Fresamento com ar quente: uma proposta para minimizar a formação de trincas térmicas em ferramentas de metal duro

This work presents the results, analyses and conclusions about a study carried out with objective of minimizing the thermal cracks formation on cemented carbide inserts during face milling. The main focus of investigation was based on the observation that milling process is an interrupted machining process, which imposes cyclic thermal loads to the cutting tool, causing frequent stresses changes in its superficial and sub-superficial layers. These characteristics cause the formation of perpendicular cracks from cutting edge which aid the cutting tool wear, reducing its life. Several works on this subject emphasizing the thermal cyclic behavior imposed by the milling process as the main responsible for thermal cracks formation have been published. In these cases, the phenomenon appears as a consequence of the difference in temperature experienced by the cutting tool with each rotation of the cutter, usually defined as the difference between the temperatures in the cutting tool wedge at the end of the cutting and idle periods (T factor). Thus, a technique to minimize this cyclic behavior with objective of transforming the milling in an almost-continuous process in terms of temperature was proposed. In this case, a hot air stream was applied into the idle period, during the machining process. This procedure aimed to minimize the T factor. This technique was applied using three values of temperature from the hot air stream (100, 350 e 580 oC) with no cutting fluid (dry condition) and with cutting fluid mist (wet condition) using the hot air stream at 580oC. Besides, trials at room temperature were carried out. Afterwards the inserts were analyzed using a scanning electron microscope, where the quantity of thermal cracks generated in each condition, the wear and others damages was analyzed. In a general way, it was found that the heating of the idle period was positive for reducing the number of thermal cracks during face milling with cemented carbide inserts. Further, the cutting fluid mist application was effective in reducing the wear of the cutting tools.

Obtenção de pós de Nb a partir da redução aluminotérmica com ignição por plasma

The aluminothermic reduction consists in an exothermic reaction between a metallic oxide and aluminum to produce the metal and the scum. The extracted melted metal of that reaction usually comes mixed with particles of Al2O3 resulting of the reduction, needing of subsequent refine to eliminate the residual impure as well as to eliminate porosities. Seeking to obtain a product in powder form with nanometric size or even submicrometric, the conventional heat source of the reaction aluminothermic , where a resistor is used (ignitor) as ignition source was substituted, for the plasma, that acts more efficient way in each particle of the sample. In that work it was used as metallic oxide the niobium pentoxide (Nb2O5) for the exothermal reaction Nb2O5 + Al. Amounts stoichiometric, substoichiometric and superestoichiometric of aluminum were used. The Nb2O5 powder was mixed with aluminum powder and milled in planetarium of high energy for a period of 6 hours. Those powders were immerged in plasm that acts in a punctual way in each particle, transfering heat, so that the reaction can be initiate and spread integrally for the whole volume of the particle. The mixture of Nb2O5 + Al was characterized through the particle size analysis by laser and X-ray diffraction (DRX) and the obtained product of reaction was characterized using the electronic microscopy of sweeping (MEV) and the formed phases were analyzed by DRX. Niobium powders with inferior sizes to 1 mm were obtained by that method. It is noticed, through the analysis of the obtained results, that is possible to accomplish the aluminothermic reduction process by plasma ignition with final particles with inferior sizes to the original oxide

Avaliação de catalisadores a base de carbeto e nitreto de molibdênio na obtenção de lactitol via hidrogenação da lactose

Seeking a greater appreciation of cheese whey was developed to process the hydrogenation of lactose for the production of lactitol, a polyol with high added value, using the catalyst Ni / activated carbon (15% and 20% nickel), the nitride Mo2N, the bimetallic carbide Ni-Mo/ activated carbon and carbide Mo2C. After synthesis, the prepared catalysts were analyzed by MEV, XRD, laser granulometry and B.E.T. The reactor used in catalytic hydrogenation of lactose was the type of bed mud with a pressure (68 atm), temperature (120 oC) and stirring speed (500 rpm) remained constant during the experiments. The system operated in batch mode for the solid and liquid and semi-continuous to gas. Besides the nature of the catalyst, we studied the influence of pH of reaction medium for Mo2C carbide as well as evaluating the character of the protein inhibitor and chloride ions on the activity of catalysts Ni (20%)/Activated Carbon and bimetallic carbide Ni-Mo/Activated Carbon. The decrease in protein levels was performed by coagulation with chitosan and adsorption of chloride ions was performed by ion exchange resins. In the process of protein adsorption and chloride ions, the maximum percentage extracted was about 74% and 79% respectively. The micrographs of the powders of Mo2C and Mo2N presented in the form of homogeneous clusters, whereas for the catalysts supported on activated carbon, microporous structure proved impregnated with small particles indicating the presence of metal. The results showed high conversion of lactose to lactitol 90% for the catalyst Ni (20%)/Activated Carbon at pH 6 and 46% for the carbide Mo2C pH 8 (after addition of NH4OH) using the commercial lactose. Monitoring the evolution of the constituents present in the reaction medium was made by liquid chromatography. A kinetic model of heterogeneous Langmuir Hinshelwood type was developed which showed that the estimated constants based catalysts promoted carbide and nitride with a certain speed the adsorption, desorption and production of lactitol

