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- Aas, Wenche
(författare)
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Constitution, dynamics and structure of binary and ternary actinide complexes
- 1999
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Stoichiometry, ligand exchange reactions, coordinationgeometry and stability of complexes of type UO2LpFq(H2O)3-n(p= 1–2,q= 1-3), where L is one of the bidentate ligandspicolinate, oxalate, carbonate or acetate have beeninvestigated using single crystal X-ray diffraction, an arrayof19F-,13C-,17O- and1H-NMR techniques and potentiometric titration usingboth F-and H+selective electrodes. The experiments wereperformed in a 1.00 M NaClO4medium. The equilibrium constants were determinedat 25°C while most of the kinetic experiments were done at- 5°C. The equilibrium constants for the stepwise additionof F-to UO2L and UO2L2indicates that the prior coordination of L toU(VI) has a fairly small effect on the subsequent bonding offluoride, except for a statistical effect determined by thenumber of available coordination sites. This indicates thatternary complexes might be important for the speciation andtransport of hexavalent actinides in ground and surface watersystems. A single crystal structure of UO2(picolinate)F32-has been determined showing the same pentagonalbipyramidal symmetry as in aqueous solution studied by NMR. Theexchangeable donor atoms are situated in a plane perpendicularto the linear uranyl group. The complexes show a variety ofdifferent exchange reactions depending on the ligand used. Ithas been possible to quantify external fluoride and the otherligands exchange reactions as well asintra-molecular reactions. This type of detailedinformation has not been observed in aqueous solution before.Water takes a critical part in the exchange mechanism, and whenit is eliminated from the inner coordination sphere a muchslower kinetics can be observed.19F-NMR has showed to be a powerful technique tostudy these reactions, both because of the sensitivity of thisNMR nucleus and also the possibility to observe reactions wherefluoride is not directly involved in the mechanism. TernaryTh(edta)F1-2and (UO2)2(edta)2F1-4have been investigated using1H and19F-NMR. The fluoride complexation to Cm(III) wasstudied using time resolved fluorescence spectroscopy (TRLFS)and the stability constant for the CmF2+complex was determined at 25°C in 1.0 mNaCl.Keywords. Ternary complexes, actinides,dioxouranium(VI), curium(III), thorium(IV), ligand exchange,isomers, NMR, potentiometric titrations, aqueous solution,oxalate, picolinate, acetate, EDTA.
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- Aas, Wenche, et al.
(författare)
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Equilibria and dynamics in binary and ternary uranyl oxalate and acetate/fluoride complexes
- 1999
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Ingår i: Journal of the Chemical Society - Dalton Transactions. - : Royal Society of Chemistry (RSC). - 0300-9246 .- 1364-5447. ; :8, s. 1311-1317
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Tidskriftsartikel (refereegranskat)abstract
- The formation of ternary UO2(ac)pFq2-p-q (p = 1 or 2 and q = 1-3) complexes, and their equilibrium constants were investigated by potentiometric titrations and 19F NMR spectroscopy. The equilibrium constants have been determined from the emf data in a NaClO4 medium at constant sodium concentration, [Na+] = 1.00 M at 25°C, except for the UO2(ac)F32- complex where 19F NMR at -5°C was used. The magnitude of the equilibrium constant for the stepwise addition of fluoride indicates that prior co-ordination of acetate has only a small effect on the subsequent bonding of fluoride. The acetate exchange in the ternary UO2(ac)F32- complex was studied using 19F NMR. Through magnetisation transfer experiments, it was possible to confirm the provisional mechanism from a previous study and also the consistency of the rate constants for the five different exchange pathways required to describe the fluoride exchange. The exchange takes place via the intermediate UO2F3(H2O)2-, indicating that the acetate exchange follows an interchange mechanism with solvent participation in the transition state. The rates and mechanisms of the ligand exchange reactions in UO2(ox)2(H2O)2- and UO2(ac)2(H2O) have been studied using 13C NMR techniques at -5°C. The rate law is v = k-[complex][ligand], and the second order rate constant and the activation parameters for both systems have been determined. The reactions most likely take place through an Eigen-Wilkins type of mechanism, where the first step is a pre-equilibrium of an outer-sphere complex followed by a rate determining exchange of water. The rate constants for the water exchange reactions are very similar to that in UO2(H2O)52+. The information from the binary oxalate system rules out the formation of UO2(ox)2(H2O)2- as an intermediate in the exchange reactions in the previously studied UO2(ox)2F3-, also in this case confirming a previously suggested exchange mechanism. The H+/D+ isotope effects and a linear free energy relationship suggest that the main catalytic effect of H+ on ligand exchange rates is due to the formation of a protonated precursor. Hence, the catalytic effect depends on the basicity of the ligand and the site for the proton attack.
