| 1. |
- Gowda, Vasantha, 1986-
(författare)
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Experimental and Computational Magnetic Resonance Studies of Selected Rare Earth and Bismuth Complexes
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The rare-earth elements (REEs) and bismuth, being classified as the ‘most critical raw materials’ (European Raw Materials Initiatives, 2017), have a high economic importance to the EU combined with a high relative supply risk. REEs are highly important for the evolving technologies such as clean-energy applications, high-technology components, rechargeable batteries, permanent magnets, electric and hybrid vehicles, and phosphors monitors.This scientific research work aims at building a fundamental knowledge base concerning the electronic/molecular structure and properties of rare-earth element (REE) and bismuth complexes with dithiocarbamate (DTC) and 1,10-phenanthroline (PHEN) by employing state-of-the-art experimental techniques such as nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction (XRD) techniques together with ab initioquantum mechanical computational methods. This combination of methods has played a vital role in analysing the direct and significant effect of the heavy metal ions on the structural and magnetic resonance properties of the complexes, thereby, providing a framework of structure elucidation. This is of special importance for REEs, which are known to exhibit similar chemical and physical properties. The objectives of the work involve i) a systematic investigation of series of REE(III) as well as bismuth(III) complexes to get a profound understanding of the structure-properties relationship and ii) to find an appropriate theoretical modelling and NMR calculation methods, especially, for heavy metal systems in molecular and/or solid-state. This information can later be used in surface interaction studies of REE/bismuth minerals with DTC as well as in design and development of novel ligands for extraction/separation of metal ions.The REE(III) and bismuth(III) complexes with DTC and PHEN ligands have all provided aunique NMR fingerprint of the metal centre both in liquid and solid phase. The solid-state 13C and 15NNMR spectra of the diamagnetic REE(III) and bismuth(III) complexes were in accord with their structural data obtained by single crystal XRD. The density functional theory (DFT) methods were used to get complementary and refined structural and NMR parameters information for all diamagnetic complexes in the solid-state. The relativistic contributions due to scalar and spin-orbit correlations for the calculated 1H/13C/15N chemical shifts of REE complexes were analysed using two-component zeroth-order regular approximation (ZORA)/DFT while the ‘crystal-lattice’ effects on the NMR parameters were calculated by combining DFT calculations on molecular and periodic solid-state models. The paramagnetic REE complexes display huge differences in their 1H and 13C NMR spectral patterns. The experimental paramagnetic NMR (pNMR) chemical shifts, as well as the sizable difference of the 1H and 13C NMR shifts for these isoelectronic complexes, are well reproduced by the advanced calculations using ab initio/DFT approach. The accuracy of this approach is very promising for further applications to demanding pNMR problems involving paramagnetic f-block elements.The results presented in this thesis demonstrate that a multidisciplinary approach of combined experimental NMR and XRD techniques along with computational modelling and property calculations is highly efficient in studying molecular complexes and solids containing heavy metal systems, such as rare-earths and bismuth.
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| 2. |
- Kopezhanova, Aigerim
(författare)
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Summability of Fourier transforms of functions from Lorentz spaces
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This PhD thesis is devoted to the study of relations between integrability properties of functions and summability properties of its Fourier coefficients and transforms. The relations are given in terms of generalized weighted Lorentz norms, where the weights have some additional growth properties. The thesis contains six papers (papers A-F) together with an introduction, which put these papers into a general frame.In paper A some relations between weighted Lorentz norms and some corresponding sums of Fourier coefficients are studied for the case with a general orthonormal bounded system. Under certain circumstances even two-sided estimates are obtained.In paper B we study relations between summability of Fourier coefficients and integrability of the corresponding functions for generalized weighted Lorentz spaces in the case of a regular system. Some new inequalities of Hardy-Littlewood-Paley type with respect to a regular system for these generalized Lorentz spaces are obtained. It is also proved that the obtained results are in a sense sharp.In paper C we investigate integrability properties of the orthogonal series with coefficients from generalized weighted Lorentz spaces in the case of a regular system. The upper and the lower estimates of some corresponding Lorentz type norms of the Fourier coefficients are obtained.In paper D some new Boas type theorems for generalized weighted Lorentz spaces with respect to regular systems for generalized monotone functions are proved.In paper E inequalities for the Fourier transform of functions from the generalized weighted Lorentz spaces are studied. The upper and the lower estimates of the norm of the Fourier transform in generalized weighted Lorentz spaces are derived.Finally, in paper F a new inequality concerning the Fourier transform is derived. Moreover, it is described conditions so that this result is sharp in the sense that both upper and lower bounds are obtained.
