Síntese de membranas cerâmicas via método sol-gel utilizando TEOS e N,N-dimetilformamida

In this work we obtained microporous and mesoporous silica membranes by sol-gel processing. Tetraethylortosilicate (TEOS) was used as precursor. Nitric acid was used as catalyst. In order to study the affect of N,N-dimethylformamide (NDF) as drying additive, we used a molar ratio TEOS/NDF of 1/3. The performance of N,N-dimethylformamide was evaluated through monolithicity measurements. The structural evolutions occurring during the sol-gel transition and in the interconnected network of the membranes during thermal treatment were monitored by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analyses and nitrogen sorption. We noted that in the presence of N,N-dimethylformamide, polymerization goes through a temporary stabilization of oligomers. The Si-O(H) bonds are stronger and belong to a more cross-linked structure for the N,N-dimethylformamide containing sol. The membranes obtained in the presence of N,N-dimethylformamide have larger surface area and its pore structure is in the range of mesoporous. The membranes obtained without additive have pore structure in the range of microporous.

Estudo microestrutural do catalisador Ni/gama-Al2O3: efeito da adição de CeO2 na reforma do metano com dióxido de carbono

The carbon dioxide reforming of methane was carried out over nickel catalysts supported on the gamma-Al2O3/CeO2 system prepared by wet impregnation. With the increase of the CeO2 weight in the catalyst, a higher stability was observed in the catalytic activity, together with an excellent resistance to carbon deposition and a better Ni dispersion. The catalysts were characterized by means of surface area measurements, TPR, H2 chemisorption, XRD, SEM, EDX, XPS and TEM. An interaction between Ni and CeO2 was observed to the Ni/CeO2 sample after activation in a H2 atmosphere above 300 ºC. Such behavior has a significantly influence on the catalytic activity.

Alcóxidos como precursores na síntese de novos materiais através do processo sol-gel

An overview about the role of alkoxides in the most recent uses of the sol-gel process in the synthesis of new materials is presented. Special attention is focused on the uses of silicon, aluminum, zirconium and titanium alkoxides. This review shows that the alkoxides enable the synthesis of new matrices with controlled surface area, acidity and porosity, as well as some unusual properties. The property associated with the solubility of metal alkoxides opens enormous possibilities of combining them for the synthesis films of powders with a very large range of metal compositions.

Decomposição do NO sobre Cu suportado em zeólitas

Direct decomposition of NO on copper supported on zeolite catalysts such as MCM-22 and Beta was compared with that on the thoroughly studied Cu-ZSM-5. The catalysts were prepared by ion-exchange in basic media. They were characterized by atomic absorption, surface area, nitrogen adsorption at 77K, X-ray diffraction and temperature programmed reduction. The products of the reaction were analyzed by Fourier transform infrared spectroscopy using a gas cell. Catalytic activity tests indicated that zeolite catalysts, like Beta and MCM-22, lead to NO conversion values comparable to ZSM-5.

Ação promotora do zinco em catalisadores de síntese do estireno

Ethylbenzene dehydrogenation in the presence of steam is the main commercial route to produce styrene. The industrial catalyst is chromium and potassium-doped hematite, which easily deactivates with time due to potassium loss. In order to find non-toxic and potassium free catalysts, the promoter action of zinc on hematite was studied in this work. It was found that zinc acts as structural promoter by stabilizing the Fe3+ species (active phase) as maghemite. Although it decreases the specific surface area, it increases four times the catalytic activity as compared to hematite.

Métodos de preparação de nanopartículas metálicas suportadas em carbono de alta área superficial, como eletrocatalisadores em células a combustível com membrana trocadora de prótons

Fuel cells are attracting much interest as efficient and clean energy conversion devices. The main components of low temperature fuel cells are the electrocatalysts used to promote the anodic and cathodic reactions, which are based on platinum and platinum alloys. These electrocatalysts are normally prepared in the form of metal nanoparticles supported on a conductive material, usually high surface area carbon, to improve catalyst utilization and reduce cost. This work presents and comments some methods used presently to produce these electrocatalysts. The performances of the produced electrocatalysts are compared to that of state-of-the-art commercial E-TEK electrocatalysts.

