Síntese de catalisadores do tipo LaNixFe1-xO3 como precursores catalíticos para reação oxidação parcial do metano

Nickel-bases catalysts have been used in several reform reactions, such as in the partial oxidation of methane to obtain H2 or syngas (H2 + CO). High levels of conversion are usually obtained using this family of catalysts, however, their deactivation resulting from carbon deposition still remains a challenge. Different approaches have been tested aiming at minimizing this difficulty, including the production of perovskites and related structures using modern synthesis methods capable of producing low cost materials with controlled microstructural characteristics at industrial scale. To establish grounds for comparison, in the present study LaNixFe1-xO3 (x=0, 0.3 or 0.7) perovskites were prepared following the Pechini method and by microwave assisted self-combustion. All samples were sub sequently calcined at 900 °C to obtain the target phase. The resulting ceramic powders were characterized by thermogravimetric analysis, infrared spectroscopy, X ray diffraction, specific area and temperature programmed reduction tests. Calcined samples were also used in the partial oxidation reaction of methane to evaluate the level of conversion, selectivity and carbon deposition. The results showed that the calcined samples were crystalline and the target phase was formed regardless of the synthesis method. According to results obtained by Rietveld refinement, we observed the formation of 70.0% of LaNi0.3Fe0.7O3 and 30.0% of La2O3 for samples LN3F7-900- P, LN3F7-900-M and 41,6% of LaNi0.7Fe0.3O3, 30.7% of La2NiO4 and 27.7% of La2O3 for samples LN7F3-900-P and LN7F3-900-M.Temperature-programmed profiles of the LaNiO3 sample revealed the presence of a peak around 510 °C, whereas the LaFeO3 sample depicted a peak above 1000°C. The highest l evel of methane conversion was obtained for LaNiO3 synthesized by the Pechini method. Overall, catalysts prepared by the Pechini method depicted better conversion levels compared to those produced by microwave assisted self-combustion

Hidróxidos duplos lamelares aplicados à obtenção de biodiesel

In this paper, the Layered Double Hydroxides (LDH s) type hydrotalcite were synthesized, characterized and tested as basic heterogeneous catalysts for the production of biodiesel by transesterification of sunflower oil with methanol. The synthesis of materials Layered Double Hydroxides (LDH s) by co-precipitation method from nitrates of magnesium and aluminum, and sodium carbonate. The materials were submitted to the variation in chemical composition, which is the amount of Mg2+ ions replaced by Al3+. This variation affects the characteristic physico-chemical and reaction the solid. The molar ratio varied in the range of 1:1 and 3:1 magnesium / aluminum, and their values between 0.2 and 0.33. This study aims to evaluate the influence of variation of molar ratio of mixed oxides derived from LDH s and the influence of impregnation of a material with catalytic activity, the KI, the rate of conversion of sunflower oil into methyl esters (biodiesel) through transesterification by heterogeneous catalysis. .The catalysts were calcined at 550 ° C and characterized by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectroscopy of X-ray (SEM / EDS), thermogravimetric analysis (TG) and test basicity. The transesterification reaction was performed for reflux is a mixture of sunflower oil and methanol with a molar ratio of 15:1, a reaction time of 4h and a catalyst concentration of 2% by weight. The physical-chemical characterization of sunflower oil and biodiesel obtained by the route methyl submitted according NBR, EN, ASTM. Subsequently, it was with the chromatographic and thermogravimetric characterizations of oils. The results of chromatographic analysis showed that the catalysts were effective in converting vegetable oil into biodiesel, in particular the type hydrotalcite KI-HDL-R1, with a conversion of 99.2%, indicating the strong influence of the chemical composition of the material, in special due to presence of potassium in the structure of the catalyst

Reforma a vapor catalítica do metano: Otimização da produção e seletividade em hidrogênio por absorção in situ do CO2 produzido

