Nuclear magnetic resonance investigation of structure and dynamics of some electrolyte solutions

Electrolyte solutions are of importance in a wide range of scientific contexts and as such have attracted considerable theoretical and experimental effort over many years. Nuclear Magnetic resonance provides a precise and versatile tool for investigation of electrolyte solutions, both in water and in organic solvents. Many structural and dynamic properties can be obtained through NMR experiments. The solution of aluminum chloride in water was studied. Different concentrations were taken for investigation. Independence of maximum line shift from concentration and acidity was shown. Six-coordinated structure of solvation shell was confirmed by experiments on 'H and 27A1 nuclei. Diffusion coefficients were studied. The solution of nickel chloride in methanol was studied. Lines, corresponding to coordinated and bulk methanol were found. Four-, five- and six-coordinated structures were found in different temperatures. The line for coordinated -OD group of deuterated methanol was observed on 2H spectrum for the first time. Partial deuteration of CH3 group was detected. Inability to observe coordinated -OH group was explained.

NMR in Crystals and Powders of Topazes with Different Colours

The present work is a part of the large project with purpose to investigate microstructure and electronic structure of natural topazes using NMR method. To reach this task we determined the relative contents of fluorine and hydrogen in crystals blue, colorless, wine and wine irradiated topazes. Then we determined the electric field gradients in site of aluminium atoms by NMR method, calculated EFG using ab initio method, and measured relaxation time dependence on heating temperature for blue, colorless, Swiss blue and sky blue topazes. Nuclear magnetic resonance (NMR) is an effective method to investigate the local structure in the crystal. The NMR study of the single crystal gives detailed information especially about the local crystal structure. As a result of this work we have received practical data, which is possible to use in future for making personal dosimetry and for preparation of mullite, which is widely used in traditional and advanced ceramic materials.

Magnetic Resonance Experiments with Atomic Hydrogen

In this thesis three experiments with atomic hydrogen (H) at low temperatures T<1 K are presented. Experiments were carried out with two- (2D) and three-dimensional (3D) H gas, and with H atoms trapped in solid H2 matrix. The main focus of this work is on interatomic interactions, which have certain specific features in these three systems considered. A common feature is the very high density of atomic hydrogen, the systems are close to quantum degeneracy. Short range interactions in collisions between atoms are important in gaseous H. The system of H in H₂ differ dramatically because atoms remain fixed in the H₂ lattice and properties are governed by long-range interactions with the solid matrix and with H atoms. The main tools in our studies were the methods of magnetic resonance, with electron spin resonance (ESR) at 128 GHz being used as the principal detection method. For the first time in experiments with H in high magnetic fields and at low temperatures we combined ESR and NMR to perform electron-nuclear double resonance (ENDOR) as well as coherent two-photon spectroscopy. This allowed to distinguish between different types of interactions in the magnetic resonance spectra. Experiments with 2D H gas utilized the thermal compression method in homogeneous magnetic field, developed in our laboratory. In this work methods were developed for direct studies of 3D H at high density, and for creating high density samples of H in H₂. We measured magnetic resonance line shifts due to collisions in the 2D and 3D H gases. First we observed that the cold collision shift in 2D H gas composed of atoms in a single hyperfine state is much smaller than predicted by the mean-field theory. This motivated us to carry out similar experiments with 3D H. In 3D H the cold collision shift was found to be an order of magnitude smaller for atoms in a single hyperfine state than that for a mixture of atoms in two different hyperfine states. The collisional shifts were found to be in fair agreement with the theory, which takes into account symmetrization of the wave functions of the colliding atoms. The origin of the small shift in the 2D H composed of single hyperfine state atoms is not yet understood. The measurement of the shift in 3D H provides experimental determination for the difference of the scattering lengths of ground state atoms. The experiment with H atoms captured in H2 matrix at temperatures below 1 K originated from our work with H gas. We found out that samples of H in H2 were formed during recombination of gas phase H, enabling sample preparation at temperatures below 0.5 K. Alternatively, we created the samples by electron impact dissociation of H₂ molecules in situ in the solid. By the latter method we reached highest densities of H atoms reported so far, 3.5(5)x10¹⁹ cm^-3. The H atoms were found to be stable for weeks at temperatures below 0.5 K. The observation of dipolar interaction effects provides a verification for the density measurement. Our results point to two different sites for H atoms in H2 lattice. The steady-state nuclear polarizations of the atoms were found to be non-thermal. The possibility for further increase of the impurity H density is considered. At higher densities and lower temperatures it might be possible to observe phenomena related to quantum degeneracy in solid.

