Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems

The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (I 10), (0 10), (10 1) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For, comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximate to (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.

Methods to estimate the number of surface nucleation sites on glass particles

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.

Quantification of Peroxide Ion Passage in Dentin, Enamel, and Cementum After Internal Bleaching With Hydrogen Peroxide

The aim of this study was to evaluate the amount of peroxide passage from the pulp chamber to the external enamel surface during the internal bleaching technique. Fifty bovine teeth were sectioned transversally 5 mm below the cemento-enamel junction (CEJ), and the remaining part of the root was sealed with a 2-mm layer of glass ionomer cement. The external surface of the samples was coated with nail varnish, with the exception of standardized circular areas (6-mm diameter) located on the enamel, exposed dentin, or cementum surface of the tooth. The teeth were divided into three experimental groups according to exposed areas close to the CEJ and into two control groups (n=10/group), as follows: GE, enamel exposure area; GC, cementum exposed area; GD, dentin exposed area; Negative control, no presence of internal bleaching agent and uncoated surface; and Positive control, pulp chamber filled with bleaching agent and external surface totally coated with nail varnish. The pulp chamber was filled with 35% hydrogen peroxide (Opalescence Endo, Ultradent). Each sample was placed inside of individual flasks with 1000 mu L of acetate buffer solution, 2 M (pH 4.5). After seven days, the buffer solution was transferred to a glass tube, in which 100 mu L of leuco-crystal violet and 50 mu L of horseradish peroxidase were added, producing a blue solution. The optical density of the blue solution was determined by spectrophotometer and converted into microgram equivalents of hydrogen peroxide. Data were submitted to Kruskal-Wallis and Dunn-Bonferroni tests (alpha=0.05). All experimental groups presented passage of peroxide to the external surface that was statistically different from that observed in the control groups. It was verified that the passage of peroxide was higher in GD than in GE (p<0.01). The GC group presented a significantly lower peroxide passage than did GD and GE (p<0.01). It can be concluded that the hydrogen peroxide placed into the pulp chamber passed through the dental hard tissues, reaching the external surface and the periodontal tissue. The cementum surface was less permeable than were the dentin and enamel surfaces.

On-line redox speciation analysis of antimony using L-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection

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

Mechanical strength and subcritical crack growth under wet cyclic loading of glass-infiltrated dental ceramics

Objectives. Evaluate the flexural strength (sigma) and subcritical crack growth (SCG) under cyclic loading of glass-infiltrated alumina-based (IA, In-Ceram Alumina) and zirconia-reinforced (IZ, In-Ceram Zirconia) ceramics, testing the hypothesis that wet environment influences the SCG of both ceramics when submitted to cyclic loading.Methods. Bar-shaped specimens of IA (n = 45) and IZ ( n = 45) were fabricated and loaded in three-point bending (3P) in 37 degrees C artificial saliva (IA(3P) and IZ(3P)) and cyclic fatigued (F) in dry (D) and wet (W) conditions (IA(FD), IA(FW), IZ(FD), IZ(FW)). The initial sigma and the number of cycles to fracture were obtained from 3P and F tests, respectively. Data was examined using Weibull statistics. The SCG behavior was described in terms of crack velocity as a function of maximum stress intensity factor (K(Imax)).Results. The Weibull moduli (m = 8) were similar for both ceramics. The characteristic strength (sigma(0)) of IA and IZ was and 466 MPa 550 MPa, respectively. The wet environment significantly increased the SCG of IZ, whereas a less evident effect was observed for IA. In general, both ceramics were prone to SCG, with crack propagation occurring at K(I) as low as 43-48% of their critical K(I). The highest sigma of IZ should lead to longer lifetimes for similar loading conditions.Significance. Water combined with cyclic loading causes pronounced SCG in IZ and IA materials. The lifetime of dental restorations based on these ceramics is expected to increase by reducing their direct exposure to wet conditions and/or by using high content zirconia ceramics with higher strength. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Apatite coatings onto titanium surfaces submitted to laser ablation with different energy densities

