77 resultados para Surface Organometallic Chemistry on Metals

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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Based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory, we propose two new models to describe the crystallisation kinetics of glass particles and use them to determine the density of nucleation sites, N(s), on glass powders. We tested these models with sintered compacts of diopside glass particles using sinter-crystallisation treatments at 825 degrees C (T(g)similar to 727 degrees C), that covered from null to almost 100% crystallised volume time fraction. We measured and compared the evolution of the crystallised volume fractions by optical microscopy and x-ray diffraction. Then we fit our expressions to experimental data using Ns and R (the average particle radius) as adjustable parameters. For comparison, we also fit to our data existing expressions that describe the crystallised volume fraction in glass powders. We demonstrate that all the methods allow one to estimate N(s) with reasonable accuracy. For our ground and water washed diopside glass powder, N(s) is between 10(10)-10(11) sites.m(-2). The reasonable agreement between experimental and adjusted R confirms the consistency of all five models tested. However, one of our equations does not require taking into account the change of crystallisation mode from 3-dimensional to 1-dimensional, and this is advantageous.

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Brazil has extensive area with acid soils. Using phosphogypsum and soil acidity tolerant cultivars are alternatives to crop establishment in no-till system without previous limestone incorporation in many agricultural soils of Brazil. However, it remains unknown how phosphogypsum and limestone surface application affects rice (Oryza sativa L.) and common bean (Phaseolus vulgaris L.) nutrition and yield under a no-till system. A field experiment was conducted in a sandy clay loam, kaolinitic, thermic Typic Haplorthox, previously cultivated under conventional tillage, in Botucatu, Sao, Paulo State, Brazil. Treatments included four dolomitic limestone rates (0, 1100, 2700, and 4300 kg ha(-1)), two phosphogypsum rates (0 and 2100 kg ha(-1)), and two upland rice cultivars (Caiapo and IAC 202). in 2002-2003, and two bean cultivars (Perola and Carioca), in 2003-2004. Both amendments were applied on the surface, without soil incorporation. The content of Ca, Mg, and Mn in flag leaves and rice yield increased with limestone surface application. Liming increased the shoot dry matter of IAC 202 rice. Phosphogypsum increased S contents in leaves of both rice cultivars, and resulted in higher grain yield in the Caiapo rice. Liming increased K contents in leaves of both bean cultivars. In the absence of phosphogypsum, liming increased S contents and grain yield of bean. Content of Mg in leaves was reduced by phosphogypsum in lower limestone rates. In phosphogypsum presence, liming reduced Zn contents in leaves and increased bean shoot dry matter. Phosphogypsum increased Ca and S, and reduced Mg contents in bean leaves. Using soil acidity tolerant cultivars promoted higher crop yields in no-till systems establishment, even when the effective soil amelioration had not yet been achieved.

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

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Statement of problem. According to manufacturers, bonding with self-adhesive resin cements can be achieved without any pretreatment steps such as etching, priming, or bonding. However, the benefit of saving time with these simplified luting systems may be realized at the expense of compromising the bonding capacity.Purpose. The purpose of this study was to assess whether different dentin conditioning protocols influence the bond performance of self-adhesive resin cements to dentin.Material and methods. Flat dentin surfaces from 48 human molars were divided into 4 groups (n=12): 1) control, no conditioning; 2) H(3)PO(4), etching with 37% H(3)PO(4) for 15 seconds; 3) SEBond, bonding with self-etching primer adhesive (Clearfil SE Bond); and 4) EDTA, etching with 0.1M EDTA for 60 seconds. The specimens from each dentin pre-treatment were bonded using the self-adhesive cements RelyX Unicem, Maxcem or Multilink Sprint (n=4). The resin-cement-dentin specimens were stored in water at 37 degrees C for 7 days, and serially sectioned to produce beam specimens of 1.0 mm(2) cross-sectional area. Microtensile bond strength (mu TBS) testing was performed at 1.0 mm/min. Data (MPa) were analyzed by 2-way ANOVA and Tukey multiple comparisons test (alpha=.05). Fractured specimens were examined with a stereomicroscope (x40) and classified as adhesive, mixed, or cohesive. Additional bonded interfaces were evaluated under a scanning electron microscope (SEM).Results. Cement-dentin mu TBS was affected by the dentin conditioning approach (P <.001). RelyX Unicem attained statistically similar bond strengths to all pre-treated dentin surfaces. H(3)PO(4)-etching prior to the application of Maxcem resulted in bond strength values that were significantly higher than the other groups. The lowest mu TBS were attained when luting Multilink Sprint per manufacturers' recommendations, while H(3)PO(4)-etching produced the highest values followed by Clearfil SE bonding and EDTA. SEM observations disclosed an enhanced potential of the self-adhesive cements to form a hybrid layer when applied following manufacturer's instructions.Conclusions. When evaluated self-adhesive resin cements are used, selectively etching dentin with H(3)PO(4) prior to luting results in the most effective bonding. (J Prosthet Dent 2011;105:227-235)

