Literatura académica sobre el tema "Kemi - Fysikalisk kemi"

This Thesis presents studies of phase transitions ocurring in porous media. The investigated phase transitions include melting/crystallization, surface pre-melting and liquid-liquid phase separation of binary mixtures. A combination of NMR techniques, already existing and newly developed and ranging from cryoporometry to elaborate self-diffusion and spin-relaxation experiments, was applied in order to detect and quantify the effect of finite size constraints on those phase transitions. By relating the results to physico-chemical models, the difference in behaviour with respect to that of bulk was exploited and related to pore morphology and surface properties in diverse porous systems. NMR cryoporometry is based on the detection of the melting/freezing temperature shifts with respect to those in the bulk state to obtain mean pore size and pore size distribution. We extended the size range in which this can be done in porous matrices of both hydrophilic and hydrophobic nature to a 1 μm-600 nm upper limit. This was achieved by introducing two new probe liquids namely octamethylcyclotetrasiloxane (OMCTS) and zinc nitrate hexahydrate Zn(NO)3•H2O. The thickness of the pre-molten surface layer that appears at the interface of frozen octamethylcyclotetrasiloxane (OMCTS) to the matrix in controlled porous glasses was quantified and modeled including its temperature and wall-curvature dependence. The results reveal that the layer thickness depends logarithmically on the deviation from the pore melting point, while for the largest pore investigated this turns into a power law with the exponent of –1/2. Diverse NMR techniques were used not only to detect solely the surface layer and the evolution of the surface melting, but also to distinguish the latter from the volume melting transition within the pores. The morphologies of two nanostructured materials, sintered films of TiO2 nanoparticles and a mesoporous foam obtained by surfactant-templated synthesis, were investigated. These two porous matrices have very different structures but fall into the size range accessible by NMR cryopormetry and their characterization plays an important role in their future applications. They were studied by exploiting the difference between melting and freezing temperature shifts ΔTm and ΔTf, respectively, with respect to that of bulk. NMR cryoporometry was shown to be a suitable alternative and an excellent complement to other porosimetry techniques, namely mercury intrusion and gas sorption porosimetries to analyze the pore structure and pore size distribution because of the unique and model-independent access to information about pore shape. By combining NMR cryoporometry with NMR diffusion experiments holds great potential for accessing information about pore interconnectivity. By diverse NMR techniques we provided experimental evidence that corroborate that liquid-liquid phase separation of a binary mixture imbibed in porous media actually occurs within the individual pores. The size distribution of the phase-separated domains was measured.
QC 20100927

When making paper, fibers and additives are suspended in water to a fiber suspension. The sheet is formed by draining a specific amount of suspension through a wire-cloth. The procedure is well known, but the underlying mechanisms are not fully understood. To understand how the different particles such as fines, fibers, retention aids and other additives interact with each other, further research is needed. This knowledge is important because in the production of paper, the retention and the distribution of fines and additives within a paper structure are vital parameters for the properties and also for the profitability of the final product. In this study fluorescence microscopy was used to study fines from bleached kraft pulp which were labeled with fluorophores. When the fines exhibit fluorescence we can study their individual trajectories and understand more about the interactions between fibers, fines and additives in different chemical environments. Fines from bleached kraft pulp have no fluorescent properties and therefore it is necessary to bind a fluorophore to the material. It was difficult to find a suitable fluorophore which binds covalently to the cellulose, the dominating part of fines. The result from this study was that the labeled fines did exhibited fluorescence. As the fines were aggregated no individual trajectories could be analyzed with fluorescence microscopy. Further development of the technique for labeling fines must be carried out to avoid aggregation of fines.
Vid tillverkning av papper, blandas fibrer och tillsatser i vatten till en fibersuspension. Arket bildas genom att avvattna suspensionen genom en vira. Förfarandet är välkänt men för att förstå mekanismerna måste vi förstå hur olika partiklar som fines, fibrer, retentionsmedel och andra tillsatser interagerar med varandra. Denna kunskap är viktigt eftersom i produktionen av papper är retention och distribution av fines och tillsatser i en pappersstruktur avgörande parametrar för de egenskaper, och även för lönsamheten, som erhålls i den slutliga produkten. I denna studie används fluorescensmikroskopi för att kunna studera fines av blekt sulfatmassa som blivit märkta med fluoroforer. När materialet uppvisar fluorescens kan deras individuella rörelsemönster studeras och därmed kan interaktionen som sker mellan fibrer, fines och tillsatser i olika kemiska miljöer förstås. Fines av blekt sulfatmassa har inga fluorescerande egenskaper och därför är det nödvändigt att binda en fluorfor till materialet. Det var svårt att hitta en lämplig fluorofor som binder kovalent till cellulosa, den dominerande delen av fines. Resultatet från denna studie visar att lösningarna med fluorescentmärkta fines uppvisade fluorescens. Eftersom det skedde en aggregering av fines kunde inte deras individuella rörelsemönster analyseras med fluorescensmikroskopi. Modifiering av märkningen måste göras för att kunna undvika aggregeringen av fines.

Organic photovoltaics is a promising environmentally friendly technology, due to their printability, light-weight nature and mechanical flexibility, and the possibility to use off-grid. Research and development in this field has resulted in power conversion efficiencies of over 15%. To further improve the efficiency, it is important to understand the connection between the morphology of the active layer and the performance of the device.  This thesis focuses on understanding on a molecular level of the morphology formation in a thin coated film of a polymer bend, using two different approaches. One approach will focus on the thermodynamics of conjugated polymers in relation to the morphology, by using the Hansen solubility Parameters (HSP) and solution chemistry. The second approach focuses on understanding phase separation between the two polymers in the active layer. To be able to study phase separation, films were fabricated under microgravity conditions, as previous studies show that in these conditions phase separation mechanism is slowed down. Atomic force microscopy is used to characterize the resulting morphology of the thin films.  Preliminary studies in this thesis showed that using HSP is a good tool, to understanding solvent-solute and solute-solute interactions in solution and to guide the final film morphology in relation to solubility. Furthermore, HSP is a good tool for the preliminary screening of alternative solvents and solvent blends for environmentally friendly processing solvents for upscaling. It was also found that dip coating of films under microgravity conditions provides a tool to study the early stages of the phase separation, as well as facilitate the study of the dependence of the morphology on the thicknesses of the coating. More work is needed to be able to separate the complex effect of hypergravity and to eliminate uncertainty concerning if the deposited wet film is completely dried under the microgravity phase.