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Effect of sub-micrometer structural features on rheology of polymer nanocomposites
Lepcio, Petr ; Chodák,, Ivan (oponent) ; doc.Ing.Marián Lehocký, Ph.D. (oponent) ; Jančář, Josef (vedoucí práce)
Polymer nanocomposites (PNCs) hold a great promise as future lightweight functional materials processable by additive manufacturing technologies. However, their rapid deployment is hindered by their performance depending strongly on the nanoparticle (NP) spatial organization. Therefore, the ability to control the nanoparticle dispersion in the process of PNCs preparation is a crucial prerequisite for utilizing their potential in functional composites. This work investigates solution blending of PNCs in a model glass forming polymer matrix, a bulk processing technique of a tailored NP spatial organization controlled by structural and kinetic variables of the preparation protocol. The presented results describe the differences between nanoparticle induced changes on the rheological behavior of a polystyrene solution under large amplitude oscillation shear (LAOS). High-affinity OP-POSS NPs seem to interact with the PS at low filler loadings and form stiffened aggregates, whereas low-affinity OM-POSS NPs remained rather uninvolved in the polymer deformation at these conditions. Furthermore, an interest was focused on the impact of the blending solvent on the NP spatial arrangement in silica/PMMA and silica/PS nanocomposites, which has already been suggested as the controlling parameter of the solid-state structure. An emphasis was put on the qualitative differences between “poorly dispersed” NP arrays which, by combination of rheological assessment and structural analysis (TEM, USAXS), were identified as chain bound clusters and two types of aggregates, one of thermodynamic and the other of a kinetic origin, which are characterized by substantially distinct formation kinetics and mismatched properties compared to individually dispersed NPs and each other. The currently observed types of NP dispersion were quantitatively linked with their rheological properties during the solution blending step and the amount of polymer adsorption and depletion attraction. The results were compared to the PRISM theory. Finally, the importance of NP spatial organization was demonstrated on the comparison of glass transition temperatures of various structures at constant chemical composition.
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Partial slip in liquids studied with high-frequency shear oscillations
Vlachová, Jana ; doc.Ing.Marian Lehocky, Ph.D. (oponent) ; Johannsmann, Diethelm (vedoucí práce)
The sphere-plate contact under normal and tangential load in water was studied. As a source of shear oscillation the acoustic resonator (a quartz crystal microbalance - QCM) was used. The contact of a sphere with the surface of resonator induces a shift of resonance frequency and bandwidth. The dependence of the frequency shift f and bandwidth shift on the amplitude of oscillation were measured. With increasing amplitude, a decrease in f and an increase in were observed. This behaviour is characteristic for partial slip. Applying the Cattaneo-Mindlin model, the contact radius and the friction coefficient were calculated. The contact radius in the limit of small amplitudes increases with increasing normal load. For this dependency, the data fit well to the JKR model. The friction coefficient is of the order of unity, as it should be. It slightly decreases with increasing external normal force, which can be explained with an adhesive force contributing to the total normal force. The formalism yields two separate values for friction coefficient, the first is derived from the frequency shift and the second is derived from the shift in bandwidth. These two values agree with each other within ± 20 % for experiments in liquids, while they differ by about a factor of two for experiments with hydrophilic surfaces in air. This is tentatively explained with capillary forces. The discrepancy points to a shortcoming of the Cattaneo Mindlin theory.
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Effect of sub-micrometer structural features on rheology of polymer nanocomposites
Lepcio, Petr ; Chodák,, Ivan (oponent) ; doc.Ing.Marián Lehocký, Ph.D. (oponent) ; Jančář, Josef (vedoucí práce)
Polymer nanocomposites (PNCs) hold a great promise as future lightweight functional materials processable by additive manufacturing technologies. However, their rapid deployment is hindered by their performance depending strongly on the nanoparticle (NP) spatial organization. Therefore, the ability to control the nanoparticle dispersion in the process of PNCs preparation is a crucial prerequisite for utilizing their potential in functional composites. This work investigates solution blending of PNCs in a model glass forming polymer matrix, a bulk processing technique of a tailored NP spatial organization controlled by structural and kinetic variables of the preparation protocol. The presented results describe the differences between nanoparticle induced changes on the rheological behavior of a polystyrene solution under large amplitude oscillation shear (LAOS). High-affinity OP-POSS NPs seem to interact with the PS at low filler loadings and form stiffened aggregates, whereas low-affinity OM-POSS NPs remained rather uninvolved in the polymer deformation at these conditions. Furthermore, an interest was focused on the impact of the blending solvent on the NP spatial arrangement in silica/PMMA and silica/PS nanocomposites, which has already been suggested as the controlling parameter of the solid-state structure. An emphasis was put on the qualitative differences between “poorly dispersed” NP arrays which, by combination of rheological assessment and structural analysis (TEM, USAXS), were identified as chain bound clusters and two types of aggregates, one of thermodynamic and the other of a kinetic origin, which are characterized by substantially distinct formation kinetics and mismatched properties compared to individually dispersed NPs and each other. The currently observed types of NP dispersion were quantitatively linked with their rheological properties during the solution blending step and the amount of polymer adsorption and depletion attraction. The results were compared to the PRISM theory. Finally, the importance of NP spatial organization was demonstrated on the comparison of glass transition temperatures of various structures at constant chemical composition.
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Partial slip in liquids studied with high-frequency shear oscillations
Vlachová, Jana ; doc.Ing.Marian Lehocky, Ph.D. (oponent) ; Johannsmann, Diethelm (vedoucí práce)
The sphere-plate contact under normal and tangential load in water was studied. As a source of shear oscillation the acoustic resonator (a quartz crystal microbalance - QCM) was used. The contact of a sphere with the surface of resonator induces a shift of resonance frequency and bandwidth. The dependence of the frequency shift f and bandwidth shift on the amplitude of oscillation were measured. With increasing amplitude, a decrease in f and an increase in were observed. This behaviour is characteristic for partial slip. Applying the Cattaneo-Mindlin model, the contact radius and the friction coefficient were calculated. The contact radius in the limit of small amplitudes increases with increasing normal load. For this dependency, the data fit well to the JKR model. The friction coefficient is of the order of unity, as it should be. It slightly decreases with increasing external normal force, which can be explained with an adhesive force contributing to the total normal force. The formalism yields two separate values for friction coefficient, the first is derived from the frequency shift and the second is derived from the shift in bandwidth. These two values agree with each other within ± 20 % for experiments in liquids, while they differ by about a factor of two for experiments with hydrophilic surfaces in air. This is tentatively explained with capillary forces. The discrepancy points to a shortcoming of the Cattaneo Mindlin theory.
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