Efeito do cromo nas propriedades catalíticas da MCM-41

The effect of chromium on the catalytic properties of MCM-41 was evaluated in order to develop new catalysts for the trimethylbenzene transalkylation with benzene to produce ethylbenzene, a high-value aromatic in the industry. It was found that chromium decreases the specific surface area but increases the acidity, turning MCM-41 into an active and selective catalyst for ethylbenzene and toluene production. The coke produced on the catalyst is hydrogenated and mainly located outside the pores and thus can be easily removed. The catalyst is more active and selective than mordenite, a commercial catalyst, and thus more promising for commercial applications.

Síntese e caracterização de alfa-fosfato de zircônio(IV) contendo agregados de cobre metálico

The alpha-zirconium (IV) hydrogenphosphate (alpha-ZrP) has received great attention in the last years due to its properties like ion exchange, intercalation, ionic conductivity and catalytic activity. This work reports a method to produce metallic copper clusters on alpha-ZrP to be used as catalysts in petrochemical processes. It was found that the solids were non-crystalline regardless of the uptake of copper and the reduction. The specific surface area increased as a consequence of the increase of the interlayer distance to accept the copper ions between the layers. During the reduction, big clusters of copper (0,5-11µ) with different sizes and shapes were produced.

Influência do agente precipitante na preparação do óxido de nióbio (V) hidratado pelo método da precipitação em solução homogênea

This work reports the preparation, characterization and study of the ion exchange behavior of hydrous niobium oxide prepared by a homogeneous precipitation method. The precipitating agent was obtained in aqueous solution by thermal decomposition of urea or ammonium carbonate. The compounds were chemically and physically characterized by X-ray diffractometry, thermal analysis (TG/DTG), surface area measurements and ion exchange behavior with sodium. The materials prepared with ammonium carbonate presented a higher degree of crystallinity and better ion exchange capacity with sodium than materials prepared with urea. In the homogeneous precipitation method, materials were obtained with specific surface area of 123 - 224 m² g-1. A variation of the preparation process produced hydrous niobium oxide with a different degree of hydration and specific surface area. This provided materials with different physico-chemical properties.

Pilarização de uma argila brasileira com poliidroxications de alumínio: preparação, caracterização e propriedades catalíticas

Montmorillonite clay from Brazil was pillared with aluminium polyhydroxications. The influence of aging of the pillaring solution and the concentration of the clay suspension on the properties of the prepared materials was studied. The materials were characterized by chemical analysis, XRD and pore analysis by N2 adsorption. The catalytic properties were evaluated in the cumene cracking reaction. Results showed that the pillarization process increases the basal spaces of natural clay from 9.7 to 18.5 Å and the surface area from 41 to 300 m²/g.

Size Effect and Notch Size Effect in Metal Fatigue

It is a well known phenomenon that the constant amplitude fatigue limit of a large component is lower than the fatigue limit of a small specimen made of the same material. In notched components the opposite occurs: the fatigue limit defined as the maximum stress at the notch is higher than that achieved with smooth specimens. These two effects have been taken into account in most design handbooks with the help of experimental formulas or design curves. The basic idea of this study is that the size effect can mainly be explained by the statistical size effect. A component subjected to an alternating load can be assumed to form a sample of initiated cracks at the end of the crack initiation phase. The size of the sample depends on the size of the specimen in question. The main objective of this study is to develop a statistical model for the estimation of this kind of size effect. It was shown that the size of a sample of initiated cracks shall be based on the stressed surface area of the specimen. In case of varying stress distribution, an effective stress area must be calculated. It is based on the decreasing probability of equally sized initiated cracks at lower stress level. If the distribution function of the parent population of cracks is known, the distribution of the maximum crack size in a sample can be defined. This makes it possible to calculate an estimate of the largest expected crack in any sample size. The estimate of the fatigue limit can now be calculated with the help of the linear elastic fracture mechanics. In notched components another source of size effect has to be taken into account. If we think about two specimens which have similar shape, but the size is different, it can be seen that the stress gradient in the smaller specimen is steeper. If there is an initiated crack in both of them, the stress intensity factor at the crack in the larger specimen is higher. The second goal of this thesis is to create a calculation method for this factor which is called the geometric size effect. The proposed method for the calculation of the geometric size effect is also based on the use of the linear elastic fracture mechanics. It is possible to calculate an accurate value of the stress intensity factor in a non linear stress field using weight functions. The calculated stress intensity factor values at the initiated crack can be compared to the corresponding stress intensity factor due to constant stress. The notch size effect is calculated as the ratio of these stress intensity factors. The presented methods were tested against experimental results taken from three German doctoral works. Two candidates for the parent population of initiated cracks were found: the Weibull distribution and the log normal distribution. Both of them can be used successfully for the prediction of the statistical size effect for smooth specimens. In case of notched components the geometric size effect due to the stress gradient shall be combined with the statistical size effect. The proposed method gives good results as long as the notch in question is blunt enough. For very sharp notches, stress concentration factor about 5 or higher, the method does not give sufficient results. It was shown that the plastic portion of the strain becomes quite high at the root of this kind of notches. The use of the linear elastic fracture mechanics becomes therefore questionable.

