Well-Alloyed PtFe/C Nanocatalysts of Controlled Composition and Same Particle Size: Oxygen Reduction and Methanol Tolerance

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

Composition-resolved size distributions of volcanic aerosols in the Mt. Etna plumes

Particle size distributions for soluble and insoluble species in Mt. Etna's summit plumes were measured across an extended size range (10 nm < d < 100 mu m) using a combination of techniques. Automated scanning electron microscopy (QEMSCAN) was used to chemically analyze many thousands of insoluble particles (collected on pumped filters) allowing the relationships between particle size, shape, and composition to be investigated. The size distribution of fine silicate particles (d < 10 mu m) was found to be lognormal, consistent with formation by bursting of gas bubbles at the surface of the magma. The compositions of fine silicate particles were found to vary between magmatic and nearly pure silica; this is consistent with depletion of metal ions by reactions in the acidic environment of the gas plume and vent. Measurements of the size, shape and composition of fine silicate particles may potentially offer insights into preemission, synemission, and postemission processes. The mass flux of fine silicate particles from Mt. Etna released during noneruptive volcanic degassing in 2004 and 2005 was estimated to be similar to 7000 kg d(-1). Analysis of particles in the range 0.1 < d/mu m < 100 by ion chromatography shows that there are persistent differences in the size distributions of sulfate aerosols between the two main summit plumes. Analysis of particles in the range 0.01 mu m < d < 0.1 mu m by scanning transmission electron microscopy (STEM) shows that there are significant levels of nanoparticles in the Mt. Etna plumes although their compositions remain uncertain.

Effect of calcium pre-rinse and fluoride dentifrice on remineralisation of artificially demineralised enamel and on the composition of the dental biofilm formed in situ

Objective: This in situ blind crossover study investigated the effect of calcium (Ca) rinse prior to the use fluoride (F) dentifrice on remineralisation of artificially demineralised enamel and on the composition of biofilm. Design: During four phases of 14 days, 10 volunteers wore appliances containing two artificially demineralised bovine enamel blocks. Three times a day, they rinsed with 10 mL, of Ca (150 mM) or placebo rinse (1 min). A slurry (1:3, w/v) of F (1030 ppm) or placebo dentifrice was dripped onto the blocks. During I min, the volunteers brushed their teeth with the respective dentifrice. The appliance was replaced into the mouth and the volunteers rinsed with water. The biofilm formed on the blocks was analysed for F and Ca. Enamel alterations were evaluated by the percentage of surface microhardness change (%SMHC), cross-sectional microhardness (% mineral volume) and alkali-soluble F analysis. Data were analysed by ANOVA (p < 0.05). Results: the use of the Ca pre-rinse before the F dentifrice produced a six- and four-fold increase in biofilm F and Ca concentrations, respectively. For enamel, the remineralisation was significantly improved by the Ca pre-rinse when compared to the other treatments. There was a significantly higher concentration of alkali-soluble F in enamel when the F dentifrice was used, but the Ca pre-rinse did not have any significant additive effect. Conclusions: According to our protocol, the Ca pre-rinse significantly increased biofilm F concentration and, regardless the use of F dentifrice, significantly enhanced the remineralisation of artificially demineralised enamel. (c) 2007 Elsevier Ltd. All rights reserved.

A theoretical analysis of the TiO2/Sn doped (110) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sri, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. (c) 2005 Elsevier B.V. All rights reserved.

The influence of internal surface treatments on tensile bond strength for two ceramic systems

