Changes of physical properties of glass surfaces exposed to KNO3 vapors

Modifications of glass surfaces were studied after exposure of samples to an atmosphere resulting from the decomposition of molten KNO3. The diffusion coefficient of K+ ions migrating into the surfaces of float glass and synthesized glasses doped with up to 5 wt% SnO2 was calculated by the Boltzmann-Matano technique. The Vickers hardness and the refractive index increase with exposure time. Infrared spectra show that the migration of K+ is responsible for an increase in the number of non-bridging oxygens in the exposed samples. The spectra of the synthesized glasses present evidences that their surfaces undergo crystallization during the exposure. All results lead to the conclusion that the presence of tin in the glasses hinders the diffusion of K+ ions, thus affecting the Vickers hardness, the refractive index and the infrared spectra. It is shown that the exposure method can be used as an alternative process to promote the K+ migration into glass surfaces. (c) 2006 Elsevier B.V. All rights reserved.

Sintering and characterization of PLZT (9/65/35)

PLZT(9/65/35) obtained by association between the Pechini method (ZT) and partial oxalate (PLZT) was prepared. The stoichiometric phase and monophasic (cubic) PLZT obtained by calcination did not occur after sintering. The sintering process, by using two stages, caused a liquid phase formation due to a PbO excess (5 and 10 wt%). Samples with high density (similar to 8 g/cm(3)) and optical transparency(similar to 12%) were obtained. However, an equilibrium between the excess of PbO of sample/atmosphere PbO leads to a segregated PbO phase on the boundaries of the microstructure. A diffusion of Zr, Ti and La ions from PLZT to PbO phase promoted a stoichiometric deviation of the matrix and modified the optical and dielectric characteristics. (C) 2000 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Light-induced relief gratings and a mechanism of metastable light-induced expansion in chalcogenide glasses

We report on a metastable light-induced volume expansion in Ge25+xGa10-xS65 glasses under irradiation with band gap (UV) light, which can result in recording of relief gratings on their surface in the case of irradiation with two interfering beams. We propose a mechanism for the expansion, which is based on the light-induced change in the polarizability of secondary (van der Waals type) bonds and the effect of this change on primary (covalent type) bonds of the glass. The effect is suggested to be due to an interference of electrons, which belong to a chalcogen atom and participate in the formation of secondary and primary bonds, respectively. We suggest that a minimum point of the Lennard-Jones potential, which corresponds to the equilibrium position of a chalcogen atom is shifted in the course of irradiation to a larger interatomic distance. This shift causes a volume expansion and allows a diffusion of chalcogen atoms into the irradiated area. We show that light-induced polymerization of the glass network is an important attribute of the light-induced volume expansion.

Physical properties of silicate glasses doped with SnO2

The presence of tin in the network of silicate glasses produces changes in several of their physico-chemical properties. Glasses with the composition (mol%) 22Na(2)O (.) 8CaO (.) 70SiO(2) containing up to 5 wt% of SnO2 were analyzed under several experimental techniques. Dilatometric measurements showed an increase of the glass transition temperature with increasing tin content, while the average thermal expansion coefficient is reduced. Vickers microhardness, density, and refractive index also increase with the tin content. Diffuse reflectance spectra in the infrared (DRIFT) showed that the presence of tin, even at low concentrations, is responsible for some structural changes since there is an increase of the bridging oxygen concentration. The doped glasses present a brown color and optical absorption spectra measurements are interpreted as being due to precipitation of tin in the form of colloidal particles during cooling of the melted glass. In the Na+ <-> K+ ion exchange process the presence of tin in the glass network hinders the diffusion of these ions. The diffusion coefficients of those ions were calculated by the Boltzmann-Matano technique, after concentration profiles obtained by EDS measurements. All results obtained present evidences that Sn4+ cation acts as a glass network former. (c) 2005 Elsevier B.V. All rights reserved.

Morphology characterization of layer-by-layer films from PAH/MA-co-DR13: the role of film thickness

We report on the use of dynamic scale theory and fractal analyses in the Study of distinct growth stages of layer-by-layer (LBL) films of poly(allylamine hydrochloride) (PAH) and a side-chain-substituted azobenzene copolymer (Ma-co-DR13). The LBL films were adsorbed oil glass substrates and characterized with atomic force microscopy with the Ma-co-DR13 at the top layer. The ganular morphology exhibited by the films allowed the observation of the growth process inside and outside the grains. The growth outside the grains was found to follow the Kardar-Parisi-Zhang model, with fractal dimensions of ca. 2.6. One could expect that inside the grains the morphology would be close to a Euclidian surface with fractal dimension of ca. 2 for any growth stage. The latter, however, was observed only for thicker films containing more than 10 bilayers. For thinner films the morphology was well described by a self-affine fractal. Such dependence of the growth behavior with the film thickness is associated with a more complete coverage of adsorption sites in thicker films due to diffusion of polymer molecules. (c) 2004 Elsevier B.V. All rights reserved.

