Afin d'améliorer les modèles prédictifs permettant l'évaluation des rejets de produits radioactifs lors d'un accident du cœur d'un réacteur à eau sous pression (REP), il est nécessaire d'évaluer le relâchement des produits de fission (PF) hors du combustible nucléaire. Le PF étudié ici est le molybdène, abondamment produit lors de la fission (6% des fissions de l'235U), qui est un élément clé de la chimie du combustible. Son comportement est fortement lié à l'évolution du potentiel oxygène dans la matrice combustible. De plus, en situation accidentelle, le molybdène peut former de nouveaux composés avec d'autres PF modifiant ainsi leur comportement.L'objectif de cette thèse est d'étudier le comportement du molybdène dans UO2 et UO2+x sous l'effet de hautes températures et /ou d'irradiations dans différents domaines d'énergie afin de découpler les types d'endommagement (balistique ou électronique). La première étape a consisté à élaborer des échantillons d'UO2+x par deux méthodes d'oxydation, sous flux gazeux ou en atmosphère humide. Ensuite, le molybdène a été introduit dans des échantillons d'UO2 (oxydé ou non) par implantation ionique. Les échantillons ont subi des recuits à haute température couplés ou non à des irradiations. Les profils de concentration du Mo implanté ont été suivis par SIMS (Secondary Ion Mass Spectrometry) avant et après traitement des échantillons. Les résultats montrent que le molybdène est peu, voire pas, mobile dans UO2 et UO2+x sous effet thermique. Cela est mis en regard avec les résultats de calculs ab-initio montrant que cet élément se stabilise dans la structure UO2 au sein d'octaèdres d'atomes d'oxygène. L'effet combiné de l'irradiation et de la température induit une mobilité du Mo, avec un fort impact des excitations électroniques. Les analyses Raman et DRX montrent que la migration du Mo est directement liée à la restructuration du matériau, l'effet étant amplifié dans l'UO2 sur-stœchiométrique / The fission products (FP) migration in oxide nuclear fuels are of primary importance in order to control the performance of nuclear power plants and their safety during operation. Molybdenum is one the most abundant fission products and has a very complex chemistry. Indeed, its chemical form depends strongly on the atmosphere conditions and the fuel stoichiometry.The aim of this work is to study the migration of molybdenum in uranium dioxide stoichiometric and hyper-stoichiometric at high temperature and under irradiation under several energy conditions in order to vary the damage regimes (ballistic or electronic). The first step was to prepare UO2+x samples by two oxidation methods, with a dry gas or under wet conditions. Then Mo was introduced in polycrystalline UO2 and UO2+x pellets by ion implantation at a maximum concentration of 0.8 at%. Irradiation conditions were chosen in order to understand, from a fundamental point of view, the effect of ballistic or electronic effects. The thermal Mo behaviour was also investigated by high temperature annealing (1600°C). The Mo concentration profiles before and after treatments were measured by SIMS (Secondary Ion Mass Spectrometry). We show that the sole effect of temperature is not efficient to involve a Mo migration in UO2 and UO2+x. This result is in agreement with ab-initio calculation results showing that Mo is well integrated in the uranium dioxide structure where its position is stabilized by the surrounding oxygen atoms. The combined effect of irradiation and temperature leads to the migration of Mo, especially in high electronic stopping regime. This can be relied to the thermal spike mechanism. Raman spectroscopy and DRX were used to probe the defect creation or annealing in the material microstructure, showing that the Mo mobility can be relied to the matrix restructuration

