Kinetic studies on the reactions of Ru(II) tetraammines with CS2N- 3

The kinetics of the reactions of Ru(II) complexes with CS2N- 3 ions were studied spectrophotometrically. The formation rate constants data for trans-[Ru(NH3)4L(CS2N3)] are 2.2 × 102, 1.8 × 10 and 1.3 × 102 M-1 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3), respectively [μ = 1.0 M (NaCF3COO), 25°C]. Under the same experimental conditions, the values of k-1 (specific rate for the aquation reaction) are 1.5 × 10-2, 5.0 × 10-2 and 4.5 × 10 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3, respectively. The free-energy change (ΔG≠) for the systems where L = P(OEt)3 and SO2- 3 are in agreement within the experimental error. It was observed that the affinity of the CS2N- 3 ion decreases with the increasing π-acidity of the auxiliary ligand L. The order of affinity of the CS2N- 3 ion for the Ru(II) center studies is SO2- 3 > HSO- 3 > P(OEt)3 >SO2. © 1986.

The influence of crystallization route on the SrBi2Nb2O9 thin films

Polycrystalline SrBi2Nb2O9-layered ferroelectric thin films were synthesized on Pt/Ti/SiO2/Si substrate using the polymeric precursors solution. The dip-coated films were specular and crack-free and crystallized during firing at 700 °C. Single-, double-, and triple-layered films were obtained by several dips in the deposition solution, and the influence of crystallization between each dip was studied. Microstructure and morphological evaluation were followed by grazing incident x-ray diffraction (GIXRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Multilayered films obtained using the intermediate-crystallized layer route present a dense microstructure with spherical grains, with a preferential orientation in the 〈215〉 direction; films obtained using the intermediate-amorphous layer route are polycrystalline and present elongated grains around 250 nm in size.

Densification and residual stresses induced in glass surfaces by Vickers indentations

Images and profiles of Vickers impressions produced on as-received float-glass were obtained using atomic force microscopy (AFM). The images show that the impression edges undergo elastic recovery parallel to surface. The profiles made it possible to measure vertical elastic recovery, ev(r). For a 40 g nominal load, maximum penetration depth of indenter was (2.20 ± 0.03) μm, and recovery at the impression center was ev(0) = (0.98 ± 0.03) μm. Vertical elastic recovery was non-uniform along profiles. Permanent impressions produced resulted from glass mass displacement downward, producing an increase in glass density in impression vicinity, which is discussed in terms of changes in O-Si-O and Si-O-Si bond angles and Si-O bond length. Near impression edges, pileup was observed for which a simplified model is proposed taking into account the compaction and stresses near the impressions. © 2000 Elsevier Science B.V. All rights reserved.

Comparison between different conditions of the chemical polymerization of polyaniline on top of PET films

Composites produced during the in situ chemical polymerization of aniline on top of a poly(ethylene terephthalate) (PET) film, in different conditions, were studied by open-circuit potential (Voc), ultraviolet-visible, and infrared spectroscopy, electrical conductivity measurements, scanning electron microscopy, and atomic force microscopy. The polymerization monitoring by Voc showed a maximum associated with the intermediate pernigraniline oxidation state and a final formation of polyaniline (PANI) in the doped emeraldine salt (ES) form. Furthermore, high electrical conductivity values were obtained for the PANI-ES coating prepared under selected conditions. A globular formation was observed for the doped PANI-ES coating with globules of sizes of the same order and same shape of the PET, demonstrating the influence of the substrate on the coating morphology.

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb1-xLaxTiO3 thin films, (X=0.0; 13 and 0.27mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO2/Si(111), Si(100) and glass substrates by spin coating, and annealed in the 200-300°C range in an O2 atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO3. The films deposited on Pt/Ti/SiO2/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration. © 2002 Elsevier Science B.V. All rights reserved.

Friction and wear properties of functionally graded aluminum matrix composites

Aluminum matrix composites are currently considered as promising materials for tribological applications in the automotive, aircraft and aerospace industries due to their great advantage of a high strength-to-weight ratio. A superior combination of surface and bulk mechanical properties can be attained if these composites are processed as functionally graded materials (FGM's). In this work, homogeneous aluminum based matrix composite, cast by gravity, and aluminum composites with functionally graded properties, obtained by centrifugal cast, are tested against nodular cast iron in a pin-on-disc tribometer. Three different volume fractions of SiC reinforcing particles in each FGM were considered in order to evaluate their friction and wear properties. The sliding experiments were conducted without lubrication, at room temperature, under a normal load of 5 N and constant sliding speed of 0.5 ms-1. The worn surfaces as well as the wear debris were characterized by SEM/EDS and by atomic force microscopy (AFM). The friction coefficient revealed a slightly decrease (from 0.60 to 0.50) when FGM's are involved in the contact instead of the homogeneous composite. Relatively low values of the wear coefficient were obtained for functionally graded aluminum matrix composites (≈10-6 mm3N-1 m-1), which exhibited superior wear resistance than the homogeneous composite and the opposing cast iron surface. Characterization of worn surfaces indicated that the combined effect of reinforcing particles as load bearing elements and the formation of protective adherent iron-rich tribolayers has a decisive role on the friction and wear properties of aluminum matrix composites.

