The initial oxidation of transition metal surfaces

Due to their numerous novel technological applications ranging from the example of exhaust catalysts in the automotive industry to the catalytic production of hydro- gen, surface reactions on transition metal substrates have become to be one of the most essential subjects within the surface science community. Although numerous applications exist, there are many details in the different processes that, after many decades of research, remain unknown. There are perhaps as many applications for the corrosion resistant materials such as stainless steels. A thorough knowledge of the details of the simplest reactions occuring on the surfaces, such as oxidation, play a key role in the design of better catalysts, or corrosion resistant materials in the future. This thesis examines the oxidation of metal surfaces from a computational point of view mostly concentrating on copper as a model material. Oxidation is studied from the initial oxidation to the oxygen precovered surface. Important parameters for the initial sticking and dissociation are obtained. The saturation layer is thoroughly studied and the calculated results arecompared with available experimental results. On the saturated surface, some open questions still remain. The present calculations demonstrate, that the saturated part of the surface is excluded from being chemically reactive towards the oxygen molecules. The results suggest, that the reason for the chemical activity of the saturated surface is due to a strain effect occuring between the saturated areas of the surface.

Hyvinvointipalvelutuottajien uudet yhteistyön toimintamallit - Orimattilalaisten yritysten työhyvinvointipilotti

Tutkimuksessa selvitettiin pk-sektorilla toimivien yritysten tarpeita liittyen hyvinvointipalvelujen tarjontaan sekä palvelujen koettuun laatuun. Lisäksi selvitettiin millainen hyvinvointitoimijoiden joukko toimii pk-yritysten ympärillä ja millaiset ovat näiden toimijoiden yhteistyön ja verkostoitumisen mahdollisuudet. Tutkimuksen tavoitteena oli luoda malleja ja ideoita siihen, miten hajallaan oleva palvelutarjonta saataisiin paremmin kohtaamaan pk-yritysten moninaiset tarpeet. Tutkimuksessa haastateltiin 20 Orimattilalaista pk-yritystä teollisuuden sekä kaupan- ja palvelun alalta. Lisäksi kerättiin tietoa muiden toimijoiden kuten työterveyshuoltojen ja hyvinvointipalveluntuottajien tarjontatavoista. Tutkimuksen teoriaosuudessa tutkittiin hyvinvointipalvelutuottajien verkostoitumisen edellytyksiä arvoverkkojen, yritysten välisen yhteistyön mallien sekä liiketoiminnan uudelleen konseptoinnin kautta. Tutkimuksen tuloksista ilmeni, että yritysten, työterveyshuoltojen ja hyvinvointipalveluntuottajien yhteistyön lisäämisellä voidaan kehittää palveluntarjontatapoja paremmin kysyntää vastaavaksi. Erityisesti työterveyshuoltojen rooli yritysten työhyvinvointiprosesseissa korostui. Niiden mukanaolon koetaan parantavan palvelun laatua.

Dispersal is a major driver of the latitudinal diversity gradient of Carnivora

AimUnderstanding the relative contribution of diversification rates (speciation and extinction) and dispersal in the formation of the latitudinal diversity gradient - the decrease in species richness with increasing latitude - is a main goal of biogeography. The mammalian order Carnivora, which comprises 286 species, displays the traditional latitudinal diversity gradient seen in almost all mammalian orders. Yet the processes driving high species richness in the tropics may be fundamentally different in this group from that in other mammalian groups. Indeed, a recent study suggested that in Carnivora, unlike in all other major mammalian orders, net diversification rates are not higher in the tropics than in temperate regions. Our goal was thus to understand the reasons why there are more species of Carnivora in the tropics. LocationWorld-wide. MethodsWe reconstructed the biogeographical history of Carnivora using a time-calibrated phylogeny of the clade comprising all terrestrial species and dispersal-extinction-cladogenesis models. We also analysed a fossil dataset of carnivoran genera to examine how the latitudinal distribution of Carnivora varied through time. ResultsOur biogeographical analyses suggest that Carnivora originated in the East Palaearctic (i.e. Central Asia, China) in the early Palaeogene. Multiple independent lineages dispersed to low latitudes following three main paths: toward Africa, toward India/Southeast Asia and toward South America via the Bering Strait. These dispersal events were probably associated with local extinctions at high latitudes. Fossil data corroborate a high-latitude origin of the group, followed by late dispersal events toward lower latitudes in the Neogene. Main conclusionsUnlike most other mammalian orders, which originated and diversified at low latitudes and dispersed out of the tropics', Carnivora originated at high latitudes, and subsequently dispersed southward. Our study provides an example of combining phylogenetic and fossil data to understand the generation and maintenance of global-scale geographical variations in species richness.

