A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2

The potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.

Effect of microwave disinfection on the bond strength of denture teeth to acrylic resins

During microwave disinfection, the dentures are exposed to water at high temperature and this may affect the bond between the denture teeth and the acrylic resin from which dentures are made. In this study, a shear test was used to evaluate the effect of microwave disinfection (650W/6 min) on the bond strength of two types of denture teeth to three acrylic resins, with different polymerization methods. The specimens were submitted to the shear tests (0.5 mm/min) after: immersion in water (37 degrees C) for 48 h or 8 days (controls); two or seven cycles of microwave disinfection (test groups). Data (MPa) were analyzed using three-way ANOVA and Tukey HSD test (alpha = 0.05). Microwave disinfection did not adversely affect the bond strength of all tested materials with the exception of QC-20 bonded to SR Vivodent PE, for which a significant reduction was recorded after seven cycles of irradiation. (C) 2007 Elsevier Ltd. All rights reserved.

Study on the initial stages of water corrosion of fluorozirconate glasses

The surface corrosion process associated with the hydrolysis of fluorozirconate glass, ZBLAN (53ZrF(4), 20BaF(2), 20NaF, 4LaF(2), 3AlF(3)) was investigated using X-ray photoelectron spectroscopy (XPS), grazing-incidence small angle X-ray scattering (GISAXS), X-ray reflectivity (XRR) and scanning electron microscopy (SEM). After a short exposure period (25 min) of the glass surface to deionized water the XPS data indicate an increase of the oxygen content accompanied by a decrease of fluorine concentration. The analysis of the chemical bonding structure identified the predominant surface reaction products as zirconium hydroxyfluoride and oxyfluoride species. The second most abundant glass component, bariumfluoride, remains almost unaffected by oxygen, while sodium fluoride is completely removed from the attacked surface region. The detected structural and compositional changes are related to the selective dissolution of the glass components leading to the formation of a new surface phase. This process is accompanied by a visible surface roughening caused by reprecipitated species, observed by SEM. The modification of the glass surface is responsible for an increase of the GISAXS intensity. The scattering was attributed to nanovoids formed at the surface region of the glass with an average size of 2.4 +/- 0.05 nm. (C) 2004 Elsevier B.V. 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.

Morphological characterization of aqueous tin oxyhydroxide gel

Light scattering, electron microscopy and X-ray diffraction are used to determine the morphology and size of particles in diluted aqueous gel of tin (IV) oxyhydroxide. Data show that the gel is composed of spherical 2-3 nm sized crystalline particles aggregated as rigid branched chains. It is suggested that stiffness of chains results from dissolution-precipitation equilibria and chemical bonding between particles within the chains. © 1994.

Sintering and mass transport features of (Sn,Ti)O2 polycrystalline ceramics

Different (Sn,Ti)O2 compositions were sintered at 1450 °C for 2 h with the purpose of investigating their sintering and mass transport properties. Highly dense ceramics were obtained and their structural properties studied by X-ray diffraction and scanning electron microscopy. The changes in lattice parameters were analyzed by the Rietveld method and two mass transport mechanisms were observed during sintering in different temperature ranges, evidenced by the linear shrinkage rate as a function of temperature. The effect of the concentration of TiO2 on mass transport and densiffication during sintering was analyzed by considering the intrinsic defects. System densiffication was attributed to a mass transport mechanism in the SnO2 matrix, caused by the presence of TiO2, which formed a solid solution phase. The change in the mass transport mechanism was attributed to chemical bonding between SnO2 and TiO2, which improves ionic difusion as the concentration of TiO2 increased in (Sn,Ti)O2 compositions. © 2002 Elsevier Science Ltd. All rights reserved.