Adult education policy in the European Union during the Lisbon decade : the shift to vocational adult learning and work skills matching

This doctoral dissertation investigates the adult education policy of the European Union (EU) in the framework of the Lisbon agenda 2000–2010, with a particular focus on the changes of policy orientation that occurred during this reference decade. The year 2006 can be considered, in fact, a turning point for the EU policy-making in the adult learning sector: a radical shift from a wide--ranging and comprehensive conception of educating adults towards a vocationally oriented understanding of this field and policy area has been observed, in particular in the second half of the so--called ‘Lisbon decade’. In this light, one of the principal objectives of the mainstream policy set by the Lisbon Strategy, that of fostering all forms of participation of adults in lifelong learning paths, appears to have muted its political background and vision in a very short period of time, reflecting an underlying polarisation and progressive transformation of European policy orientations. Hence, by means of content analysis and process tracing, it is shown that the new target of the EU adult education policy, in this framework, has shifted from citizens to workers, and the competence development model, borrowed from the corporate sector, has been established as the reference for the new policy road maps. This study draws on the theory of governance architectures and applies a post-ontological perspective to discuss whether the above trends are intrinsically due to the nature of the Lisbon Strategy, which encompasses education policies, and to what extent supranational actors and phenomena such as globalisation influence the European governance and decision--making. Moreover, it is shown that the way in which the EU is shaping the upgrading of skills and competences of adult learners is modeled around the needs of the ‘knowledge economy’, thus according a great deal of importance to the ‘new skills for new jobs’ and perhaps not enough to life skills in its broader sense which include, for example, social and civic competences: these are actually often promoted but rarely implemented in depth in the EU policy documents. In this framework, it is conveyed how different EU policy areas are intertwined and interrelated with global phenomena, and it is emphasised how far the building of the EU education systems should play a crucial role in the formation of critical thinking, civic competences and skills for a sustainable democratic citizenship, from which a truly cohesive and inclusive society fundamentally depend, and a model of environmental and cosmopolitan adult education is proposed in order to address the challenges of the new millennium. In conclusion, an appraisal of the EU’s public policy, along with some personal thoughts on how progress might be pursued and actualised, is outlined.

Sodaliittien Na8(AlSiO4)6(Cl,S)2 tenebresenssin ja luminesenssin tutkiminen NMR ja EPR spektroskopioita apuna käyttäen

Sodaliitit ovat mineraaleja, joiden ominaisuuksia ovat tenebresenssi, luminesenssi ja kestoluminesenssi. Sodaliitteja voidaan löytää luonnosta, mutta niitä pystytään valmistamaan myös laboratoriossa kiinteän olomuodon menetelmällä. Yksi sodaliittien erityistapauksista on hackmaniitti. Hackamiittiin tutustumalla voidaan helposti tutustua yleisesti sodaliitteihin. Hackamniitin rakenne perustuu rakennekaavaan Na8[AlSiO4]6[Cl,S]2. Rakenteeseen voidaan kuitenkin tehdä hienovaraisia muutoksia, joilla saadaan aikaan ominaisuuksien muutoksia syntyvissä tuotteissa. Työssä valmistettiin synteettisiä sodaliitteja, joiden kloori- ja rikkiatomien suhdetta ja vakanssien määrää muutettiin. Syntyneiden tuotteiden kiderakenne vastasi luonnollisen sodaliitin kiderakennetta. Kiderakenteen sisällä olevat muutokset vaikuttivat kuitenkin sodaliittien luminesenssin intensiteettiin ja tenebresenssissä syntyvän värin tummuuteen ja värin kestoon. Koska rakenne selkeästi vaikuttaa sodaliitin ominaisuuksiin, pyrittiin työssä löytämään parhaat menetelmät, joilla rakennetta voidaan tutkia. Perinteisten rakennetutkimusmenetelmien, (kuten XPD:n) lisäksi tutkittiin magneettiseen värähtelyyn perustuvien tekniikoiden (NMR ja EPR) käyttöä sodaliittien tutkimisessa. Sodaliitteja on tutkittu toistaiseksi kovin vähän. Tulevaisuudessa sodaliitit ovat kuitenkin mielenkiintoinen tutkimuskohde, sillä niissä saadaan aikaan useita optisia ominaisuuksia eri viritysaallonpituuksilla. Työssä esitettyjen tutkimusmenetelmien avulla sodaliitteja voidaan jatkossa tutkia entistä paremmin ja niiden rakenteesta

The TTIP, ISDS and the shift towards transparency in investor-state arbitration

The negotiations between the EU and the US over the Transatlantic Trade and Investment Partnership (TTIP) have generated a lot of discussion about investor-state dispute settlement (ISDS). This discussion provided the inspiration for this thesis, with the TTIP in the background, setting the scene. In this thesis I study the nature of ISDS and the principle of transparency within investor-state arbitration. I aim to determine whether the use of ISDS is restricted to international arbitration and whether ISDS can be considered to constitute a system or regime. Furthermore, I consider whether the introduction of the UNCITRAL Rules on Transparency in Treaty-based Investor-State Arbitration (2014, the UNCITRAL Transparency Rules) changes investor-state arbitration in relation to transparency. To achieve this, I examine ISDS provisions in several different international investment agreements (IIAs) and evaluate the ways in which transparency is incorporated into investment law. Moreover, I compare the provisions on transparency and confidentiality in institutional arbitration rules with the UNCITRAL Transparency Rules. I have formed several conclusions, including that the ISDS provisions may contain methods other than international arbitration and that ISDS does not constitute a system. Furthermore, the UNCITRAL Transparency Rules do change – theoretically, at least – investor-state arbitration to become more transparent. Whether the UNCITRAL Transparency Rules will make investor-state arbitration fully transparent depends on the actions of the contracting state parties when negotiating new IIAs and whether they choose to incorporate the UNCITRAL Transparency Rules in the IIAs already concluded.