Carbon dioxide reforming of ethanol over Ni/Y(2)O(3)-ZrO(2) catalysts

Supported nickel catalysts of composition Ni/Y(2)O(3)-ZrO(2) were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y(2)O(3)-ZrO(2) in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO(2) conversion of 61% on the 5NiYZ catalyst at 800 degrees C, representing a better response than for the catalyst of the same composition prepared by wet impregnation. (C) 2009 Published by Elsevier B.V.

Synthesis, Characterization, and Electrocatalytic Activity toward Methanol Oxidation of Carbon-Supported Pt(x)-(RuO(2)-M)(1-x) Composite Ternary Catalysts (M = CeO(2), MoO(3), or PbO(x))

Carbon-supported platinum is commonly used as an anode electrocatalyst in low-temperature fuel cells fueled with methanol. The cost of Pt and the limited world supply are significant barriers for the widespread use of this type of fuel cell. Moreover, Pt used as anode material is readily poisoned by carbon monoxide produced as a byproduct of the alcohol oxidation. Although improvements in the catalytic performance for methanol oxidation were attained using Pt-Ru alloys, the state-of-the-art Pt-Ru catalyst needs further improvement because of relatively low catalytic activity and the high cost of noble Pt and Ru. For these reasons, the development of highly efficient ternary platinum-based catalysts is an important challenge. Thus, various compositions of ternary Pt(x)-(RuO(2)-M)(1-x)/C composites (M = CeO(2), MoO(3), or PbO(x)) were developed and further investigated as catalysts for the methanol electro-oxidation reaction. The characterization carried out by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry point out that the different metallic oxides were successfully deposited on the Pt/C, producing small and well-controlled nanoparticles in the range of 2.8-4.2 nm. Electrochemical experiments demonstrated that the Pt(0.50)(RuO(2)-CeO(2))(0.50)/C composite displays the higher catalytic activity toward the methanol oxidation reaction (lowest onset potential of 207 mV and current densities taken at 450 mV, which are 140 times higher than those at commercial Pt/C), followed by the Pt(0.75)(RuO(2)-MoO(3))(0.25)/C composite. In addition, both of these composites produced low quantities of formic acid and formaldehyde when compared to a commercially available Pt(0.75)-Ru(0.25)/C composite (from E-Tek, Inc.), suggesting that the oxidation of methanol occurs mainly by a pathway that produces CO(2) forming the intermediary CO(ads).

Effect of cantilever length and framework alloy on the stress distribution of mandibular-cantilevered implant-supported prostheses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Microstructural Characterization of Ti-6Al-7Nb Alloy After Severe Plastic Deformation

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

Activity of Mo(II) allylic complexes supported in MCM-41 as oxidation catalysts precursors

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

Hydrodechlorination of 1,2-dichloroethane by rhodium catalysts under water gas shift reaction conditions

Homogeneous catalysts prepared from rhodium trichloride in aqueous aromatic amines have been shown to reduce C-CI bonds under mild water gas shift conditions (T=100 degrees C, P-CO = 1.0 atm). In a 4-picoline/water solvent mixture, 1,2-dichloroethane is reduced to ethylene and ethane in yields compatible with the consumption of the reducing agent CO and with the formation of CO2. Variation of the catalyst solutions by using different substituted pyridines shows a pattern of catalytic activity parallel to that reported previously for H-2 production from the shift reaction, There is a moderate dependence of activity on the basicity of the aromatic amine, but a methyl group at the alpha-position exercises a strong negative steric effect. Long term studies show decrease of the activity with the time perhaps due to the build up of chloride in the medium. (C) 1999 Elsevier B.V. B.V. All rights reserved.

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.

