The partial oxidation of methane over Pd/Al2O3 catalyst nanoparticles studied in-situ by near ambient-pressure x-ray photoelectron spectroscopy

Near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to study the chemical state of methane oxidation catalysts in-situ. Al2O3{supported Pd catalysts are prepared with different particle sizes ranging from 4 nm to 10 nm. These catalysts were exposed to conditions similar to those used in the partial oxidation of methane (POM) to syn-gas and simultaneously monitored by NAP-XPS and mass spectrometry. NAP-XPS data show changes in the oxidation state of the palladium as the temperature in- creases, from metallic Pd0 to PdO, and back to Pd0. Mass spectrometry shows an increase in CO production whilst the Pd is in the oxide phase, and the metal is reduced back under presence of newly formed H2. A particle size effect is observed, such that CH4 conversion starts at lower temperatures with larger sized particles from 6 nm to 10 nm. We find that all nanoparticles begin CH4 conversion at lower temperatures than polycrystalline Pd foil.

Reduction of oil uptake in deep fat fried chicken nuggets using edible coatings based on cassava starch and methylcellulose

The aim of this study was to evaluate the effect of edible coatings based on methylcellulose (MC) and cassava starch (CS) to reduce oil uptake and improve water retention of chicken nuggets during deep fat frying. Edible coatings were prepared with I g of MC/100 g solution and 4 g of CS/100 g solution, with 25 or 55 g glycerol/100 g biopolymer. These solutions were applied to nugget samples before battering. Pre-fried and fried nuggets were analyzed to determine lipid and water contents. Color and texture were also measured in the fried nuggets. In general, there was no effect of the two concentrations of plasticizer of either of the biopolymers on the water retention of whole nuggets. But, higher oil uptake reduction, and consequently, lower lipid content was observed on nuggets coated with CS and 25% plasticizer. The coated samples were darker and had a brighter yellow color when compared with the control. There was also a significant decrease in the shearing force of the fried coated samples, indicating reduced hardness of these samples.

Co/Al2O3 catalysts promoted with noble metals for production of hydrogen by methane steam reforming

The effect of noble metal addition on the catalytic properties of Co/Al2O3 was evaluated for the steam reforming of methane. Co/Al2O3 catalysts were prepared with addition of different noble metals (Pt, Pd, Ru and Ir 0.3 wt.%) by a wetness impregnation method and characterized by UV-vis spectroscopy, temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) of the reduced catalysts. The UV-vis spectra of the samples indicate that, most likely, large amounts of the supported cobalt form Co species in which cobalt is in octahedral and tetrahedral symmetries. No peaks assigned to cobalt species from aluminate were found for the promoted and unpromoted cobalt catalysts. TPO analyses showed that the addition of the noble metals on the Co/Al2O3 catalyst leads to a more stable metallic state and less susceptible to the deactivation process during the reforming reaction. The Co/Al2O3 promoted with Pt showed higher stability and selectivity for H(2)production during the methane steam reforming. (C) 2007 Elsevier Ltd. All rights reserved.

Production of hydrogen by ethanol steam reforming on Co/Al2O3 catalysts: Effect of addition of small quantities of noble metals

The catalytic performance of Co/Al2O3 catalysts promoted with small amounts noble metals (Pt, Pd, Ru, Ir) for steam reforming of ethanol (SRE) has been investigated. The catalysts were characterized by the energy dispersive X-ray, X-ray diffraction, BET surface area, X-ray absorption fine structure and temperature reduction programmed techniques. The results showed that the promoting effect of noble metals included a marked decrease of the reduction temperatures of both Co3O4 and cobalt surface species interacting with the support due to the hydrogen spillover effect, leading to a significant increase of the reducibilities of the promoted catalysts. The better catalytic performance for the ethanol steam reforming at 400 degrees C was obtained for the CoRu/Al2O3 catalyst, which presented an effluent gaseous mixture with the highest H, selectivity and the reasonable low CO formation. (C) 2007 Published by Elsevier B.V.

Anticorrosive cerium-based coatings prepared by the sol-gel method

The development of efficient anti-corrosion and environmentally friendly coating systems are needed for the replacement of the highly toxic Cr-based conversion coatings for corrosion protection of aluminum alloys. In this study, we demonstrate that the direct application of ceramic cerium-based sol-gel coatings to AA7075-T6 substrates produces high-performance anti-corrosion layers. Electrochemical experiments and analyses of the microstructure demonstrate that the protective layers are very efficient for the passivation of the alloy surfaces operating as both passive and active barrier for corrosion protection.

