Determination of interfacial co-ion concentration in ionic micelles by chemical trapping: Halide concentration at the interface of sodium dodecyl sulfate micelles

Products from the spontaneous reaction of a long-chain arenediazonium salt, 2,6-dimethyl-4-hexadecylbenzenediazonium tetrafluoroborate(16-ArN2BF4), in aqueous micellar solutions of sodium dodecyl sulfate (SDS)? are used to estimate the local concentration of chloride and bromide ions at the micellar surface. The arenediazonium ion, 16-ArN2+, which is totally bound to the SDS micelle, reacts by rate-determining loss of N-2 to give an aryl cation that traps available nucleophiles, i,e., H2O, Cl-, and Br-, to give stable phenol, 16-ArOH, and halobenzene products, 16-ArCl and 16-ArBr, respectively. Product yields, determined by HPLC, are related to local concentrations using calibration curves obtained from independent standards. The local concentrations determined by this method are consistent with co-ion concentrations calculated, using a cell model, by numerical integration of the Poisson-Boltzmann equation (PBE) taking into account salt-induced micellar growth. The salt dependence of the intel facial concentrations of Cl- and Br- are identical. indicating no specific interactions in the interfacial co-ion compartment. PBE calculations predict that, in micellar SDS, increasing the concentration of a particular halide salt (NaX) at constant concentration of another halide (NaY) should result in an increase in the local concentrations of both co-ions. Using this chemical-trapping method, this prediction was demonstrated experimentally.

Evaluation of shear bond strength at the interface of two porcelains and pure titanium injected into the casting mold at three different temperatures

Statement of problem. Titanium has physical and mechanical properties, which have led to its increased use in dental prostheses despite casting difficulties due to high melting point and formation of oxide layers which affect the metal-ceramic bond strength.Purpose. This in vitro study evaluated the shear bond strength of the interface of 2 dental porcelains and pure titanium injected into a mold at 3 different temperatures.Material and methods. Using commercially pure (cp) titanium bars (Titanium, Grade I) melted at 1668degreesC and cast at mold temperatures of 430degreesC, 700degreesC or 900degreesC, 60 specimens were machined to 4 x 4 mm, with a base of 5 x 1 mm. The 4-mm surfaces were airborne-particle abraded with 100 mum aluminum oxide before applying and firing the bonding agent and evaluating the 2 porcelains (Triceram/Triline ti and Vita Titankeramik). Ten specimens were prepared for each temperature and porcelain combination Shear bond testing was performed in a universal testing machine, with a 500-kg load cell and crosshead speed of 0.5 mm/min. The specimens were loaded until failure. The interfaces of representative fractured specimens of each temperature were examined with a scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). Data for shear bond strength (MPa) were statistically analyzed by 2-way ANOVA and the Tukey test (alpha = .05).Results. The results showed significant differences for the metal/porcelain interaction effect (P = .0464). There were no significant differences for the 2 porcelains (P = .4250). The Tukey test showed a significant difference between the pair cp Ti 430degreesC Triceram and cp Ti 900degreesC Triceram, with respective mean values and SDs of 59.74 +/- 11.62 and 34.03 +/- 10.35 MPa.Conclusion. Triceram porcelain showed a bond strength decrease with an increase in the mold temperature for casting titanium. The highest bond strength for Vita porcelain and the best metal-ceramic interface observed with the SEM were found with the mold temperature of 700degreesC.

THEORY OF NON-STEADY-STATE ELECTRICAL CHARACTERISTICS OF METAL-INSULATOR-METAL STRUCTURES WITH SCHOTTKY BARRIERS AND UNIFORMLY DISTRIBUTED INTERFACE IMPURITY STATES

The metal-insulator (or amorphous semiconductor) blocking contact is still not well understood. In the present paper, we discuss the non steady state characteristics of Metal-lnsulator-Metal Structure with non-intimate blocking contacts (i.e. Metal-Oxide-Insulator-Metal Structure). We consider a uniform distribution (in energy) of impurity states in addition to impurity states at a single energy level within the depletion region. We discuss thermal as well as isothermal characteristics and present expressions for the temperature of maximum current (T-m) and a method to calculate the density of uniformly distributed impurity states. The variation of mobility with electrical field has also been considered. Finally we plot the theoretical curves under different conditions. The present results are closing into available experimental results.

pH at the micellar interface: Synthesis of pH probes derived from salicylic acid, acid-base dissociation in sodium dodecyl sulfate micelles, and Poisson-Boltzmann simulation

The study of the H+ concentration at the micellar interface is a convenient system for modeling the distribution of H+ at interfaces. We have synthesized salicylic acid derivatives to analyze the proton dissociation of both the carboxylic and phenol groups of' the probes, determining spectrophotometrically the apparent pK(a)'s (pK(ap)) in sodium dodecyl Sulfate, SDS, micelles with and without added salt. The synthesized probes were 2-hydroxy-5-(2-trimethylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumacetyl)benzoate- 2-hydroxy-5-(2-dimethylhexadecylammoniumhexanoyl)benzoate-, 2-hydroxy-5-(2-diniethylhexadecylammoniumundecanoyl)betizoate; 2-hydroxy-5-acetylbenzoic acids and 2-hydroxy-5-dodecanoylbenzoic acid. Upon incorporation into SDS micelles the pK(ap)'s of both carboxylic and phenol groups increased by ca. 3 pH units and NaCl addition caused a decrease in the probe-incorporated pKap. The experimental results were fitted with a cell model Poisson-Boltzmann (P-B) equation taking in consideration the effect of salt on the aggregation number of SDS and using the distance of' the dissociating group as a parameter. The conformations of the probes were analyzed theoretically using two dielectric constants, e.g., 2 and 78. Both the P-B analysis and conformation calculations can be interpreted by assuming that the acid groups dissociate very close to, or at, the interface. Our results are consistent with the assumption that the intrinsic pK(a)'s of both carboxylic and phenol groups of the salicylic acid probes used here can be taken as those in water. Using this assumption the micellar and salt effects on the pKap's of the (trialkylammonium)benzoate probes were described accurately using a cell model P-B analysis. (c) 2005 Elsevier B.V. All rights reserved.

