Determination of copper, iron, nickel and zinc in gasoline by FAAS after sorption and preconcentration on silica modified with 2-aminotiazole groups

Silica gel chemically modified with 2-aminotiazole groups (SiAT), was used for preconcentration of cupper, zinc, nickel and iron from gasoline, normally used as a engine fuel. Surface characteristics and surface area of the silica gel were obtained before and after chemical modification using FT-IR, Kjeldhal and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques. The experimental parameters, such as shaking time in batch technique, flow rate and concentration of the eluent (HCl-0.25-2.00 mol 1(-1)) and the amount of silica, on retention and elution, have been investigated. Detection limits of the method for cupper, iron, nickel and zinc are 0.8, 3, 2 and 0.1 mug 1(-1), respectively. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in gasoline using flame AAS for their quantification. (C) 2004 Published by Elsevier Ltd.

Determination of Cd(II), Cu(II) and Ni(II) in aqueous samples by ICP-OES after on-line preconcentration in column packed with silica modified with 2-aminothiazole

This work describes the synthesis and characterization of 2-aminothiazole modified silica gel (SiAT) and the studies of adsorption and pre-concentration (in batch and using a flow-injection system coupled with optical emission spectrometer) of Cd(II), Cu(II) and Ni(II) in aqueous medium. The adsorption capacity for each metal ions in mmolg(-1) was: Cu(II) = 1.18, Ni(II) = 1.15 and Cd(II) = 1.10. The results obtained in the flow experiments showed about 100% of recovering of the metal ions adsorbed in a mini-column packed with 100 mg of SiAT, using 100 mu L of 2.0 mol L-1 HCl solution as eluent. The quantitative sorption-desorption of the metal ions made possible the application of a flow-injection system in the pre-concentration and quantification by ICP-OES of metal ions at trace level in natural water samples.

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni2+ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni2+ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni2+ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)2 complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 x 10(-9) to 1.0 x 10(-6) mol L-1 with detection limit of 2.0 x 10(-9) mol L-1. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 mu mol L-1 Ni2+ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni2+ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni2+ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step. (c) 2006 Elsevier B.V. All rights reserved.

Determination of metal ions in natural waters by flame-AAS after preconcentration on a 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel.

5-amino-1,3,4-thiadiazole-2-thiol groups attached on a silica gel surface have been used for adsorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) from aqueous solutions. The adsorption capacities for each metal ion were (in mmol.g(-1)): Cd(II)= 0.35, Co(II)= 0.10, Cu(II)= 0.15, Fe(III)= 0.20, Hg(Il)= 0.46, Ni(II)= 0.16, Pb(II)= 0.13 and Zn(II)= 0.15. The modified silica gel was applied in the preconcentration and quantification of trace level metal ions present in water samples (river, and bog water).

Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at -0.3 V versus Ag/AgCl(sat) a linear range from 7.5 x 10(-8) to 2.5 x 10(-6) mol L(-1) with detection limit of 3.1 x 10(-8) mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods. (c) 2006 Elsevier B.V. All rights reserved.

Characterization of silica-carbon mesoporous matrix with embedded nickel nanoparticles synthesized by the polymeric precursor method

Nickel nanoparticles into silica-carbon matrix composites were prepared by using the polymeric precursor method. The effects of the polyester type and the time of pyrolysis on the mesoporosity and nickel particle dispersion into non-aqueous amorphous silica-carbon matrix were investigated by thermogravimetric analysis, adsorption/desorption isotherms and TEM. A well-dispersed metallic phase could be only obtained by using ethylene glycol. Weightier polyesters affected the pyrolysis process due to a combination of more amounts of carbonaceous residues and delaying of pyrolysis process. The post-pyrolyzed composites were successfully cleaned at 200 degrees C for I h in oxygen atmosphere leading to an increase in the surface area and without the occurrence of carbon combustion or nickel nanoparticles oxidation. The matrix composites presented predominantly mesoporous with pore size well defined in 38 angstrom, mainly when tetraethylene glycol was used as polymerizing agent. (C) 2007 Elsevier B.V. All rights reserved.

