Surface Corrosion of Ti-16Si-4B Powder Alloy Implanted With Nitrogen by Plasma-Based Technique

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

A Study of the Effect of Nitrogen and Air Plasma Immersion Ion Implantation Treatments on the Properties of Carbon Fiber

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

Plasma immersion ion implantation of nitrogen into H13 steel under moderate temperatures

Ion implantation of nitrogen into samples of tempered and quenched H13 steel was carried out by plasma immersion technique. A glow discharge plasma of nitrogen species was the ion source and the negative high voltage pulser provided 10-12 kV, 60 mu s duration and 1.0-2.0 kHz frequency, flat voltage pulses. The temperatures of the samples remained between 300 and 450 degrees C, sustained solely by the ion bombardment. In some of the discharges, we used a N-2 + H-2 gas mixture with 1:1 ratio. PIII treatments as long as 3, 6, 9 and up to 12 h were carried out to achieve as thickest treated layer as possible, and we were able to reach over 20 mu m treated layers, as a result of ion implantation and thermal (and possibly radiation enhanced) diffusion. The nitrogen depth profiles were obtained by GDOS (Glow Discharge Optical Spectroscopy) and the exact composition profiles by AES (Auger Electron Spectroscopy). The hardness of the treated surface was increased by more than 250%, reaching 18.8 GPa. No white layer was seen in this case. A hardness profile was obtained which corroborated a deep hardened layer, confirming the high efficacy of the moderate temperature PIII treatment of steels. (c) 2005 Elsevier B.V. All rights reserved.

Effects of nitrogen ion irradiation on plasma polymerized films produced from titanium tetraiso pro poxide-oxygen-helium mixtures

In this work films were produced by the plasma enhanced chemical vapor deposition (PECVD) of titanium tetraisopropoxide-oxygen-helium mixtures and irradiated with 150 keV singly-charged nitrogen ions (N(+)) at fluences, phi, between 10(14) and 10(16) cm(-2). Irradiation resulted in compaction, which reached about 40% (measured via the film thickness) at the highest fluence. Infrared reflection-absorption spectroscopy (IRRAS) revealed the presence of Ti-O bonds in all films. Both O-H and C-H groups were present in the as-deposited films, but the density of each of these decreased with increasing phi and was absent at high phi, indicating a loss of hydrogen. X-ray photoelectron spectroscopy (XPS) analyses revealed an increase in the C to Ti atomic ratio as phi increased, while the O to Ti ratio hardly altered, remaining at around 2.8. The optical gap of the films, derived from data obtained by ultraviolet-visible spectroscopy (UVS), remained at about 3.6 eV for all fluences except the highest, for which an abrupt fall to around 1.0 eV was observed. For the irradiated films, the electrical conductivity, measured using the two-point method, showed a systematic increase with increasing phi. (c) 2008 Elsevier B.V. All rights reserved.

Polymer treatment by plasma immersion ion implantation of nitrogen for formation of diamond-like carbon film

Nitrogen ions were implanted by plasma immersion in Kapton, Mylar and polypropylene, with the objective of forming a diamond-like carbon layer on these polymers. The Raman spectrum of the implanted polypropylene showed typical Diamond-Like Carbon (DLC) graphite (G) and disorder (D) peaks, with an sp 3/sp2 hybridization ratio of approximately 0.4 to 0.6. The XPS analysis of the three implanted polymers also showed peaks of C-C and N-C bonds in the sp3 configuration, with hybridization ratios in the same range as the Raman result. The implanted polymers were exposed to oxygen plasma to test the resistance of the polymers to oxygen degradation. Mass loss rate results, however, showed that the DLC layer formed is not sufficiently robust for this application. Nevertheless, the layer formed can be suitable for other applications such as in gas barriers in beverage containers. Further study of implantation conditions may improve the quality of the DLC layer.

Effects of Plasma Immersion Ion Implantation (PIII) of nitrogen on hardness, composition and corrosion resistance of Ti-6Al-4V alloy

Ti-6Al-4V samples have been treated by PHI processing at different temperatures (400-800°C), treatment time (30-150 min) and plasma potential (100 and 420 V). Hardness measurements results showed an enhancement of the hardness for all implanted samples. XRD results detected the Ti 2N phase and the best corrosion resistance was found for the samples processed at higher temperature and lower PIII time.