Corrosion protection of fluorzirconate glasses coated by a layer of surface modified tin oxide nanoparticles

The protection efficiency against water corrosion of fluorozirconate glass, ZBLAN, dip-coated by nanocrystalline tin oxide film containing the organic molecule Tiron® was investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The chemical bonding structure of the surface region and morphology were studied before and after two water exposure periods of 5 and 30 min. The results of the analysis for the as-grown sample revealed a SnO1.6 phase containing carbon and sulfur, related to Tiron®, and traces of elements related to ZBLAN (Zr, F, Ba). This fact and the clear evidence of the presence of tin oxifluoride specie (SnOxF y) indicates a diffusion of the glass components into the porous coating. After water exposure, the increase of the oxygen concentration accompanied by a strong increase of Zr, F, Ba and Na content is interpreted as filling of the nanopores of the film by glass compounds. The formation of a compact protective layer is supported by the morphological changes observed by AFM. © 2005 Elsevier B.V. All rights reserved.

Caracterização de superfície, adesiva e mecânica de uma zircônia parcialmente estabilizada por ítria em função da partícula ou do momento do jateamento

Pós-graduação em Reabilitação Oral - FOAR

Surface modification of polymeric materials by cold atmospheric plasma jet

In this work we report the surface modification of different engineering polymers, such as, polyethylene terephthalate (PET), polyethylene (PE) and polypropylene (PP) by an atmospheric pressure plasma jet (APPJ). It was operated with Ar gas using 10 kV, 37 kHz, sine wave as an excitation source. The aim of this study is to determine the optimal treatment conditions and also to compare the polymer surface modification induced by plasma jet with the one obtained by another atmospheric pressure plasma source the dielectric barrier discharge (DBD). The samples were exposed to the plasma jet effluent using a scanning procedure, which allowed achieving a uniform surface modification. The wettability assessments of all polymers reveal that the treatment leads to reduction of more than 40 degrees in the water contact angle (WCA). Changes in surface composition and chemical bonding were analyzed by x-ray photoelectron spectroscopy (XPS) and Fourier-Transformed Infrared spectroscopy (FTIR) that both detected incorporation of oxygen-related functional groups. Surface morphology of polymer samples was investigated by Atomic Force Microscopy (AFM) and an increase of polymer roughness after the APPJ treatment was found. The plasma-treated polymers exhibited hydrophobic recovery expressed in reduction of the O-content of the surface upon rinsing with water. This process was caused by the dissolution of low molecular weight oxidized materials (LMWOMs) formed on the surface as a result of the plasma exposure. (C) 2014 Elsevier B.V. All rights reserved.

Quantum chemical topological analysis of hydrogen bonding in HX…HX and CH3X…HX dimers (X = Br, Cl, F)

We present a systematic investigation of the nature and strength of the hydrogen bonding in HX···HX and CH3X…HX (X = Br, Cl and F) dimers using ab initio MP2/aug-cc-pVTZ calculations in the framework of the quantum theory of atoms in molecules (QTAIM) and electron localisation functions (ELFs) methods. The electron density of the complexes has been characterised, and the hydrogen bonding energy, as well as the QTAIM and ELF parameters, is consistent, providing deep insight into the origin of the hydrogen bonding in these complexes. It was found that in both linear and angular HX…HX and CH3X…HX dimers, F atoms form stronger HB than Br and Cl, but they need short (∼2 Å) X…HX contacts.

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)

Cytotoxic effects of cleansing solutions recommended for chemical lavage of pulp exposures