El poblament tardoantic al sector meridional de la Tarraconensis (sud de Catalunya i nord del País Valencià). Concomitàncies i diferències

Les darreres recerques dutes a terme en el Projecte Ager Tarraconensis (PAT) han permès augmentar considerablement els coneixements existents sobre l’antiguitat tardana al territorium de Tarraco, tema que ja havíem estudiat parcialment en la nostra tesi doctoral (1992), que inclou també altres àrees del Camp de Tarragona no incloses al PAT. D’altra banda, en els darrers anys hem tingut també ocasió d’estudiar parcialment el poblament antic a la zona de les terres de l’Ebre i al nord del País Valencià, molt especialment a les comarques de l’Alt Palància i la Plana de Castelló. El conjunt d’aquests estudis ens permet plantejar una visió general sobre el poblament tardoantic en una zona determinada que correspon a la part costanera meridional de l’antiga provincia Tarraconensis, amb els límits i la denominació que rep a partir de la divisió de Dioclecià. L’estudi comparatiu del poblament tardoantic d’aquestes àrees permet contrastar, a més de punts en comú, també algunes diferències, tant en el diferent grau de pervivència dels hàbitats després de la crisi del segle III com en l’aparició de nous tipus d’hàbitats (poblats en altura) que no apareixen en totes les àrees, sinó només en les més meridionals. S’aborda també la problemàtica de l’existència d’unes poques vil·les luxoses durant el segle IV (especialment la controvertida de Centcelles), en contrast amb altres hàbitats més modestos, així com el pas de la vil·la a un altre tipus de poblament dispers.

Síntese de catalisadores Ziegler-Natta: algumas rotas e suas dificuldades

The Ziegler-Natta catalyst and the polymerization thereof are systems which require careful handling and special treatment of chemicals. In spite of the use of inert atmosphere and dry chemicals, some Ziegler-Natta systems may present low activities or even may deactivate because of unsuitable handling. Some features of the TiCl3 synthesis and its characterization when related to the presence of impurities are described. Evidences of poor handling of chemicals and/or laboratory devices while in synthesis of the catalyst are emphasized. The problems arising from butadiene polymerization and some relevant details in propylene polymerization are also presented with teaching objectives.

Immediate ecotoxicological effects of short-lived oil spills on marine biota.

Marine environments are frequently exposed to oil spills as a result of transportation, oil drilling or fuel usage. Whereas large oil spills and their effects have been widely documented, more common and recurrent small spills typically escape attention. To fill this important gap in the assessment of oil-spill effects, we performed two independent supervised full sea releases of 5 m(3) of crude oil, complemented by on-board mesocosm studies and sampling of accidentally encountered slicks. Using rapid on-board biological assays, we detect high bioavailability and toxicity of dissolved and dispersed oil within 24 h after the spills, occurring fairly deep (8 m) below the slicks. Selective decline of marine plankton is observed, equally relevant for early stages of larger spills. Our results demonstrate that, contrary to common thinking, even small spills have immediate adverse biological effects and their recurrent nature is likely to affect marine ecosystem functioning.

Recuperação de metais de catalisadores usados de hidrotratamento (NiMo E CoMo/AL2O3)

This work presents a detailed study of the leaching behavior of deactivated hydrotreating catalysts (CoMo, NiMo/Al2O3) in presence of oxalate and NH4+ ions in various media. The yield of metals recovery may be optimized by adjusting several experimental parameters (time, temperature, etc). Leaching is limited by physical factors (diffusional effects caused by coke) and by the existence of silicate/spinel-like species which are poorly soluble in leaching solutions. Coke may be eliminated by an oxidation step at temperatures between 300-400ºC. Above 400ºC, solubilization of Ni and Co is drastically reduced. 50-90% wt of sulphate species and 15-30% wt of phosphate ions are solubilized during leaching. Silicon (as SiO2) is not solubilized. The best Ni-Co-Mo recoveries are in the 70-90% wt range; Fe recovery may be quantitative, whereas Al leaching may be lower than 5% wt.

