Mécanismes de déformation de nanoparticules d’Au par irradiation ionique

Résumé Dans la présente thèse, nous avons étudié la déformation anisotrope par bombardement ionique de nanoparticules d'or intégrées dans une matrice de silice amorphe ou d'arséniure d’aluminium cristallin. On s’est intéressé à la compréhension du mécanisme responsable de cette déformation pour lever toute ambigüité quant à l’explication de ce phénomène et pour avoir une interprétation consistante et unique. Un procédé hybride combinant la pulvérisation et le dépôt chimique en phase vapeur assisté par plasma a été utilisé pour la fabrication de couches nanocomposites Au/SiO2 sur des substrats de silice fondue. Des structures à couches simples et multiples ont été obtenues. Le chauffage pendant ou après le dépôt active l’agglomération des atomes d’Au et par conséquent favorise la croissance des nanoparticules. Les nanocomposites Au/AlAs ont été obtenus par implantation ionique de couches d’AlAs suivie de recuit thermique rapide. Les échantillons des deux nanocomposites refroidis avec de l’azote liquide ont été irradiés avec des faisceaux de Cu, de Si, d’Au ou d’In d’énergie allant de 2 à 40 MeV, aux fluences s'étendant de 1×1013 à 4×1015 ions/cm2, en utilisant le Tandem ou le Tandetron. Les propriétés structurales et morphologiques du nanocomposite Au/SiO2 sont extraites en utilisant des techniques optiques car la fréquence et la largeur de la résonance plasmon de surface dépendent de la forme et de la taille des nanoparticules, de leur concentration et de la distance qui les séparent ainsi que des propriétés diélectriques du matériau dans lequel les particules sont intégrées. La cristallinité de l’arséniure d’aluminium est étudiée par deux techniques: spectroscopie Raman et spectrométrie de rétrodiffusion Rutherford en mode canalisation (RBS/canalisation). La quantité d’Au dans les couches nanocomposites est déduite des résultats RBS. La distribution de taille et l’étude de la transformation de forme des nanoparticules métalliques dans les deux nanocomposites sont déterminées par microscopie électronique en transmission. Les résultats obtenus dans le cadre de ce travail ont fait l’objet de trois articles de revue. La première publication montre la possibilité de manipuler la position spectrale et la largeur de la bande d’absorption des nanoparticules d’or dans les nanocomposites Au/SiO2 en modifiant leur structure (forme, taille et distance entre particules). Les nanoparticules d’Au obtenues sont presque sphériques. La bande d’absorption plasmon de surface (PS) correspondante aux particules distantes est située à 520 nm. Lorsque la distance entre les particules est réduite, l’interaction dipolaire augmente ce qui élargit la bande de PS et la déplace vers le rouge (602 nm). Après irradiation ionique, les nanoparticules sphériques se transforment en ellipsoïdes alignés suivant la direction du faisceau. La bande d’absorption se divise en deux bandes : transversale et longitudinale. La bande correspondante au petit axe (transversale) est décalée vers le bleu et celle correspondante au grand axe (longitudinale) est décalée vers le rouge indiquant l’élongation des particules d’Au dans la direction du faisceau. Le deuxième article est consacré au rôle crucial de la déformation plastique de la matrice et à l’importance de la mobilité des atomes métalliques dans la déformation anisotrope des nanoparticules d’Au dans les nanocomposites Au/SiO2. Nos mesures montrent qu'une valeur seuil de 2 keV/nm (dans le pouvoir d'arrêt électronique) est nécessaire pour la déformation des nanoparticules d'or. Cette valeur est proche de celle requise pour la déformation de la silice. La mobilité des atomes d’Au lors du passage d’ions est confirmée par le calcul de la température dans les traces ioniques. Le troisième papier traite la tentative de formation et de déformation des nanoparticules d’Au dans une matrice d’arséniure d’aluminium cristallin connue pour sa haute résistance à l’amorphisation et à la déformation sous bombardement ionique. Le résultat principal de ce dernier article confirme le rôle essentiel de la matrice. Il s'avère que la déformation anisotrope du matériau environnant est indispensable pour la déformation des nanoparticules d’or. Les résultats expérimentaux mentionnés ci-haut et les calculs de températures dans les traces ioniques nous ont permis de proposer le scénario de déformation anisotrope des nanoparticules d’Au dans le nanocomposite Au/SiO2 suivant: - Chaque ion traversant la silice fait fondre brièvement un cylindre étroit autour de sa trajectoire formant ainsi une trace latente. Ceci a été confirmé par la valeur seuil du pouvoir d’arrêt électronique. - L’effet cumulatif des impacts de plusieurs ions conduit à la croissance anisotrope de la silice qui se contracte dans la direction du faisceau et s’allonge dans la direction perpendiculaire. Le modèle de chevauchement des traces ioniques (overlap en anglais) a été utilisé pour valider ce phénomène. - La déformation de la silice génère des contraintes qui agissent sur les nanoparticules dans les plans perpendiculaires à la trajectoire de l’ion. Afin d’accommoder ces contraintes les nanoparticules d’Au se déforment dans la direction du faisceau. - La déformation de l’or se produit lorsqu’il est traversé par un ion induisant la fusion d’un cylindre autour de sa trajectoire. La mobilité des atomes d’or a été confirmée par le calcul de la température équivalente à l’énergie déposée dans le matériau par les ions incidents. Le scénario ci-haut est compatible avec nos données expérimentales obtenues dans le cas du nanocomposite Au/SiO2. Il est appuyé par le fait que les nanoparticules d’Au ne se déforment pas lorsqu’elles sont intégrées dans l’AlAs résistant à la déformation.

