainless steel batch reactor at 40 degreesC and in a 150 bar CO2/H-2 mixture. Homogeneous dispersion of the microemulsion containing Pd nanoparticles in scCO(2) is observed through a sapphire window reactor at W-0 ratios (molar water-to-surfactant ratios) ranging from 2 to 30. It is also evidenced that the use of micelle assemblies as new metal catalyst nanocarriers could indeed exert a great influence on product selectivity. The hydrogenation of a citral molecule that contains three reducible groups (aldehyde, double bonds at the 2,3-position and the 6,7-position) is studied. An unusually high selectivity toward citronellal (a high regioselectivity toward the reduction of the 2,3-unsaturation) is observed in supercritical carbon dioxide. On the other hand, when the catalysis is carried out in the conventional liquid or vapor phase over the same reaction time, total hydrogenation of the two double bonds is achieved. It is thought that the high kinetic reluctance for double bond hydrogenation of the citral molecule at the hydrophobic end (the 6,7-position) is due to the unique micelle environment that is in close proximity to the metal surface in supercritical carbon dioxide that guides a head-on attack of the molecule toward the core metal particle.

To what extent are EU steel companies susceptible to competitive loss due to climate policy?

In recognition of their competitive vulnerability, a set of special rules have been devised for managing sectors such as steel and cement within the EU ETS. These rules basically seek to set sector specific performance benchmarks and reward top performers. However, the steel sector as a whole will receive the vast majority of its allowances for free in Phase III. Perceptions of competitive vulnerability have been largely based on inherently hypothetical analyses which rely heavily on counterfactual scenario and abatement cost estimates often provided by firms themselves. This paper diverges from these approaches by providing a qualitative assessment of the two key reasons underpinning the competitive vulnerability argument of the EU Steel Companies based on interviews and case study involving the three largest producers of steel within the EU – AcerlorMittal, Corus, and ThyssenKrupp. We find that these arguments provide only partial and weak justifications for competitive loss and discriminatory treatment in the EUETS. This strategy is difficult to counter by governments due to information asymmetry; and it appears to have proved very successful insofar as it has helped the industry to achieve free allocation in Phases I-III of EU ETS by playing up the risk of carbon leakage.

Carbon fiber non-crimp multi-axial reinforcement and epoxy mono-component system composite: fatigue behavior

Fiber reinforced polymer composites have been widely applied in the aeronautical field. However, composite processing, which uses unlocked molds, should be avoided in view of the tight requirements and also due to possible environmental contamination. To produce high performance structural frames meeting aeronautical reproducibility and low cost criteria, the Brazilian industry has shown interest to investigate the resin transfer molding process (RTM) considering being a closed-mold pressure injection system which allows faster gel and cure times. Due to the fibrous composite anisotropic and non homogeneity characteristics, the fatigue behavior is a complex phenomenon quite different from to metals materials crucial to be investigated considering the aeronautical application. Fatigue sub-scale specimens of intermediate modulus carbon fiber non-crimp multi-axial reinforcement and epoxy mono-component system composite were produced according to the ASTM 3039 D. Axial fatigue tests were carried out according to ASTM D 3479. A sinusoidal load of 10 Hz frequency and load ratio R = 0.1. It was observed a high fatigue interval obtained for NCF/RTM6 composites. Weibull statistical analysis was applied to describe the failure probability of materials under cyclic loads and fractures pattern was observed by scanning electron microscopy. (C) 2010 Published by Elsevier Ltd.

Fatigue Strength of X45CrSi93 stainless steel applied as internal combustion engine valves

Stainless steels are used to intake and exhaust valves production applied as internal combustion engines. In general valves are requested to support cyclic stresses applied due to opening and closing processes during the operation. The objective of this research is to study the influence on the axial fatigue strength of the resulting microstructure after heat treatment at the martensitic X45CrSi93 steel, combined with different surface treatments as hard chrome-plating, nitride and grinding. It was verified a significant increase on the fatigue strength of the martensitic steel after nitriding, compared with results from the chrome-plating specimens. A slight increase in the tensile strength was also noticed on nitrided parts as a consequence of a resistance increase due to nitrogen and carbon solid solution. (C) 2011 Published by Elsevier Ltd. Selection and peer-review under responsibility of ICM11

Aging behaviour of 25Cr-17Mn high nitrogen duplex stainless steel

The precipitation behaviour of a nickel free stainless steel containing 25% chromium, 17% manganese and 0.54% nitrogen, with duplex ferritic-austenitic microstructure, was studied using several complementary techniques of microstructural analysis after aging heat treatments between 600 and 1 000 degrees C for periods of lime between 15 and 6 000 min. During aging heat treatments, ferrite was decomposed into sigma phase and austenite by a eutectoid reaction, like in the Fe-Cr-Ni duplex stainless steel. Chromium nitride precipitation occurred in austenite, which had a high nitrogen supersaturation. Some peculiar aspects were observed in this austenite during its phase transformations. Chromium nitride precipitation occurred discontinuously in a lamellar morphology, such as pearlite in carbon steels. This kind of precipitation is not an ordinary observation in duplex stainless steels and the high levels of nitrogen in austenite can induce this type of precipitation, which has not been previously reported in duplex stainless steels. After chromium nitride precipitation in austenite, it was also observed sigma phase formation near the cells or colonies of discontinuously precipitated chromium nitride. Sigma phase formation was made possible by the depletion of nitrogen in those regions. Time-temperature-transformation (precipitation) diagrams were determined.