Topics of research related to energy and environment have significantly grown in recent years, with the need of its own energy as hydrogen. More particularly, numerous researches have been focused on hydrogen as energy vector. The main portion of hydrogen is presently obtained by reforming of methane or light hydrocarbons (steam, oxy, dry or auto reforming). During the methane steam reforming process the formation of CO2 undesirable (the main contributor to the greenhouse effect) is observed. Thus, an oxide material (sorbent) can be used to capture the CO2 generated during the process and simultaneously shifting the equilibrium of water gas shift towards thermodynamically more favorable production of pure hydrogen. The aim of this study is to develop a material with dual function (catalyst/sorbent) in the reaction of steam reforming of methane. CaO is well known as CO2 sorbent due to its high efficiency in reactions of carbonation and easy regeneration through calcination. However the kinetic of carbonation decreases quickly with time and carbonation/calcination cycles. A calcium aluminate (Ca12Al14O33) should be used to avoid sintering and increase the stability of CaO sorbents for several cycles. Nickel, the industrial catalyst choice for steam reforming has been added to the support from different manners. These bi-functional materials (sorbent/catalyst) in different molar ratios CaO.Ca12Al14O33 (48:52, 65:35, 75:25, 90:10) were prepared by different synthesis methodologies, among them, especially the method of microwave assisted self-combustion. Synthesis, structure and catalytic performances of Ni- CaO.Ca12Al14O33 synthesized by the novel method (microwave assisted selfcombustion) proposed in this work has not being reported yet in literature. The results indicate that CO2 capture time depends both on the CaO excess and on operating conditions (eg., temperature and H2O/CH4 ratio). To be efficient for CO2 sorption, temperature of steam reforming needs to be lower than 700 °C. An optimized percentage corresponding to 75% of CaO and a ratio H2O/CH4 = 1 provides the most promising results since a smaller amount of water avoids competition between water and CO2 to form carbonate and hydroxide. If this competition is most effective (H2O/CH4 = 3) and would have a smaller amount of CaO available for absorption possibly due to the formation of Ca(OH)2. Therefore, the capture time was higher (16h) for the ratio H2O/CH4 = 1 than H2O/CH4 = 3 (7h) using as catalyst one prepared by impregnating the support obtained by microwave assisted self-combustion. Therefore, it was demonstrated that, with these catalysts, the CO2 sorption on CaO modifies the balance of the water gas-shift reaction. Consequently, steam reforming of CH4 is optimized, producing pure H2, complete conversion of methane and negligible concentration of CO2 and CO during the time of capture even at low temperature (650 °C). This validates the concept of the sorption of CO2 together with methane steam reforming

Effect of microwave disinfection on the flexural strength of hard chairside reline resins

Objectives: This study investigated the effect of microwave disinfection (650 W/6 min) on the flexural strength of five hard chairside reline resins (Kooliner, Duraliner II, Tokuso Rebase Fast, Ufi Get Hard, New Truliner) and one denture base resin (Lucitone 550).Methods: Thirty-two specimens (3.1x10x64 mm) from each acrylic resin were produced and divided into four groups of eight specimens each. The flexural test was performed after polymerization (G1), after two cycles of microwave disinfection (G2), after 7 days storage in water at 37 degrees C (G3) and after seven cycles of microwave disinfection (G4). Specimens from group G4 were microwaved daily being stored in water at 37 degrees C between exposures. The specimens were placed in three-point bend fixture in a MTS machine and loaded until failure. The flexural values (MPa) were submitted to ANOVA and Tukey's test (p=0.05).Results: Two cycles of microwave disinfection promoted a significant increase in flexural strength for materials Kooliner and Lucitone 550. After seven cycles of microwave disinfection, materials Kooliner and New Truliner showed a significant increase (p<0.05) in flexural values. The flexural strength of the material Tokuso Rebase was not significantly affected by microwave irradiation. Seven cycles of microwave disinfection resulted in a significant decrease in the flexural strength of material Duraliner II. Material Ufi Get Hard was the only resin detrimentally affected by microwave disinfection after two and seven cycles.Conclusions: Microwave disinfection did not adversely affect the flexural strength of all tested materials with the exception of material Ufi Get Hard. (c) 2005 Elsevier Ltd. All rights reserved.