The effects of ice-water storage on blood gas and acid-base measurements

Objective: To determine the effects of storage of arterial and venous blood samples in ice water on blood gas and acid-base measurements.Design: Prospective, in vitro, laboratory study.Setting: School of veterinary medicine.Subjects: Six healthy dogs.Measurements and main results: Baseline measurements of partial pressure of oxygen (PO2), partial pressure of carbon dioxide (PCO2), pH, hemoglobin concentration (tHb), oxyhemoglobin saturation, and oxygen content (ContO(2)) were made. Bicarbonate (HCO3) and standard base excess (SBE) were calculated. Arterial and venous blood samples were separated into 1 and 3 mL samples, anaerobically transferred into 3 mL plastic syringes, and stored in ice water for 6 hours. Measurements were repeated at 15, 30 minutes, and 1, 2, 4, and 6 hours after baseline measurements. Arterial (a) PO2 increased significantly from baseline after 30 minutes of storage in the 1 mL samples and after 2 hours in the 3 mL samples. Venous (v) PO2 was significantly increased from baseline after 4 hours in the 1 mL samples and after 6 hours in the 3 mL samples. The pHa significantly decreased after 2 hours of storage in the 1 mL samples and after 4 hours in the 3 mL samples. In both the 1 and 3 mL samples, pHv decreased significantly only after 6 hours. Neither the arterial nor the venous PCO2 values changed significantly in the 1 mL samples and increased only after 6 hours in the 3 mL samples. No significant changes in tHb, ContO(2), SBE, or HCO3 were detected.Conclusions: the PO2 of arterial and venous blood increased significantly when samples were stored in plastic syringes in ice water. These increases are attributable to the diffusion of oxygen from and through the plastic of the syringe into the blood, which occurred at a rate that exceeded metabolic consumption of oxygen by the nucleated cells.

Documenting the advantages and limitations of different classes of molecular markers in a well-established phylogeographic context: lessons from the Iberian endemic Golden-striped salamander, Chioglossa lusitanica (Caudata: Salamandridae)

Previous analyses of mitochondrial (mt)DNA and allozymes covering the range of the Iberian endemic golden-striped salamander, Chioglossa lusitanica, suggested a Pleistocene split of the historical species distribution into two population units (north and south of the Mondego river), postglacial expansion into the northernmost extant range, and secondary contact with neutral diffusion of genes close to the Mondego river. We extended analysis of molecular variation over the species range using seven microsatellite loci and the nuclear P-fibrinogen intron 7 (beta-fibint7). Both microsatellites and beta-fibint7 showed moderate to high levels of population structure, concordant with patterns detected with mtDNA and allozymes; and a general pattern of isolation-by-distance, contrasting the marked differentiation of two population groups suggested by mtDNA and allozymes. Bayesian multilocus analyses showed contrasting results as populations north and south of the Douro river were clearly differentiated based on microsatellites, whereas allozymes revealed differentiation north and south of the Mondego river. Additionally, decreased microsatellite variability in the north supported the hypothesis of postglacial colonization of this region. The well-documented evolutionary history of C. lusitanica, provides an excellent framework within which the advantages and limitations of different classes of markers can be evaluated in defining patterns of population substructure and inferring evolutionary processes across distinct spatio-temporal scales. The present study serves as a cautionary note for investigations that rely on a single type of molecular marker, especially when the organism under study exhibits a widespread distribution and complex natural history. (C) 2008 The Linnean Society of London, Biological Journal of the Linnean Society, 2008, 95, 371-387.

P-type semiconducting gas sensing behavior of nanoporous rf sputtered CaCu3Ti4O12 thin films

The fabrication of nanoporous sputtered CaCu3Ti4O12 thin films with high gas sensitivity is reported in this work. The porous microstructure and the nanocrystalline nature of the material promoted the diffusion of the atmosphere into the film, shortening the response time of the samples. Behaving as p-type semiconductor, the material presents enhanced sensitivity even at low working temperatures. Impedance spectroscopy measurements were performed in order to investigate the mechanisms responsible for the performance of the devices. (C) 2008 American Institute of Physics.

An AM1 semiempirical study of the mechanism of sintering for ZnO in the presence of water and carbon dioxide

AM1 calculations were performed for the absorption of H2O and CO2 molecules on the surface of model ZnO crystals. The absorption of isolated molecules of each species and the co-absorption of both compounds simultaneously were considered. It was found that the absorption of H2O near a site where CO; is already absorbed favors the process of sintering, in agreement with the experimental findings. This is explained by the formation of Zn(OH)CO3H bound to the surface, a more mobile species than the ZnO unit itself. The roundening of the grains observed in atmospheres containing dry CO2 but suppressed when H2O is present, is also explained by these calculations. After absorption of CO2, the rupture of one bond - so that diffusion of the ZnCO3 species on the surface is allowed - requires much less energy than the breaking of two bonds, necessary for ZnO migration. These facts explain why the speed of surface transport does not decrease in CO2 atmospheres while sintering is indeed slowed down. © 1994.