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Objectives. This study evaluated the effect of two different surface conditioning methods on the repair bond strength of a bis-GMA-adduct/bis-EMA/TEGDMA based resin composite after three aging conditions.Methods. Thirty-six composite resin blocks (Esthet X, Dentsply) were prepared (5 mm x 6 mm x 6 mm) and randomly assigned into three groups for aging process: (a) immersion in citric acid (pH 3.0 at 37 degrees C, 1 week) (CA); (b) boiling in water for 8h (BW) and (c) thermocycling (x5000, 5-55 degrees C, dwell time: 30s) (TC). After aging, the blocks were assigned to one of the following surface conditioning methods: (1) silica coating (30 mu m SiOx) (CoJet, 3M ESPE) + silane (ESPE-Sil) (CJ), (2) phosphoric acid + adhesive resin (Single Bond, 3M ESPE) (PA). Resin composite (Esthet.X (R)) was bonded to the conditioned substrates incrementally and light polymerized. The experimental groups formed were as follows: Gr1:CA + PA; Gr2:CA + CJ Gr3:BW + PA; Gr4: BW + CJ; Gr5:TC + PA; Gr6: TC + CJ. The specimens were sectioned in two axes (x and y) with a diamond disc under coolant irrigation in order to obtain non-trimmed bar specimens (sticks, 10 mm x 1 mm x 1 mm) with 1 mm(2) of bonding area. The microtensile test was accomplished in a universal testing machine (crosshead speed: 0.5 mm min(-1)).Results. The means and standard deviations of bond strength (MPa +/- S.D.) per group were as follows: Gr1: 25.5 +/- 10.3; Gr2: 46.3 +/- 10.1; Gr3: 21.7 +/- 7.1; Gr4: 52.3 +/- 15.1; GrS: 16.1 +/- 5.1; Gr6, 49.6 +/- 13.5. The silica coated groups showed significantly higher mean bond values after all three aging conditions (p < 0.0001) (two-way ANOVA and Tukey tests, alpha = 0.05). The interaction effect revealed significant influence of TC aging on both silica coated and acid etched groups compared to the other aging methods (p < 0.032). Citric acid was the least aggressive aging medium.Significance. Chairside silica coating and silanization provided higher resin-resin bond strength values compared to acid etching with phosphoric acid followed by adhesive resin applications. Thermocycling the composite substrates resulted in the lowest repair bond strength compared to citric acid challenge or boiling in water. (C) 2006 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

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The interactions governing adsorption of layer-by-layer (LBL) films from an azopolymer, PS-119(R), and poly(allylamine hydrochloride) (PAH) have been controlled by modifying the pH of the solutions used to form the films. The thickness per bilayer was varied by one order of magnitude, from 10 to 240 A, as the pH changed from 4 to 10. Thick layers were formed at higher pHs because in this case the PAH is only partially charged adopting a loopy conformation. This change in molecular conformation caused the kinetics of isomerization and mass transport to be much slower than at lower pHs. The writing time defined as the time to achieve 50% of maximum birefringence dropped from 110 to 18 min for films prepared from solutions with pH 10 and pH 4, respectively. This decrease is probably due to the higher free volume for isomerization in the films prepared at lower pHs, in which PAH molecules are less coiled than at higher pHs. For the same reason, the rate of inscription of surface-relief gratings with an interference pattern of p-polarized light was also much slower at higher pHs. (C) 2003 Elsevier B.V. All rights reserved.