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

In Vitro Evaluation of ICDAS and Radiographic Examination of Occlusal Surfaces and Their Association With Treatment Decisions

This in vitro study evaluated the performance of visual (International Caries Detection and Assessment System [ICDAS]) and radiographic (bitewing [BW]) examinations for occlusal caries detection and their associations with treatment decision (TD). Permanent teeth (n=104) with occlusal surfaces varying from sound to cavitated were selected. Sites were identified from 10x occlusal surface photographs. Standardized bitewing (BW) radiographs were taken. Four dentists with at least five years of experience scored all teeth twice (one-week interval) for ICDAS (0-6), BW (0=sound, 1=caries restricted to enamel, 2=caries in outer third dentin, 3=caries in inner third dentin), and TD (0=no treatment, 1=sealant, 2=microabrasion and sealant, 3=round bur sealant, 4a=resin, 4b=amalgam). Histological validation was performed by observation under a light microscope, with lesions classified on a five-point scale. Intraexaminer and inter-examiner repeatability were assessed using two-way tables and intraclass correlation coefficients (ICCs). Comparisons between percentage correct, specificity, sensitivity, and area under the receiver-operating characteristic (ROC) curve were performed using bootstrap analyses. ICCs for intraexaminer and interexaminer repeatability indicated good repeatability for each examiner, ranging from 0.78 to 0.88, and among examiners, ranging from 0.74 to 0.81. Correlation between ICDAS and TD was 0.85 and between BW and TD was 0.78. Correlation between the methods and histological scores was moderate (0.63 for ICDAS and 0.61 for BW). The area under the ROC curve was significantly greater for ICDAS than for BW (p<0.0001). ICDAS had significantly lower specificity than BW did (p=0.0269, 79% vs 94%); however, sensitivity was much higher for ICDAS than for BW (p<0.0001, 83% vs 44%). Data from this investigation suggested that the visual examination (ICDAS) showed better performance than radiographic examination for occlusal caries detection. The ICDAS was strongly associated with TD. Although the correlation between the ICDAS and BW was lower, it is still valuable in the clinical decision-making process.

Growth of silver nano-particle embedded in tellurite glass: Interaction between localized surface plasmon resonance and Er3+ ions

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

Optical spectroscopy and upconversion luminescence in Nd3+ doped Ga10Ge25S65 glass

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Stokes and anti-Stokes luminescence of Er3+ doped Ga10Ge25S65 glass excited at 980 and 532 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Frequency upconversion in a Pr(3+) doped chalcogenide glass containing silver nanoparticles

We report on orange-to-blue frequency upconversion (UC) in Pr(3+) doped chalcogenide glass (Ga(10)Ge(25)S(65)) doped with Ag(2)S and heat treated under different conditions to nucleate silver nanoparticles (NPs). The experiments were performed using 7 ns pulses from a dye laser that operates at similar to 590 nm, in resonance with the (3)H(4)->(1)D(2) transition of Pr(3+) ions. The enhancement observed in the UC emission at similar to 494 nm, ascribed as (3)P(0)->(3)H(4) transition of the Pr(3+) ion, is attributed to the large local field acting on the emitting ions due to the presence of the metallic NPs. (C) 2008 American Institute of Physics.

Enhanced luminescence of Tb3+/Eu3+ doped tellurium oxide glass containing silver nanostructures

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Microstructured chalcogenide optical fibers from As2S3 glass: towards new IR broadband sources

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

Fully relativistic calculations on the potential energy surfaces of the lowest 23 states of molecular chlorine

The electronic structure and spectroscopic properties (R(e), omega(e), omega(e)x(e), beta(e), and T(e)) of the ground state and the 22 lowest excited states of chlorine molecule were studied within a four-component relativistic framework using the MOLFDIR program package. The potential energy curves of all possible 23 covalent states were calculated using relativistic complete open shell configuration interaction approach. In addition, four component multireference configuration interaction with single and double excitation calculations were performed in order to infer the effects due to dynamical correlation in vertical excitations. The calculated properties are in good agreement with the available experimental data.

Localized surface plasmon resonance interaction with Er3+-doped tellurite glass

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