Ph.D. / This study comprises the preparation and characterization of new carbene complexes of iron, molybdenum, gold, copper and silver from azolyl and thienyl precursors. In addition, the syntheses of aminoacyl chelate and metallacyclic iron compounds as well as unique 6-membered dimeric and 18-membered trimeric thienyl gold compounds are reported. Furthermore, di(vinyl)carbene complexes, which are not yet known for gold and which are very rare for most other metals, are also described. In contrast to most other carbene complexes that result from precursors in which the heteroatom is situated a or y to the coordinated carbon atom, the new amino(organo)-, organo(thio)- and di(organo) carbene complexes are unique in that they have been prepared from azolyl or thienyl precursors in which the nucleophilic heteroatom is located outside the coordinated ring system and is separated from the coordinated carbon by several bonds. The complex [CpFe(CO)2C1] reacts with lithiated pyrazole, (thienyl)oxazoline or (thienyl)pyridine to form precursor pyrazolyl and thienyl iron(II) compounds which upon alkylation or protonation with CF3SO3Me or CF3SO3H afford amino(organo)-, organo(thio)- or heterometallacyclic alkoxy(amino)- and hydroxy(amino)carbene complexes as well as compounds which show pyridinium character. The heterometallacyclic complexes incorporate unusual ferropyridine or ferropyrole rings. ' 3C-{'}I} NAIR data of the above compounds show that the coordinated carbons of the azolyl and thienyl ligands are significantly affected upon carbene formation, although an X-ray crystallographic investigation indicates that carbene formation has little if any effect on bond distances in the azolyl ligand when it becomes a coordinated azolinylidene. The molecular structures of the pyrazolyl complex [CpFe(C0) 2{C=CHCH=NNPh}], the pyrazolinylidene complex [CPFe(C0) 2{CCHHNHI4P11}1[CF3S03], the 2-(2'-oxazolinyl)thien- 5-ylidene complex [CpFe(C0)2{CCHHC(1\1HCMe2CH26)}1[CF3S03] and the heterometallacyclic complex [CpFe(C0){CC(=&CMe 2CH2(5)SCH---9-1)] indicate small variations in iron-carbon distances of 1.981(2), 1.969(5), 1.99(1) and 1.959(7) A. Four equivalents of 2-(4',5'-dihydro-4',4'-dimethy1-2'-oxazolinyl)thien-3-yllithium reacts with the acetate [Mo2(O2CMe)4] to form the stable, neutral, quadruply bonded dimolybdenum complex [Mo2{C=C(6=NCMe2CH26)SCH2CH2} 2(02CMe)2], while 4-methylthiazoly1 lithium reacts with the same acetate to form the unstable, thiazolyl molybdate [Mo 2{6=NCMe—Cfg} 8]4". Reaction of [AuCI(tht)] (tetrahydrothiophene) with 2-(4',5'-dihydro-4',4'-dimethy1-2'-oxazoliny1)- thien-3-yllithium or 2-(4',5'-dihydro-4',4'-dimethy1-2'-oxazolinyl)thien-5-yllithium afforded dimeric and trimeric thienyl oligomers of gold(I). The molecular structure of the six-membered dimeric compound [Au{C=C(=NCMe 2CH2O)SCH=CH}li shows a Au...Au separation of 2.8450(6)A, while such interactions are absent in the trimeric compound [Au{C=C(C=NCMe2CH2O)SCH=CH}] 3 . Protonation of the former compound as well as the stable monomers obtained from [Au(tht)C 6F5] or [Au(Cl)PPh 3J afforded unique di(vinyl)carbene as well as imine complexes. Reaction of 2-(2'-pyridyl)thien-5-yllithium with [Au(COPPh 3] and subsequent alkylation yields an organo(thio)carbene compound. Finally, a series of cationic copper(I) bis(carbene) complexes were formed upon sequential treatment of copper(I) trifluoromethanesulfonate with thiazolyl- or pyrazolyllithium and CF3SO3Me. A similar reaction with 4-methylthiazol-2-yllithium and silver triflate produced the first amino(thio)carbene complex of silver.