Determination of Cu, Ni, and Zn in fuel ethanol by FAAS after enrichment in column packed with 2-aminothiazole-modified silica gel

This work describes the synthesis and characterization of 2-aminothiazole-modified silica gel (SiAT), as well as its application for preconcentration (in batch and column technique) of Cu(II), Ni(II) and Zn(II) in ethanol medium. The adsorption capacities of SiAT determined for each metal ion were (mmol g(-1)): Cu(II)=1.20, Ni(II)=1.10 and Zn(II)=0.90. In addition, results obtained in flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 500 mg of SiAT. The eluent was 2.0 mol L-1 HCl. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in fuel ethanol using flame AAS for their quantification.

Effect of Airborne-Particle Abrasion and Mechanico-Thermal Cycling on the Flexural Strength of Glass Ceramic Fused to Gold or Cobalt-Chromium Alloy

Purpose: To evaluate the effect of airborne-particle abrasion and mechanico-thermal cycling on the flexural strength of a ceramic fused to cobalt-chromium alloy or gold alloy.Materials and Methods: Metallic bars (n = 120) were made (25 mm x 3 mm x 0.5 mm): 60 with gold alloy and 60 with Co-Cr. At the central area of the bars (8 mm x 3 mm), a layer of opaque ceramic and then two layers of glass ceramic (Vita VM13, Vita Zahnfabrick) were fired onto it (thickness: 1 mm). Ten specimens from each alloy group were randomly allocated to a surface treatment [(tungsten bur or air-particle abrasion (APA) with Al(2)O(3) at 10 mm or 20 mm away)] and mechanico-thermal cycling (no cycling or mechanically loaded 20,000 cycles; 10 N distilled water at 37 degrees C and then thermocycled 3000 cycles; 5 degrees C to 55 degrees C, dwell time 30 seconds) combination. Those specimens that did not undergo mechanico-thermal cyclingwere stored inwater (37 degrees C) for 24 hours. Bond strength was measured using a three-point bend test, according to ISO 9693. After the flexural strength test, failure types were noted. The data were analyzed using three factor-ANOVA and Tukey's test (alpha = 0.05).Results: There were no significant differences between the flexural bond strength of gold and Co-Cr groups (42.64 +/- 8.25 and 43.39 +/- 10.89 MPa, respectively). APA 10 and 20 mm away surface treatment (45.86 +/- 9.31 and 46.38 +/- 8.89 MPa, respectively) had similar mean flexural strength values, and both had significantly higher bond strength than tungsten bur treatment (36.81 +/- 7.60 MPa). Mechanico-thermal cycling decreased the mean flexural strength values significantly for all six alloy-surface treatment combinations tested when compared to the control groups. The failure type was adhesive in the metal/ceramic interface for specimens surface treated only with the tungsten bur, and mixed for specimens surface treated with APA 10 and 20 mm.Conclusions: Considering the levels adopted in this study, the alloy did not affect the bond strength; APA with Al(2)O(3) at 10 and 20 mm improved the flexural bond strength between ceramics and alloys used, and the mechanico-thermal cycling of metal-ceramic specimens resulted in a decrease of bond strength.

Effect of the addition of silanated silica on the mechanical properties of microwave heat-cured acrylic resin

Effect of the addition of silanated silica on the mechanical properties of microwave heat-cured acrylic resinObjectives: The purpose of this study was to evaluate the flexural strength and Vickers hardness of a microwave energy heat-cured acrylic resin by adding different concentrations of silane surface-treated nanoparticle silica.Methods: Acrylic resin specimens with dimensions of 65 x 10 x 2.5 mm were formed and divided into five experimental groups (n = 10) according to the silica concentration added to the acrylic resin mass (weight %) prior to polymerisation : G1, without silica; G2, 0.1% silica; G3, 0.5% silica; G4, 1.0% silica; and G5, 5.0% silica. The specimens were submitted to a three-point flexural strength test and to the Vickers hardness test (HVN). The data obtained were statistically analysed by ANOVA and the Tukey test (alpha = 0.05).Results: Regarding flexural strength, G5 differed from the other experimental groups (G1, G2, G3 and G4) presenting the lowest mean, while G4 presented a significantly higher mean, with the exception of group G3. Regarding Vickers hardness, a decrease in values was observed, in which G1 presented the highest hardness compared with the other experimental groups.Conclusion: Incorporating surface-treated silica resulted in direct benefits in the flexural strength of the acrylic resin activated by microwave energy; however, similar results were not achieved for hardness.