Effects of milling condition on the surface integrity of hot forged steel

This paper presents a study on the influence of milling condition on workpiece surface integrity focusing on hardness and roughness. The experimental work was carried out on a CNC machining center considering roughing and finishing operations. A 25 mm diameter endmill with two cemented carbide inserts coated with TiN layer were used for end milling operation. Low carbon alloyed steel Cr-Mo forged at 1200 degrees C was used as workpiece on the tests. Two kinds of workpiece conditions were considered, i.e. cur cooled after hot forging and normalized at 950 degrees C for 2 h. The results showed that finishing operation was able to significantly decrease the roughness by at least 46% without changing the hardness. on the other hand, roughing operation caused an increase in hardness statistically significant by about 6%. The machined surface presented deformed regions within feed marks, which directly affected the roughness. Surface finish behavior seems to correlate to the chip ratio given the decrease of 25% for roughing condition, which damaged the chip formation. The material removal rate for finishing operation 41% greater than roughing condition demonstrated to be favorable to the heat dissipation and minimized the effect on material hardness.

Hydrogenated amorphous carbon as protective coating for a forming tool

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

Key features of alumina/magnesia/graphite refractories for steel ladle lining

The corrosion resistance of resin bonded alumina/magnesia/graphite refractories containing different kinds of aggregates were investigated when submitted to the action of slags of several CaO/SiO2 ratios. The laboratory testing was performed by means of the rotary slag attack test. Specifically evaluated was the influence of alumina/carbon ratio and magnesia and silica contents on the refractories corrosion resistance. It was found that this property could be improved by increasing the refractory Al2O3/SiO2 ratio as well as by choosing the appropriate Al2O3/C ratio. © 2000 Elsevier Science Ltd.

Plasma nitriding and nitrocarburising of a supermartensitic stainless steel

Supermartensitic stainless steels (SMSSs) are a new generation of the classic 13%Cr martensitic steels, lower in carbon and with additional alloying of nickel and molybdenum offering better weldabilty and low temperature toughness. Several works have shown that plasma nitriding and nitrocarburising of stainless steels at low temperatures produces a hard surface layer which results in increased wear resistance. In this work, SMSS samples were plasma nitrided and nitrocarburised at 400, 450 and 500 °C. The plasma treated SMSS samples were characterised by means of optical microscopy, microhardness, X-ray diffraction and dry wear tests. The thickness of the layers produced increases as temperature is raised, for both plasma nitriding and nitrocarburising. X-ray diffraction demonstrates that the chromium nitride content grows with temperature for nitriding and nitrocarburising, which also showed increasing content of iron and chromium carbides with temperature. After plasma treating, it was found that the wear volume decreases for all temperatures and the wear resistance increased as the treatment temperature was raised. The main wear mechanism observed for both treated and untreated samples was grooving abrasion. © 2012 IHTSE Partnership Published by Maney on behalf of the Partnership.

Ion beam analysis of a-C:H films on alloy steel substrate

An a-C:H thin film deposited by plasma immersion ion implantation and deposition on alloy steel (16MnCr5) was analyzed using a self-consistent ion beam analysis technique.In the self-consistent analysis, the results of each individual technique are combined in a unique model, increasing confidence and reducing simulation errors.Self-consistent analysis, then, is able to improve the regular ion beam analysis since several analyses commonly used to process ion beam data still rely on handling each spectrum independently.The sample was analyzed by particle-induced x-ray emission (for trace elements), elastic backscattering spectrometry (for carbon), forward recoil spectrometry (for hydrogen) and Rutherford backscattering spectrometry (for film morphology).The self-consistent analysis provided reliable chemical information about the film, despite its heavy substrate.As a result, we could determine precisely the H/C ratio, contaminant concentration and some morphological characteristics of the film, such as roughness and discontinuities.© 2013 Elsevier B.V.All rights reserved.

