Etude spectroscopique d’un plasma micro-onde à la pression atmosphérique et son application à la synthèse de nanostructures

L’objectif de ce mémoire de maîtrise est de caractériser la distribution axiale des plasmas tubulaires à la pression atmosphérique créés et entretenus par une onde électromagnétique de surface ainsi que d’explorer le potentiel de ces sources pour la synthèse de matériaux et de nanomatériaux. Un précédent travail de thèse, qui avait pour objectif de déterminer les mécanismes à l’origine de la contraction radiale du plasma créé dans des gaz rares, a mis en lumière un phénomène jusque-là inconnu dans les plasmas d’onde de surface (POS). En effet, la distribution axiale varie différemment selon la puissance incidente ce qui constitue une différence majeure par rapport aux plasmas à pression réduite. Dans ce contexte, nous avons réalisé une étude paramétrique des POS à la pression atmosphérique dans l’Ar. À partir de nos mesures de densité électronique, de température d’excitation et de densité d’atomes d’Ar dans un niveau métastable (Ar 3P2), résolues axialement, nous avons conclu que le comportement axial de l’intensité lumineuse avec la puissance n’est pas lié à un changement de la cinétique de la décharge (qui est dépendante de la température des électrons et de la densité d’atomes d’Ar métastables), mais plutôt à une distribution anormale de dissipation de puissance dans le plasma (reliée à la densité d’électrons). Plus précisément, nos résultats suggèrent que ce dépôt anormal de puissance provient d’une réflexion de l’onde dans le fort gradient de densité de charges en fin de colonne, un effet plus marqué pour de faibles longueurs de colonnes à plasma. Ensuite, nous avons effectué une étude spectroscopique du plasma en présence de précurseurs organiques, en particulier le HMDSO pour la synthèse de matériaux organosiliciés et l’IPT pour la synthèse de matériaux organotitaniques. Les POS à la PA sont caractérisés par des densités de charges très élevées (>10^13 cm^-3), permettant ainsi d’atteindre des degrés de dissociation des précurseurs nettement plus élevés que ceux d'autres plasmas froids à la pression atmosphérique comme les décharges à barrière diélectrique. Dans de tels cas, les matériaux synthétisés prennent la forme de nanopoudres organiques de taille inférieure à 100 nm. En présence de faibles quantités d’oxygène dans le plasma, nous obtenons plutôt des nanopoudres à base d’oxyde de silicium (HMDSO) ou à base de titanate de silicium (IPT), avec très peu de carbone.

Tensile bond strength of cast commercially pure titanium and cast gold-alloy posts and cores cemented with two luting agents

Statement of problem. In vitro studies on the retentive strengths of various cements used to retain posts have reported conflicting results. Purpose. The purpose of this study was to compare the tensile strength of commercially pure titanium and type III cast gold-alloy posts and cores cemented with zinc phosphate or resin cement. Material and methods. Forty-two extracted human canines were endoclontically treated. The root preparations were accomplished using Largo reamers (10 mm in depth and 1.7 mm in diameter). Acrylic resin patterns for the posts and cores were made, and specimens were cast in commercially pure titanium and in type III gold alloy (n=7). Fourteen titanium cast posts and cores were submitted to surface treatment with Kroll acid solution and to scanning electron microscopy (SEM), before and after acid etching. The groups (n=7) were cemented with zinc phosphate cement or resin cement (Panavia F). Tensile strengths were measured in a universal testing machine at a crosshead speed of 0.5 mm/min. The results (Kgf) were statistically analyzed by 2-way ANCIVA (alpha=.05). Results. The 2-way ANOVA indicated that there were no significant differences among the groups tested. Retentive means for zinc phosphate and Panavia F cements were statistically similar. The bond strength was not Influenced by the alloy, the luting material, or the etching treatment. SEM analysis indicated that the etched surfaces were smoother than those that did not receive surface treatment, but this fact did not influence the results. Conclusions. Commercially pure titanium cast posts and cores cemented with zinc phosphate and resin cements demonstrated similar mean tensile retentive values. Retentive values were also similar to mean values recorded for cast gold-alloy posts and cores cemented with zinc phosphate cement and resin cements.