Vertical and in-plane electrical transport in InAs/InP semiconductor nanostructures

Vertical and in-plane electrical transport in InAs/InP semiconductors wires and dots have been investigated by conductive atomic force microscopy (C-AFM) and electrical measurements in processed devices. Localized I-V spectroscopy and spatially resolved current images (at constant bias), carried out using C-AFM in a controlled atmosphere at room temperature, show different conductances and threshold voltages for current onset on the two types of nanostructures. The processed devices were used in order to access the in-plane conductance of an assembly with a reduced number of nanostructures. On these devices, signature of two-level random telegraph noise (RTN) in the current behavior with time at constant bias is observed. These levels for electrical current can be associated to electrons removed from the wetting layer and trapped in dots and/or wires. A crossover from conduction through the continuum, associated to the wetting layer, to hopping within the nanostructures is observed with increasing temperature. This transport regime transition is confirmed by a temperature-voltage phase diagram. © 2005 Materials Research Society.

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.

Electrical properties of individual and small ensembles of InAs/InP nanostructures

We investigate electrical properties of InAs/InP semiconductor nanostructures by conductive atomic force microscopy (C-AFM) and current measurements at low temperatures in processed devices. Different conductances and threshold voltages for current onset were observed for each type of nanostructure. In particular, the extremity of the wire could be compared to a dot with similar dimensions. The processed devices were used in order to access the in-plane conductance of an assembly of a reduced number of nanostructures. Here, fluctuations on I-V curves at low temperatures (<40 K) were observed. At these low temperatures and for a suitable range of applied voltages, random telegraph noise (RTN) in the current was observed for devices with dots. These fluctuations can be associated to electrons trapped in dots, as suggested by numerical simulations. A crossover from a semiconductor-like to a metallic transport behavior is also observed for similar parameters. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA.

Coincidences of self-maps on Klein bottle fiber bundles over the circle

The main purpose of this work is to study coincidences of fiber-preserving self-maps over the circle S 1 for spaces which are fiberbundles over S 1 and the fiber is the Klein bottle K. We classify pairs of self-maps over S 1 which can be deformed fiberwise to a coincidence free pair of maps. © 2012 Pushpa Publishing House.

Effect of airborne particle abrasion protocols on surface topography of Y-TZP ceramic

This study aimed to evaluate Y-TZP surface after different airborne particle abrasion protocols. Seventy-six Y-TZP ceramic blocks (5×4×4) mm3 were sintered and polished. Specimens were randomly divided into 19 groups (n=4) according to control group and 3 factors: a) protocol duration (2 and 4 s); b) particle size (30 μm, alumina coated silica particle; 45 μm, alumina particle; and 145 μm, alumina particle) and; c) pressure (1.5, 2.5 and 4.5 bar). Airborne particle abrasion was performed following a strict protocol. For qualitative and quantitative results, topography surfaces were analyzed in a digital optical profilometer (Interference Microscopic), using different roughness parameters (Ra, Rq, Rz, X-crossing, Mr1, Mr2 and Sdr) and 3D images. Surface roughness also was analyzed following the primer and silane applications on Y-TZP surfaces. One-way ANOVA revealed that treatments (application period, particle size and pressure of particle blasting) provided significant difference for all roughness parameters. The Tukey test determined that the significant differences between groups were different among roughness parameters. In qualitative analysis, the bonding agent application reduced roughness, filing the valleys in the surface. The protocols performed in this study verified that application period, particle size and pressure influenced the topographic pattern and amplitude of roughness.