Statement of the Problem: the ceramic composition and surface microstructure of all-ceramic restorations are important components of an effective bonding substrate. Hydrofluoric acid and sandblasting are well-known procedures for surface treatment; however, surface treatment for high alumina-containing and lithium disilicate ceramics have not been fully investigated.Purpose: This in vitro study evaluated the tensile bond strength of resin cement to two types of ceramic systems with different surface treatments.Methods and Materials: Thirty specimens of each ceramic system were made according to the manufacturer's instructions and embedded in polyester resin. Specimens of In-Ceram Alumina [1] and IPS Empress 2 [E] were distributed to three groups with differing surface treatments (n=10): sandblasting with 50 jam aluminum oxide (APA); sandblasting with 110 pm aluminum oxide modified with silica particles (ROCATEC System-RS); a combination of sandblasting with APA and 10% hydrofluoric acid etching (HA) for two minutes on In-Ceram and for 20 seconds for IPS Empress 2. After the respective surface treatments, all the specimens were silanated, and Rely-X resin cement was injected onto the ceramic surface and light polymerized. The specimens were stored in distilled water at 37 degrees C for 24 hours and thermally cycled 1,100 times (5 degrees C/55 degrees C). The tensile bond strength test was performed in a universal testing machine at a 0.5 mm/minute crosshead speed.Results: the mean bond strength values (AWa) for IPS Empress 2 were 12.01 +/- 5.93 (EAPA), 10.34 +/- 1.77 (ERS) and 14.49 +/- 3.04 (EHA). The mean bond strength values for In-Ceram Alumina were 9.87 +/- 2.40 JAPA) and 20.40 +/- 6.27 (IRS). All In-Ceram specimens treated with 10% hydrofluoric acid failed during thermal cycling.Conclusion: the Rocatec system was the most effective surface treatment for In-Ceram Alumina ceramics; whereas, the combination of aluminum oxide sandblasting and hydrofluoric acid etching for 20 seconds worked more effectively for Empress 2 ceramics.

Structural and surface properties of thermally prepared Ti/RhxTi(1-x)Oy electrodes: I - influence of preparation parameters

Electrodes of RhxTi(1-x) O-y nominal composition were prepared by thermal decomposition of the chloride or nitrate precursor salts dissolved in strongly acidic medium and applied by brush to both sides of a Tidegrees support. A systematic study of the influence of calcination temperature and time as well as oxygen flux was conducted. The coatings were characterised by SEM, EDAX, XRD, open circuit potential measurements and cyclic voltammetry (CV). Visible-ultraviolet spectrophotometry was employed to identify the chemical form of the precursor in solution while thermogravimetric analysis (TGA) was used to assess the decomposition temperature ranges. Optimisation of the coating preparation parameters showed coatings obtained from [Rh(H2O)(6)](NO3)(3) precursor dissolved in HNO3 1:2 (v/v) and fired at 430 degreesC for 2 h in a 5 1 min (-1) oxygen stream-furnished stable electrodes having the highest electrochemically active surface area. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Role of the surface state and structural feature in the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The sols produced by admixture of ZrOCl2 acidified solutions to hot H2SO4 aqueous solutions were studied to clarify the effects of Cl- and SO42- ions on the kinetic stability of nanoparticles and to obtain some new evidence concerning the mechanism of a thermoreversible sol-gel transition observed in this system. The study of suspensions prepared with different molar ratios R-S = [Zr]/[SO42-] and R-Cl = [Zr]/[Cl-] revealed domains of composition of formation of thermoreversible gels, thermostable sols, and powder precipitation. The effects of R-S and R-Cl on the structural features of nanoparticles and on the particle solution interface were systematically analyzed for samples of thermoreversible and thermostable sol domains. Small-angle X-ray scattering measurements revealed the presence of small fractal aggregates in all samples of thermoreversible domains, while compact packing aggregates of primary particles are present in the thermostable sol. Extended X-ray absorption fine structure and elemental chemical analysis revealed that irrespective of the nominal value of R-S and R-Cl all studied samples of the thermoreversible domain are constituted by a well-defined compound possessing an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded on the surface by complexing sulfate ligands. zeta potentials of powders extracted by freeze-drying from the thermoreversible gel revealed a point of surface charge inversion attributed to the specific adsorption of SO42- ion. Thermoreversible gel formation is rationalized by considering the effect of the specific adsorption on the electrical double-layer repulsion together with the temperature dependency of the physical chemical properties of ions in solution.