Electrochemical modified electrodes based on metal-salen complexes

A general view of the electroanalytical applications of metal-salen complexes is discussed in this review. The family of Schiff bases derived from ethylenediamine and ortho-phenolic aldehydes (N,N'-ethylenebis(salicylideneiminato) - salen) and their complexes of various transition metals, such as Al, Ce, Co, Cu, Cr, Fe, Ga, Hg, Mn, Mo, Ni, and V have been used in many fields of chemical research for a wide range of applications such as catalysts for the oxygenation of organic molecules, epoxidation of alkenes, oxidation of hydrocarbons and many other catalyzed reactions; as electrocatalyst for novel sensors development; and mimicking the catalytic functions of enzymes. A brief history of the synthesis and reactivity of metal-salen complexes will be presented. The potentialities and possibilities of metal-Salen complexes modified electrodes in the development of electrochemical sensors as well as other types of sensors, their construction and methods of fabrication, and the potential application of these modified electrodes will be illustrated and discussed.

Electrical properties of polymer/metal interface in polymer light-emitting devices: electron injection barrier suppression

The electrical characterization of a high efficient multilayer polymer light emitting diode using poly[(2-methoxy-5-hexyloxy)-p-phenylenevinylene] as the emissive layer and an anionic fluorinated surfactant as the electron transport layer was performed. For the sake of comparison, a conventional single layer device was fabricated. The density current vs. voltage measurements revealed that the conventional device has a higher threshold voltage and lower current compared to the surfactant modified device. The effective barrier height for electron injection was suppressed. The influence of the interfaces and bulk contributions to the dc and high frequencies conductivities of the devices was also discussed. (c) 2006 Springer Science + Business Media, Inc.

Separating interface state response from parasitic effects in conductance measurements on organic metal-insulator-semiconductor capacitors

A simple model is developed for the admittance of a metal-insulator-semiconductor (MIS) capacitor which includes the effect of a guard ring surrounding the Ohmic contact to the semiconductor. The model predicts most of the features observed in a MIS capacitor fabricated using regioregular poly(3-hexylthiophene) as the active semiconductor and polysilsesquioxane as the gate insulator. In particular, it shows that when the capacitor is driven into accumulation, the parasitic transistor formed by the guard ring and Ohmic contact can give rise to an additional feature in the admittance-voltage plot that could be mistaken for interface states. When this artifact and underlying losses in the bulk semiconductor are accounted for, the remaining experimental feature, a peak in the loss-voltage plot when the capacitor is in depletion, is identified as an interface (or near interface) state of density of similar to 4 x 10(10) cm(-2) eV(-1). Application of the model shows that exposure of a vacuum-annealed device to laboratory air produces a rapid change in the doping density in the channel region of the parasitic transistor but only slow changes in the bulk semiconductor covered by the gold Ohmic contact. (C) 2008 American Institute of Physics.

Determining the interfacial density of states in metal-insulator-semiconductor devices based on poly(3-hexylthiophene)

Low frequency admittance measurements are used to determine the density of interface states in metal-insulator-semiconductor diodes based on the unintentionally doped, p-type semiconductor poly(3-hexylthiophene). After vacuum annealing at 90 degrees C, interface hole trapping states are shown to be distributed in energy with their density decreasing approximately linearly from similar to 20x10(10) to 5x10(10) cm(-2) eV(-1) over an energy range extending from 0.05 to 0.25 eV above the bulk Fermi level. (c) 2008 American Institute of Physics.