Marked influence of the bridging carbonyl ligands on the photo- and electrochemistry of the clusters [Ru-3(CO)(8)(mu-CO)(2)-(alpha-diimine)] (alpha-diimine = 2,2 '-bipyridine, 4,4 '-dimethyl-2,2 '-bipyridine and 2,2 '-bipyrimidine)

Bonding, photochemical and electrochemical properties of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] (alpha-diimine=2,2'-bipyridine (1), 4,4'-dimethyl-2,2'-bipyridine (2) and 2,2'-bipyrimidine (3)) are strongly influenced by the presence of bridging carbonyl ligands. Irradiation at 471 nm initially results in the population of a sigma(Ru-3)pi*(alpha-diimine) excited state. From this state, fast decay takes place to the optically hardly directly accessible pi(Ru/mu-CO) pi*(alpha-diimine) lowest excited state. These assignments agree with theoretical (TD-DFT) results, resonance Raman and picosecond time-resolved infrared spectra. The involvement of the bridging carbonyl ligands in the electron transfer increases the energetic barrier for the formation of open-structure photoproducts such as biradicals and zwitterions. Zwitterions were therefore only obtained in strongly coordinating media such as pyridine at 250 K. The bridging carbonyl ligands also stabilize the radical anions produced upon one-electron reduction of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] and observed with cyclic voltammetry, EPR and IR spectroelectrochemistry (for alpha-diimine=2,2'-bipyrimidine). In contrast, open-triangle intermediates formed along the reduction path to [Ru(CO)(2)(alpha-diimine)](n) and [Ru-2(CO)(8)](2-) are more reactive than their triosmium analogues.

Effects of the particle size and nucleation temperature on tellurite 20Li(2)O-80TeO(2) glass crystallization

20Li(2)O-80TeMO(2) glasses were heat annealed at different temperatures between T-g and T-x and studied by using XRD, FTIR spectroscopy and DSC techniques to understand the crystallization kinetics in this glass matrix. The infrared band structure of this glass is similar to what was observed in glassy TeO2. XRD results reveal the presence of three distinct crystalline gamma-TeO2, alpha-TeO2 and Li2Te2O5 phases during the crystallization process. This is a first report of gamma-TeO2 phase crystallization in this glass matrix. DSC results confinn the crystallization of three distinct structures in the glass. In summary, our results suggest a crystallization hierarchy on this glass matrix since the gamma-TeO2 and alpha-TeO2 phases crystallization occurs before the Li2Te2O5 phase crystallization. (c) 2006 Elsevier B.V. All rights reserved.

