| 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. |
- Grenman, Tiia
(författare)
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Dusty Globules and Globulettes
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Interstellar gas and dust can condense into clouds of very different size, ranging from giant molecular cloud complexes to massive, isolated, dark cloudlets, called globules with a few solar masses.This thesis focuses on a new category of small globules, named globulettes.These have been found in the bright surroundings of H II regions of young, massive stellar clusters. The globulettes are much smaller and less massive than normal globules. The analysis is based on H-alpha images ofe.g., the Rosette Nebula and the Carina Nebula collected with the Nordic Optical Tele-scope and the Hubble Space Telescope.Most globulettes found in different H II regions have distinct contours and are well isolated from the surrounding molecular shell structures. Masses and densities were derived from the extinction of light through the globulettes and the measured shape of the objects. A majority of the globulettes have planetary masses,<13MJ (Jupiter masses). Very few objects have masses above 100MJ≈0.1M(Solar masses). Hence, there is no smooth overlap between globulettes and globules, which makes us conclude that globulettes represent a distinct, new class of objects.Globulettes might have been formed either by the fragmentation of larger filaments, or by the disintegration of large molecular clouds originally hosting compact and small cores. At a later stage, globulettes expand, disrupt or evaporate. However, preliminary calculations of their lifetimes show that some might survive for a relatively long time, in several cases even longer than their estimated contraction time.The tiny high density globulettes in the Carina Nebula indicate that they are in a more evolved state than those in the Rosette Nebula, and hence they may have survived for a longer time. It is possible that the globulettes could host low mass brown dwarfs or planets.Using the virial theorem on the Rosette Nebula globulettes and including only the thermal and gravitational potential energy indicated that the 133 found globulettes are all either expanding or disrupting. When the ram and the radiation pressure were included, we found that about half of our objectsare gravitationally bound or unstable to contraction and could collapse to form brown dwarfs or free floating planets.We also estimated the amount of globulettes and the number of free floating planetary mass objects, originating from globulettes, during the history of the Milky Way. We found that a conservative value of the number of globulettes formed is 5.7×1010. A less conservative estimate gave 2×1011globulettes andif 10% of these forms free floating planets then the globulettes have contributed about 0.2 free floating planets per star.In the Crab Nebula, which is a supernova remnant from the explosion of a massive old star, one can find dusty globules appearing as dark spots against the background nebulosity. These globules are very similar to the globulettes we have found in H II regions. The total mass of dust in globules was estimated to be 4.5×10−4M, which corresponds to.2% of the total dust content of the nebula. These globules move outward from the center with transversal velocities of 60–1600 km s−1. Using the extinction law for globules, we found that the dust grains are similar to the interstellar dust grains. This means that they contribute to the ISM dust population. We concluded that the majority of the globules are not located in bright filaments and we proposed that these globules may be products of cell-like blobs or granules in the atmosphere of the progenitor star. Theses blobs collapse and form globules during the passage of the blast wave during the explosion.