Influence of Microwave Disinfection on the Dimensional Stability of Denture Reline Polymers

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

Flexural strength and hardness of reline and denture base acrylic resins after different exposure times of microwave disinfection

Objectives: To evaluate the effect of microwave disinfection on the flexural strength and Vickers hardness of 4 autopolymerized resins (Kooliner [K], Tokuso Rebase Fast [T], Ufi Gel Hard [U], and New Truliner [N]) and 1 denture base resin (Lucitone 550 [L]). Method and Materials: For each material, 48 specimens (64 x 10 x 3.3 mm) were made and divided into 6 equal groups (n = 8). In the control group, specimens were untreated. Before testing, specimens were immersed in 200 mL of distilled water and submitted to disinfection for 1 of the following irradiation times: 1, 2, 3, 4, or 5 minutes. The irradiation procedure was performed twice. The flexural strength was determined using a testing machine MTS-810 and measurements of Vickers hardness were made on Micromet 2100. The values were submitted to ANOVA and Tukey's test (P = .05). Results: The K material showed a significant increase (P = .0010) in flexural strength following 5 minutes of disinfection compared to control specimens. The flexural strength mean values of materials T, U, and N were not significantly affected (P > .05) by disinfection. Compared to the control group, the K material showed a significant increase in hardness (P < .001) following disinfection for 3, 4, and 5 minutes. For material U, disinfection for 4 and 5 minutes produced specimens with significantly increased hardness values (P < .001) compared to the control group. For material N, disinfection for 5 minutes resulted in significantly higher hardness values (P < .001) than the control group. Conclusion: Regardless of the irradiation time, the flexural strength and hardness of the materials evaluated were not detrimentally affected by microwave disinfection. (Quintessence Int 2008;39:833-840)

Microwave Disinfection of Complete Dentures Contaminated In Vitro with Selected Bacteria

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

Effect of microwave disinfection on the surface roughness of three denture base resins after tooth brushing

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

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.

Sol-gel synthesis of titania-alumina catalyst supports

Titanium oxide is a good candidate as new support for hydrotreating (HDT) catalysts, but has the inconvenience of presenting small surface area and poor thermal stability. To overcome these handicaps TiO2-Al2O3 mixed oxides were proposed as catalyst support. Here, the results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal complexing ratios [acac]/[Ti] and of sol aging temperature on the structural features of nanometric particles was analyzed by quasi-elastic light scattering (QELS) and N-2 adsorption isotherm measurements. These characterizations have shown that the addition of acac and the increase of aging temperature favor the full dispersion of primary nanoparticles in mother acid solution. The dried powder presents a monomodal distribution of slit-shaped micropores, formed by irregular packing of platelet primary particles, surface area superior to 200 m(2) g(-1) and mean pore size of about 1 nm. These characteristics of porous texture are preserved after firing at 673 K. The diffraction patterns of sample fired above 973 K show only the presence of anatase crystalline phase. The crystalline structure of the support remained unaltered after molybdenum adsorption, but the surface area and the micropore volume were drastically reduced. (C) 2002 Published by Elsevier B.V. B.V.

Preparation and characterization of LiNi0.8Co0.2O2/PANI microcomposite electrode materials under assisted ultrasonic irradiation

A preparation method for a new electrode material based on the LiNi0.8Co0.2O2/polyaniline (PANI) composite is reported. This material is prepared by in situ polymerization of aniline in the presence of LiNi0.8Co0.2O2 assisted by ultrasonic irradiation. The materials are characterized by XRD, TG-DTA, FTIR, XPS, SEM-EDX, AFM, nitrogen adsorption (BET surface area) and electrical conductivity measurements. PANI in the emeraldine salt form interacts with metal-oxide particles to assure good connectivity. The dc electrical conductivity measurements at room temperature indicate that conductivity values are one order of magnitude higher in the composite than in the oxide alone. This behavior determines better reversibility for Li-insertion in charge-discharge cycles compared to the pristine mixed oxide when used as electrode of lithium batteries. (c) 2005 Elsevier B.V. All rights reserved.