Hitsatun kerrossihtilevyrakenteen soveltuvuus sellutehtaan laitteiden suodatinpinnaksi

Tässä diplomityössä tutkittiin hitsaamalla valmistettavan kerrossihtilevyn soveltuvuutta eri sellutehtaan laitteisiin mekaanisen kuormituskokeen, korroosiokokeen ja syrjäytyskokeiden avulla. Tutkimusympäristönä käytettiin puukuitupesuria, sillä kerrossihtilevyrakenteen todennäköisimpiä käyttökohteita ovat erilaiset massan pesuun tarkoitetut laitteet. Mekaanisen kuormituksen kokeessa tarkasteltiin kerrossihtilevyn staattista ja dynaamista kuormituksen kestoa painevaihteluiden avulla pesurin koelokerossa ja verrattiin sitä porattuun reikälevyyn. Kokeessa käytetyn kerrossihtilevyversion todettiin olevan huomattavasti porattua saman paksuista reikälevyä heikompi dynaamisen kuormituksen alaisena. Syrjäytyskokeilla määritettiin syrjäytysnopeus erilaisilla reiänhalkaisijoilla ja –jaoilla sekä tutkittiin väriaineen avulla sokeiden tukikannasten vaikutusta syrjäytyspesun homogeenisuuteen levyn pinnassa. Syrjäytysnopeuden todettiin heikentyvän vapaan reikäpinta-alan pienentyessä. Väriaineellisissa kokeissa ei havaittu tukikannasten merkittävästi alentavan syrjäytysnopeutta. Korroosiokokeilla tutkittiin ja vertailtiin laser- ja vastuspistehitsien korroosionkestokykyä kloridipitoisissa olosuhteissa lämpötilan säätelyn mahdollistavan olosuhdekaapin avulla. Laserhitsauksessa parametrien ei havaittu vaikuttavan merkittävästi hitsin herkistymislämpötilaan. Vastuspistehitsaamalla on mahdollista saavuttaa laserhitsien korroosionkesto.

Estudo comparativo entre sílica obtida por lixívia ácida da casca de arroz e sílica obtida por tratamento térmico da cinza de casca de arroz

A comparison between silica by acid leaching of rice husk (RH) and silica obtained from thermal treatment of rice husk ash (RHA) is presented. The best leaching results were obtained using 10% hydrochloric acid followed by washing with water. The alternative method, calcination of RHA at 700 ºC for 6 h followed by grinding for 80 min, was more effective. Silica obtained from RH was about 97% amorphous, had a 17.37 µm mean particle size, and a specific surface area of 296 m²/g. On the other hand, for silica obtained from RHA the values were about 95% amorphous material 0.68 µm, and 81 m²/g.

Adsorção de fenol sobre carvão ativado em meio alcalino

The present study describes phenol adsorption on commercial active carbon (CAF) under alkaline conditions in the concentration range of 0.01 to 2.08 mmol L-1. Surface characterization has been performed by means of surface area measurements, IR spectroscopy and Boehm titration. The effect of temperature on the adsorption equilibrium isotherm was investigated at 23, 30, 40, 50 and 60 °C. The results showed that adsorption capacity decreased with increasing temperature. The adsorption kinetics and the role of surface characteristics on the adsorption of phenol also discussed.

Síntese e propriedades catalíticas em reações de oxidação de goethitas contendo nióbio

Nb-substituted goethites have been prepared and characterized by Mössbauer spectroscopy, XRD, SEM and BET surface area measurements. Mössbauer and XRD analyses suggested that Nb replaces Fe3+ in the structure with duplet formation. The insertion of Nb into the goethite structure caused a significant increase in the BET surface area of the material. The prepared alpha-Fe1-xNb xOOH was investigated for the H2O2 decomposition to O2 and for the Fenton reaction to oxidize the dye methylene blue. It was observed that the introduction of Nb in to goethite produced a strong increase in the activity of oxidation of the dye contaminant by H2O2.