Interface morphology snapshots of vertically segregated thin films of semiconducting polymer/polystyrene blends

We present atomic force microscopic images of the interphase morphology of vertically segregated thin films spin coated from two-component mixtures of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene-vinylene] (MEH-PPV) and polystyrene (PS). We investigate the mechanism leading to the formation of wetting layers and lateral structures during spin coating using different PS molecular weights, solvents and blend compositions. Spinodal decomposition competes with the formation of surface enrichment layers. The spinodal wavelength as a function of PS molecular weight follows a power-law similar to bulk-like spinodal decomposition. Our experimental results indicate that length scales of interface topographical features can be adjusted from the nanometer to micrometer range. The importance of controlled arrangement of semiconducting polymers in thin film geometries for organic optoelectronic device applications is discussed. (c) 2007 Elsevier Ltd. All rights reserved.

Effect of bur type and conditioning on the surface and interface of dentine

The purpose of this in vitro study was to evaluate the surface and resin-dentine interface characteristics of permanent tooth dentine cut with diamond or carbide burs and treated with phosphoric acid (PA) or an acidic conditioner. Labial surfaces of permanent incisors were prepared into dentine with high-speed carbide or diamond burs and divided into two halves. Phosphoric acid 36% was applied on one half and non-rinse conditioner (NRC) was applied on the other half. Ten randomly selected scanning electron microscopy (SEM) fields from each specimen (n = 15) were evaluated. Occlusal surfaces of third molars were divided in two halves for evaluation of the resin-dentine interface. The halves were randomly assigned to one of each conditioner and restored with Prime & Bond NT/Spectrum. Ten specimens were analysed by SEM to evaluate hybrid layer formation and interfacial seal. We observed that surfaces prepared with carbide bur presented less residual smear plugs (P < 0.05) than surfaces prepared with diamond burs. Surfaces conditioned with NRC, which is a smear layer modifier, presented more residual smear plugs than surfaces conditioned with PA (P < 0.05). Treatment with PA resulted in more sealed interfaces than specimens treated with NRC. Within the limitations of this study the results showed that carbide burs leave a surface that is more conducive to bonding than diamond burs.

Development of a graphical interface for the Rietveld refinement program DBWS

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Modification of glassy carbon electrodes with a poly-L-lysine/glutaraldehyde film

A film of poly-L-lysine (PLL) adheres better to the surface of a glassy carbon electrode when the PLL is partially cross-linked by means of glutaraldehyde. A film composition of 97.5% PLL/2.5% glutaraldehyde gives good adhesion and retains the anionic exchange capability of the PLL. The performance of the film was tested with hexacyanoferrate(III) using electrochemical and nonelectrochemical accumulation.

Surface modification of Ti dental implants by Nd: YVO4 laser irradiation

Surface modifications have been applied in endosteal bone devices in order to improve the osseointegration through direct contact between neoformed bone and the implant without an intervening soft tissue layer. Surface characteristics of titanium implants have been modified by addictive methods, such as metallic titanium, titanium oxide and hydroxyapatite powder plasma spray, as well as by subtractive methods, such as acid etching, acid etching associated with sandblasting by either AlO2 or TiO2, and recently by laser ablation. Surface modification for dental and medical implants can be obtained by using laser irradiation technique where its parameters like repetition rate, pulse energy, scanning speed and fluency must be taken into accounting to the appropriate surface topography. Surfaces of commercially pure Ti (cpTi) were modified by laser Nd:YVO4 in nine different parameters configurations, all under normal atmosphere. The samples were characterized by SEM and XRD refined by Rietveld method. The crystalline phases alpha Ti, beta Ti, Ti6O, Ti3O and TiO were formed by the melting and fast cooling processes during irradiation. The resulting phases on the irradiated surface were correlated with the laser beam parameters: the aim of the present work was to control titanium oxides formations in order to improve implants osseointegration by using a laser irradiation technique which is of great importance to biomaterial devices due to being a clean and reproducible process. (c) 2007 Elsevier B.V. All rights reserved.

Performance evaluation of a novel hybrid multipulse rectifier for utility interface of power electronic converters

This paper presents an improved analysis of a novel Programmable Power-factor-corrected-Based Hybrid Multipulse Power Rectifier (PFC-HMPR) for utility interface of power electronic converters. The proposed hybrid multipulse rectifier is composed of an ordinary three-phase six-pulse diode-bridge rectifier (Graetz bridge) with a parallel connection of single-phase switched converters in each three-phase rectifier leg. In this paper, the authors present a complete discussion about the controlled rectifiers' power contribution and also a complete analysis concerning the total harmonic distortion of current that can be achieved when the proposed converter operates as a conventional 12-pulse rectifier. The mathematical analysis presented in this paper corroborate, with detailed equations, the experimental results of two 6-kW prototypes implemented in a laboratory.