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L-1 H2SO4 solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA](n), polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases ill solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L-1 H2SO4 in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper. (C) 2007 Elsevier Ltd. All rights reserved.

Hydroxyapatite/titania sol-gel coatings on titanium-zirconium alloy for biomedical applications

A simple sol–gel method was developed for hydroxyapatite/titania (HA/TiO2) coatings on non-toxic titanium–zirconium (TiZr) alloy for biomedical applications. The HA/TiO2-coated TiZr alloy displayed excellent bioactivity when soaked in a simulated body fluid (SBF) for an appropriate period. Differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy-energy dispersive spectrometry were used to characterize the phase transformations and the surface structures and to assess the in vitro tests. The HA/TiO2 layers were spin-coated on the surface of TiZr alloy at a speed of 3000 rpm for 15 s, followed by a heat treatment at 600 °C for 20 min in an argon atmosphere sequentially. The TiO2 layer exhibited a cracked surface and an anatase structure and the HA layer displayed a uniform dense structure. Both the TiO2 and HA layers were 25 μm thick, and the total thickness of the HA/TiO2 coatings was 50 μm. The TiZr alloy after the above HA/TiO2 coatings displayed excellent bone-like apatite-forming ability when soaked in SBF and can be anticipated to be a promising load-bearing implant material.

Biomimetic processing of nanocrystallite bioactive apatite coating on titanium-zirconium alloy

In this paper nanocrystallite apatite coating on TiZr substrate was prepared by a biomimetic process. Surface morphology, thickness, crystalline phases a~nd bond strength of the coating were investigated by SEM, XRD and tensIle test, respectively. Results show that the apatite coating exhibIts a nanocrystalIite structure with similar stoichiometry to that of natural bone. The apatite layer becomes thicker with the increasing of the SBF immersion time and is firmly adhered to the substrate with the highest average bond strength of 15.5 MPa. This nanocrystallite apatite coating is expected to bond to surrounding bone tissue directly in vivo after implantation.

In vitro osteoblast-like cell proliferation on nano-hydroxyapatite coatings with different morphologies on a titanium-niobium shape memory alloy

The morphology of nanomaterials significantly affects their physical, chemical, and biological properties. In the present study, nano-hydroxyapatite coatings with different morphologies were produced on the surface of a titanium-niobium shape memory alloy via a hydrothermal process. The effect of the nano-hydroxyapatite coatings on the in vitro proliferation of SaOS-2 osteoblast-like cells was investigated. Factors including crystallinity, surface micro-roughness, and surface energy of the nano-hydroxyapatite coatings were discussed. Results show that in vitro proliferation of the osteoblast-like cells was significantly enhanced on the nano-hydroxyapatite-coated titanium-niobium alloy compared to the titanium-niobium alloy without coating. The cell numbers on the nano-hydroxyapatite-coated titanium-niobium alloy changed consistently with the surface energy of the hydroxyapatite coatings. This study suggests that surface energy as a characteristic parameter influencing the in vitro proliferation of osteoblast-like cells was predominant over the crystallinity and surface micro-roughness of the nano-hydroxyapatite coatings.

Collagen type-I leads to in vivo matrix mineralization and secondary stabilization of Mg-Zr-Ca alloy implants

Biodegradable magnesium-zirconia-calcium (Mg-Zr-Ca) alloy implants were coated with Collagen type-I (Coll-I) and assessed for their rate and efficacy of bone mineralization and implant stabilization. The phases, microstructure and mechanical properties of these alloys were analyzed using X-ray diffraction (XRD), optical microscopy and compression test, respectively, and the corrosion behavior was established by their hydrogen production rate in simulated body fluid (SBF). Coll-I extracted from rat tail, and characterized using fourier transform infrared (FT-IR) spectroscopy, was used for dip-coating the Mg-based alloys. The coated alloys were implanted into the femur bones of male New Zealand white rabbits. In vivo bone formation around the implants was quantified by measuring the bone mineral content/density (BMC/BMD) using dual-energy X-ray absorptiometry (DXA). Osseointegration of the implant and new bone mineralization was visualized by histological and immunohistochemical analysis. Upon surface coating with Coll-I, these alloys demonstrated high surface energy showing enhanced performance as an implant material that is suitable for rapid and efficient new bone tissue induction with optimal mineral content and cellular properties. The results demonstrate that Coll-I coated Mg-Zr-Ca alloys have a tendency to form superior trabecular bone structure with better osteoinduction around the implants and higher implant secondary stabilization, through the phenomenon of contact osteogenesis, compared to the control and uncoated ones in shorter periods of implantation. Hence, Coll-I surface coating of Mg-Zr-Ca alloys is a promising method for expediting new bone formation in vivo and enhancing osseointegration in load bearing implant applications.