Ação promotora do berílio em catalisadores da síntese do estireno

The catalytic dehydrogenation of ethylbenzene in presence of steam is the main commercial route to produce styrene. The industrial catalysts are potassium- and chromia-doped hematite which show low surface areas leading to bad performance and short life. In order to develop catalysts with high areas, the effect of beryllium on the textural properties and on the catalytic performance of this iron oxide was studied. The influence of the amount of the dopant, the starting material and the calcination temperature were also studied. In sample preparations, iron and beryllium salts (nitrate or sulfate) were hydrolyzed with ammonia and then calcinated. The experiments followed a factorial design with two variables in two levels (Fe/Be= 3 and 7; calcination temperature= 500 and 700ºC). Solids without any dopant were also prepared. Samples were characterized by elemental analysis, infrared spectroscopy, surface area and porosity measurements, X-ray diffraction, DSC and TG. The catalysts were tested in a microreactor at 524ºC and 1 atm, by using a mole ratio of steam/ ethylbenzene=10. The selectivity was measured by monitoring styrene, benzene and toluene formation. It was found that the effect of beryllium on the characteristics of hematite and on its catalytic performance depends on the starting material and on the amount of dopant. Surface areas increased due to the dopant as well as the nature of the precursor; samples produced by beryllium sulfate showed higher areas. Beryllium-doped solids showed a higher catalytic activity when compared to pure hematite, but no significant influence of the anion of starting material was noted. It can be concluded that beryllium acts as both textural and structural promoter. Samples with Fe/Be= 3, heated at 500ºC, lead to the highest conversion and were the most selective. However, catalysts prepared from beryllium sulfate are the most promising to ethylbenzene dehydrogenation due to their high surface area which could lead to a longer life.

Anticorpos catalíticos: expandindo o alcance da catálise enzimática

The vast binding repertoire of the immune system has been exploited for the generation of tailor-made selective catalysts. Since the first reports of chemical reactions catalyzed by antibodies were published, research in this field, which borders chemistry and biology, has been rapidly established and a number of catalytic antibodies that carry out a wide range of reactions, have been developed. Recent advances have led to antibodies that catalyse complex, multi-step reactions and difficult chemical transformations, as well as reactions that do not have an organic equivalent at all. Current research in this field has been devoted to practical applications of this technology.

Troca iônica no estado sólido de európio3+ em zeólita Y: influência do tempo de reação

Rare earth elements supported in zeolites are the most important catalysts in the fluid cracking of petroleum. The solid state ion exchange of Eu3+ in Y zeolite was investigated. First of all, the hydrated EuCl3 was well mixed in a ball mill and was then heated at 300ºC for different times. The quantitative determination of Eu3+ showed that the degree of ion exchange depends on the reaction time at constant temperature, being ~95% in 4 h. The X-ray study showed that the crystallinity of the zeolite is little affected by the exchange procedure. The study of spectroscopic properties of Eu3+, emission spectra and lifetime, give information about the migration and position of the ion in the zeolite cages.

Construção e avaliação de um eletrodo tubular sensível ao íon hidrogênio como detector em sistemas de análise em fluxo

The construction of a tubular hydrogen ion-selective potentiometric electrode without inner reference solution, based on the tridodecylamine (TDDA) ionophore, and its evaluation in a flow system are described. TDDA was dissolved in 2-nitrophenyl octyl ether, dispersed in a PVC membrane and applied directly to a conducting support which consisted of an epoxy resin and graphite mixture. The electrode was designed with a tubular geometry to effort facilities to be coupled as part of a flow injection network. The main working characteristics such as response time, linear pH range, selectivity and life time were evaluated and compared with those obtained which a conventionally shaped electrode based on the same sensor. The electrode showed a slope of 51-52 mV dec-1 within a linear pH range from 4.0 up to 12.0.