Influence of Surface Treatment on the Shear Bond Strength of Ceramics Fused to Cobalt-Chromium

Purpose: To evaluate the influence of surface treatment on the shear bond strength between a Co-Cr alloy and two ceramics.Materials and Methods: Forty-eight metal cylinders were made (thickness: 4 mm, height: 3.7 mm) according ISO TR 11405. The 48 metallic cylinders were divided into four groups (n = 12), according to the veneering ceramic (StarLight Ceram and Duceram Kiss) and surface treatments: air-particle abrasion with Al(2)O(3) or tungsten drill (W). Gr1: StarLight + Al(2)O(3); Gr2: StarLight + W; Gr3: Duceram + Al(2)O(3); and Gr4: Duceram + W. The specimens were aged using thermal cycling (3000 x, 5 to 55 degrees C, dwell time: 30 seconds, transfer time: 2 seconds). The shear test was performed with a universal testing machine, using a load cell of 100 kg (speed: 0.5 mm/min) and a specific device. The bond strength data were analyzed using ANOVA and Tukey's test (5%), and the failure modes were analyzed using an optical microscope (30x).Results: The means and standard deviations of the shear bond strengths were (MPa): G1 (57.97 +/- 11.34); G2 (40.62 +/- 12.96); G3 (47.09 +/- 13.19); and G4 (36.80 +/- 8.86). Ceramic (p = 0.03252) and surface treatment (p = 0.0002) significantly affected the mean bond strength values.Conclusions: Air-particle abrasion with Al(2)O(3) improved the shear bond strength between metal and ceramics used.

Opaque Layer Firing Temperature and Aging Effect on the Flexural Strength of Ceramic Fused to Cobalt-Chromium Alloy

Purpose: To evaluate the effect of the opaque layer firing temperature and mechanical and thermal cycling on the flexural strength of a ceramic fused to commercial cobalt-chromium alloy (Co-Cr). The hypotheses were that higher opaque layer temperatures increase the metal/ceramic bond strength and that aging reduces the bond strength.Materials and Methods: Metallic frameworks (25 x 3 x 0.5 mm(3); ISO 9693) (N = 60) were cast in Co-Cr and airborne-particle abraded (Al(2)O(3): 150 mu m) at the central area of the frameworks (8 x 3 mm(2)) and divided into three groups (N = 20), according to the opaque layer firing temperature: Gr1 (control)-900 degrees C; Gr2-950 degrees C; Gr3-1000 degrees C. The opaque ceramic (Opaque, Vita Zahnfabrick, Bad Sackingen, Germany) was applied, and the glass ceramic (Vita Omega 900, Vita Zahnfabrick) was fired onto it (thickness: 1 mm). While half the specimens from each group were randomly tested without aging (water storage: 37 degrees C/24 hours), the other half were mechanically loaded (20,000 cycles; 50 N load; distilled water at 37 degrees C) and thermocycled (3000 cycles; 5 degrees C to 55 degrees C, dwell time: 30 seconds). After the flexural strength test, failure types were noted. The data were analyzed using 2-way ANOVA and Tukey's test (alpha = 0.05).Results: Gr2 (19.41 +/- 5.5 N) and Gr3 (20.6 +/- 5 N) presented higher values than Gr1 (13.3 +/- 1.6 N) (p = 0.001). Mechanical and thermal cycling did not significantly influence the mean flexural strength values (p > 0.05). Increasing the opaque layer firing temperature improved the flexural bond strength values (p < 0.05). The hypotheses were partially accepted.Conclusion: Increasing of the opaque layer firing temperature improved the flexural bond strength between ceramic fused to Co-Cr alloy.

