Enhancement of oxidation rate of a-Si nanoparticles during dehydrogenation

Oxidation of amorphous silicon (a-Si) nanoparticles grown by plasma-enhanced chemical vapor deposition were investigated. Their hydrogen content has a great influence on the oxidation rate at low temperature. When the mass gain is recorded during a heating ramp in dry air, an oxidation process at low temperature is identified with an onset around 250°C. This temperature onset is similar to that of hydrogen desorption. It is shown that the oxygen uptake during this process almost equals the number of hydrogen atoms present in the nanoparticles. To explain this correlation, we propose that oxidation at low temperature is triggered by the process of hydrogen desorption

The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation: log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed.

EISCAT observations of ion composition and temperature anisotropy in the high-latitude F-region

The papers by Winser et al. [(1990) J. atmos. terr. Phys.52, 501] and Häggström and Collis [(1990) J. atmos. terr. Phys.52, 519] used plasma flows and ion temperatures, as measured by the EISCAT tristatic incoherent scatter radar, to investigate changes in the ion composition of the ionospheric F-layer at high latitudes, in response to increases in the speed of plasma convection. These studies reported that the ion composition rapidly changed from mainly O+ to almost completely (>90%) molecular ions, following rapid increases in ion drift speed by >1 km s−1. These changes appeared inconsisent with theoretical considerations of the ion chemistry, which could not account for the large fractions of molecular ions inferred from the obsevations. In this paper, we discuss two causes of this discrepancy. First, we reevaluate the theoretical calculations for chemical equilibrium and show that, if we correct the derived temperatures for the effect of the molecular ions, and if we employ more realistic dependences of the reaction rates on the ion temperature, the composition changes derived for the faster convection speeds can be explained. For the Winser et al. observations with the radar beam at an aspect angle of ϕ = 54.7° to the geomagnetic field, we now compute a change to 89% molecular ions in < 2 min, in response to the 3 km s−1 drift. This is broadly consistent with the observations. But for the two cases considered by Häggström and Collis, looking along the field line (ϕ = 0°), we compute the proportion of molecular ions to be only 4 and 16% for the observed plasma drifts of 1.2 and 1.6 km s−1, respectively. These computed proportions are much smaller than those derived experimentally (70 and 90%). We attribute the differences to the effects of non-Maxwellian, anisotropic ion velocity distribution functions. We also discuss the effect of ion composition changes on the various radar observations that report anisotropies of ion temperature.

Facile Synthesis of Koser`s Reagent and Derivatives from Iodine or Aryl Iodides

The first one-pot synthesis of neutral and electron-rich [hydroxy(tosyloxy)iodo]arenes (HTIBs) from iodine and arenes is presented, thereby avoiding the need for expensive iodine(III) precursors. A large set of including a polyfluorinated analogue, can be obtained from the corresponding aryl iodide under the same conditions. The reaction proceeds under mild conditions, without excess reagents, and is fast and high-yielding. Together, the two presented routes give access to a wide range of HTIBs, which are useful reagents in a variety of synthetic transformations.

Room Temperature, Metal-Free Synthesis of Diaryl Ethers with Use of Diaryliodonium Salts

A fast, high-yielding synthesis of diaryl ethers with use of mild and metal-free conditions has been developed. The scope includes bulky ortho-substituted diaryl ethers, which are difficult to obtain by metal-catalyzed protocols. Halo-substituents, racemization-prone amino acid derivatives, and heteroaromatics are also tolerated. The methodology is expected to be of high utility in the synthesis of complex molecules and in the pharmaceutical industry.

A Diastereoselective Total Synthesis of trans-Trikentrin A: A Ring Contraction Approach

A new route to obtain the polyalkylated indole (+/-)-trans-trikentrin A was developed. The synthesis of this natural alkaloid features a thallium(III)mediated ring contraction reaction to obtain the trans-1,3-disubstituted five-membered ring in a diastereoselective manner. Thallium(III) is chemoselective in this rearrangement, reacting with the olefin without oxidation of the indole moiety. Other key transformations are the Bartoli`s reaction to construct the heterocyclic ring and a Heck coupling to add the carbons atom that will originate the nonaromatic cycle.