Effect of iron on bovine enamel and on the composition of the dental biofilm formed in situ

Objectives: This study investigated in situ the effect of iron (Fe) on the reduction of demineralization of bovine enamel, as well as on the composition of dental biofilm.Design and methods: Twelve volunteers were included in this blind crossover study, which was conducted in two stages of 14 days each. For each stage, the volunteers received palatal appliances containing four blocks of bovine enamel (4 mm x 4 mm x 2.5 mm). Six volunteers dripped a solution of 15 mmol L-1 ferrous sulphate onto the fragments and the remaining six dripped deionized water (eight times per day). After five minutes, a fresh 20% (w/v) sucrose solution was dripped onto all enamel blocks. During the experimental period the volunteers brushed their teeth with non-fluoridated dentifrice. After each stage, the percentage of surface microhardness change (%SMHC) and area of mineral toss (Delta Z) were determined on enamel and the dental biofilm formed on the blocks was collected and analysed for F, P, Ca, Fe and alkali-soluble carbohydrates. The concentrations of F, Ca and Fe in enamel were also analysed after acid biopsies.Results: There was a statistically significant increase in the P and Fe concentrations in the biofilms treated with ferrous sulphate (p < 0.05), which was not observed for F, Ca and alkali-soluble carbohydrates. The group treated with ferrous sulphate had significantly lower %SMHC and Delta Z when compared to control (p < 0.05).Conclusions: These results showed that ferrous sulphate reduced the demineralization of enamel blocks and altered the ionic composition of the dental biofilm formed in situ. (c) 2005 Elsevier Ltd. All rights reserved.

XPS study on water corrosion of fluorzirconate glasses and their protection by a layer of surface modified tin dioxide nanoparticles

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, Z-BLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)), and the corrosion protection efficiency of a nanocrystalline transparent SnO2 layer were investigated by X-ray photoelectron spectroscopy. The tin oxide film was deposited by the sol-gel dip-coating process in the presence of Tiron(R) as particle surface modifier agent. The chemical bonding structure and composition of the surface region of coated and non-coated ZBLAN were studied before water contact and after different immersion periods (5-30 min). In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species inducing the formation of a new surface phase consisting of stable zirconium oxyfluoride, barium fluoride and lanthanum fluoride species, the results for the SnO2-coated glass showed that the hydrolytic attack induces a filling of the film nanopores by dissolved glass material and the formation of tin oxylluoride and zirconium oxyfluoride species. This process results in a modified film, which acts as a hermetic diffusion barrier protecting efficiently the glass surface. (C) 2006 Elsevier B.V. All rights reserved.

Influence of sugar cane burning on aerosol soluble ion composition in Southeastern Brazil

Seasonal variability in the major soluble ion composition of atmospheric particulate matter in the principal sugar cane growing region of central São Paulo State indicates that pre-harvest burning of sugar cane plants is an important influence on the regional scale aerosol chemistry. Samples of particulate matter were collected between April 1999 and February 2001 in coarse (> 3.5 mum) and fine (< 3.5 mum) fractions, and analysed for HCOO-, CH3COO-, C2C42-, SO42- . Results indicated that the principal sources of the aerosols investigated NO3-, Cl-, Na+, K+, NH4+, Mg2+ and Ca2+ were local or regional in nature (scale of tens to a few hundreds of km), and that differences between air masses of varying origins were small. Fine particles were typically acidic, containing secondary nitrates, sulphates and organic species. Coarse fraction concentrations were mainly influenced by physical parameters (wind speed, movement of vehicles and surface condition) affecting rates of re-suspension, although secondary nitrate and sulphate were also present in the larger particles.Concentrations of all measured species except sodium and chloride were higher during the burning season. Although concentrations were lower than often found in polluted urban environments, the massive increases during much of the year, due to a single anthropogenic activity (sugar cane burning) are indicative of a very large perturbation of the lower troposphere in the region relative to the natural condition. These aerosols are suspected of promoting respiratory disease. They also represent an important mechanism for the tropospheric transport of species relevant to surface acidification (sulphates, nitrates, ammonium and organic acids) and soil nutrient status (potassium, nitrogen, ammonium, calcium), so their impact on fragile natural ecosystems (following deposition) needs to be considered. (C) 2004 Elsevier Ltd. All rights reserved.

Modification of surface properties of Ti-16Si-4B powder alloy by plasma immersion ion implantation

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

Dental implants: Surface modification of cp-Ti using plasma spraying and the deposition of hydroxyapatite

The commercial pure titanium (cp-Ti) is currently being used with great success in dental implants. In this work we investigate how the cp-Ti implants can be improved by modifying the metal surface morphology, on which a synthetic material with properties similar to that of the inorganic part of the bone, is deposited to facilitate the bone/implant bonding. This synthetic material is the hydroxyapatite, HA, a calcium-phosphate ceramic. The surface modification consists in the application of a titanium oxide (TiO2) layer, using the thermal aspersion - plasma spray technique, with posterior deposition of HA, using the biomimetic method. The X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray (EDX) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) techniques have been used for characterizing phases, microstructures and morphologies of the coatings. The TiO2 deposit shows a mixture of anatase, rutilo and TiO2-x phases, and a porous and laminar morphology, which facilitate the HA deposition. After the thermal treatment, the previously amorphous structured HA coating, shows a porous homogeneous morphology with particle size of about 2-2.5 μm, with crystallinity and composition similar to that of the biological HA.