Morphological and Structural changes of CaxSr1-xTiO3 Powders Obtained by the Microwave-Assisted Hydrothermal Method

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

Ultrathin films of lignins as a potential transducer in sensing applications involving heavy metal ions

Lignins extracted from sugar cane bagasse using different alcohols in the organosolv-CO(2) supercritical pulping process have been applied in the fabrication of ultrathin films through the Langmuir-Blodgett technique. Langmuir films were characterized by surface pressure versus mean molecular area (Pi-A) isotherms to exploit the sensitivity of nanostructured lignin films to metallic ions (Cu(2+), Cd(2+) and Pb(2+)). The Pi-A isotherms were shifted to larger molecular areas when heavy metal ions are present into the subphase, which might be related to electrostatic repulsions between metallic ions entrapped within the lignin molecular structure. Taking the advantage of metal incorporation, Langmuir monolayers were transferred onto solid substrates forming Langmuir-Blodgett (LB) films to be used as a transducer in an "electronic tongue" system to detect Cu(2+) in aqueous solution below threshold standard established by the Brazilian regulation. Both techniques impedance spectroscopy and electrochemistry have been used in these experiments. Complementary, Fourier transform infrared (FTIR) spectroscopy recorded for LB films before and after soaking into Cu(2+) aqueous solution revealed an interaction between the lignin phenyl groups and the metallic ion. (C) 2007 Elsevier B.V.. All rights reserved.

Surface-enhanced raman scattering: metal nanostructures coated with langmuir-blodgett films

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

Structural and electrochemical properties of LiCoO2 prepared by combustion synthesis

LiCoO2 powders were prepared by combustion synthesis, using metallic nitrates as the oxidant and metal sources and urea as fuel. A small amount of the LiCoO2 phase was obtained directly from the combustion reaction, however, a heat treatment was necessary for the phase crystallization. The heat treatment was performed at the temperature range from 400 up to 700 degreesC for 12 h. The powders were characterized by X-ray diffraction (XRD), X ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and specific surface area values were obtained by BET isotherms. Composite electrodes were prepared using a mixture of LiCoO2, carbon black and poly(vinylidene fluoride) (PVDF) in the 85:10:5% w/w ratio. The electrochemical behavior of these composites was evaluated in ethylene carbonate/dimethylcarbonate solution, using lithium perchlorate as supporting electrolyte. Cyclic voltammograms showed one reversible redox process at 4.0/3.85 V and one irreversible redox process at 3.3 V for the LiCoO2 obtained after a post-heat treatment at 400 and 500 degreesC.Raman spectroscopy showed the possible presence of LiCoO2 with cubic structure for the material obtained at 400 and 500 degreesC. This result is in agreement with X-ray data with structural refinement for the LiCoO2 powders obtained at different temperatures using the Rietveld method. Data from this method showed the coexistence of cubic LiCoO2 (spinel) and rhombohedral (layered) structures when LiCoO2 was obtained at lower temperatures (400 and 500 degreesC). The single rhombohedral structure for LiCoO2 was obtained after post-heat treatment at 600 degreesC. The maximum energy capacity in the first discharge was 136 mA g(-1) for the composite electrode based on LiCoO2 obtained after heat treatment at 700 degreesC. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Factors affecting nucleolytic efficiency of some ternary metal complexes with DNA binding and recognition domains. Crystal and molecular structure of Zn(phen)(edda)

The binding selectivity of the M(phen)(edda) (M = Cu, Co, Ni, Zn; phen = 1,10-phenanthroline, edda = ethylenediaminediacetic acid) complexes towards ds(CG)(6), ds(AT)(6) and ds(CGCGAATTCGCG) B-form oligonucleotide duplexes were studied by CD spectroscopy and molecular modeling. The binding mode is intercalation and there is selectivity towards AT-sequence and stacking preference for A/A parallel or diagonal adjacent base steps in their intercalation. The nucleolytic properties of these complexes were investigated and the factors affecting the extent of cleavage were determined to be: concentration of complex, the nature of metal(11) ion, type of buffer, pH of buffer, incubation time, incubation temperature, and the presence of hydrogen peroxide or ascorbic acid as exogenous reagents. The fluorescence property of these complexes and its origin were also investigated. The crystal structure of the Zn(phen)(edda) complex is reported in which the zinc atom displays a distorted trans-N4O2 octahedral geometry; the crystal packing features double layers of complex molecules held together by extensive hydrogen bonding that inter-digitate with adjacent double layers via pi...pi interactions between 1,10-phenanthroline residues. The structure is compared with that of the recently described copper(II) analogue and, with the latter, included in molecular modeling. (C) 2008 Elsevier B.V. All rights reserved.