Development of an electrochemical sensor for determination of dissolved oxygen by nickel-salen polymeric film modified electrode

An amperometric oxygen sensor based on a polymeric nickel-salen (salen = N,N'-ethylene bis(salicylideneiminato)) film coated platinum electrode was developed. The sensor was constructed by electropolymerization of nickel-salen complex at platinum electrode in acetonitrile/tetrabutylammonium perchlorate by cyclic voltammetry. The voltammetric behavior of the sensor was investigated in 0.5 mol L-1 KCl solution in the absence and presence of molecular oxygen. Thus, with the addition of oxygen to the solution, the increase of cathodic peak current (at -0.25 V vs. saturated calomel electrode (SCE)) of the modified electrode was observed. This result shows that the nickel-salen film on electrode surface promotes the reduction of oxygen. The reaction can be brought about electrochemically, where the nickel(II) complex is first reduced to a nickel(I) complex at the electrode surface. The nickel(I) complex then undergoes a catalytic oxidation by the molecular oxygen in solution back to the nickel(II) complex, which can then be electrochemically re-reduced to produce an enhancement of the cathodic current. The Tafel plot analyses have been used to elucidate the kinetics and mechanism of the oxygen reduction. A plot of the cathodic current vs. the dissolved oxygen concentration for chronoamperometry (fixed potential = -0.25 V vs. SCE) at the sensor was linear in the 3.95-9.20 mg L-1 concentration range and the concentration limit was 0.17 mg L-1 O-2. The proposed electrode is useful for the quality control and routine analysis of dissolved oxygen in commercial samples and environmental water. The results obtained for the levels of dissolved oxygen are in agreement with the results obtained with a commercial O-2 sensor. (C) 2012 Elsevier B.V. All rights reserved.

An electrochemical sensor for dipyrone determination based on nickel-salen film modified electrode

An amperometric dipyrone sensor based on a polymeric nickel-salen (salen = N,N'-ethylenebis(salicydeneiminato)) film coated platinum electrode was developed. The sensor was constructed by electropolymerization of nickel-salen complex at a platinum electrode in acetonitrile/tetrabuthylamonium perchlorate by cyclic voltammetry. After cycling the modified electrode in a 0.50 mol L-1 KCl solution, the estimated surface concentration was found to be equal to 1.29 x 10(-9) mol cm(-2). This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the nickel(II)/nickel(III) couple. A plot of the anodic current versus the dipyrone concentration for chronoamperometry (potential fixed = +0.50 V) at the sensor was linear in the 4.7 x 10(-6) to 1.1 x 10(-4) mol L-1 concentration range and the concentration limit was 1.2 x 10(-6) mol L-1. The proposed electrode is useful for the quality control and routine analysis of dipyrone in pharmaceutical formulations.

Development of Nanostructured Electrochemical Sensor Based on Polymer Film Nickel-Salen for Determination of Dissolved Oxygen

An amperometric oxygen sensor based on a polymeric nickel-salen (salen = N,N '-ethylenebis(salicydeneiminato)) film coated platinum electrode was developed. The sensor was constructed by electropolymerization of nickel-salen complex at a platinum electrode in acetonitrile/tetrabuthylamonium perchlorate by cyclic voltammetry. The voltammetric behavior of the modified electrode was investigated in 0.5 mol L-1 KCl solution in the absence and presende of molecular oxygen. A significant increased of cathodic peak current (at -0.20 vs. SCE) of the modified electrode with addition of oxygen to the solution was observed. This result shows that the nickel-salen film on the surface of the electrode promotes the reduction of oxygen. The reaction can be brought about electrochemically where in the nickel(II) complex is first reduced to a nickel(I) complex at the electrode surface. The nickel(I) complex then undergoes a catalytic oxidation by the oxygen molecular in solution back to the nickel(II) complex, which can then be electrochemically re-reduced to produce an enhancement of the cathodic current. The plot of the cathodic current versus the dissolved oxygen concentration for chronoamperometry (potential fixed = -0.20 V) at the sensor was linear in the concentration range of 3.95 to 9.20 mg L-1 with concentration limit of 0.17 mg L-1 O-2. The modified electrode proposed is useful for the quality control and routine analysis of dissolved oxygen in commercial water and environmental water samples. The results obtained for the levels of dissolved oxygen are in agreement with the results obtained with an O-2 commercial sensor. (C) 2011 Published by Elsevier Ltd.

Gelatin microparticles containing propolis obtained by spray-drying technique: preparation and characterization

Gelatin microparticles containing propolis extractive solution (PES) were prepared by spray-drying technique. The optimization of the spray-drying operating conditions and the proportions of gelatin and mannitol were investigated. Regular particle morphology was obtained when mannitol was used, whereas mannitol absence produced a substantial number of coalesced and agglomerated microparticles. Microparticles had a mean diameter of 2.70 mum without mannitol and 2.50 mum with mannitol. The entrapment efficiency for propolis of the microparticles was upto 41 % without mannitol and 39% with mannitol. The microencapsulation by spray-drying technique maintained the activity of propolis against Staphylococcus aureus. These gelatin microparticles containing propolis would be useful for developing intermediary or eventual propolis dosage form without the PES' strong and unpleasant taste, aromatic odour, and presence of ethanol. (C) 2003 Elsevier B.V. All rights reserved.