The present study involves the use of main group organometallics: organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are well stabilized by the π‐donor substituents such as alkoxy and amino groups and low oxidation state metals such as Group 6 (Chromium, Molybdenum or Tungsten). Carbenes are an important intermediate in the synthesis of a range of compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and successful characterisation of three α‐alkoxystannanes was achieved via nucleophilic addition of tributylstannyllithium to the respective aldehydes, followed by an immediate MOM protection of the resulting alcohol. Six α‐aminostanannes were synthesised, consisting of N‐BOC, N‐acetyl and N‐ethyl derivatives of pyrrolidine and piperidine, via α‐lithiation and subsequent tinlithium transmetallation in the presence of TMEDA. The ¹³C NMR analysis highlighted an interesting phenomenon of tin‐carbon coupling that revealed unique structural information of both types of stannanes. DFT analysis was completed on the series of stannanes; a predicted frequency analysis was obtained which complemented the experimental Infra‐red data in elucidation of the compounds. The α‐alkoxy and α‐aminostannanes provided stable precursors to the organolithiums required for the synthesis of the novel Fischer chromium carbenes. The organolithiums were obtained via tinlithium exchange at low temperatures, followed by the addition of chromium hexacarbonyl to form the acylpentacarbonyl‐chromate salt. Alkylation of this intermediate using a Meerwein salt, Me₃OBF₄, gave rise to the novel Fischer chromium carbene complexes. Fischer chromium carbenes derived from the two isomeric butyl and isobutyl stannanes and the two N‐ethyl α‐aminostannanes were successfully synthesised. The difficulty encountered in the purification of the Fischer carbene complexes hindered the full characterisation, due to the presence of a by‐product, tetrabutyltin.

No description available.

Feeds often contain molybdenum (Mo) and sulfur (S) in excess of recommended allowances for adequate copper (Cu) absorption by ruminant livestock. Two randomized-block experiments were conducted using lambs given a cereal-based diet (90% of dry matter (DM) intake), containing 8 mg Cu, 0.7 mg Mo and 2.1g S per kg DM, that was either unsupplemented or supplemented with ammonium molybdate or sodium sulfate alone or in combination, to determine the effects of Mo, S and Mo+S on growth, hematology, serum Cu and Mo concentrations and reproductive function. Short term intake (4 weeks) by rams, aged 18 and 20 weeks, of 26 mg Mo alone or in combination with 2g S per kg DM, had no effect on growth, hematology or the concentration of total Cu in serum (TCu). However, supplemented groups had lower (P<0.05) concentrations of serum Cu soluble in trichloroacetic acid (TCA-Cu), but the group given Mo+S had the highest (P<0.05) concentration of serum residual Cu (RCu). Luteinizing hormone (LH) peak amplitude was affected by age*diet interaction (P<0.05), because of high amplitude LH peaks in the serum of lambs, aged 24 wks, given Mo alone. Testosterone serum secretory profiles did not differ among diet groups, but testosterone peak frequency was higher (P<0.05) for older ram lambs. Long term intake (32-39 wks) by ewe, ram and wether lambs (gonadal influence) of 12 mg Mo, or 2g S alone or combined per kg DM also had no effect on hematology or TCu. Food intake and liver weights were higher (P<0.05), but TCA-Cu was lower (P<0.05) for groups given S. Serum concentrations of total Mo (TMo) were higher (P<0.05) for Mo-supplemented groups, but RCu was highest only for the Mo+S group. Growth was affected by Mo*S*gonadal influence*time interaction (P<0.05); until autumn, the body weight of Mo-supplemented groups were higher than those of ram and wether lambs given Mo+S. Ovarian or testicular functions were delayed more severely for Mo- than Mo+S-supplemented groups. Mean concentrations of LH were affected by Mo*S*gonadal influence*time interaction (P<0.05); the mean LH values of Mo-supplemented ram and ewe lambs were higher than the Mo+S-supplemented group, whereas a reverse trend was observed for wether lambs. The amplitude of LH peaks was affected by Mo*S*gonadal influence*time interaction (P<0.05); for ram lambs, LH peak amplitude was higher for Mo than Mo+S-supplemented