Effect of Er,Cr:YSGG and Er:YAG laser irradiation on the adhesion of blood components on the root surface and on root morphology

The aim of this study was to conduct an in vitro evaluation, by scanning electron microscopy (SEM), of the adhesion of blood components on root surfaces irradiated with Er,Cr:YSGG (2.78 mu m) or Er:YAG (2.94 mu m) laser, and of the irradiation effects on root surface morphology. Sixty samples of human teeth were previously scaled with manual instruments and divided into three groups of 20 samples each: G1 (control group) - no treatment; G2 - Er,Cr:YSGG laser irradiation; G3 - Er:YAG laser irradiation. After performing these treatments, blood tissue was applied to 10 samples of each group, whereas 10 samples received no blood tissue application. After performing the laboratory treatments, the samples were observed under SEM, and the resulting photomicrographs were classified according to a blood component adhesion scoring system and root morphology. The results were analyzed statistically (Kruskall-Wallis and Mann Whitney tests, alpha = 5%). The root surfaces irradiated with Er:YAG and Er,Cr:YSGG lasers presented greater roughness than those in the control group. Regarding blood component adhesion, the results showed a lower degree of adhesion in G2 than in G1 and G3 (G1 x G2: p = 0.002; G3 x G2: p = 0.017). The Er:YAG and Er,Cr:YSGG laser treatments caused more extensive root surface changes. The Er:YAG laser treatment promoted a greater degree of blood component adhesion to root surfaces, compared to the Er,Cr:YSGG treatment.

Denture disinfection by microwave irradiation: A randomized clinical study

Processo FAPESP: 05/02384-4

Adhesion strength characterization of PVDF/HA coating on cp Ti surface modified by laser beam irradiation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

EFFECT of DIFFERENT AIRBORNE-PARTICLE ABRASION/BONDING AGENT COMBINATIONS on THE BOND STRENGTH of A RESIN CEMENT TO A BASE METAL ALLOY

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

Effect of microwave irradiation and water storage on the viscoelastic properties of denture base and reline acrylic resins

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

Disinfection of Bovine Enamel by Microwave Irradiation: Effect on the Surface Microhardness and Demineralization/Remineralization Processes

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

Effect of disinfection by microwave irradiation on the strength of intact and relined denture bases and the water sorption and solubility of denture base and reline materials

This study evaluated the influence of microwave disinfection on the strength of intact and relined denture bases. Water sorption and solubility were also evaluated. A heat-polymerized acrylic resin (Lucitone 550) was used to construct 4-mm-thick (n = 40) and 2-mm-thick (n = 160) denture bases. Denture bases (2mm) were relined with an autopolymerizing resin (Tokuso Rebase Fast, Ufi Gel Hard, Kooliner, or New Truliner). Specimens were divided into four groups (n = 10): without treatment, one or seven cycles of microwave disinfection (650 W for 6 min), and water storage at 37 degrees C for 7 days. Specimens were vertically loaded (5 mm/min) until failure. Disc-shaped specimens (50 min x 0.5 mm) were fabricated (n = 10) to evaluate water sorption and solubility. Data on maximum fracture load (N), deflection (%), and solubility (%) were analyzed by two-way analysis of variance and Student-Newman-Keuls tests (alpha = 0.05). One cycle of microwave disinfection decreased the deflection at fracture and fracture energy of Tokuso Rebase Fast and New Truliner specimens. The strength of denture bases microwaved daily for 7 days was similar to the strength of those immersed in water for 7 days. Microwave disinfection increased the water sorption of all materials and affected the solubility of the reline materials. (C) 2007 Wiley Periodicals, Inc.

Nd:YAG Laser Irradiation of Etched/Unetched Dentin Through an Uncured Two-step Etch-and-Rinse Adhesive and its Effect on Microtensile Bond Strength

Purpose: To evaluate whether Nd:YAG laser irradiation of etched and unetched dentin through an uncured adhesive affected the microtensile bond strength (pTBS).Materials and Methods: Flat dentin surfaces were created in 19 extracted human third molars. Adper Single Bond (SB) adhesive was applied over etched (groups 1 to 3) or unetched dentin (groups 4 to 6). The dentin was then irradiated with a Nd:YAG laser through the uncured adhesive, using 0.75 or 1 W power settings, except for the control groups (groups 1 and 4). The adhesive was light cured and composite crowns were built up. After 24 h, the teeth were sectioned into beams, with cross-sectional areas of 0.49 mm(2), and were stressed under tension. Data were statistically analyzed using two-way ANOVA and Tukey's test (alpha = 5%). Dentin surfaces of fractured specimens and the interfaces of untested beams were observed under scanning electron microscopy (SEM).Results: Acid etching, laser irradiation, and their interaction significantly affected bonding (p < 0.05). Laser irradiation did not improve bonding of etched dentin to resin (p > 0.05). However, higher pTBS means were found on unetched lased dentin (groups 5 and 6), but only in comparison to group 4, where neither lasing nor etching was performed. Groups 4 to 6 showed the lowest pTBS means among all groups tested (p < 0.05). Laser irradiation did not change the characteristics of the hybrid layers created, while solidification globules were observed on lased dentin surfaces under SEM.Conclusion: Laser irradiation of dentin through the uncured adhesive did not significantly improve the pTBS in comparison to the suggested manufacturer's technique.