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| 3. |
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| 4. |
- Trublet, Mylene
(författare)
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Titanium(IV) Phosphates : The Next Generation of Wastewater Sorbents
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Treatment of industrial waters containing heavy metal ions is essential before being discharged into the environment. Consequently, European regulations have been established to control and limit the amount of heavy metals released. There is a need to develop efficient water treatment techniques that can remove contaminants with respect to these EU regulations.Ion-exchange is one of the processes that is being investigated due to fast kinetics, high treatment capacity and its ability to remove heavy metal ions present in trace amounts. Titanium phosphates (TiP) are a group of inorganic ion-exchangers that have demonstrated to be particularly selective towards transition metal ions in aqueous solutions. Two types of ion-exchange units are present in TiP material, which are –HPO4 and –H2PO4 groups. Their structural characteristic is highly dependent on the synthesis conditions, which include the source of titanium, temperature, reaction time and P2O5:TiO2 ratio. Most of the studies have been performed on amorphous TiP containing a mixture of both exchange units, with –HPO4 groups being predominant; as crystalline TiP and –H2PO4 based TiP are often obtained in difficult conditions, high temperature (up to 250 °C) and/or long reaction time (up to 30 days) and/or using autoclave. Despite promising properties depicted in batch conditions, very few data in continuous flow systems (fixed-bed columns) have been reported.In this work, amorphous TiP composed of entirely –H2PO4 ion-exchange units (TiP1) was synthesized at mild conditions using a TiOSO4 solution and HCl/deionized water as post-synthesis treatments. The sorbent was characterized using a range of techniques (solid-state 31P MAS NMR, Raman, XRD, TGA, BET, Elemental analysis, EXAFS and XANES,) and tested in batch and column set-ups towards single and multi-component waters. The chemical formula of TiP1 was established as TiO(OH)(H2PO4)·H2O and it was found that the synthesis of TiP1 was also dependent on the TiO2/H2SO4 content in the primary titanium solution.The material displayed a high maximum exchange capacity of ca. 6.4 meq.g-1, expressed as the sodium uptake. The actual ion-exchange capacity towards divalent metal ions was calculated to be ca. 3.4 meq.g-1 in batch condition and up to 4.1 meq.g-1 in fixed-bed column, which is to date the highest recorded for TiP materials. Kinetics of the exchange processes have been studied and the equilibrium was reached within 5-20 minutes. Modeling of the breakthrough curves was achieved using the Thomas model, indicating that the rate driving forces of the processes follow second-order reversible kinetics. The TiP1 sorbent has shown to maintain a high selectivity towards heavy metal ions in multi-component systems (including closed-mine waters) when column studies were performed. The sorption behavior of TiP1 in batch experiments correlates very well with data obtained in fixed-bed column conditions, confirming that prediction of the sorption behavior on the basis of batch data is conceivable.Another important aspect of this work also involves the mild syntheses of crystalline α-TiP, Ti(HPO4)·H2O, and LTP (Linked Titanium Phosphate) composed of α-TiP and TiP1, where the structural characteristics of these materials were investigated using solid-state NMR, XRD, TGA, EXAFS and XANES.
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| 5. |
- Brethes, Anaïs
(författare)
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An integrated study of geological, magnetic and electromagnetic data for mineral exploration in the Jameson Land Basin, central East Greenland
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The Jameson Land Basin, located in central East Greenland, initiated in Devonian time with the collapse of the over-thickened Caledonian Orogen. The basin developed during different phases of rifting from the late Paleozoic to the Mesozoic and has accumulated between 16-18 km of sediments. In Paleogene time, the basin was affected by intense magmatism due to the opening of the North Atlantic Ocean c. 55 Ma ago. Due to a significant uplift in Miocene time, the sedimentary sequence is well exposed along the basin margins, revealing numerous mineral occurrences hosted within almost the entire stratigraphic succession. The major types of mineralization comprise: (1) intrusion-related Mo (± Pb, Zn, Cu, Ag) mineralization associated with Paleogene intrusive complexes; (2) stratabound and/or stratiform Cu, Pb, Zn, (Ag) within Upper Permian and Triassic clastic and marine sedimentary formations; (3) stratabound and structurally controlled Pb-Zn, Cu, Ba, (Sr) mineralization in Upper Permian carbonates; and (4) structurally-controlled Pb, Zn, Cu (±Sb, Bi, Ag, Au) vein-type mineralization within Caledonian and Paleozoic rocks.It is well acknowledged that structures such as faults, thrusts, detachments, shear zones and associated fracture systems play an important role as fluid conduits connecting metal sources and sites of mineral precipitation. In particular, previous studies showed that mineral occurrences within the East Greenland Caledonides are closely related to lineaments and intrusions. In this context, the Crusmid-3D project was initiated in 2014, aiming at establishing the links between the crustal structures and the mineral occurrences in the Jameson Land Basin using a combination of geological and geophysical data. The