Application of acoustoelasticity to measure the stress generated by milling in ASTM A36 steel plates

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Suitability of carbon fiber-reinforced polymers as power cable cores: Galvanic corrosion and thermal stability evaluation

The increasing demand for electrical energy and the difficulties involved in installing new transmission lines presents a global challenge. Transmission line cables need to conduct more current, which creates the problem of excessive cable sag and limits the distance between towers. Therefore, it is necessary to develop new cables that have low thermal expansion coefficients, low densities, and high resistance to mechanical stress and corrosion. Continuous fiber-reinforced polymers are now widely used in many industries, including electrical utilities, and provide properties that are superior to those of traditional ACSR (aluminum conductor steel reinforced) cables. Although composite core cables show good performance in terms of corrosion, the contact of carbon fibers with aluminum promotes galvanic corrosion, which compromises mechanical performance. In this work, three different fiber coatings were tested (phenol formaldehyde resin, epoxy-based resin, and epoxy resin with polyester braiding), with measurements of the galvanic current. The use of epoxy resin combined with polyester braiding provided the best inhibition of galvanic corrosion. Investigation of thermal stability revealed that use of phenol formaldehyde resin resulted in a higher glass transition temperature. On the other hand, a post-cure process applied to epoxy-based resin enabled it to achieve glass transition temperatures of up to 200 degrees C. (C) 2014 Elsevier Ltd. All rights reserved.

Synthesis of Carbon Nanomaterials through Up-Cycling Agricultural and Municipal Solid Wastes

This work addresses the synthesis of carbon nanomaterials (CNMs) by up-cycling common solid wastes. These feedstocks could supersede the use of costly and often toxic or highly flammable chemicals, such as hydrocarbon gases, carbon monoxide, and hydrogen, which are commonly used as feedstocks in current nanomanufacturing processes for CNMs. Agricultural sugar cane bagasse and corn residues, scrap tire chips, and postconsumer polyethylene (PE) and polyethylene terephthalate (PET) bottle shreddings were either thermally treated by sole pyrolysis or by sequential pyrolysis and partial oxidation. The resulting gaseous carbon-bearing effluents were then channeled into a heated reactor. CNMs, including carbon nanotubes, were catalytically synthesized therein on stainless steel meshes. This work revealed that the structure of the resulting CNMs is determined by the feedstock type, through the disparate mixtures of carbon-bearing gases generated when different feedstocks are pyrolyzed. CNM characterization was conducted by scanning and transmission electron microscopy as well as by Raman spectroscopy and by thermogravimetric analysis. Gas chromatography was used to characterize the gases in the synthesis chamber. This work demonstrated an alternative method for efficient manufacturing of CNMs using both biodegradable and nonbiodegradable agricultural and municipal carbonaceous wastes.

Flexural strengthening of reinforced concrete beams with carbon fibers reinforced polymer (CFRP) sheet bonded to a transition layer of high performance cement-based composite

Resistance to corrosion, high tensile strength, low weight, easiness and rapidity of application, are characteristics that have contributed to the spread of the strengthening technique characterized by bonding of carbon fibers reinforced polymer (CFRP). This research aimed to develop an innovate strengthening method for RC beams, based on a high performance cement-based composite of steel fibers (macro + microfibers) to be applied as a transition layer. The purpose of this transition layer is better control the cracking of concrete and detain or even avoid premature debonding of strengthening. A preliminary study in short beams molded with steel fibers and strengthened with CFRP sheet, was carried out where was verified that the conception of the transition layer is valid. Tests were developed to get a cement-based composite with adequate characteristics to constitute the layer transition. Results showed the possibility to develop a high performance material with a pseudo strain-hardening behavior, high strength and fracture toughness. The application of the strengthening on the transition layer surface had significantly to improve the performance levels of the strengthened beam. It summary, it was proven the efficiency of the new strengthening technique, and much information can be used as criteria of projects for repaired and strengthened structures.

Effects Of The Flash Welding Process On Mechanical And Microstructural Properties Of Structural Steel Joints Assessed Using Dest

ASTM A529 carbon¿manganese steel angle specimens were joined by flash butt welding and the effects of varying process parameter settings on the resulting welds were investigated. The weld metal and heat affected zones were examined and tested using tensile testing, ultrasonic scanning, Rockwell hardness testing, optical microscopy, and scanning electron microscopy with energy dispersive spectroscopy in order to quantify the effect of process variables on weld quality. Statistical analysis of experimental tensile and ultrasonic scanning data highlighted the sensitivity of weld strength and the presence of weld zone inclusions and interfacial defects to the process factors of upset current, flashing time duration, and upset dimension. Subsequent microstructural analysis revealed various phases within the weld and heat affected zone, including acicular ferrite, Widmanstätten or side-plate ferrite, and grain boundary ferrite. Inspection of the fracture surfaces of multiple tensile specimens, with scanning electron microscopy, displayed evidence of brittle cleavage fracture within the weld zone for certain factor combinations. Test results also indicated that hardness was increased in the weld zone for all specimens, which can be attributed to the extensive deformation of the upset operation. The significance of weld process factor levels on microstructure, fracture characteristics, and weld zone strength was analyzed. The relationships between significant flash welding process variables and weld quality metrics as applied to ASTM A529-Grade 50 steel angle were formalized in empirical process models.