Evaluation of titanium implants with surface modification by laser beam. Biomechanical study in rabbit tibias

The purpose of the present study was to evaluate, using a biomechanical test, the force needed to remove implants with surface modification by laser (Nd:YAG) in comparison with implants with machined surfaces. Twenty-four rabbits received one implant with each surface treatment in the tibia, machined surface (MS) and laser-modified surface (LMS). After 4, 8 and 12 weeks of healing, the removal torque was measured by a torque gauge. The surfaces studied were analyzed according to their topography, chemical composition and roughness. The average removal torque in each period was 23.28, 24.0 and 33.85 Ncm for MS, and 33.0, 39.87 and 54.57 Ncm for LMS, respectively. The difference between the surfaces in all periods of evaluation was statistically significant (p < 0.05). Surface characterization showed that a deep and regular topography was provided by the laser conditioning, with a great quantity of oxygen ions when compared to the MS. The surface micro-topography analysis showed a statistical difference (p < 0.01) between the roughness of the LMS (R a = 1.38 ± 0.23 μm) when compared to that of the MS (R a = 0.33 ± 0.06 μm). Based on these results, it was possible to conclude that the LMS implants' physical-chemical properties increased bone-implant interaction when compared to the MS implants. © 2009 Sociedade Brasileira de Pesquisa Odontológica.

In vitro surface roughness of different glass ionomer cements indicated for ART restorations

Aim: The aim of this in vitro study was to evaluate the surface roughness of three glass ionomer cements (GICs) indicated for ART restorations. Methods: Ten cylindrical specimens of three commercial glass ionomers cements (Vidrion R - S.S. White, Maxxion R - FGM and Vitromolar DFL) were prepared (n=30) without surface finishing or protection. Twenty-four hours after preparation, the surface roughness measurements were obtained as the mean of three readings of the surface of each specimen by profilometry. The roughness values (Ra, μm) were subjected to one-way ANOVA and Tukey's test (p<0.05). Results: No statistically significant differences were observed between Vidrion R (0.18 ± 0.05) and Vitromolar (0.21 ± 0.05), whereas Maxxion R presented significantly higher roughness values than those of the other materials. Conclusions: It may be concluded that characteristics of particle size and composition of the different GICs affected their surface roughness 24 h after preparation.

Synthesis and evaluation of diethylethylamine-chitosan for gene delivery: Composition effects on the in vitro transfection efficiency

Chitosan has been indicated as a safe and promising polycation vector for gene delivery. However its low transfection efficiency has been a challenging obstacle for its application. To address this limitation, we synthesized chitosan derivatives which had increasing amounts of diethylethylamine groups (DEAE) attached to the chitosan main chain. The plasmid DNA VR1412 (pDNA), encoding the ß-galactosidase (ß-gal) reporter gene was used to prepare nanoparticles with the chitosan derivatives, and the transfection studies were performed with HeLa cells. By means of dynamic light scattering and zeta potential measurements, it was shown that diethylethylamine-chitosan derivatives (DEAEx-CH) were able to condense DNA into small particles having a surface charge depending on the polymer/DNA ratio (N/P ratio). Nanoparticles prepared with derivatives containing 15 and 25% of DEAE groups (DEAE15-CH and DEAE25-CH) exhibited transfection efficiencies ten times higher than that observed with deacetylated chitosan (CH). For derivatives with higher degrees of substitution (DS), transfection efficiency decreased. The most effective carriers showed low cytotoxicity and good transfection activities at low charge ratios (N/P). Vectors with low DS were easily degraded in the presence of lysozyme at physiological conditions in vitro and the nontoxicity displayed by these vectors opens up new opportunities in the design of DEAE-chitosan-based nanoparticles for gene delivery. © 2013 IOP Publishing Ltd.