interest for mineral exploration in the area led exploration companies and institutions to carry out magnetic and electromagnetic surveys, and the data derived from these constitute the base of this study.This thesis provides a detailed structural interpretation of aeromagnetic data in the Jameson Land Basin where several magnetic trends associated with Tertiary dikes and sills as well as with reactivated Paleozoic and Triassic faults were delineated. These data, in combination with a literature review and compilation of the mineral occurrences in the Jameson Land Basin, allowed highlighting seven prospective areas for structurally-controlled base metal mineralization.New structural data from geological fieldwork, drilling results and geophysical data (magnetic, electromagnetic and seismic data) along the eastern margin of the basin allowed a new interpretation of the geometry of the Triassic rift in East Greenland, represented by NE-SW-trending basins and highs segmented by NW-SE-trending transfer zones. It can be correlated with its European conjugate margin, displaying analogies with the Triassic Froan and Helgeland Basins in the Norwegian offshore and with the Papa and West Shetlands Basins north of the Shetland Islands.The proposed structural model of the Triassic rift was further investigated using 3D-geologically-constrained inversion of magnetic data in order to refine the architecture of the eastern margin of the Jameson Land Basin. Modelling results confirmed the presence of a shallow westward dipping peneplained crystalline basement in the southern part of the area while the northern part is characterized by faulted blocks, which accommodated relatively thick red bed sedimentary sequences, thereby representing a good potential source of base metals.Furthermore, Induced Polarization (IP) effects observed in airborne time-domain electromagnetic data acquired in the eastern margin of the basin were investigated using Self-Organizing Maps (SOM). The analysis of the shape and amplitude of the transient response curves using the SOM allowed identifying four areas where the transient curve patterns exhibit strong IP effects. These are shown to be collocated with Tertiary sills and dikes, clay-altered rocks as well as with a sulfide-bearing brecciated granite and with Triassic stratigraphic horizons hosting disseminated base metal sulfides.
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| 6. |
- Hedman, Daniel, 1989-
(författare)
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Single-Walled Carbon Nanotubes : A theoretical study of stability, growth and properties
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Since their discovery over 25 years ago, scientists have explored the remarkable properties of single-walled carbon nanotubes (SWCNTs) for use in high-tech materials and devices, such as strong light-weight composites, efficient electrical wires, supercapacitors and high-speed transistors. However, the mass production of such materials and devices is still limited by the capability of producing uniform high-quality SWCNTs. The properties of a SWCNT are determined by the orientation of the hexagonal grid of carbon atoms constituting the tube wall, this is known as the chirality of the SWCNT.Today's large-scale methods for producing SWCNTs, commonly known as growth, give products with a large spread of different chiralities. A mixture of chiralities give products with a mixture of different properties. This is one of the major obstacles preventing large-scale use of SWCNTs in future materials and devices. The goal is to achieve growth where the resulting product is uniform, meaning that all SWCNTs have the same chirality, a process termed chirality-specific growth. To achieve this requires a deep fundamental understanding of how SWCNTs grow, both from an experimental and a theoretical perspective.This work focuses on theoretical studies of SWCNTs and their growth mechanisms. With the goal of achieving a deeper understanding of how chirality arises during growth and how to control it. Thus, taking us ever closer to the ultimate goal of achieving chirality-specific growth. In this thesis, an introduction to the field is given and the current research questions are stated. Followed by chapters on carbon nanomaterials, SWCNTs and computational physics. A review of the state-of-the-art experimental and theoretical works relating to chirality specific growth is also given.The results presented in this thesis are obtained using first principle density functional theory calculations. Results show that the stability of short SWCNT-fragments can be linked to the products observed in experiments. In 84% of the investigate cases, the chirality of experimental products matches the chirality of the most stable SWCNT-fragments (within 0.2 eV). Further studies also reveal a previously unknown link between the stability of SWCNT-fragments and their length. Calculations show that at specific lengths the most stable chirality changes. Thus, introducing the concept of a switching length for SWCNT stabilities.This newly found property of SWCNTs is used in combination with previously published works to create a state-of-the-art analytical model to investigate growth of SWCNTs any temperature. Results from the model show that the most stable chirality obtained is dependent on the diameter, length of the SWCNT, the growth temperature and the composition of the catalyst. Finally, a detailed study on the ability of catalyst metals to sustain SWCNT growth points to Pt as an interesting candidate to achieve growth of rarely seen chiralities. The new knowledge gained from these results takes us even closer to achieving chirality-specific growth.