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- Aastrup, Teodor
(författare)
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In situ investigations of the metal/atmophere interface
- 1999
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presents a new experimental setup for surfaceanalysis studies, incorporating chemical information frominfrared reflection absorption spectroscopy (IRAS) andquantitative information from quartz crystal microbalance(QCM). The integrated IRAS/QCM surface analysis system enablesin situstudies to be conducted of the metal/atmosphereinteraction on a sub-monolayer level. In combination withtopographical information from tapping mode atomic forcemicroscopy (TM-AFM), it was possible to follow the formation ofcorrosion products providing information about chemicalidentity, quantity and lateral distribution. The newlydeveloped system was used to study the influence of relativehumidity (RH) and levels of sulfur dioxide (SO2), ozone (O3)and nitrogen dioxide (NO2) down to concentrations of subparts-per-million (ppm), on the initial stages of atmosphericcorrosion of copper.Exposure to RH led to the formation of small grains ofcuprous oxide (Cu2O), with an average diameter of approximately40 nm. The grain nucleation rate increased with increasing RHdue to the increasing amount of physisorbed water on thesurface.Exposure to RH and SO2 led to the formation of coppersulfite (CuSO3•xH2O) species as well as reduction in therate of Cu2O formation. The formation of CuSO3•xH2Ooccurred through the dissolution and consecutive precipitationof surface-bound copper sulfite complexes.The roles of O3 and NO2 in the SO2-induced atmosphericcorrosion of copper was also investigated. O3 was found to havea two-fold effect, resulting in the oxidation of the coppersulfite species to copper sulfate and the enhancement of Cu2Oformation. NO2 promoted the oxidation of copper sulfitespecies, though less efficiently than O3, and reduced Cu2Oformation. In addition, copper nitrate formation wasobserved.IRAS was also used to investigate the interaction betweenSO2 and surfaces made of platinum and palladium. Sulfuric acidformation was observed on both metals, showing the importanceof the surface on the formation of the metal/atmospherereaction products.Keywords:Atmospheric corrosion, IR-spectroscopy, IRAS,QCM, AFM, SO2, O3, NO2, Cu.
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- Aberg, B, et al.
(författare)
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Delayed left ventricular free wall rupture complicating coronary artery bypass surgery. A case report.
- 1985
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Ingår i: Scandinavian journal of thoracic and cardiovascular surgery. - : Informa UK Limited. - 0036-5580. ; 19:3, s. 273-7
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Tidskriftsartikel (refereegranskat)abstract
- Rupture of the left ventricular free wall is a not uncommon life-threatening complication of acute myocardial infarction and after prosthetic mitral valve replacement. To our knowledge, no case of left ventricular rupture after coronary artery bypass surgery has been reported. A case is now described in which coronary artery bypass grafting was complicated by delayed rupture, which was successfully repaired. Different etiologic factors are discussed, but the cause considered most likely was trauma from elevation of and traction on the heart in exposure of its posterior aspect.
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- Aberg, D, et al.
(författare)
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Ultra-shallow thermal donor formation in oxygen-containing ambient
- 1998
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Ingår i: Physica status solidi. B, Basic research. - 0370-1972 .- 1521-3951. ; 210, s. 527-532
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Tidskriftsartikel (refereegranskat)abstract
- Czochralski-grown phosphorus-doped (approximate to 2 x 10(14) cm(-3)) silicon wafers have been annealed in nitrogen, wet nitrogen, argon, oxygen, and vacuum ambients at 470 degrees C for times up to 500 h. Sample characterization was made with capacitance-voltage, four-point probe, DLTS, thermally stimulated capacitance, admittance spectroscopy, secondary ion-mass spectrometry, and Fourier transform infrared spectroscopy. This study finds a strong relation between the previously reported ultra-shallow thermal donors (USTDs) and shallow thermal donors (STDs), and it is shown that the net concentration of thermally formed donors is independent on annealing ambient within the experimental accuracy. It was found that the majority of formed donors for long anneals consisted of either STDs or USTDs, however, it was found that oxygen-containing ambient is indispensable for forming USTDs.
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| 10. |
- Aberg, D, et al.
(författare)
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Ultrashallow thermal donor formation in silicon by annealing in ambient oxygen
- 1999
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Ingår i: Journal of Applied Physics. - 0021-8979 .- 1089-7550. ; 85, s. 8054-8059
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Tidskriftsartikel (refereegranskat)abstract
- Czochralski-grown silicon wafers doped with phosphorus (similar to 10(14) cm(-3)) have been annealed in nitrogen, wet nitrogen, oxygen, argon, and vacuum ambients at 470 degrees C for times up to 500 h. Sample characterization was made using predominantly electrical techniques such as admittance spectroscopy and thermally stimulated capacitance measurements but also secondary ion mass spectrometry (SIMS) and Fourier transform infrared spectroscopy were employed. In all samples, an increasing concentration of free carrier electrons is observed with increasing annealing time, reaching a maximum of similar to 10(16) cm(-3) at 100 h. For durations in excess of 100 h gradual decrease of the free electron concentration takes place except for the samples treated in wet nitrogen and oxygen atmospheres, which display donors stable even after 200 h. These stable centers are found to have shallower donor level positions in the energy band gap (similar to 25 meV below the conduction band edge E-c) than those of the centers formed in vacuum, argon, and nitrogen atmospheres (similar to 35 meV below E-c). The latter centers are associated with the well-established shallow thermal donors (STDs) while the origin of the former ones, which are labeled ultrashallow thermal donors (USTDs) is less known. However, on the basis of a wealth of experimental results we show that the USTDs are most likely perturbated STDs modified through interaction with fast-in diffusing oxygen species, possibly oxygen dimers. Further, comparison between the electrical data and the SIMS measurements reveals unambiguously that neither the STD nor the USTD centers involve nitrogen, in contrast to recent suggestions in the literature. (C) 1999 American Institute of Physics. [S0021-8979(99)06512-3].
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