Purpose: To evaluate the in vitro cytotoxic effects of three cleansing solutions used for chemical lavage of pulp exposures. Materials and Methods: the immortalized odontoblast cell line (MDPC-23) was plated (30,000 cells/cm(2)) and incubated for 72 hrs in 24-well dishes. After counting the cell number under inverted light microscopy, 20 mul of the experimental and control solutions were added to 980 mul of fresh culture medium. Then, hydrogen peroxide (3%, H2O2), sodium hypochlorite (6%, NaOCl) or calcium hydroxide-saline solution (5g of Ca(OH)(2) in 10 mi of sterile distilled water) were added to wells for experimental Groups 1, 2 and 3, respectively. The positive and negative control groups received Syntac Sprint bonding agent (SS) and phosphate buffered saline (PBS), respectively. Following incubation for 120 min the cell number was counted again, the cell morphology was evaluated by scanning electron microscopy (SEM) and the cell metabolism was determined by the methyltetrazolium (MTT) assay. The scores obtained from cell counting and MTT assay were analyzed with an ANOVA followed by Fisher's PLSD tests. Results: H2O2 NaOCl solutions, and SS bonding agent were more cytotoxic than Ca(OH)2 or PBS. In the groups with H2O2 Or SS, only a few cells remained attached to the bottom of wells. The difference between these two groups was not statistically significant. H2O2, NaOCl and SS depressed the mitochondrial enzyme response by 97.7%, 97.3%, and 95.0%, respectively. on the other hand, Ca(OH)2 depressed the metabolic activity of cells by only 5%. While H2O2, NaOCl and SS caused extreme changes on the cell morphology, neither Ca(OH)2 nor PBS promoted dramatic changes in the cell morphology.

The influence of chemical activation on hardness of dual-curing resin cements.

During the cementation of metallic restorations, the polymerization of dual-curing resin cements depends exclusively on chemical activation. This study evaluated the influence of chemical activation compared with dual-curing (chemical and light activation), on the hardness of four dual-curing resin cements. In a darkened environment, equal weight proportions of base and catalyst pastes of the cements Scotchbond Resin Cement, Variolink II, Enforce and Panavia F were mixed and inserted into moulds with cavities of 4 mm in diameter and 2 mm in height. Subsequently, the cements were: 1) not exposed to light (chemical activation = self-cured groups) or 2) photoactivated (dual-curing = dual-cured groups). The Vickers hardness number was measured at 1 hour, 24 hours and 7 days after the start time of cements' spatulation. For all the cements, the hardness values of self-cured groups were lower than those of the respective dual-cured groups at 1 hour and 24 hours. At 7 days, this behavior continued for Variolink II and Panavia F, whilst for Scotchbond Resin Cement and Enforce there was no statistical difference between the two activation modes. All cements showed a significant increase in their hardness values from 1 hour to 7 days for both activation modes. Of the self-cured groups, Scotchbond Resin Cement and Variolink II presented the highest and the lowest hardness values, respectively, for all three times tested. Within the limitations of this study, up to the time of 24 h, chemical activation alone was unable to promote similar hardness as to that obtained with dual-curing.

In vitro evaluation of marginal leakage in bonded restorations, with mechanical or chemical-mechanical (Carisolv) removal of carious tissue

This study carried out an in vitro evaluation and comparison of the occurrence of marginal leakage in bonded restorations using mechanical or chemical-mechanical (Carisolv) removal of carious tissue. For that purpose, 40 extracted decayed human molars were divided into 4 groups: GI (burs + Prime & Bond NT + TPH), GII (Carisolv + Prime & Bond NT + TPH), GIII (burs + SBMP + Z100) and GIV (Carisolv + SBMP + Z100). After accomplishment of the restorations and thermal cycling, the teeth were exposed to dye, sectioned and qualitatively evaluated. The results demonstrated that the system of removal of carious tissue did not influence the results of microleakage at any of the cavity margins. At dentinal margins, use of the Prime & Bond NT + TPH restorative system allowed the occurrence of less microleakage than the SBMP + Z100 system.

Hydrogen bonding donation of N-methylformamide with dimethylsulfoxide and water

20% N-methylformamide (NMF) mixtures with water and with dimethylsulfoxide (DMSO) have been studied. A comparison between the hydrogen bonding (H-bond) donation of N-methylformamide with both solvents in the mixtures is presented. Results of radial distribution functions, pair distribution energies, molecular dipole moment correlation, and geometry of the H-bonded species in each case are shown. The results indicate that the NMF-solvent H-bond is significantly stronger with DMSO than with water. The solvation shell is best organized in the DMSO mixture than in the aqueous one. © 2013 Elsevier B.V. All rights reserved.