groups, whereas for wether and ewe lambs the reverse trend was noted. Mean concentrations of serum Cortisol and Cortisol peak amplitude were affected by Mo*S interaction (P<0.05); the mean Cortisol concentration and peak amplitude for the Mo-supplemented group were higher than those for the Mo+S-supplemented group. The frequency of LH and Cortisol peaks did not differ (P>0.10) among diet groups. In conclusion, Mo supplementation of cereal-based diets containing a high concentration of Cu did not adversely affect lamb growth. However, the effect of high dietary Mo on reproductive function appears to depend on the dietary level of S and the induction of high serum RCu (thiomolybdate). Further investigations on the effects of Mo and thiomolybdate on endocrine function may provide a nutritional basis for improving reproductive efficiency in ruminants. / Land and Food Systems, Faculty of / Graduate

In recent years our understanding of the genesis of porphyry copper systems has advanced to a sufficient level to be able to construct predictive models that enhance exploration for these deposits. Our understanding of primary and secondary geochemical dispersion around these deposits is not so advanced as variables such as climate and topography cause geochemical patterns to be distorted or masked at surface with the result of different deposits having quite different geochemical characteristics. In this study the geology and geochemistry of a porphyry copper-molybdenum from the Canadian Cordillera is examined with the aim of demonstrating how primary geochemical patterns are affected by the development of a supergene enrichment blanket and leached capping. Topographic controls on the extent of leaching and supergene enrichment are also explored. The Berg porphyry copper-molybdenum deposit is in the Tahtsa Mountain Ranges, approximately 84 km southwest of Houston, central British Columbia. Mineralized zones are centered on a circa 50 Ma composite quartz monzonite stock. Hydrothermal alteration zones are similar to those of the classic model by Lowell and Guilbert. Central zones are potassic (orthoclase and biotite) while peripheral zones are propylitic (chlorite, epidote, carbonate). Intense phyllic alteration (quartz, sericite, pyrite) occurs at the north and south margins of the stock. Hypogene mineralization (characterized by pyrite, chalcopyrite and molybdenite) is concentrated in an annular zone straddling the quartz monzonite contact. Best grades are localized in altered quartz diorite and altered and hornfelsed Telkwa Formation (Hazelton Group) volcanic rocks at the east side of the deposit. The nature of these altered hornfelsed rocks has been a subject for much debate in previous studies. One school of thought suggests that they are part of a hornfels aureole associated with the quartz diorite. Others suggest that it is an alteration zone associated with the quartz monzonite stock. Thirteen diamond drill holes on a north south cross section of the deposit were logged (GEOLOG) and sampled. Outcrop samples were collected where possible close to each drill hole. Major elements were determined by XRF, trace metals by flame AAS and fluorine by specific ion electrode. A sequential extraction was used to study the distribution of copper between different host minerals. The origin of the hornfelsed rocks is solved by field mapping and geochemistry. In the field cross cutting relationships show that the quartz diorite predates the stock and that the hornfels zone is spacially related to it. Major element binary and ternary plots demonstrate that significant amounts of potassium have been added to these rocks in the mineralized zone. This implies that biotite alteration was superimposed onto an earlier hornfels. Trace metal data was partitioned into anomalous and background populations with probability graphs. In the hypogene zone Cu, Mo and Ag occur in an annular zone corresponding with the mineralogically defined potential ore zones. Fluorine is anomalous over the area of the potassic alteration zone. Lead and zinc are anomalous in peripheral haloes around the potential orebodies. These zones can be traced to surface through an extensive supergene enrichment blanket and leached capping. Three zones of supergene mineralization are recognized: supergene sulphide (covellite, digenite, chalcocite), supergene