Estudo da sinterabilidade de ligas de níquel obtidas por meio dos portadores de liga sic, si3n4 ou si metálico com grafita

Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 μm and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 μm. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 μm, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 μm, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ° C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ° C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 °C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 μm active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy

Estudo da molhabilidade de ligas de adição à base de prata sobre insertos cerâmicos para aplicação em brocas perfuração de poços de petróleo

Metal-ceramic interfaces are present in tricone drill bits with hard ceramic inserts for oil well drilling operations. The combination of actions of cutting, crushing and breaking up of rocks results in the degradation of tricone drill bits by wear, total or partial rupture of the drill bit body or the ceramic inserts, thermal shock and corrosion. Also the improper pressfitting of the ceramic inserts on the bit body may cause its total detachment, and promote serious damages to the drill bit. The improvement on the production process of metal-ceramic interfaces can eliminate or minimize some of above-mentioned failures presented in tricone drill bits, optimizing their lifetime and so reducing drilling metric cost. Brazing is a widely established technique to join metal-ceramic materials, and may be an excellent alternative to the common mechanical press fitting process of hard ceramic inserts on the steel bit body for tricone drill bit. Wetting phenomena plays an essential role in the production of metal/ceramic interfaces when a liquid phase is present in the process. In this work, 72Silver-28Copper eutectic based brazing alloys were melted onto zirconia, silicon nitride and tungsten carbide/Co substrates under high vacuum. Contact angle evolution was measured and graphically plotted, and the interfaces produced were analysed by SEM-EDX. The AgCu eutectic alloy did not wet any ceramic substrates, showing high contact angles, and so without chemical interaction between the materials. Better results were found for the systemns containing 3%wt of titanium in the AgCu alloy. The presence os titanium as a solute in the alloy produces wettable cand termodinamically stable compounds, increasing the ceramics wetting beahviour

Structural and optical properties of chlorinated plasma polymers

Amorphous hydrogenated chlorinated carbon (a-C:H:Cl) films were produced by the plasma polymerization of chloroform-acetylene-argon mixtures in a radiofrequency plasma enhanced chemical vapor deposition system. The main parameter of interest was the proportion of chloroform in the feed, R(C), which was varied from 0 to 80%. Deposition rates of 80 nm min (1) were typical for the chlorinated films. Infrared reflection-absorption spectroscopy revealed the presence of C-Cl groups in all the films produced with chloroform in the feed. X-ray photoelectron spectroscopy confirmed this finding, and revealed a saturation of the chlorine content at similar to 47 at.% for R(C)>= 40%. The refractive index and optical gap, E(04), of the films were roughly in the 1.6 to 1.7, and the 2.8 to 3.7 eV range. These values were calculated from transmission ultraviolet-visible-near infrared spectra. Chlorination leads to an increase in the water surface contact angle from similar to 40 degrees to similar to 77 degrees. (C) 2011 Elsevier B.V. All rights reserved.

Corrosion behavior of Ti-6Al-4V alloy treated by plasma immersion ion implantation process

Ti-6Al-4V alloy is one of the most frequently used Ti alloys with diverse applications in aerospace and biomedical areas due to its favorable mechanical properties, corrosion resistance and biocompatibility. Meanwhile, its surface can stiffer intense corrosion caused by wear processes due to its poor tribological properties. Thus in the present study, PIII processing of Ti-6Al-4V alloy was carried out to evaluate its corrosion resistance in 3.5% NaCl solution. Two different sets of Ti-6Al-4V samples were PIII treated, varying the plasma gases and the treatment time. The corrosion behavior is correlated with the surface morphology, and the nitrogen content. SEM micrographs of the untreated sample reveal a typical two-phase structure. PIII processing promotes surface sputtering and the surface morphology is completely different for samples treated with N-2/H-2 mixture and N-2 only. The highest penetration of nitrogen (similar to 88 nm), corresponding to 33% of N-2 was obtained for the sample treated with N-2/H-2 mixture for 1:30 h. The corrosion behavior of the samples was investigated by a potentiodynamic polarization method. A large passive region of the polarization curves (similar to 1.5 V), associated with the formation of a protective film, was observed for all samples. The passive current density (similar to 3 x 10(-6) A cm(-2)) of the PIII-treated Ti-6Al-4V samples is about 10 times higher than for the untreated sample. This current value is still rather low and maintains good corrosion resistance. The anodic branches of the polarization curves for all treated Ti-6Al-4V samples demonstrate also that the oxide films break down at approximately 1.6 V, forming an active region. Although the sample treated by N-2/H-2 mixture for 1.30 It has thicker nitrogen enriched layer, better corrosion resistance is obtained for the PIII process performed with N, gas only. (c) 2007 Elsevier B.V. All rights reserved.