Shear bond strength of a ceramic to Co-Cr alloys

Statement of problem. Different combinations of Co-Cr alloys bonded to ceramic have been used in dentistry; however, the bond strength of ceramic to metal can vary because of different compositions of these alloys.Purpose. The purpose of this study was to evaluate the shear bond strength of a dental ceramic to 5 commercially available Co-Cr alloys.Material and methods. Five Co-Cr alloys (IPS d.SIGN 20, IPS d.SIGN 30, Remanium 2000, Heranium P, and Wirobond C) were tested and compared to a control group of an Au-Pd alloy (Olympia). Specimen disks, 5 mm high and 4 mm in diameter, were fabricated with the lost-wax technique. Sixty specimens were prepared using opaque and dentin ceramics (VITA Omega 900), veneered, 4 mm high and 4 mm in diameter, over the metal specimens (n = 10). The shear bond strength test was performed in a universal testing machine with a crosshead speed of 0.5 mm/min. After shear bond testing, fracture surfaces were evaluated in a stereomicroscope under x25 magnification. Ultimate shear bond strength (MPa) data were analyzed with 1-way ANOVA and the Tukey HSD test (alpha = .05).Results. The mean (SID) bond strengths (MPa) were: 61.4 (7.8) for Olympia; 94.0 (18.9) for IPS 20; 96.8 (10.2) for I PS 30; 75.1 (12.4) for Remanium; 71.2 (14.3) for Heranium P; and 63.2 (10.9) for Wirobond C. Mean bond strengths for IPS 20 and IPS 30 were not significantly different, but were significantly (P<.001) higher than mean bond strengths for the other 4 alloys, which were not significantly different from each other.Conclusions. Bond strength of a dental ceramic to a Co-Cr alloy is dependent on the alloy composition.

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.

Influence of particle size on the properties of Pt-Ru/C catalysts prepared by a microemulsion method

Pt-Ru/C nanocatalysts were prepared by a microemulsion method using different values of water/surfactant molar ratio in order to get different particle sizes. Crystallite sizes and structural properties were determined by X-ray diffraction. Particle size and distribution were characterized by transmission electron microscopy and average composition was determined by energy-dispersive X-ray analysis. Thermogravimetric analysis was used to estimate the amount of supported metals. Differential scanning calorimetry measurements indicated the presence of hydrous ruthenium oxides in the as-prepared catalysts. Results for the oxidation of adsorbed CO as well as for methanol oxidation revealed significant differences in the behavior of the prepared catalysts. All together, the results demonstrate that the variation of particle size produces changes in other properties of the Pt-Ru/C catalysts and that to establish direct correlations between electrocatalytic activity and particle size is not possible because the effects of the different parameters cannot be separated. (c) 2007 the Electrochemical Society.

Influence of HVOF parameters on the corrosion and wear resistance of WC-Co coatings sprayed on AA7050 T7

Thermal spray WC-based coatings are widely used in the aircraft industry mainly for their resistance to wear, reworking and rebuilding operations and repair of worn components on landing gear, hydraulic cylinders, actuators, propeller hub assemblies, gas turbine engines, and so on. The aircraft industry is also trying to use thermal spray technology to replace electroplating coatings such as hard chromium. In the present work, WC-Co coatings were built up on an AA 7050 aluminum alloy using high velocity oxygen fuel (HVOF) technology and a liquid nitrogen cooling prototype system. The influence of the spray parameters (standard conditions, W19S, increasing the oxygen flux, W19H, and also increasing the carrier gas flux, W19F) on corrosion, friction, and abrasive wear resistance were also studied. The coatings were characterized using optical (OM) and scanning electron (SEM) microscopy, and X-ray diffraction (XRD). The friction and abrasive wear resistance of the coatings were studied using Rubber Wheel and Ball on Disk tests. The electrochemical studies were conducted using open-circuit potential (E(oc)) measurements and electrochemical impedance spectroscopy (EIS). Differences among coated samples were mainly related to the variation of the thermal spray parameters used during the spray process. No significant differences were observed in the wear resistance for the coatings studied, and all of them showed a wear rate around 10 times lower than that of the aluminum alloy. The results of mass loss and wear rate were interpreted considering different mechanisms. Comparing the different spray parameters, the oxygen flux (higher flame temperature) produced the sample which showed the highest corrosion resistance in aerated and unstirred 3.5% NaCl solution. Aluminum ions were detected on the surface almost immediately after the immersion of samples W19S and W19F in chloride solution, showing that the electrolyte reached the substrate and galvanic corrosion probably occurred. For sample W19H, aluminum ions were not detected even after 120 min of immersion in NaCl solution. (C) 2008 Elsevier B.V. All rights reserved.

Dependence on composition of electronic properties and stability of Pt-Fe/C catalysts for oxygen reduction

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

Site-selective ethanol conversion over supported copper catalysts

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Pd-based catalysts: Influence of the second metal on their stability and oxygen reduction activity

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

Alloys and oxides on carbon-supported Pt-Sn electrocatalysts for ethanol oxidation

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