Thermal behavior and stability of biodegradable spray-dried microparticles containing triamcinolone

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

Thermal analysis of biodegradable microparticles containing ciprofloxacin hydrochloride obtained by spray drying technique

Thermal analysis has been extensively used to obtain information about drug-polymer interactions and to perform pre-formulation studies of pharmaceutical dosage forms. In this work, biodegradable microparticles of poly(D,L-lactide-co-glycolide) (PLGA) containing ciprofloxacin hydrochloride (CP) in various drug:polymer ratios were obtained by spray drying. The main purpose of this study was to investigate the effect of the spray drying process on the drug-polymer interactions and on the stability of microparticles using differential scanning calorimetry (DSC), thermogravimetry (TG) and derivative thermogravimetry (DTG) and infrared spectroscopy (IR). The results showed that the high levels of encapsulation efficiency were dependant on drug:polymer ratio. DSC and TG/DTG analyses showed that for physical mixtures of the microparticles components the thermal profiles were different from those signals obtained with the pure substances. Thermal analysis data disclosed that physical interaction between CP and PLGA in high temperatures had occurred. The DSC and TG profiles for drug-loaded microparticles were very similar to the physical mixtures of components and it was possible to characterize the thermal properties of microparticles according to drug content. These data indicated that the spray dryer technique does not affect the physicochemical properties of the microparticles. In addition, the results are in agreement with IR data analysis demonstrating that no significant chemical interaction occurs between CP and PLGA in both physical mixtures and microparticles. In conclusion, we have found that the spray drying procedure used in this work can be a secure methodology to produce CP-loaded microparticles. (C) 2007 Elsevier B.V. All rights reserved.

Effect of electroless nickel interlayer on the fatigue strength of chromium electroplated AISI 4340 steel

Deposition of wear-resistant hard chromium plating leads to a decrease in the fatigue strength of the base material. Despite the effective protection against wear and corrosion, fatigue life and environmental requirements result in pressure to identify alternatives or to improve conventional chromium electroplating mechanical characteristics. An interesting, environmentally safer and cleaner alternative for the replacement of hard chronic plating is tungsten carbide thermal spray coating, applied by high velocity oxyfuel (HVOF) process.To improve the fatigue strength of aeronautical steel chromium electroplated, shot peening is a successfully used method. Multiple lacer systems of coatings are considered to have larger resistance to crack propagation in comparison with simple layer.The aim of this study was to analyze the effect of nickel underplate on the fatigue strength of hard chromium plated AISI 4340 steel in two mechanical conditions: HRc 39 and HRc 52.Rotating bending fatigue tests results indicate that the clectroless nickel plating underlayer is responsible for the increase in fatigue strength of AISI 4340 steel chromium electroplated. This behavior may be attributed to the largest toughness/ductility and compressive residual stresses which, probably, arrested or delayed the inicrocrack propagation from the hard chromium external layer. The compressive residual stress field (CRSF) induced by the electroplating process was determined by X-ray diffraction method. The evolution of fatigue strength compressive residual stress field CRSF and crack sources are discussed and analyzed by SEM. (c) 2006 Elsevier Ltd. All rights reserved.

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

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 have resulted in the search for possible alternatives. Zinc-nickel (Zn-Ni) alloys have received considerable interest recently, because these coatings show advantages such as a good resistance to white and red rust, high plating rates, and acceptance in the market. In this study, the effect of electroplated Zn-Ni coatings on AISI 4340 high-strength steel was analyzed for rotating bending fatigue strength, corrosion, and adhesion resistance. The compressive residual stress field was measured by x-ray diffraction prior to fatigue tests. Optical microscopy documented coating thickness, adhesion characteristics, and coverage extent for nearly all substrates. Fractured fatigue specimens were investigated using scanning electron microscopy (SEM). Three different Zn-Ni coating thicknesses were tested, and comparisons with the rotating bending fatigue data from electroplated Cd specimens were performed. Experimental results differentiated the effects of the various coatings on the AISI 4340 steel behaviour when submitted to fatigue testing and the influence of coating thickness on the fatigue strength.

Wear resistance of nickel-titanium endodontic files after surface treatment

Objectives The purpose of this work was to submit the Nitinol files to plasma immersion ion implantation (PIII) and evaluate the effects of the surface treatment. Materials and Methods Wear resistance was determined in vitro by using an equipment for the application of horizontal movements on previously prepared notched plates made of resin. Vickers microhardness was measured in plates and files, before and after surface treatment and the surface chemical composition of the instruments was determined by X-rays photoelectron spectroscopy. Results The hardness values found for the treated Nitinol files were significantly lower than the hardness values measured before the implantation process. The comparison of commercially available instruments shows that the wear resistance of the stainless steel file is higher than the resistance of the Nitinol. Conclusions The results found led to the conclusion that the surface treatment significantly increased the Nitinol files wear resistance.