Effect of Airborne-Particle Abrasion and Mechanico-Thermal Cycling on the Flexural Strength of Glass Ceramic Fused to Gold or Cobalt-Chromium Alloy

Purpose: To evaluate the effect of airborne-particle abrasion and mechanico-thermal cycling on the flexural strength of a ceramic fused to cobalt-chromium alloy or gold alloy.Materials and Methods: Metallic bars (n = 120) were made (25 mm x 3 mm x 0.5 mm): 60 with gold alloy and 60 with Co-Cr. At the central area of the bars (8 mm x 3 mm), a layer of opaque ceramic and then two layers of glass ceramic (Vita VM13, Vita Zahnfabrick) were fired onto it (thickness: 1 mm). Ten specimens from each alloy group were randomly allocated to a surface treatment [(tungsten bur or air-particle abrasion (APA) with Al(2)O(3) at 10 mm or 20 mm away)] and mechanico-thermal cycling (no cycling or mechanically loaded 20,000 cycles; 10 N distilled water at 37 degrees C and then thermocycled 3000 cycles; 5 degrees C to 55 degrees C, dwell time 30 seconds) combination. Those specimens that did not undergo mechanico-thermal cyclingwere stored inwater (37 degrees C) for 24 hours. Bond strength was measured using a three-point bend test, according to ISO 9693. After the flexural strength test, failure types were noted. The data were analyzed using three factor-ANOVA and Tukey's test (alpha = 0.05).Results: There were no significant differences between the flexural bond strength of gold and Co-Cr groups (42.64 +/- 8.25 and 43.39 +/- 10.89 MPa, respectively). APA 10 and 20 mm away surface treatment (45.86 +/- 9.31 and 46.38 +/- 8.89 MPa, respectively) had similar mean flexural strength values, and both had significantly higher bond strength than tungsten bur treatment (36.81 +/- 7.60 MPa). Mechanico-thermal cycling decreased the mean flexural strength values significantly for all six alloy-surface treatment combinations tested when compared to the control groups. The failure type was adhesive in the metal/ceramic interface for specimens surface treated only with the tungsten bur, and mixed for specimens surface treated with APA 10 and 20 mm.Conclusions: Considering the levels adopted in this study, the alloy did not affect the bond strength; APA with Al(2)O(3) at 10 and 20 mm improved the flexural bond strength between ceramics and alloys used, and the mechanico-thermal cycling of metal-ceramic specimens resulted in a decrease of bond strength.

Relativistic particle dynamics in D=2+1

We propose a SUSY variant of the action for a massless spinning particles via the inclusion of twistor variables. The action is constructed to be invariant under SUSY transformations and tau-reparametrizations even when an interaction field is including. The constraint analysis is achieved and the equations of motion are derived. The commutation relations obtained for the commuting spinor variables lambda(alpha) show that the particle states have fractional statistics and spin. At once we introduce a possible massive term for the non-interacting model.

Influence of particle size on the photoactivity of Ti/TiO2 thin film electrodes, and enhanced photoelectrocatalytic degradation of indigo carmine dye

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

Structural and spectroscopic analysis of gamma-Al2O3 to alpha-Al2O3-CoAl2O4 phase transition

Co-doped alumina powders were synthesized by means of the polymeric precursor method to obtain ceramic pigments. The effect of different contents of Co2+ on phase transition gamma to alpha-Al2O3 and appearing of CoAl2O4 spinel were studied by means of X-ray diffraction. A partial phase diagram of the system CoAl2O3 was proposed from these data by means of determination of the percentages of these phases according to the calcining temperature. Critical particle size to phase transition was determined by means of calculations of crystallite size and determination of superficial area through the BET method. UV-vis spectroscopy of the samples allow to compare the band shift with the phase transition. Besides, a study of thermal stability and intensity of the blue coloration of the synthesized powders with the presence of cobalt in relation to the calcining temperature was accomplished and compared to the phase transition. The results show that the higher blue color intensity was obtained for the powders with Co-doped gamma-Al2O3 closest of phase transition to alpha-Al2O3 + CoAl2O4. (c) 2005 Elsevier B.V. All rights reserved.