Plasma-polymerized acetylene nanofilms modified by nitrogen ion implantation

Thin films were prepared by plasma enhanced chemical vapour deposition (PECVD) from a mixture of acetylene and argon, and post deposition-treated by plasma immersion ion implantation (PIII). The effect of PIII on the nanofilms properties was evaluated as a function of treatment time. The average thickness and roughness were diminished upon PIII. On the other hand, hardness (0.7-3.9 GPa) and elastic modulus (29-54 GPa) increased upon 60 min of ion bombardment. Such results are ascribed mainly to the densification of the film structure caused by the increment in the crosslinking degree with increasing the energy deposited in the films. Wettability of the samples, investigated by contact angle measurements, was reduced (from 64 to 21°) right after PIII. This result, attributed to the introduction of polar groups in the film structure, was not preserved as the sample was aged in atmosphere. After aging, contact angles were larger than 70° but still smaller than 90°. Although the wettability has decreased with aging, the hydrophilic character of the samples was preserved. For certain treatment times, nitrogen PIII turned the plasma-polymerized acetylene films smoother, denser, mechanically and tribologicaly more resistant than the as-deposited material. © 2013 Elsevier B.V.

The effects of nitrogen mustard on plasma membrane function

The antitumour bifunctional alkylating agent nitrogen mustard (HN2) inhibited the unidirectional influx of the potassium congener, 86 rubidium, into murine PC6A plasmacytoma cells and L1210 leukaemia cells. The proliferation of L1210 cells in vitro was characterised and shown to be sentitive to HN2. 86Rubidium influx into cells from rapidly-dividing cultures was more sensitive to inhibition by HN2 than that of cells from stationary cultures. Three components of unidirectional 86Rb+ & K+ influx into proliferating L1210 cells were identified pharmacologically: approximately 40% was active to the Na+ K+ ATPase inhibitor ouabain (10-3M), 40% was sensitive to the `loop' diuretics bumetanide (10-4M) and furosemide (10-3M) and the remainder was insensitive to both ouabain and furosemide. HN2 (10-5M) selectively inhibited the diuretic-sensitive component, which was entirely dependent upon extracellular Na+ and Cl- ions, and was presumed to represent Na+ K+ Cl- cotransport activity. The system did not mediate K+ /K+ exchange or unidirectional 86Rb+ efflux; accordingly, 86Rb+ efflux was insensitive to HN2. Inhibition of 86Rb & K+ influx by 10-5M HN2 was accompanied by approximately 35% of cell volume under isosmotic conditions; thus intracellular Na+ and K+ concentrations remained unchanged. These effects followed lethal damage to the cells but preceded actual cell death; other cellular functions were maintained including accumulation of cycloleucine, transmembrane potential, permeability to trypan blue, intracellular pH, total intracellular glutathione and calcium concentrations. No evidence was found that elevated cAMP levels or reduced ATP levels were involved in modulation of 86Rb+ & K+ influx. However, the Na+ - depedent transport of an amino acid was inhibited in a manner which appeared to be independent of 86Rb & K+ influx. An HN2-resistant L1210R cell line was also resistant to furosemide, and lacked a component of 86Rb+ & K+ influx which was sensitive to furosemide (10-3M). The results strongly suggest that the Na+ K+ Cl- costransporter of L1210 cells is a cellular target for HN2. This lesion is discussed with reference to the cytotoxic effects of the agent.

High rate growth of nanocrystalline diamond films using high microwave power and pure nitrogen/methane/hydrogen plasma

In this work, we investigate the impact of minute amounts of pure nitrogen addition into conventional methane/hydrogen mixtures on the growth characteristics of nanocrystalline diamond (NCD) films by microwave plasma assisted chemical vapour deposition (MPCVD), under high power conditions. The NCD films were produced from a gas mixture of 4% CH4/H2 with two different concentrations of N2 additive and microwave power ranging from 3.0 kW to 4.0 kW, while keeping all the other operating parameters constant. The morphology, grain size, microstructure and texture of the resulting NCD films were characterized by using scanning electron microscope (SEM), micro-Raman spectroscopy and X-ray diffraction (XRD) techniques. N2 addition was found to be the main parameter responsible for the formation and for the key change in the growth characteristics of NCD films under the employed conditions. Growth rates ranging from 5.4 μm/h up to 9.6 μm/h were achieved for the NCD films, much higher than those usually reported in the literature. The enhancing factor of nitrogen addition on NCD growth rate was obtained by comparing with the growth rate of large-grained microcrystalline diamond films grown without nitrogen and discussed by comparing with that of single crystal diamond through theoretical work in the literature. This achievement on NCD growth rate makes the technology interesting for industrial applications where fast coating of large substrates is highly desirable.