STUDY of THE TURNING NICKEL BASE ALLOY PYROMET (R) 31V (SAE HEV8)

Considering the constant technological developments in the aeronautical, space, automotive, shipbuilding, nuclear and petrochemical fields, among others, the use of materials with high strength mechanical capabilities at high temperatures has been increasingly used. Among the materials that meet the mechanical strength and corrosion properties at temperatures around 815 degrees C one can find the nickel base alloy Pyromet 31V (SAE HEV8). This alloy is commonly applied in the manufacturing of high power diesel engines exhaust valves where it is required high resistance to sulphide, corrosion and good resistance to creep. However, due to its high mechanical strength and low thermal conductivity its machinability is made difficult, creating major challenges in the analysis of the best combinations among machining parameters and cutting tools to be used. Its low thermal conductivity results in a concentration of heat at high temperatures in the interfaces of workpiece-tool and tool-chip, consequently accelerating the tools wearing and increasing production costs. This work aimed to study the machinability, using the carbide coated and uncoated tools, of the hot-rolled Pyromet 31V alloy with hardness between 41.5 and 42.5 HRC. The nickel base alloy used consists essentially of the following components: 56.5% Ni, 22.5% Cr, 2,2% Ti, 0,04% C, 1,2% Al, 0.85% Nb and the rest of iron. Through the turning of this alloy we able to analyze the working mechanisms of wear on tools and evaluate the roughness provided on the cutting parameters used. The tests were performed on a CNC lathe machine using the coated carbide tool TNMG 160408-23 Class 1005 (ISO S15) and uncoated tools TNMG 160408-23 Class H13A (ISO S15). Cutting fluid was used so abundantly and cutting speeds were fixed in 75 and 90 m/min. to feed rates that ranged from 0.12, 0.15, 0.18 and 0.21 mm/rev, and cutting depth of 0.8mm. The results of the comparison between uncoated tools and coated ones presented a machined length of just 30% to the first in relation to the performance of the second. The coated tools has obtained its best result for both 75 and 90 m/min. with feed rate of 0.15 mm/rev, unlike the uncoated tool which obtained its better results to 0.12 mm/rev.

Validation of an HPLC Method for quantitative Determination of Benzocaine in PHBV-Microparticles and PLA-Nanoparticles

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

The Ability of Different Nickel-Titanium Rotary Instruments To Induce Dentinal Damage During Canal Preparation

The purpose of this study was to compare the incidence of dentinal defects (fractures and craze lines) after canal preparation with different nickel-titanium rotary files. Two hundred sixty mandibular premolars were selected. Forty teeth were left unprepared (n = 40). The other teeth were prepared either with manual Flexofiles (n = 20) or with different rotary files systems: ProTaper (Dentsply-Maillefer, Ballaigues, Switzerland), ProFile (Dentsply-Maillefer), SystemGT (Dentsply-Maillefer), or S-ApeX (FKG Dentaire, La Chaux-de-Fonds, Switzerland) (n = 50 each). Roots were then sectioned 3, 6, and 9 mm from the apex and observed under a microscope. The presence of dentinal defects was noted. There was a significant difference in the appearance of defects between the groups (p < 0.05). No defects were found in the unprepared roots and those prepared with hand files and S-ApeX. ProTaper, ProFile, and GT preparations resulted in dentinal defects in 16%, 8%, and 4% of teeth, respectively. Some endodontic preparation methods might damage the root and induce dentinal defects. (J Endod 2009;35:236-238)

Analysis of depth of the microporosity in a nickel-chromium system alloy: effects of electrolytic, chemical and sandblasting etching

The present study was designed to analyse the average depth of the microporosity of a nickel-chromium (Ni-Cr) system alloy (Verabond II). The metal surface was subject to one of the following surface treatment: (i) Electrolytic etching in nitric acid 0.5 N at a current density of 250 mA cm(-2) ; (ii) chemical etching with CG-Etch etchant; and (iii) Sandblasting with alumina particles 50 mum. Half of the samples were polished before the surface treatments. The depth of porosity was measured through photomicrographs (500x) with a profilometer, and the data were statistically analysed using an analysis of variance (anova) followed by Tukey's test. The conclusions were (i) Differents surface treatment of the Ni-Cr system alloy lead to different depths of microporosity; (ii) the greatest depth of porosity was observed in non-polished alloy; (iii) the greatest and identical depth of microporosity was observed following electrolytic etching and chemical etching; (iv) the least and identical depth of microporosity was observed with chemical etching and sandblasting with alumina particles 50 mum, and (v) Chemical etching showed an intermediary depth.