Feeding ecology and movements of the Barolo shearwater Puffinus baroli baroli in the Azores, NE Atlantic

Trophic ecology and movements are critical issues for understanding the role of marine predators in food webs and for facing the challenges of their conservation. Seabird foraging ecology has been increasingly studied, but small elusive species, such as those forming the"little shearwater" complex, remain poorly known. We present the first study on the movements and feeding ecology of the Barolo shearwater Puffinus baroli baroli in a colony from the Azores archipelago (NE Atlantic), combining global location-sensing units, stable isotope analyses of feathers (δ13C and δ15N), stomach flushings and data from maximum depth gauges. During the chick-rearing period, parents visited their nests most nights, foraged mainly south of the colony and fed at lower trophic levels than during the non-breeding period. Squid was the most diverse prey (6 families and at least 10 different taxa), but species composition varied considerably between years. Two squid families, Onychoteuthidae and Argonautidae, and the fish family Phycidae accounted for 82.3% of ingested prey by number. On average, maximum dive depths per foraging trip reached 14.8 m (range: 7.9 to 23.1 m). After the breeding period, birds dispersed offshore in all directions and up to 2500 km from the breeding colony, and fed at higher trophic levels. Overall, our results indicate that the Barolo shearwater is a non-migratory shearwater feeding at the lowest trophic level among Macaronesian seabirds, showing both diurnal and nocturnal activity and feeding deeper in the water column, principally on small schooling squid and fish. These traits contrast with those of 3 other Azorean Procellariiformes (Cory"s shearwater Calonectris diomedea, the Madeiran storm-petrel Oceanodroma castro and Monteiro"s storm-petrel O. monteiroi), indicating ecological segregation within the Azorean seabird community.

Hidróxidos duplos lamelares: síntese, estrutura, propriedades e aplicações

The layered double hydroxides, known as anionic clays and represented by the general formula [M2+1-x M3+x (OH) 2]x+ Am-x/m·nH 2O, are a group of materials which are of much interest currently. They present a variety of potential applications as adsorbents, catalysts and catalyst support, ion-exchangers, antacids and as a polymer stabilizer. It is possible to obtain a broad variety of layered double hydroxides (LDHs), depending on the identity and ratio of the cations M2+ and M3+, as well as the interlamelar anion. The aim of this review is to give out some information about this class of materials, concerning to the synthesis, characterization, properties and applications.

Propriedades texturais e catalíticas de óxidos de ferro contendo cromo e cobre

Chromium and copper-doped hematites were prepared with the aim of studying the synergistic effect of these dopants on the textural and on the catalytic properties of the iron oxides towards the high temperature shift reaction. It was found that the most active catalysts were those with the highest amount of copper. They had the Fe(II)/Fe(III) ratio near the stoichiometric value of magnetite, the highest surface areas under the reactional atmosphere and the greatest tendency to produce the active form; they also were poorly crystalline solids. The best performance was shown by the catalyst with Fe/Cu=10, heated at 300ºC. It can thus be concluded that copper acts both as textural and structural promoter in these catalysts.

Fischer-Tropsch Slurry Bubble Column Reactor Modeling

The literature part of the work reviews overall Fischer-Tropsch process, Fischer-Tropsch reactors and catalysts. Fundamentals of Fischer-Tropsch modeling are also presented. The emphasis is on the reactor unit. Comparison of the reactors and the catalysts is carried out to choose the suitable reactor setup for the modeling work. The effects of the operation conditions are also investigated. Slurry bubble column reactor model operating with cobalt catalyst is developed by taking into account the mass transfer of the reacting components (CO and H2) and the consumption of the reactants in the liquid phase. The effect of hydrostatic pressure and the change in total mole flow rate in gas phase are taken into account in calculation of the solubilities. The hydrodynamics, reaction kinetics and product composition are determined according to literature. The cooling system and furthermore the required heat transfer area and number of cooling tubes are also determined. The model is implemented in Matlab software. Commercial scale reactor setup is modeled and the behavior of the model is investigated. The possible inaccuraries are evaluated and the suggestions for the future work are presented. The model is also integrated to Aspen Plus process simulation software, which enables the usage of the model in more extensive Fischer-Tropsch process simulations. Commercial scale reactor of diameter of 7 m and height of 30 m was modeled. The capacity of the reactor was calculated to be about 9 800 barrels/day with CO conversion of 75 %. The behavior of the model was realistic and results were in the right range. The highest uncertainty to model was estimated to be caused by the determination of the kinetic rate.