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| 7. |
- Karvonen, Niklas, 1979-
(författare)
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Unobtrusive Activity Recognition in Resource-Constrained Environments
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis discusses activity recognition from a perspective of unobtrusiveness, where devices are worn or placed in the environment without being stigmatising or in the way. The research focuses on performing unobtrusive activity recognition when computational and sensing resources are scarce. This includes investigating unobtrusive ways to gather data, as well as adapting data modelling and classification to small, resource-constrained, devices.The work presents different aspects of data collection and data modelling when only using unobtrusive sensing. This is achieved by considering how different sensor placements affects prediction performance and how activity models can be created when using a single sensor, or when using a number of simple binary sensors, to perform movement analysis, recognise everyday activities, and perform stress detection. The work also investigates how classification can be performed on resource-constrained devices, resulting in a novel computation-efficient classifier and an efficient hand-made classification model. The work finally sets unobtrusive activity recognition into real-life contexts where it can be used for interventions to reduce stress, sedentary behaviour and symptoms of dementia.The results indicate that activities can be recognised unobtrusively and that classification can be performed even on resource-constrained devices. This allows for monitoring a user’s activities over extensive periods, which could be used for creating highly personal digital interventions and in-time advice that help users make positive behaviour changes. Such digital health interventions based on unobtrusive activity recognition for resource-constrained environments are important for addressing societal challenges of today, such as sedentary behaviour, stress, obesity, and chronic diseases. The final conclusion is that unobtrusive activity recognition is a cornerstone necessary for bringing many digital health interventions into a wider use.
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| 8. |
- Schmidt, Mischa
(författare)
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EVOX-CPS : A Methodology For Data-Driven Optimization Of Building Operation
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Existing building stock’s energy efficiency must improve due to its significant proportion of the global energy consumption mix. Predictive building control promises to increase the efficiency of buildings during their operational phase and thus lead to a reduction of the lion’s share of buildings’ lifetime energy consumption. Predictive control complements other means to increase performance, such as refurbishments as well as modernization of systems.This thesis contributes EVOX-CPS, a holistic methodology to develop data-driven predictive control for (existing) buildings and deploy the control in day-to-day use. EVOX-CPS evolves buildings into Cyber-Physical Systems and addresses the development of data-driven predictive control using computational methods. The thesis’ focus rests on accounting for the situation of existing buildings - which vary greatly regarding their physical characteristics, usage patterns, system installation, and instrumentation levels. The methodology addresses the aspect of building stock variety with its capability to flexibly adapt to different buildings’ characteristics, e.g., by supporting the integration of varying levels of pre-existing building instrumentation. Furthermore, EVOX-CPS supports using different data mining, regression, or control techniques (i) to strengthen the support for a variety of buildings, and (ii) to cater to researchers’ and practitioners’ differing skills, experiences, or preferences concerning different data analysis techniques. Through its flexibility, the methodology addresses a vast potential installation base and lowers the barriers for adoption in day-to-day use, e.g., by being able to leverage prior investments in building instrumentation and supporting different data-analysis techniques. At the same time, EVOX-CPS provides researchers and practitioners with comprehensive guidance relevant to their daily work. Besides, EVOX-CPS supports addressing a building’s known limitations in the daily operation, e.g., uncomfortable indoor conditions.The experimentation in two real buildings validates the effectiveness of EVOX-CPS’ data-driven control with high reliability due to prolonged experimentation periods combined with applying energy normalization and inferential statistics. The experiments during routine heating system operation establish high confidence in the recorded effect sizes: the improvements in operational efficiency are profound and statistically significant. More specifically, the experiments of controlling the grass heating system of the soccer stadium Commerzbank Arena, Frankfurt, Germany, in two winters saved up to 66% (2014/2015) and 85% (2015/2016) of energy consumption. Extrapolation to an average heating season leads to expected savings of 775 MWh (148 t of CO2 emissions) and 1 GWh (197 t CO2), respectively. The experiments also show that EVOX-CPS allowed alleviating the known operational limitation of heating supply shortages which required nightly preheating in the stadium’s standard operating procedures. In another set of experiments, we applied the methodology to control the heating system of the Sierra Elvira School in Granada, Spain. The experimentation occurred during the regular class hours of 43 school days in winter 2015/2016. A first experiment demonstrated the possibility to lower consumption by one-third while maintaining indoor comfort. Another experiment raised average indoor temperatures by 2K with 5% additional energy consumption. Again, that illustrates EVOX-CPS’ capability to address a building’s known operational issues.