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

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Purpose: This study evaluated the effect of different surface conditioning protocols on the repair strength of resin composite to the zirconia core / veneering ceramic complex, simulating the clinical chipping phenomenon.Materials and Methods: Forty disk-shaped zirconia core (Lava Zirconia, 3M ESPE) (diameter: 3 mm) specimens were veneered circumferentially with a feldspathic veneering ceramic (VM7, Vita Zahnfabrik) (thickness: 2 mm) using a split metal mold. They were then embedded in autopolymerizing acrylic with the bonding surfaces exposed. Specimens were randomly assigned to one of the following surface conditioning protocols (n = 10 per group): group 1, veneer: 4% hydrofluoric acid (HF) (Porcelain Etch) + core: aluminum trioxide (50-mu m Al2O3) + core + veneer: silane (ESPE-Sil); group 2: core: Al2O3 (50 mu m) + veneer: HF + core + veneer: silane; group 3: veneer: HF + core: 30 mu m aluminum trioxide particles coated with silica (30 mu m SiO2) + core + veneer: silane; group 4: core: 30 mu m SiO2 + veneer: HF + core + veneer: silane. Core and veneer ceramic were conditioned individually but no attempt was made to avoid cross contamination of conditioning, simulating the clinical intraoral repair situation. Adhesive resin (VisioBond) was applied to both the core and the veneer ceramic, and resin composite (Quadrant Posterior) was bonded onto both substrates using polyethylene molds and photopolymerized. After thermocycling (6000 cycles, 5 degrees C-55 degrees C), the specimens were subjected to shear bond testing using a universal testing machine (1 mm/min). Failure modes were identified using an optical microscope, and scanning electron microscope images were obtained. Bond strength data (MPa) were analyzed statistically using the non-parametric Kruskal-Wallis test followed by the Wilcoxon rank-sum test and the Bonferroni Holm correction (alpha = 0.05).Results: Group 3 demonstrated significantly higher values (MPa) (8.6 +/- 2.7) than those of the other groups (3.2 +/- 3.1, 3.2 +/- 3, and 3.1 +/- 3.5 for groups 1, 2, and 4, respectively) (p < 0.001). All groups showed exclusively adhesive failure between the repair resin and the core zirconia. The incidence of cohesive failure in the ceramic was highest in group 3 (8 out of 10) compared to the other groups (0/10, 2/10, and 2/10, in groups 1, 2, and 4, respectively). SEM images showed that air abrasion on the zirconia core only also impinged on the veneering ceramic where the etching pattern was affected.Conclusion: Etching the veneer ceramic with HF gel and silica coating of the zirconia core followed by silanization of both substrates could be advised for the repair of the zirconia core / veneering ceramic complex.

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This paper presents electrochemical experiments on natural pyrite that combine potentiostatic and voltammetric techniques. X-ray microanalysis is used as an auxiliary technique. The layer growth on pyrite surface is conducted in a wide range of pH and potential range: 3.4 <= pH <= 5.9 with E = 0.80 V (versus SHE), and 0.80 V <= E <= 1.00 V with pH 4.5 (versus SHE) in acetic acid-acetate buffer. This work is unique for two reasons: (1) phenomenological model about layer growth is applied and mathematical-physic consistence is verified and (2) Meyer's hypotheses of chemical mechanism are used to explain kinetic parameters of the phenomenological model. (c) 2005 Elsevier B.V. All rights reserved.

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The intense valuation of an esthetic pleasant smile guided the dentistry to bleached tooth due the popularity of whitening treatments. The consequence of it is an increasing interest in searching the effect of peroxides in hard dental tissues. The aim of this work was to analyze qualitatively in vitro the human enamel after three different bleaching treatments: Opalescence PF 10%, White Class 7.5% and Opalescence Xtra Boost 38%, correlating the structural changes in the surface of the enamel with its respective pH. A total of 40 sound human pre-molars were randomly divided into four groups of 10 elements, which had been immersed in artificial saliva during all the experiment. Bleaching protocols followed the recommendations of the respective manufacturers. Each bleached sample and control group were submitted to a scanning electronic microscopy analysis and compared with one another. Bleaching agents used in this experiment had modified the morphologic aspect of the surface of the dental enamel; however, it did not have correlation between the degrees of severity of the alterations and pH. There is a correlation between hydrogen peroxide concentration and changes in the enamel, where G4 showed more severe alterations, followed for G3 and G2.

