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.

Effects of high temperature plasma immersion ion implantation on wear resistance of Ti-Si-B sintered alloys

Although titanium and its alloys own good mechanical properties and excellent corrosion resistance, these materials present poor tribological properties for specific applications that require wear resistance. In order to produce wear-resistant surfaces, this work is aimed at achieving improvement of wear characteristics in Ti-Si-B alloys by means of high temperature nitrogen plasma immersion ion implantation (PIII). These alloys were produced by powder metallurgy using high energy ball milling and hot pressing. Scanning electron microscopy (SEM) and X-ray diffraction identified the presence of α-titanium, Ti6Si2B, Ti5Si3, TiB and Ti3Si phases. Wear tests were carried out with a ball-on-disk tribometer to evaluate the friction coefficient and wear rate in treated and untreated samples. The worn profiles were measured by visible light microscopy and examined by SEM in order to determine the wear rates and wear mechanisms. Ti-7.5Si-22.5B alloy presented the highest wear resistance amongst the untreated alloys produced in this work. High temperature PIII was effective to reduce the wear rate and friction coefficient of all the Ti-Si-B sintered alloys. © 2013 Elsevier B.V.

Improvements of plasma immersion ion implantation (PIII) and deposition (PIII&D) processing for materials surface modification

Plasma immersion ion implantation (PIII) process is a three dimensional surface modification method that is quite mature and well known to the surface engineering community nowadays, especially to those working in the field of plasma-materials interaction, aiming at both industrial and academic applications. More recently, deposition methods have been added to PIII, the PIII&D, opening possibilities of broader range of applications of these techniques. So, PIII&D is becoming a routine method of surface modification, with the advantage of pushing up the retained dose levels limited by the sputtering due to ion implantation. Therefore, well adherent, thick, three-dimensional films without stress are possible to be achieved, at relatively low cost, using PIII&D. In this paper, we will discuss about a few PIII and PIII&D experiments that have been performed recently to achieve surface improvements in different materials: 1 - high temperature nitrogen PIII in Ti6Al4V alloy in which a deep nitrogen rich treated layer resulted in surface improvements as increase of hardness, corrosion resistance and resistance to wear of the Ti alloy; 2 - nanostructures in ZnO films, obtained by PIII&D of vaporized & ionized Zn source; 3 - combined implantation and deposition of calcium for biomaterial activity of Ti alloy (PIII&D), allowing the growth of hydroxyapatite in a body solution; 4 - magnetron sputtering deposition of Cr that was enhanced by the glow discharge Ar plasma to allow implantation and deposition of Cr on SAE 1070 steel (PIII&D) resulting in surfaces with high resistance to corrosion; and 5 - implantation of nitrogen by ordinary PIII into this Cr film, which improved resistance to corrosion, while keeping the tribological properties as good as for the SAE 1070 steel surface. © 2012 Elsevier B.V.

Optical, mechanical and surface properties of amorphous carbonaceous thin films obtained by plasma enhanced chemical vapor deposition and plasma immersion ion implantation and deposition

Diverse amorphous hydrogenated carbon-based films (a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:Si:O) were obtained by radiofrequency plasma enhanced chemical vapor deposition (PECVD) and plasma immersion ion implantation and deposition (PIIID). The same precursors were used in the production of each pair of each type of film, such as a-C:H, using both PECVD and PIIID. Optical properties, namely the refractive index, n, absorption coefficient, α, and optical gap, ETauc, of these films were obtained via transmission spectra in the ultraviolet-visible near-infrared range (wavelengths from 300 to 3300 nm). Film hardness, elastic modulus and stiffness were obtained as a function of depth using nano-indentation. Surface energy values were calculated from liquid drop contact angle data. Film roughness and morphology were assessed using atomic force microscopy (AFM). The PIIID films were usually thinner and possessed higher refractive indices than the PECVD films. Determined refractive indices are consistent with literature values for similar types of films. Values of ETauc were increased in the PIIID films compared to the PECVD films. An exception was the a-C:H:Si:O films, for which that obtained by PIIID was thicker and exhibited a decreased ETauc. The mechanical properties - hardness, elastic modulus and stiffness - of films produced by PECVD and PIIID generally present small differences. An interesting effect is the increase in the hardness of a-C:H:Cl films from 1.0 to 3.0 GPa when ion implantation is employed. Surface energy correlates well with surface roughness. The implanted films are usually smoother than those obtained by PECVD. ©2013 Elsevier B.V. All rights reserved.

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.