Caracterização de superfícies de titânio modificado por oxidação à plasma

Recent years have seen a significant growth in surface modifications in titanium implants, resulting in shorter healing times in regions with low bone density. Among the different techniques, subtraction by chemical agents to increase oxidation has been applied for surface treatment of dental implants. However, this technique is generally unable to remove undesirable oxides, formed spontaneously during machining of titanium parts, raising costs due to additional decontamination stages. In order to solve this problem, the present study used plasma as an energy source to both remove these oxides and oxidize the titanium surface. In this respect, Ti disks were treated by hollow cathode discharge, using a variable DC power supply and vacuum system. Samples were previously submitted to a cleaning process using an atmosphere of Ar, H2 and a mixture of both, for 20 and 60 min. The most efficient cleaning condition was used for oxidation in a mixture of argon (60%) and oxygen (40%) until reaching a pressure of 2.2 mbar for 60 min at 500°C. Surfaces were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), adhesion and cell proliferation. SEM showed less cell spreading and a larger number of projections orfilopodia in the treated samples compared to the control sample. AFM revealed surface defects in the treated samples, with varied geometry between peaks and valleys. Biological assays showed no significant difference in cell adhesion between treated surfaces and the control. With respect to cell proliferation, the treated surface exhibited improved performance when compared to the control sample. We concluded that the process was efficient in removing primary oxides as well as in oxidizing titanium surfaces

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.

Nanohardness and contact angle of Si wafers implanted with N and C and Al alloy with N by plasma ion implantation

Surfaces of silicon wafers implanted with N and C, respectively, and aluminum 5052 implanted with N alone by plasma immersion ion implantation WHO were probed by a nanoindentor and analyzed by the contact-angle method to provide information on surface nanohardness and wettability. Silicon nitride and silicon carbide are important ceramic materials for microelectronics, especially for high-temperature applications. These compounds can be synthesized by high-dose ion implantation. The nanohardness of a silicon sample implanted with 12-keV nitrogen PIII (with 3 X 10(17) cm(-2) dose) increased by 10% compared to the unimplanted sample, in layers deeper than the regions where the formation of the Si,N, compound occurred. A factor of 2.5 increase in hardness was obtained for C-implanted Si wafer at 35 keV (with 6 X 10(17) cm(-2) dose), again deeper than the SiC-rich layer, Both compounds are in the amorphous state and their hardness is much lower than that of the crystalline compounds, which require an annealing process after ion implantation. In the same targets, the contact angle increased by 65% and 35% for N- and C-implanted samples, respectively. Compared to the Si target, the nitrogen PIII-irradiated Al 5052 (wish 15 keV) showed negligible change in its hydrophobic character after ion implantation. Its near-surface nanohardness measurement showed a slight increase for doses of 1 X 10(17) cm(-2). We have been searching for an AlN layer of the order of 1000 A thick, using such a low-energy PIII process, but oxide formation during processing has precluded its synthesis. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Wear resistance of nickel-titanium endodontic files after surface treatment

Objectives The purpose of this work was to submit the Nitinol files to plasma immersion ion implantation (PIII) and evaluate the effects of the surface treatment. Materials and Methods Wear resistance was determined in vitro by using an equipment for the application of horizontal movements on previously prepared notched plates made of resin. Vickers microhardness was measured in plates and files, before and after surface treatment and the surface chemical composition of the instruments was determined by X-rays photoelectron spectroscopy. Results The hardness values found for the treated Nitinol files were significantly lower than the hardness values measured before the implantation process. The comparison of commercially available instruments shows that the wear resistance of the stainless steel file is higher than the resistance of the Nitinol. Conclusions The results found led to the conclusion that the surface treatment significantly increased the Nitinol files wear resistance.