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This study aims at identifying the influence of soil surface roughness from small to large aggregates (random roughness) on runoff and soil loss and to investigate the interaction with soil surface seal formation. Bulk samples of a silty clay loam soil were sieved to four aggregate-size classes of 3 to 12, 12 to 20, 20 to 45, 45 to 100 mm, and packed in soil trays set at a 5% slope. Rainfall simulations using an oscillating nozzle simulator were conducted for 90 min at an average rainfall intensity of 50.2 mm h(-1). Soil surface roughness was measured using an instantaneous profile laser scanner and surface sealing was studied by macroscopic analysis of epoxy impregnated soil samples. The rainfall simulations revealed longer times to initiate runoff with increasing soil surface roughness. For random roughness levels up to 6 mm, a decrease in final runoff rate with increasing roughness was observed. This can be attributed to a decreased breakdown of the larger roughness elements on rougher surfaces, thus keeping infiltration rate high. For a random roughness larger than 6 mm, a greater final runoff rate was observed. This was caused by the creation of a thick depositional seal in the concentrated flow areas, thus lowering the infiltration rates. Analysis of impregnated soil sample blocks confirmed the formation of a structural surface seal on smooth surfaces, whereas thick depositional seals were visible in the depressional areas of rougher surfaces. Therefore, from our observations it can be learned that soil surface roughness as formed by the presence of different aggregate sizes reduces runoff but that its effect diminishes due to aggregate breakdown and the formation of thick depositional seals in the case of rough soil surfaces. Sediment concentration increased with increasing soil surface roughness, due to runoff concentration in flow paths. Nevertheless, final soil loss rates were comparable for all soil roughness categories, indicating that random roughness is only important in influencing runoff rates and the time to initiate runoff, but not in influencing sediment export through soil loss rates.

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A polymeric precursor method based on the Pechini process was successfully used to synthesize zirconia-12 mol% ceria ceramic powders, the influence of the main process variables (citric acid-ethylene glycol ratio, citric acid-total oxides ratio and calcination temperature) on phase formation and powder morphology (surface area and crystallite size) were investigated. The thermal decomposition behavior of the precursor is presented. X-ray diffraction (XRD) patterns of powders revealed a crystalline tetragonal zirconia single-phase, with crystallite diameter ranging from 6 to 15 nm. The BET surface areas were relatively high, reaching 95 m(2) g(-1) Nitrogen adsorption/desorption on the powders suggested that nonaggregated powders could be attained, depending on the synthesis conditions. Copyright (C) 1999 John Wiley & Sons, Ltd.

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The aim of this study was to evaluate the effects of dentin surface treatments on the tensile bond strength (TBS) of the self-etching primer Clearfil SE Bond (CSE) and the one-step self-etching One-Up Bond F (OUB). The exposed flat dentin surfaces of twenty-four sound third molars were prepared with diamond bur at high-speed, carbide bur at low-speed or wet ground with #600 grit SiC paper. The adhesive systems were applied to the dentin surfaces and light-cured according to the manufacturers' instructions. A 6-mm high composite crown was incrementally built-up and each increment was light-cured for 40 seconds. After being stored in water (37°C/24 h), the samples were serially sectioned parallel to the long axis, forming beams (n = 20) with a cross-sectional area of approximately 0.8 mm 2. The specimens were tested in a Universal Testing Machine at 0.5 mm/min. The cross-sectional area was measured and the results (MPa) were analyzed by two-way ANOVA and Tukey Test (p < 0.05). Overall, the groups treated with CSE exhibited the highest TBS for all surface treatments. Dentin surfaces prepared with carbide bur at low speed reduced TBS in the CSE group; however, OUB was not affected by surface treatments. The effect of surface abrasive methods on TBS was material-dependent.