Impact of high microwave power on hydrogen impurity trapping in nanocrystalline diamond films grown with simultaneous nitrogen and oxygen addition into methane/hydrogen plasma

In this work, we study for the first time the influence of microwave power higher than 2.0 kW on bonded hydrogen impurity incorporation (form and content) in nanocrystalline diamond (NCD) films grown in a 5 kW MPCVD reactor. The NCD samples of different thickness ranging from 25 to 205 μm were obtained through a small amount of simultaneous nitrogen and oxygen addition into conventional about 4% methane in hydrogen reactants by keeping the other operating parameters in the same range as that typically used for the growth of large-grained polycrystalline diamond films. Specific hydrogen point defect in the NCD films is analyzed by using Fourier-transform infrared (FTIR) spectroscopy. When the other operating parameters are kept constant (mainly the input gases), with increasing of microwave power from 2.0 to 3.2 kW (the pressure was increased slightly in order to stabilize the plasma ball of the same size), which simultaneously resulting in the rise of substrate temperature more than 100 °C, the growth rate of the NCD films increases one order of magnitude from 0.3 to 3.0 μm/h, while the content of hydrogen impurity trapped in the NCD films during the growth process decreases with power. It has also been found that a new H related infrared absorption peak appears at 2834 cm-1 in the NCD films grown with a small amount of nitrogen and oxygen addition at power higher than 2.0 kW and increases with power higher than 3.0 kW. According to these new experimental results, the role of high microwave power on diamond growth and hydrogen impurity incorporation is discussed based on the standard growth mechanism of CVD diamonds using CH4/H2 gas mixtures. Our current experimental findings shed light into the incorporation mechanism of hydrogen impurity in NCD films grown with a small amount of nitrogen and oxygen addition into methane/hydrogen plasma.

Investigation of bonded hydrogen defects in nanocrystalline diamond films grown with nitrogen/methane/hydrogen plasma at high power conditions

In this work, we investigate the influence of some growth parameters such as high microwave power ranging from 3.0 to 4.0 kW and N2 additive on the incorporation of bonded hydrogen defects in nanocrystalline diamond (NCD) films grown through a small amount of pure N2 addition into conventional 4% CH4/H2 plasma using a 5 kW microwave plasma CVD system. Incorporation form and content of hydrogen point defects in the NCD films produced with pure N2 addition was analyzed by employing Fourier-transform infrared (FTIR) spectroscopy for the first time. A large amount of hydrogen related defects was detected in all the produced NCD films with N2 additive ranging from 29 to 87 µm thick with grain size from 47 nm to 31 nm. Furthermore, a specific new H related sharp absorption peak appears in all the NCD films grown with pure N2/CH4/H2 plasma at high powers and becomes stronger at powers higher than 3.0 kW and is even stronger than the 2920 cm−1 peak, which is commonly found in CVD diamond films. Based on these experimental findings, the role of high power and pure nitrogen addition on the growth of NCD films including hydrogen defect formation is analyzed and discussed.

Study of particulate matter removal mechanism by using non-thermal plasma technology

Numbers of diesel engines in both stationary and mobile applications are increasing nowadays. Diesel engines emit lower Hydrocarbon (HC) and Carbon monoxide (CO) than gasoline engines. However, they can produce more nitrogen oxides (NOx) and have higher particulate matter (PM). On the other hand, emissions standards are getting stringent day by day due to considerable concerns about unregulated pollutants and particularly ultrafine particles deleterious effect on human health. Non-thermal plasma (NTP) treatment of exhaust gas is known as a promising technology for both NOx and PM reduction by introducing plasma inside the exhaust gas. Vehicle exhaust gases undergo chemical changes when exposed to plasma. In this study, the PM removal mechanism using NTP by applying high voltage pulses of up to 20 kVpp with a repetition rate of 10 kHz are investigated. It is found that, voltage increase not necessarily has a positive effect on PM removal in diesel engine emissions.

First-principle studies of electronic structure and C-doping effect in boron nitride nanoribbon

Structural and electronic properties have been studied for Boron Nitride nanoribbons (BNNR) with both zigzag and armchair shaped edge (Z-BNNR and A-BNNR) by first-principle spin-polarized total energy calculations. We found that the energy band gap of Z-BNNR is indirect and decreases monotonically with the increasing ribbon width, whereas direct energy band gap oscillation was observed for A-BNNRs. Additionally, C-substitution at either single boron or nitrogen atom site in BNNRs could induce spontaneous magnetization. Our results could be potentially useful to design magnetic nano-devices based on BNNRs.

Effect of pulsed power on particle matter in diesel engine exhaust using a DBD plasma reactor

Nonthermal plasma (NTP) treatment of exhaust gas is a promising technology for both nitrogen oxides (NOX) and particulate matter (PM) reduction by introducing plasma into the exhaust gases. This paper considers the effect of NTP on PM mass reduction, PM size distribution, and PM removal efficiency. The experiments are performed on real exhaust gases from a diesel engine. The NTP is generated by applying high-voltage pulses using a pulsed power supply across a dielectric barrier discharge (DBD) reactor. The effects of the applied high-voltage pulses up to 19.44 kVpp with repetition rate of 10 kHz are investigated. In this paper, it is shown that the PM removal and PM size distribution need to be considered both together, as it is possible to achieve high PM removal efficiency with undesirable increase in the number of small particles. Regarding these two important factors, in this paper, 17 kVpp voltage level is determined to be an optimum point for the given configuration. Moreover, particles deposition on the surface of the DBD reactor is found to be a significant phenomenon, which should be considered in all plasma PM removal tests.