Mechanism of phase formation in Pb(ZrxTi1-x)O3 synthesized by a partial oxalate method

The phase formation mechanism, as well as the morphotropic phase boundary, of lead zirconate titanate (PZT) processed by a partial oxalate method was investigated by simultaneous thermal analysis (TG-DTA) and by qualitative and quantitative X-ray diffraction (XRD). The results show that the ZrxTi1-xO2 (ZT) phase reacts with PbO forming the PZT phase without intermediate phases. XRD analysis showed the coexistence of rhombohedral and tetragonal phases for 0.47 ≤ x ≤ 0.55 with the phase boundary composition for x = 0.51. For low calcination temperatures, preferential formation of the PZT rhombohedral phase was observed. A model for phase formation of PZT by the partial oxalate method is proposed based on the existence of two interfaces of reaction (PbO-PZT and PZT-ZT) and diffusion of cations.

Effect of barium titanate seed particles on the sintering and lattice parameters in PbMg1/3Nb2/3O3 ceramics

PbMg1/3Nb2/3O3 (PMN) powder was prepared by citrate organic solution, and barium titanate (BT) seed particles were added to encourage the perovskite phase formation. Sintering was followed using the constant heating rate mode of a dilatometer, and it was observed that the seed concentration affected the PMN shrinkage rate and crystal structure. The study of the lattice parameters of the samples after the sintering process indicates that the diffusion of the titanium and of the barium inside perovskite and pyrochlore PMN phases occurs. Moreover, this substitution provoked a decrease of the lattice parameters as showed by the Rietveld refinement.

Photo-oxidation of polyphenylenevinylene chains in Langmuir-Blodgett and cast films

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). These derivatives are highly susceptible to photooxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Photodegradation experiments were carried out by illuminating the films with white light from a halogen lamp (50W, 12 V), placed at a fixed dstance from the sample. The decay was monitored by UV-Vis and FTIR spectroscopies. The results showed that cast films are completely degraded in ca. 300 min, while LB took longer times, ca. 1000 min, i.e. 3 times the values for the cast films. The degradation process occurs in at least two stages, the rates of which were calculated assuming that the reaction follows a first order kinetics. The characteristic times for the first stage were 3.6×10-2 and 1.3×10-3 min-1 for cast and LB films, respectively. For the second stage the characteristic times were 5.6×10-2 and 5.0×10 -3 min-1. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process.

Effects of electroplated zinc-nickel alloy coatings on the fatigue strength of AISI 4340 high strength steel

It is well known that fatigue behaviour is an important parameter to be considered in mechanical components subjected to constant and variable amplitude loadings. In combination with corrosion phenomenon, fatigue effects were responsible for proximally 64% of fails that occur in metallic parts of aeronautical accidents in the last 30 years. Recovered substrates have been extensively used in the aerospace field. Cadmium electroplating has been widely applied to promote protective coatings in aeronautical components, resulting in excellent corrosion protection combined with a good performance in cyclic loading. Ecological considerations allied to the increasing demands for corrosion resistance, resulted in the search for possible alternatives. Zinc-nickel alloys received considerable interest recently, since these coatings showed some advantages such as a good resistance to white and red rust, high plating rates and acceptation in the market. In this study the effects of zinc-nickel coatings electroplated on AISI 4340 high strength steel were analysed on rotating bending and axial fatigue strength, corrosion and adhesion resistance. Compressive residual stress field was measured by a X-ray tensometry prior to fatigue tests. Optical microscopy images showed coating thicknesses, adhesion and the existence of an uniform coverage of nearly all substrates. The fractured fatigue specimens were investigated using a scanning electron microscope. Three different zinc-nickel coating thicknesses were tested and comparison with rotating bending fatigue data from specimens cadmium electroplated and heat treated at 190°C for 3, 8 and 24 hours to avoid the diffusion of hydrogen in the substrate, was performed. Experimental results showed effect of coatings on the AISI 4340 steel behaviour when submitted to fatigue testing and the existence of coating thickness influence on the fatigue strength.

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.

Biocompatibility of resin-based dental materials applied as liners in deep cavities prepared in human teeth

Background: Since only a few data have been published concerning the effects of resinous dental materials on the pulp-dentin complex, the aim of this study was to evaluate the biocompatibility of resin-based materials applied as liners in deep cavities prepared in duman teeth. Methods: After preparing class V cavities, the following dental materials were applied on the axial walls: group 1, Vitrebond™ (VIT; 3M ESPE); group 2, Ultra-Blend® Plus™ (UBP; Untradent); and group 3, Clearfil™ SE Bond (CSEB; Kuraray). In group 4 (control), the hard-setting calcium hydroxide cement Dycal (CH; Caulk/Dentsply) was used. The teeth extracted at 7 days or between 30 and 85 days after the clinical procedures were processed for histological evaluation. Results: For all the experimental and control groups, most of specimens exhibited no pulpal response or slight inflammatory reaction associated with slight tissue disorganization at 7-day period. Moderate inflammatory pulpal response occurred only in one tooth (RDT = 262 μm) of group 3 in which transdentinal diffusion of resin components was observed. Conclusion: The resin-based dental cements VIT and UBP as well as the bonding agent CSEB presented acceptable biocompatibility when applied in deep cavities prepared in sound human teeth. © 2006 Wiley Periodicals, Inc.