oxide (malachite/azurite, cuprite, tenorite, native Cu) and leached capping. Sulphides are the dominant host for Cu throughout most of the deposit but locally on steep slopes where supergene oxide is developed Cu is hosted in carbonate and oxide minerals. Enrichment or depletion of elements in the supergene is demonstrated with interelement ratios. Enrichment factors can be derived in two ways: a) by ratioing supergene values to hypogene values, or, b) by ratioing to a constant (e.g. TiO₂ ) for each zone and then ratioing this value between zones. Enrichment factors of <1 therefore imply depletion and >1, enrichment (1=hypogene grade). Results show that all elements (studied) are enriched in the supergene sulphide and oxide zones. In the leached cap Cu, Mn and Zn are depleted while Mo, Pb and Ag are significantly enriched. These elements are incorporated into immobile limonite mineral's (ferrimolybdite, jarosite, goethite etc.). / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

Orientadores: Paulo Roberto Mei , Amilton Sinatora / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-26T20:19:05Z (GMT). No. of bitstreams: 1 Fonseca_SolangeTamarada_D.pdf: 21576321 bytes, checksum: ed8a1cccc8774fff4540b331b49b44b8 (MD5) Previous issue date: 2015 / Resumo: Uma das maneiras de se reduzir os custos no transporte de cargas é aumentando a quantidade de carga transportada por vagão, isto eleva a tensão no eixo do vagão e, consequentemente, a roda deve possuir maior dureza sem perda da tenacidade para suportar o desgaste. Para atingir os níveis de dureza necessários estão sendo desenvolvidas rodas ferroviárias com aços microligados que são definidos como aços carbono-manganês contendo pequenos teores (menores que 0,5% em massa) de elementos de liga, que são fortes formadores de carbonetos como o nióbio (Nb), vanádio (V), molibdênio (Mo) e titânio. Em 2008, a MWL do Brasil iniciou o desenvolvimento de rodas ferroviárias fabricadas com aços microligados, e a partir de 2012, com a colaboração da EPUSP foi necessário o desenvolvimento de uma máquina de ensaio de desgaste tipo disco contra disco que atendesse as especificações da norma AAR (Association of American Railroads). Além disso, havia interesse em se conhecer o comportamento desses aços, sendo assim, seria necessário obter as curvas de resfriamento contínuo (CRC) dos mesmos. A análise destas mostrou que a adição dos elementos microligantes refinou o grão austenítico por formação de finos carbonetos de Nb e V, retardou a formação de ferrita e perlita, o que reduziu o espaçamento interlamelar da perlita; e elevou a temperabilidade dos aços. Entretanto, a adição de microligantes não alterou as temperaturas de início de formação de martensita, mas melhorou a temperabilidade. A formação de martensita não foi finalizada até a temperatura ambiente e todos os aços apresentaram austenita retida junto com a martensita. A análise de corpos de prova retirados das pistas de rolamento das rodas ferroviárias prontas para uso, com estrutura ferrítica-perlítica, revelou que o aço ao V apresentou os melhores resultados em todos os ensaios (tração na temperatura ambiente e 540 ºC, energia absorvida no ensaio Charpy e KIC) quando comparado ao aço sem microligantes ou com a adição de Nb+Mo. O melhor desempenho do aço ao V foi atribuído ao seu menor tamanho de grão austenítico e espaçamento interlamelar da perlita mais refinado. No ensaio de desgaste por deslizamento, a perda de massa foi maior no aço Nb. O primeiro protótipo construído da máquina de desgaste tipo disco contra disco forneceu resultados confiáveis até 250.000 ciclos, não atingindo o valor minímo especificado pela AAR. Entretanto a experiência adquirida foi essencial para projetar um novo protótipo que está em comissionamento / Abstract: One of the main strategies to reduce cost in load transportation is through the increase of the load transported a railroad car. This increase of tension in the wagons axes, require wheels with higher hardness but without loss of ductility and toughness. Thus, to achieve the required levels of hardness, the developments are now focusing on railway wheels composed by microalloyed steels that are defined as carbon-manganese steels containing a small amount (less than 0.5% by mass) of strong carbide-forming elements such as niobium (Nb), vanadium (V), molybdenum (Mo) and/or titanium. The MWL Brazil began in 2008, together with Unicamp, a research project on the development of railway wheel made of microalloyed steel and, later on 2012, EPUSP joined to the project reinforcing the importance of the project. During this work, project developed a disk-on-disk wear test machine that would attend the specifications of the standard AAR (Association of American Railroads). Besides, there was also an interest on further knowing the behavior of these steels, that is, it would be necessary to obtain the continuous cooling curves (CCC). In this work, the analysis of CCC showed that the addition of microalloying elements contributed in refining the austenitic grain size due to fine Nb and V carbides formation; delayed the formation of ferrite and pearlite, which reduced the interlamellar spacing of pearlite; and increased the hardenability of steels. However, the addition of microalloying did not change the starting martensite formation temperature, but increased the hardenability. It was also observed that the formation of martensite was not finished at room temperature and all studied steels presented retained austenite. The analysis of samples taken from the tread of railway wheels, with ferritic-pearlitic structure revealed that the vanadium steel showed the best results in all tests of strength (at room temperature and 540 °C), K1C and Charpy test if compared to steels without microalloying or with the addition of Nb+Mo. The superior performance vanadium steel was attributed to the smallest austenite grain size and the finest interlamellar spacing of the pearlite. In the wear test, the weight loss was greater in the niobium microalloyed steel. The developed prototype of the disk-on-disk wear test machine only provided reliable results up to 250,000 cycles; it not reached the minimum value specified by the AAR. However, the experience was essential to enhance a new prototype that is commissioning / Doutorado / Materiais e Processos de Fabricação / Doutora em Engenharia Mecânica

Orientador: Paulo Roberto Mei / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-28T12:29:26Z (GMT). No. of bitstreams: 1 Finamor_FelipePereira_M.pdf: 7096775 bytes, checksum: f9779c193bdb5089e6373c577ae23cc9 (MD5) Previous issue date: 2015 / Resumo: O aumento da razão da carga transportada por eixo tem sido fundamental para redução dos custos de transporte, porém é exigido cada vez mais das interações roda-trilho. Neste aspecto para se garantir a segurança dos bens transportados e o menor desgaste da roda é necessário o desenvolvimento de novos aços com maior dureza, porém sem redução de ductilidade. Uma das estratégias é se adicionar aos mesmos microadições (< 0,5 % em massa) de nióbio ou vanádio, os quais, em solução sólida na austenita atrasam sua decomposição em produtos difusionais, elevando a resistência mecânica dos aços. Neste trabalho foram avaliados dois aços com 0,7 %C microligados ou não ao nióbio-molidbênio e produzidos pela MWL Brasil para a fabricação de rodas ferroviárias, segundo a classe D da AAR (Association of American Railroads). Foram realizados ensaios dilatométricos para o levantamento das curvas de transformação isotérmica e o estudo das curvas de escoamento à quente dos aços microligados e não microligados através dos ensaios de compressão à quente de único passe. A adição dos microligantes provocaram atrasos na cinética de transformação austenita/perlita na ordem de 4 vezes e um pequeno aumento da dureza dos produtos de reação no aço microligado ao nióbio e molibdênio para as transformações isotérmicas avaliadas por dilatometria e aumentaram numa razão de 1,3 a 1,4 as tensões de pico e em 1,5 a 3 as deformações de pico para todas as faixas de temperatura e deformação analisadas para o aço microligado / Abstract: The increase in cargo transported by axis has been a critical factor in reducing transportation costs, requiring more and more of the wheel-rail interaction. In this aspect to ensure the safety of transported goods and the a reduction in the wear of the railwheel is necessary to develop new steels with higher hardness without loosing ductility. One strategy is to add small amounts of alloy elements (<0.5 wt%) of niobium or vanadium which in solid solution in austenite retards the diffusional decomposition and raise the mechanical strength of