Mechanical and thermal cycling effects on the flexural strength of glass ceramics fused to titanium

This study evaluated the effects of mechanical and thermal cycling on the flexural strength (ISO 9693) of three brands of ceramics fused to commercially pure titanium (cpTi). Metallic frameworks of 25 x 3 x 0.5 mm dimensions (N = 84) were cast in cpTi, followed by 150-mu m aluminum oxide airborne particle abrasion at a designated area of the frameworks (8 x 3 mm). Bonder and opaque ceramic were applied on the frameworks, and then the corresponding ceramic (Triceram, Super Porcelain Ti-22, Vita Titankeramik) was fired onto them (thickness: 1 mm). Half of the specimens from each ceramic-metal combination were randomly tested without aging (only water storage at 37 degrees C for 24 hours), while the other half were mechanically loaded (20,000 cycles under 10 N load, immersion in distilled water at 37 degrees C) and thermocycled (3,000 cycles, between 5-55 degrees C, dwell time of 13 seconds). After the flexural strength test, failure types were noted. Mechanical and thermal cycling decreased the mean flexural strength values significantly (p<0.05) for all the three ceramic-cpTi combinations tested when compared to the control group. In all the three groups, failure type was exclusively adhesive at the opaque ceramic-cpTi interfacial zone with no presence of ceramic on the substrate surface except for a visible oxide layer.

Effect of multiple firing and silica deposition on the zirconia-porcelain interfacial bond strength

Objectives. To test the hypothesis that multiple firing and silica deposition on the zirconia surface influence the bond strength to porcelain.Materials and methods. Specimens were cut from yttria-stabilized zirconia blocks and sintered. Half of the specimens (group S) were silica coated (physical vapor deposition (PVD)) via reactive magnetron sputtering before porcelain veneering. The remaining specimens (group N) had no treatment before veneering. The contact angle before and after silica deposition was measured. Porcelain was applied on all specimens and submitted to two (N2 and S2) or three firing cycles (N3 and S3). The resulting porcelain-zirconia blocks were sectioned to obtain bar-shaped specimens with 1 mm(2) of cross-sectional area. Specimens were attached to a universal testing machine and tested in tension until fracture. Fractured surfaces were examined using optical microscopy. Data were statistically analyzed using two-way ANOVA, Tukey's test (alpha = 0.05) and Weibull analysis.Results. Specimens submitted to three firing cycles (N3 and S3) showed higher mean bond strength values than specimens fired twice (N2 and S2). Mean contact angle was lower for specimens with silica layer, but it had no effect on bond strength. Most fractures initiated at porcelain-zirconia interface and propagated through the porcelain.Significance. The molecular deposition of silica on the zirconia surface had no influence on bond strength to porcelain, while the number of porcelain firing cycles significantly affected the bond strength of the ceramic system, partially accepting the study hypothesis. Yet, the Weibull modulus values of S groups were significantly greater than the m values of N groups. (C) 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of silica coating combined to a MDP-based primer on the resin bond to Y-TZP ceramic

The aim of this study was to evaluate the influence of silica coating and 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based primer applications upon the bonding durability of a MDP-based resin cement to a yttrium stabilized tetragonal zirconia (Y-TZP) ceramic. Ninety-six Y-TZP tabs were embedded in an acrylic resin (free surface for adhesion: 5 x 5 mm(2)), ground finished and randomly divided into four groups (N = 24) according to the ceramic surface conditioning: (1) cleaning with isopropanol (ALC); (2) ALC + phosphoric acid etching + MDP-based primer application (MDP-primer); (3) silica coating + 3-methacryloyloxypropyl trimethoxysilane (MPS)-based coupling agent application (SiO(2) + MPS-Sil); and (4) SiO(2) + MDP-primer. The MDP-based resin cement was applied on the treated surface using a cylindrical mold (diameter=3 mm). Half of the specimens from each surface conditioning were stored in distilled water (37 C, 24 h) before testing. Another half of the specimens were stored (90 days) and thermo-cycled (12,000x) during this period (90d/TC) before testing. A shear bond strength (SBS) test was performed at a crosshead speed of 0.5 mm/min. Two factors composed the experimental design: ceramic conditioning strategy (in four levels) and storage condition (in two levels), totaling eight groups. After 90d/TC (Tukey; p < 0.05), SiO(2) + MDP-primer (24.40 MPa) promoted the highest SBS. The ALC and MDP-primer groups debonded spontaneously during 90d/TC. Bonding values were higher and more stable in the SiO2 groups. The use of MDP-primer after silica coating increased the bond strength. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part 8: Appl Biomater 95B: 69-74, 2010.

Structure and Growth Kinetics of 3-Glycidoxypropyltrimethoxysilane-Derived Organic/Silica Hybrids at Different Temperatures

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