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| 3. |
- Aguilar-Mamani, Wilson, 1981-
(författare)
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Crystallization of NBA-ZSM-5 from kaolin
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- ZSM-5 is an aluminosilicate zeolite with high Si/Al ratio with suitable properties for catalysis, ion exchange, adsorption and membrane applications. The main goal of this thesis was to study the growth of ZSM-5 zeolite crystals from inexpensive natural sources of silica and alumina, as well as n-butylamine (NBA) as a low-cost structure directing agent.The first objective of this work was to develop pathways to synthesize ZSM-5 crystals from kaolin clay or diatomaceous earth, two inexpensive natural sources of silica and alumina (Paper I). In the case of kaolin, a heat treatment was used in order to form amorphous metakaolinite. Subsequently, dealumination of the raw materials by acid leaching made it possible to reach appropriate Si/Al ratios and to reduce the amount of impurities. Finally, leached metakaolinite or diatomaceous earth was reacted with sodium hydroxide and NBA. After synthesis optimization, both sources of aluminosilicates were found to behave differently during the course of synthesis and to lead to slightly different reaction products. The final products exhibited Si/Al ratios in the range 10-20. The use of leached diatomaceous earth allowed to reach higher yield of ZSM-5 crystals within comparable synthesis times. However, low amounts of mordenite were inevitably formed as a by-product, which was related to the high calcium content of diatomaceous earth. Therefore, the rest of the thesis focused on the kaolin system.In order to study the growth mechanism of ZSM-5 from leached metakaolinite, a proper methodology to gain local compositional data by energy dispersive spectroscopy (EDS) on aluminosilicates was developed (Paper II). Zeolite A was used as a model system that could be ion-exchanged with various elements. In order to evaluate the reliability of the measurements, inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) and EDS were compared. The EDS method developed in this work resulted in molar ratios very close to theoretical values and was therefore found more reliable than ICP-SFMS. Therefore, the method developed for zeolite A was applied in the rest of the thesis work to study the formation and growth of ZSM-5 crystals.The second part of this work focused on the kaolin system in order to understand the nucleation and growth processes of the ZSM-5 crystals. This system was heterogeneous, due to the formation of a gel upon heating of the synthesis mixture. First, the internal structure of the gel was investigated (Paper III). Second, a kinetic study was performed and compared with microstructural observations (Paper IV). Finally, the mechanisms leading to Al-zoning and dendritical growth of the zeolite crystals were investigated (Paper V). The characterization of the intermediate phases during the different stages of the hydrothermal synthesis were analyzed by different analytical techniques, such as inductively coupled plasma-sector field mass spectrometry (ICP-SFMS), dynamic light scattering (DLS), extreme high resolution-scanning electron microscopy (XHR-SEM), energy dispersive spectroscopy (EDS), high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) and nitrogen gas adsorption.These investigations led to several important conclusions: 1) The walls of the gel were shown for the first time to be inhomogeneous and to possess a biphasic internal structure consisting of a mesoporous skeleton of aluminosilicate nanoparticles embedded in a silicate-rich soluble matrix of soft matter. 2) The kinetic study and microstructural evidences indicated that the early crystals were fully embedded inside the gel phase and that crystal growth was retarded, as the formation of the gel occurred simultaneously with the early growth of the crystals. Hence, nucleation and growth appeared to be solution mediated. 3) Finally, the Al zoning of the crystals was related to the biphasic internal structure of the gel, since the silicate-rich matrix was preferentially consumed first. 4) The dendrites present at the surface of the crystals during most of the growth process were shown to be caused by the presence of a web of nanoparticles, most likely originating from the mesoporous skeleton inside the gel.In the future, these findings are expected to lead to optimized synthesis pathways of catalysts with homogeneous properties and to contribute to the development of poor regions in Bolivia.
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| 4. |
- Engström, Maria, 1974-
(författare)
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Secondary currents in groundwater
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The thesis concerns the small vertical water movements created by thermal convection and the Coriolis force acting on groundwater flows. These small flows are of importance to vertical transports of temperature, nutrients and contaminants that would not be spread in the way they are. The first part analyzes thermally driven, seasonal groundwater convection by numerical simulation. The second part shows that the Coriolis force also induces secondary currents in groundwater flow through different vertical permeability distributions. Density driven convection occurs during the autumn in southern Sweden when the ambient air temperature cools the mean groundwater temperature from about 10ºC. When the shallow groundwater is cooled by the ambient air its increased density makes this water sink, slowly increasing in temperature, while pressing the warmer water upwards creating a convection cell. The process is ongoing as long as there is a thermal gradient between ground surface and the groundwater. Under favorable conditions convection can reach a depth of 6m. Such density-driven water movements occur most easily in more permeable soil. In northern Sweden, the situation is reversed, since the mean groundwater temperature is below 4ºC, at which water is at its density maximum. So, in springtime when the uppermost groundwater is heated to 4ºC by the warmer air the convection process starts. Here, the sinking groundwater does not reach the same depth, less than one meter. The Coriolis force has been considered too small to have any effect on groundwater flow, though its importance in meteorology and oceanography is well established. These theories have been applied using numerical simulations of groundwater flow. The numerical model has been validated by simulating some earlier studies of Coriolis forces in fluids. Furthermore the model has been extended to include porous media. It has been shown that secondary currents occur in nonlinear vertical permeability distributions. For simulations of constant and linear distributions no secondary currents have been seen. The development is more pronounced in confined aquifers. The structure of the bottom of the aquifer affects how the secondary currents arise. It was shown that both temperature gradients and the Coriolis force form secondary currents in groundwater and a general conclusion is that groundwater flow is more complex than previously assumed.
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