Evaluation of interface characterization and adhesion of glass ceramics to commercially pure titanium and gold alloy after thermal- and mechanical-loading

Objectives. This study evaluated the effect of thermal- and mechanical-cycling on the shear bond strength of three low-fusing glassy matrix dental ceramics to commercial pure titanium (cpTi) when compared to conventional feldspathic ceramic fused to gold alloy.Methods. Metallic frameworks (diameter: 5 min, thickness: 4 mm) (N = 96, n = 12 per group) were cast in cpTi and gold alloy, airborne particle abraded with 150 mu m aluminum oxide. Low-fusing glassy matrix ceramics and a conventional feldspathic ceramic were fired onto the alloys (thickness: 4mm). Four experimental groups were formed; Gr1 (control group): Vita Omega 900-Au-Pd alloy; Gr2: Ticeram-cpTi; Gr3: Super Porcelain Ti-22-cpTi and G4: Vita Titankeramik-cpTi. While half of the specimens from each ceramic-metal combination were randomly tested without aging (water storage at 37 C for 24h only), the other half were first thermocycled (6000 cycles, between 5 and 55 C, dwell time: 13 s) and then mechanically loaded (20,000 cycles under SON load, immersion in distilled water at 37 C). The ceramic-alloy interfaces were loaded under shear in a universal test machine (cross-head speed: 0.5 mm/min) until failure occur-red. Failure types were noted and the interfaces of the representative fractured specimens from each group were examined with stereo microscope and scanning electron microscope (SEM). in an additional study (N = 16, n = 2 per group), energy dispersive X-ray spectroscopy (EDS) analysis was performed from ceramic-alloy interfaces. Data were analyzed using ANOVA and Tukey's test.Results. Both ceramic-metal combinations (p < 0.001) and aging conditions (p < 0,001) significantly affected the mean bond strength values. Thermal- and mechanical-cycling decreased the bond strength (MPa) results significantly for Gr3 (33.4 +/- 4.2) and Gr4 (32.1 +/- 4.8) when compared to the non-aged groups (42.9 +/- 8.9, 42.4 +/- 5.2, respectively). Gr1 was not affected significantly from aging conditions (61.3 +/- 8.4 for control, 60.7 +/- 13.7 after aging) (p > 0.05). Stereomicroscope images showed exclusively adhesive failure types at the opaque ceramic-cpTi interfacial zone with no presence of ceramic on the substrate surface but with a visible dark titanium oxide layer in Groups 2-4 except Gr1 where remnants of bonder ceramic was visible. EDS analysis from the interfacial zone for cpTi-ceramic groups showed predominantly 34.5-85.1% O(2) followed by 1.1-36.7% Aland 0-36.3% Si except for Super Porcelain Ti-22 where a small quantity of Ba (1.4-8.3%), S (0.7%) and Sn (35.3%) was found. In the Au-Pd alloy-ceramic interface, 56.4-69.9% O(2) followed by 15.6-26.2% Si, 3.9-10.9% K, 2.8-6% Na, 4.4-9.6% Al and 0-0.04% Mg was observed.Significance. After thermal-cycling for 6000 times and mechanical-cycling for 20,000 times, Triceram-cpTi combination presented the least decrease among other ceramic-alloy combinations when compared to the mean bond strength results with Au-Pd alloy-Vita Omega 900 combination. (c) 2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A study of histological responses from Ti-6Al-7Nb alloy dental implants with and without plasma-sprayed hydroxyapatite coating in dogs

Titanium alloys are hoped to be used much more for applications as implant materials in the medical and dental fields because of their basic properties, such as biocompatibility, corrosion resistance and specific strength compared with other metallic implant materials. Thus, the Ti-6Al-7Nb alloy that has recently been developed for biomedical use, that is, primarily developed for orthopaedic use, is to be studied in this paper, for application in dental implants. The biocompatibility test in vivo was carried out in dogs and the osseointegration was verified through histological analysis of the samples of the Ti-6Al-7Nb alloy with and without hydroxyapatite coating that were inserted in the alveoli. Within the controlled conditions the samples did not show any toxic effects on the cells. (C) 2001 Kluwer Academic Publishers.

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.

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L-1 H2SO4 solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA](n), polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases ill solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L-1 H2SO4 in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper. (C) 2007 Elsevier Ltd. All rights reserved.