The effect of polymerization cycles on porosity of microwave-processed denture base resin

Statement of problem. Although most of the physical properties of denture base resin polymerized by microwave energy have been shown to be similar to resins polymerized by the conventional heat polymerization method, the presence of porosity is a problem.Purpose. This study evaluated the effect of different microwave polymerization cycles on the porosity of a denture base resin designed for microwave polymerization.Material and methods. Thirty-two rectangular resin specimens (65 X 40 X 5 mm) were divided into 3 experimental groups (A, B, and C; Onda-Cryl, microwave-polymerized resin) and I control group (T; Classico, heat-polymerized resin), according to the following polymerization cycles: (A) 500 W for 3 minutes, (B) 90 W for 13 minutes + 500 W for 90 seconds, (C) 320 W for 3 minutes + 0 W for 4 minutes + 720 W for 3 minutes, and (T) 74degreesC for 9 hours. Porosity was calculated by measurement of the specimen volume before and after its immersion in water. Data were analyzed using 1-way analysis of variance (alpha = .05).Results. The mean values and SDs of the percent mean porosity were: A = 1.05% +/- 0.28%, B = 0.91% +/- 0.15%, C = 0.88% +/- 0.23%, T = 0.93% +/- 0.23%. No significant differences were found in mean porosity among the groups evaluated.Conclusion. Within the limitations of this study, a denture base resin specifically designed for microwave Polymerization tested was not affected by different polymerization cycles. Porosity was similar to the conventional heat-polymerized denture base resin tested.

Residual monomer of reline acrylic resins - Effect of water-bath and microwave post-polymerization treatments

Objectives. This study compared the residual monomer (RM) in four hard chair-side reline resins (Duraliner II-D, Kooliner-K, Tokuso Rebase Fast-TRF and Ufi Gel hard-UGH) and one heat-polymerized denture base resin (Lucitone 550-L), which was processed using two polymerization cycles (short-LS and long-LL). It was also investigated the effect of two after polymerization treatments on this RM content.Methods. Specimens (n = 18) of each material were produced following the manufacturers' instructions and then divided into three groups. Group I specimens were left untreated (GI-control). Specimens of group II (GII) were given post-polymerization treatment by microwave irradiation. In group III (GIII), specimens were submitted to immersion in water at 55 degrees C (reline resins-10 min; denture base resin L-60min). The RM was analyzed using high performance liquid chromatography (HPLC) and expressed as a percentage of RM. Data were analyzed by two-way ANOVA followed by Tukey's test (alpha = 0.05).Results. Comparing control specimens, statistical differences were found among all materials (p < 0.05), and the results can be arranged as K (1.52%) > D (0.85%) > UGH (0.45%) > LL (0.24%) > TRF (0.14%) > LS (0.08%). Immersion in hot water (GIII) promoted a significant (p < 0.05) reduction in the RM for all materials evaluated compared to control (GI), with the exception of LL specimens. Materials K, UGH and TRF exhibited significantly (p < 0.05) lower values of RM after microwave irradiation (GII) than in the control specimens.Significance. The reduction in RM promoted by water-bath and microwave post-polymerization treatments could improve the mechanical properties and biocompatibility of the relining and denture base materials. (c) 2006 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Solvothermal method to obtain europium-doped yttrium oxide

Pure yttrium oxide or mixed with europium oxide (3 at%) were treated in supercritical isopropanolic suspension at 500degreesC for 20 It and filling degree of 50%. Products were supercritically dried and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), infrared spectroscopy (IR) and luminescence spectroscopy (LS). Particle shape is irregular with an equivalent diameter of ca. 5 mum. Cubic crystalline phase is mainly obtained and hydroxide ion in low concentration is detected by IR vibrational spectrum. Europium in this concentration does not extensively change such observed characteristics from the pure yttrium oxide. Luminescence spectra show that the doped product is a mixture of the two oxides added by oxyhydroxide impurities. Nevertheless, this precursor sample, after being heated at 900degreesC during 1 h, has all characteristics, especially luminescent ones, of the P22 commercial phosphor. (C) 2003 Elsevier B.V. (USA). All rights reserved.

SrTiO3 preparation through coprecipitation methods

Precursor powders to obtain SrTiO3 were prepared by using 8-hydroxyquinoline precipitant agent. The residues from the thermal decomposition, followed by TG/DTG/DTA, were characterized by XRD and it could be verified that the mixed oxides could be obtained varying the thermal decomposition conditions like atmosphere and heating rate. However, the morphology and crystallinity of these residues is highly affected by such variations. (C) 2000 Elsevier B.V. B.V. All rights reserved.