Tribological Testing of Some Potential PVD and CVD Coatings for Steel Wire Drawing Dies

Cemented carbide is today the most frequently used drawing die material in steel wire drawing applications. This is mainly due to the possibility to obtain a broad combination of hardness and toughness thus meeting the requirements concerning strength, crack resistance and wear resistance set by the wire drawing process. However, the increasing cost of cemented carbide in combination with the possibility to increase the wear resistance of steel through the deposition of wear resistant CVD and PVD coatings have enhanced the interest to replace cemented carbide drawing dies with CVD and PVD coated steel wire drawing dies. In the present study, the possibility to replace cemented carbide wire drawing dies with CVD and PVD coated steel drawing dies have been investigated by tribological characterisation, i.e. pin-on-disc and scratch testing, in combination with post-test observations of the tribo surfaces using scanning electron microscopy, energy dispersive X-ray spectroscopy and 3D surface profilometry. Based on the results obtained, CVD and PVD coatings aimed to provide improved tribological performance of steel wire drawing dies should display a smooth surface topography, a high wear resistance, a high fracture toughness (i.e. a high cracking and chipping resistance) and intrinsic low friction properties in contact with the wire material. Also, the steel substrate used must display a sufficient load carrying capacity and resistance to thermal softening. Of the CVD and PVD coatings evaluated in the tribological tests, a CVD TiC and a PVD CrC/C coating displayed the most promising results.

Estudo das propriedades de revestimentos compósitos de níquel com Al2O3 e SiC

Neste trabalho foi avaliada a resistência à corrosão dos revestimentos compósitos de níquel, obtidos a partir de um banho de níquel químico (electroless) e um banho de níquel eletrolítico tipo Watts (com e sem tensoativo), caracterizando-os comparativamente em relação ao revestimento de níquel sem partículas. Os métodos utilizados para avaliação da resistência a corrosão foram: ensaio acelerado em névoa salina, voltametria cíclica, curva de polarização potenciodinâmica (em NaCl 0,6N) e dissolução anódica à corrente constante. Os revestimentos também foram avaliados com relação à resistência ao desgaste, rugosidade, e morfologia da camada. As partículas foram caracterizadas por difração de raio- X , dispersão granulométrica e potencial zeta. Nas condições estudadas os resultados mostraram que o revestimento compósito Ni-P-Al2O3 (Al2O3 - tamanho de grão ≅ 0,1 a 1,8µm) apresentou melhor resistência à corrosão que o revestimento de níquel químico sem incorporação de partículas (Ni-P) que por sua vez, apresentou resistência a corrosão superior ao compósito Ni-P-SiC no. 23 (SiC no. 23 - tamanho de grão ≅0,8 a 19,9µm). Já o eletrodepósito de níquel sem incorporação de partículas apresentou melhor resistência à corrosão que os revestimentos compósitos. Entre estes o compósito Ni-Al2O3 apresentou resistência a corrosão superior ao compósito Ni-SiC no. 23 A adição do tensoativo lauril sulfato de sódio reduz a quantidade de partículas incorporadas no eletrodepósito, sendo este efeito mais acentuado para o SiC com maior granulometria. Para diferentes granulometrias de carbeto de silício (SiC no. 2 - tamanho de grão ≅0,3 a 6,2µm e SiC no. 23 - tamanho de grão ≅0,8 a 19,9µm), o revestimento compósito obtido com o SiC que possui menor granulometria, apresentou maior resistência à corrosão e maior resistência ao desgaste, indicando desta forma que o tamanho da partícula incorporada no depósito de níquel exerce grande influência sobre a resistência à corrosão do revestimento, bem como sobre a resistência ao desgaste.