Effect of brushing with conventional versus whitening dentifrices on surface roughness and biofilm formation of dental ceramics

The aim of this study was to evaluate the effect of conventional and whitening dentifrices on the weight loss, surface roughness, and early in situ biofilm formation on the surface of dental ceramics. Standardized feldspar ceramic specimens (Vita VM7 and Vita VM13) were submitted to the following experimental conditions: no brushing; brushing without a dentifrice; brushing with a conventional dentifrice; and brushing with a whitening dentifrice. A brushing machine was used to simulate brushing. The mass and surface roughness of all specimens from the test groups were evaluated prior to and after brushing. Ten participants used an oral device for eight hours to evaluate the biofilm formed in situ on the specimens. Scanning electron microscopy was used for qualitative and quantitative analysis of the biofilm. ANOVA and Tukey tests were used to analyze the results of weight loss, surface roughness, and presence of bacteria. A one-way Kruskal-Wallis test was used for bacterial colonization results. For both ceramics, brushing with a whitening dentifrice resulted in weight loss that was significantly greater when compared to brushing without a dentifrice or with a conventional dentifrice. Increased surface roughness was noticed on VM13 ceramic samples with both dentifrices, whereas only conventional dentifrice had a significant effect on the surface roughness of VM7 samples. For both VM7 and VM13, no difference was found between the experimental conditions with regard to the presence or number of bacteria. Cocci and short rods were the predominant microbial morphotypes. Granular or fibrillar acellular material partially covered the specimens. Brushing with a whitening dentifrice resulted in significant weight loss of ceramic restorations, while brushing with both conventional and whitening dentifrices can roughen ceramic surfaces. The increase in roughness was not clinically significant to contribute to increased biofilm formation.

Surface study of vitreous carbon obtained from glassy carbon powder

This work presents a surface study of monolithic vitreous (or glassy) carbon - MVC - obtained from vitreous carbon powder. Defective MVC pieces are crushed in a ball mill and size classified by sifting. The MVC powder is mixed with furfuryl-alcohol resin and compacted in a mould using a hydraulic press. Samples with different powder granulometries are produced in this way and carbonized in a furnace under nitrogen atmosphere. Complete carbonization of the powder is achieved in only one day and losses due to breakage of the pieces is less than 5%. These results compare very favorably with respect to traditional MVC production methods where full carbonization may require up to seven days and losses due to breakage can be as high as 70%. After carbonization, samples are sanded and polished. Surface roughness and microstructure are characterized by light microscopy. Porosity is quantified from micrographs using ImageJ software and nanometric height variations are measured by atomic force microscopy. © 2012 Materials Research Society.

Atmospheric plasma treatment of carbon fibers for enhancement of their adhesion properties

Plasma processing of carbon fibers (CFs) is aimed to provide better contact and adhesion between individual plies without decrease in the CF mechanical resistance. This paper deals with surface modification of CFs by an atmospheric pressure dielectric barrier discharge (DBD) for enhancing the adhesion between the CF and the polymeric matrix. The scanning electron microscopy of the treated samples revealed many small particles distributed over entire surface of the fiber. These particles are product of the fiber surface etching during the DBD treatment that removes the epoxy layer covering as-received samples. The alteration of the CF surface morphology was also confirmed by the Atomic force microscopy (AFM), which indicated that the CF roughness increased as a result of the plasma treatment. The analysis of the surface chemical composition provided by X-ray photoelectron spectroscopy showed that oxygen and nitrogen atoms are incorporated onto the surface. The polar oxygen groups formed on the surface lead to the increasing of the CF surface energy. The results of interlaminar shear strength test (short beam) of CFs/polypropylene composites demonstrated a greater shear resistance of the composites made with CFs treated by DBD than the one with untreated fibers. Both the increase in surface roughness and the surface oxidation contribute for the enhancement of CF adhesion properties. © 2012 IEEE.

Interface formation of nanostructured heterojunction SnO 2:Eu/GaAs and electronic transport properties

Thin films of tin dioxide (SnO2) are deposited by the sol-gel-dip-coating technique, along with GaAs layers, deposited by the resistive evaporation technique. The as-built heterojunction has potential application in optoelectronic devices, combining the emission from the rare-earth doped transparent oxide (Eu3+-doped SnO2 presents very efficient red emission) with a high mobility semiconductor. The advantage of this structure is the possibility of separation of the rare-earth emission centers from the electron scattering, leading to a strongly indicated combination for electroluminescence. Electrical characterization of the heterojunction SnO2:Eu/GaAs shows a significant conductivity increase when compared to the conductivity of the individual films, and the monochromatic light irradiation (266 nm) at low temperature of the heterojunction GaAs/SnO2:Eu leads to intense conductivity increase. Scanning electron microscopy (SEM) of the heterojunction cross section shows high adherence and good morphological quality of the interfaces substrate/SnO2 and SnO2/GaAs, even though the atomic force microscopy (AFM) image of the GaAs surface shows disordered particles, which increases with sample thickness. On the other hand, the good morphology of the SnO2:Eu surface, shown by AFM, assures the good electrical performance of the heterojunction. The observed improvement on the electrical transport properties is probably related to the formation of short conduction channels at the semiconductors interface, which may exhibit two-dimensional electron gas (2DEG) behavior. © 2012 Elsevier B.V. All rights reserved.