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| 9. |
- 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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| 10. |
- Ma, Charlie
(författare)
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Aspects of Ash Transformations in Pressurised Entrained-Flow Gasification of Woody Biomass : Pilot-scale studies
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Pressurised entrained-flow gasification (PEFG) of woody biomass has the potential to produce high purity syngas for the production of vital chemicals, e.g., biofuels. However, ash-related issues such as reactor blockages and refractory corrosion need to be addressed before this potential can be realised from a technical perspective. These undesirable consequences can be brought about by slag formation involving inorganic ash-forming elements and the chemical transformations that they undergo during fuel conversion. The objective of this study was to elucidate the ash transformations of the major ash-forming elements and the slag formation process. A pilot-scale PEFG reactor was used as the basis of the study, gasifying different woody biomass-based fuels including wood, bark, and a bark/peat mixture. Different ash fractions were collected and chemically analysed. Reactor slags had elemental distributions differing from that of the fuel ash, indicating the occurrence of fractionation of ash material during fuel conversion. Fly ash particles from a bark campaign were also heterogeneous with particles exhibiting differing compositions and physical properties; e.g., molten and crystalline formations. Si was consistently enriched in the reactor slags compared to other major ash-forming elements, while analyses of other ash fractions indicated that K was likely volatilised to a significant extent. In terms of slag behaviour, near-wall temperatures of approximately 1050-1200 °C inside the reactor were insufficient to form flowing ash slag for continuous extraction of ash material during firing the woody biomass fuels alone. However, fuel blending of a bark fuel with a silica-rich peat changed the chemical composition of the reactor slags and bulk slag flow behaviour was evident. Thermochemical equilibrium calculations supported the importance of Si in melt formation and in lowering solidus and liquidus temperatures of Ca-rich slag compositions that are typical from clean wood and bark. Viscosity estimations also showed the impact that solids have upon slag flow behaviour and corresponded qualitatively to the experimental observations. Corrosion of reactor refractory was observed. The mullite-based refractory of the reactor formed a slag with the fuel ash slag, which caused the former to flux away. Reactor blockages were also resultant because of the high viscosity of this slag near the outlet. A preliminary study into the corrosion of different refractories was also carried out, based on firing a bark/peat mixture. Alumina-rich refractories consisting of corundum, hibonite, mullite, and andalusite tended to form anorthite and exhibited varying degrees of degradation. Infiltration of slag was evident for all the samples and was a severe mode of degradation for some refractories. For fused-cast periclase and spinel-based refractories, slag infiltration was limited to voids and no extensive signs of refractory dissolution were found. This is also supported by a thermochemical equilibrium calculations mimicking slag infiltration that incorporated viscosity estimations. The findings from this thesis contribute towards the development of woody biomass PEFG by highlighting issues concerning ash fractionation, slag behaviours and ash\slash refractory interaction that should be investigated further.
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