Plasma-polymerized hexamethyldisilazane treated by nitrogen plasma immersion ion implantation technique

This paper describes the effect of nitrogen Plasma Immersion Ion Implantation (PIII) on chemical structure, refraction index and surface hardness of plasma-polymerized hexamethyldisilazane (PPHMDSN) thin films. Firstly, polymeric films were deposited at 13.56 MHz radiofrequency (RF) Plasma Enhanced Chemical Vapour Deposition (PECVD) and then, were treated by nitrogen PIII from 15 to 60 min. Fourier Transformed Infrared (FTIR) spectroscopy was employed to analyse the molecular structure of the samples, and it revealed that vibrations modes at 3350 cm(-1), 2960 cm(-1), 1650 cm(-1), 1250 cm(-1) and 1050 cm(-1) were altered by nitrogen PIII. Visible-ultraviolet (vis-UV) spectroscopy was used to evaluate film refractive index and the results showed a slight increase from 1.6 to 1.8 following the implantation time. Nanoindentation revealed a surface hardness rise from 0.5 to 2.3 GPa as PIII treatment time increased. These results indicate nitrogen PIII is very promising in improving optical and mechanical properties of PPHMDSN films.

Amorphous hydrogenated carbon films treated by SF(6) plasma

This work was performed to verify the chemical structure, mechanical and hydrophilic properties of amorphous hydrogenated carbon films prepared by plasma enhanced chemical vapor deposition, using acetylene/argon mixture as monomer. Films were prepared in a cylindrical quartz reactor, fed by 13.56 MHz radiofrequency. The films were grown during 5 min, for power varying from 25 to 125 W at a fixed pressure of 9.5 Pa. After deposition, all samples were treated by SF(6) plasma with the aim of changing their hydrophilic character. Film chemical structure investigated by Raman spectroscopy, revealed the increase of sp(3) hybridized carbon bonds as the plasma power increases. Hardness measurements performed by the nanoindentation technique showed an improvement from 5 GPa to 14 GPa following the increase discharge power. The untreated films presented a hydrophilic character, which slightly diminished after SF(6) plasma treatment.

SAXS and UV-Vis combined to Quick-XAFS monitoring of ZnO nanoparticles formation and growth

Time-resolved X-ray absorption-fine structure (Quick-XAFS) and UV-Vis absorption spectroscopies were combined for monitoring simultaneously the time evolution of Zn-based species and ZnO quantum dot (Qdot) formation and growth during the sol-gel synthesis from zinc oxy-acetate precursor solution. The time evolution of the nanostructural features of colloidal suspension was independently monitored in situ by small angle X-ray scattering (SAXS). In both cases, the monitoring was initialized just after the addition of NaOH solution (B = [OH]/[Zn] = 0.5) to the precursor solution at 40 degrees C. Combined time-resolved Quick-XAFS and UV-Vis data showed that the formation of ZnO colloids from the zinc oxy-acetate consumption achieves a quasi-steady-state chemical equilibrium in less than 200s. Afterwards, the comparison of the ZnO Qdots size and Guinier gyration radius evidences a limited aggregation process coupled to the Qdots growth. The analysis of the experimental results demonstrates that the nanocrystal coalescence and Ostwald ripening control the kinetics of the Qdot growth.

XPS investigation of plasma-deposited polysiloxane films irradiated with helium ions

This work describes an XPS investigation of plasma-deposited polysiloxane films irradiated with 170 keV He+ ions at fluences, Phi, ranging from 1 x 10(14) to 1 x 10(16) cm(-2). Modifications in the atomic concentrations of the surface atoms with (D were revealed by changes in the [O]/[Si], [O]/[C] and [C]/[Si] atomic ratios. Surface chemical structure modifications were evidenced by the increasing C1s peak width and asymmetry as Phi was increased, due to the formation of ether and carboxyl functionalities. Moreover, structural transformations were indicated by the positive binding energy shift of the Si2p peaks, due to the increasing Si oxidation. Correlations of the XPS data with other results from previous work on polysiloxanes illustrate the role of ion beam-induced bond breaking on the structural modifications.

Infrared spectroscopy investigation of various plasma-deposited polymer films irradiated with 170 keV He+ ions

This work illustrates the advantages of using p-polarized radiation at an incidence angle of 70 degrees in contrast to the conventional unpolarized beam at normal (or near-normal) incidence for the infrared spectroscopic study of polycarbosilane, polysilazane and polysiloxane thin films synthesized by plasma enhanced chemical vapor deposition (PECVD) and subsequently irradiated with 170 keV He+ ions at fluences from 1 x 10(14) to 1 x 10(16) cm(-2). Several bands not seen using the conventional mode could be observed in the polarized mode. (c) 2006 Elsevier B.V. All rights reserved.