the steels. The object of this study was to evaluate two steels with 0.7 % C microalloyed or not with niobium-molybdenum, which were produced by MWL Brasil for the production of railway wheels, according to Class D of AAR (Association of American Railroads) standards. Dilatometric tests were carried out to evaluate the isothermal transformation of microalloyed or not steels, and the flow curves were evaluated through microalloyed steels or not in a single hot compression tests. The addition of microalloying elements have delayed the kinetics of austenite transformation to pearlite in the order of 4 times and slightly increase the hardness of the reaction products in niobium and molybdenum microalloyed steel for isothermal transformations evaluated by dilatometry and increased in a ratio of 1.3 to 1.4 the peak stresses and 1.5 to 3 the peak strain for all ranges of temperature and strain analyzed for the microalloyed steel / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>U ovom radu izvr&scaron;ena su ispitivanja deaktivacije katalizatora za hidrodesulfurizaciju (HDS), uz simulaciju starenja u laboratorijskim uslovima i paralelna ispitivanja katalizatora iz realnog industrijskog postrojenja. &Scaron;irok interval uslova u laboratorijskoj simulaciji (temperatura, vreme tretmana, oksidacione i inertne atmosfere) pružio je osnov za ocenu uticaja različitih parametara na brzinu starenja katalizatora i definisanje kritičnih uslova, posebno pri regeneraciji katalizatora. Ispitivanja dva tipa HDS katalizatora, NiO-MoO₃/y-Al₂O₃ i CoO- MoO₃/y-Al₂O₃ i binarnih modelnih sistema NiO/ Al₂O₃, uz primenu komplementamih metoda za ispitivanje stukture i teksture čvrstih poroznih materijala, omogućila su uvid u mehanizme starenja u ovim složenim katalitičkim sistemima. Utvrđeno je da je oksidaciona atmosfera, posebno vodena para, kritičan faktor u kinetici stukturnih i teksturalnih promena u katalitičkom sistemu. Segregacija aktivne faze, interakcija sa nosačem, sinterovanje i gubitak aktivne faze iz sistema simultani su procesi koji dovode do trajne deaktivacije katalizatora. Visina radne temperature i moguća lokalna pregrevanja u sloju katalizatora, podstaknuta promenama difuzionih karakteristika kataličkog zrna, ključni su za destrukciju aktivne faze katalizatora, uz segregaciju prekursora oksidne faze molibdena, čiji je uticaj izrazit u fazi regeneracije. Intermedijarno prisustvo tečne faze oksida molidena, koja obliva povr&scaron;inu nosača, uslovljavajući intenzivno sinterovanje i ubrzanu interakciju izmedju ostalih faza u sistemu, predstavlja osnovni mehanizam u starenju katalizatora za HDS.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>Deactivation studies of hydrodesulphurization catalysts were performed, based on both aging simulation in laboratory conditions and investigation of catalysts from an industrial HDS plant. Broad interval of conditions applied in laboratory simulation (temperature, treatment duration, oxidation and inert atmospheres) was the basis for evaluating the effect of different parameters on catalyst aging kinetics and defining critical conditions, with emphasis on regeneration procedure. The investigations of two catalyst types, NiO-MoO3/y-Al2O3 and C0O-MoO3/y-Al2O3, and NiO/Al2O3 binary model systems, using complementary methods for structural and textural investigations of porous solid systems, enabled the insight in aging mechanisms of these complex catalytic systems. The oxidation atmosphere, especially water vapor, is critical for the rate of structural and textural changes in the catalysts. Segregation in active phase, interaction with the support, sintering and loss of active component from the catalyst are the simultaneous processes bringing about the irreversible deactivation of the catalyst. The temperature gradient in working conditions and possible formation of hot spots in catalyst reactor bed, affected also by changes of diffusion characteristics of catalyst grain, are crucial factors for segregation of molybdenum oxide precursor, which effect is pronounced during regeneration. The mechanism of HDS catalyst aging is based on intermediary presence of moIybdenum oxide liquid phase on the support surface, facilitating intensive sintering and interactions of other phases of catalytic system.</p>

Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of Cr.