Desorption of heavy metals from ion exchange resin with water and carbon dioxide

Adsorption and regeneration of ion exchange resins were studied using a subcritical solution of a CO₂-H₂O mixture and a fixed bed column. The commercial Amberlite IRC-50/IRC-86 cation exchange resins and Amberlite IRA-67 anion exchange resin were tested for heavy metals (Pb, Cu, Cd) adsorption from a solution with different initial metal concentrations at different temperatures. After adsorption, the loaded resins were regenerated with water and carbon dioxide at different temperatures and a pressure of 25 MPa. The efficiency of the IRC-50 resin was lower than that of the IRC-86 resin for the adsorption of metals like Cd, Cu and Pb. Results obtained for desorption of these metals indicated that the process could be used for Cd and in principle for Cu. Sorption of metal ions depended strongly on feed concentration. Mathematical modeling of the metal desorption process was carried out successfully as an extraction process. For this purpose, the VTII Model, which is applied to extraction from solids using supercritical solvents, was used in this work.

Cell adhesion and growth on surfaces modified by plasma and ion implantation

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

Bacterial cellulose/triethanolamine based ion-conducting membranes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of argon ion bombardment on amorphous silicon carbonitride films

Amorphous silicon carbonitride (a-SiCN:H) films were synthesized by radiofrequency (RF) Plasma Enhanced Vapor Chemical Deposition (PECVD) using hexamethyldisilazane (HMDSN) as precursor compound. Then, the films were post-treated by Plasma Immersion Ion Implantation (PIII) in argon atmosphere from 15 to 60 min The hardness of the film enhanced after ion implantation, and the sample treated at 45 min process showed hardness greater than sixfold that of the untreated sample. This result is explained by the crosslinking and densification of the structure Films were exposed to oxygen plasma for determining of the etching rate. It decreased monotonically from 33 angstrom/min to 19 angstrom/min for the range of process time, confirming structural alterations. Hydrophobic character of the a-SiCN:H films were modified immediately after ion bombardment, due to incorporation of polar groups. However, the high wettability of the films acquired by the ion implantation was diminished after aging in air. Therefore, argon PIII made a-SiCN.H films mechanically more resistant and altered their hydrophobic character.

Effect of resin composites with sodium trimetaphosphate with or without fluoride on hardness, ion release and enamel demineralization

Purpose: To evaluate the effect of the addition of sodium trimetaphosphate (TMP) with or without fluoride on enamel demineralization, and the hardness and release of fluoride and TMP of resin composites. Methods: Bovine enamel slabs (4x3x3 mm) were prepared and selected based on initial surface hardness (n= 96). Eight experimental resin composites were formulated, according to the combination of TMP and sodium fluoride (NaF): TMP/NaF-free (control), 1.6% sodium fluoride (NaF), and 1.5%, 14.1% and 36.8% TMP with and without 1.6% NaF. Resin composite specimens (n= 24) were attached to the enamel slabs with wax and the sets were subjected to pH cycling. Next, surface and cross-sectional hardness and fluoride content of enamel as well as fluoride and TNT release and hardness of the materials were evaluated. Data were statistically analyzed using ANOVA (P< 0.05). Results: The presence of fluoride in enamel was similar in fluoridated resin composites (P> 0.05), but higher than in the other materials (P< 0.05). The combination of 14.1% TMP and fluoride resulted in less demineralization, especially on lesion surface (P< 0.05). The presence of TMP increased fluoride release from the materials and reduced their hardness.

Silver ion release from electrodes of nanotubes of TiO2 impregnated with Ag nanoparticles applied in photoelectrocatalytic disinfection

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

Study of magnetic field enhanced plasma immersion ion implantation in Silicon

A comparison between experimental measurements and numerical calculations of the ion current distribution in plasma immersion ion implantation (PIII) with external magnetic field is presented. Later, Silicon samples were implanted with nitrogen ion to analyze the effect on them. The magnetic field considered is essentially non-uniform and is generated by two magnetic coils installed on vacuum chamber. The presence of both, electric and magnetic field in PIII create a crossed ExB field system, promoting drift velocity of the plasma around the target. The results found shows that magnetized electrons drifting in ExB field provide electron-neutral collision. The efficient ionization increases the plasma density around the target where a magnetic confinement is formed. As result, the ion current density increases, promoting significant changes in the samples surface properties, especially in the surface wettability.

Microwave-assisted hydrothermal synthesis of magnetite nanoparticles with potential use as anode in lithium ion batteries

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

Electrochemical Properties of the Oxo-Manganese-Phenanthroline Complex Immobilized on Ion-Exchange Polymeric Film and Its Application as Biomimetic Sensor for Sulfite Ions

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

Electrical conductivity of Ag-Na ion exchanged soda-lime glass

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