Comparative study of the whisky aroma profile based on headspace solid phase microextraction using different fibre coatings

A dynamic headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to ion trap mass spectrometry (GC–ITMS) method was developed and applied for the qualitative determination of the volatile compounds present in commercial whisky samples which alcoholic content was previously adjusted to 13% (v/v). Headspace SPME experimental conditions, such as fibre coating, extraction temperature and extraction time, were optimized in order to improve the extraction process. Five different SPME fibres were used in this study, namely, poly(dimethylsiloxane)(PDMS),poly(acrylate)(PA),Carboxen-poly(dimethylsiloxane)(CAR/PDMS),Carbowax-divinylbenzene(CW/DVB)and Carboxen-poly(dimethylsiloxane)-divinylbenzene (CAR/PDMS/DVB). The best results were obtained using a 75 m CAR/PDMS fibre during headspace extraction at 40◦C with stirring at 750rpm for 60min, after saturating the samples with salt. The optimised methodology was then appliedtoinvestigatethevolatilecompositionprofileofthreeScotchwhiskysamples—BlackLabel,BallantinesandHighlandClan.Approximately seventy volatile compounds were identified in the these samples, pertaining at several chemical groups, mainly fatty acids ethyl esters, higher alcohols, fatty acids, carbonyl compounds, monoterpenols, C13 norisoprenoids and some volatile phenols. The ethyl esters form an essential group of aroma components in whisky, to which they confer a pleasant aroma, with “fruity” odours. Qualitatively, the isoamyl acetate, with “banana” aroma,wasthemostinteresting.Quantitatively,significantcomponentsareethylestersofcaprilic,capricandlauricacids.Thehighestconcentration of fatty acids, were observed for caprilic and capric acids. From the higher alcohols the fusel oils (3-methylbutan-1-ol and 2.phenyletanol) are the most important ones.

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Obtenção de compósitos cerâmicos baseados em Al2O3/TiC através dos precursores poliméricos

The obtaining of ceramic materials from polymeric precursors is subject of numerous studies due to lower energy costs compared to conventional processing. The aim of this study is to investigate and improve the mechanism for obtaining ceramic matrix composite (CMC) based on SiOC/Al2O3/TiC by pyrolysis of polysiloxane in the presence of an active filler and inert filler in the pyrolysis temperature lower than the usually adopted for this technique, with greater strength. It also investigates the influence of pyrolysis temperature, the content of Alas active filler, the presence of infiltrating agents (Al, glass and polymer) after pyrolysis, temperature and infiltration time on some physical and mechanical properties. Alumina is used as inert filler and Al and Ti as active filler in the pyrolysis. Aluminum, glass and polysiloxane are used as agents infiltrating the post-pyrolysis. The results are analyzed with respect to porosity and bulk density by the Archimedes method, the presence of crystalline phases by X-ray diffraction (XRD) and microstructure by scanning electron microscopy (SEM). The ceramic pyrolyzed between 850 °C 1400 °C contain porosity 15% to 33%, density 2.34 g/cm3 and flexural strength at 4 points from 30 to 42 MPa. The microstructure features are porous, with an array of Al2O3 reinforced by TiC particles and AlTi3. The infiltration post-pyrolysis reveals decrease in porosity and increase density and strength. The composites have potential applications where thermal stability is the main requirement

Growth of Al2O3 thin film by oxidation of resistively evaporated Al on top of SnO2, and electrical properties of the heterojunction SnO2/Al2O3

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Development of amorphous carbon protective coatings on poly(vinyl)chloride

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

Evaluation of WC-17Co and WC-10Co-4Cr thermal spray coatings by HVOF on the fatigue and corrosion strength of AISI 4340 steel

It is known that chromium electroplating is related to the reduction in the fatigue strength of base metal. However, chromium results in protection against wear and corrosion combined with chemical resistance and good lubricity. Environmental requirements are an important point to be considered in the search for possible alternatives to hard chrome plating. Aircraft landing gear manufactures are considering WC thermal spray coating applied by the high-velocity oxygen-fuel (HVOF) process an alternative candidate, which shows performance at least comparable to results, obtained for hard chrome plating. The aim of this study is to compare the influence of WC-17Co and WC-10Co-4Cr coatings applied by HVOF process and hard chromium electroplating on the fatigue strength of AISI 4340 steel, with and without shot peening. S-N curves were obtained in axial fatigue test for base material, chromium plated and tungsten carbide coated specimens. Tungsten carbide thermal spray coating results in higher fatigue strength when compared to hard chromium electroplated. Shot peening prior to thermal spraying showed to be an excellent alternative to increase fatigue strength of AISI 4340 steel. Experimental data showed higher axial fatigue and corrosion resistance in salt fog exposure for samples WC-10Co-4Cr HVOF coated when compared with WC-17Co. Fracture surface analysis by scanning electron microscopy (SEM) indicated the existence of a uniform coverage of nearly all substrates. (C) 2004 Elsevier B.V. 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.