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Thermal and Dynamic Glass Transition in Ultrathin Films of Homopolymers and a Miscible Polymer Blend
(2014)
Nowadays nanoscale thin polymer films are widely used in many fields like coatings, membranes, sensors, electronic devices and so on. Meanwhile, a lot of research work has evidenced the fact that many physical properties (glass transition, crystallization, dewetting, physical aging, etc.) of ultrathin polymer films show strong deviations from their bulk behavior. Since the aforementioned properties of polymer are closely related to their application and functionality, the discrepancies motivated us to obtain a more complete understanding of how nanoscale confinement affects the physical properties of polymer. The research work presented in this thesis is focused on understanding how the free surface (air- polymer interface), the polymer-substrate interface and the film thickness influence the glass transition temperature (Tg) and the related segmental dynamics (α-relaxation process) in both homopolymers and miscible polymer blends of thin films. Complementary experimental techniques including Differential Scanning Calorimetry (DSC), Capacitive Scanning Dilatometry (CSD), Broadband Dielectric Spectroscopy (BDS) and Specific Heat Spectroscopy (SHS) have been used to investigate the glass transition of thin polymer films from both the thermodynamic and the kinetic point of view. In the thesis the film thickness dependence of Tg and segmental dynamics of different thin polymer films have been investigated. For ultrathin polycarbonate (PC) films capped between two aluminum (Al) layers an increase of both the glass transition temperature (Tg) and Vogel temperature (T0) with decreasing film thickness (d) was observed when the thickness became lower than 20 nm. The segmental relaxation time at a fixed temperature was found to increase for the ultrathin PC film of 19 nm measured by BDS, whereas no thickness dependency of the segmental dynamics was detected within the experimental error limit for the PC films supported on silicon dioxide (SiO2) (10-192 nm) in the SHS measurements. These properties are discussed in terms of the thin film geometry and the relevant interfacial interaction between the polymer and the substrate. In the case of thin polystyrene (PS) films with high molecular weight (Mw), Tg is decreasing with reducing film thickness while the segmental dynamics is independent of film thickness. Moreover, the effects of the Mw and the annealing protocol performed on thin PS films on their Tg and segmental dynamics is studied. In the part of thin poly(vinyl methyl ether) (PVME) films, no thickness dependence of the segmental dynamics was observed in the SHS measurements. The last part of the thesis was concentrated on the thin films of a miscible polymer blend, PS/PVME with the weight fraction of 50/50. It was observed that the segmental dynamics became faster with reducing the film thickness. This phenomenon is explained in terms of surface enrichment of PVME in the polymer blend system where PVME has a lower surface energy than PS. The segmental dynamics of the PVME-enriched free surface layer are faster than the bulk dynamics. Such free surface effect becomes so predominant with reducing the film thickness that it affects the segmental dynamics of the whole films detected by SHS using differential AC chip-based calorimetry. X-ray photoelectron spectroscopy (XPS) was used to probe the surface composition in order to confirm such surface enrichment phenomena.
The influence of distinct carbon based nanofillers: expanded graphite (EG), conducting carbon black (CB), thermally reduced graphene oxide (TRGO) and multi-walled carbon nanotubes (CNT) on the thermal, dielectric, electrical and rheological properties of polybutylene terephthalate (PBT) was examined. The glass transition temperature (Tg) of PBT nanocomposites is independent of the filler type and content. The carbon particles act as nucleation agents and significantly affect the melting temperature (Tm), the crystallization temperature (Tc) and the degree of crystallinity of PBT composites. PBT composites with EG show insulating behaviour over the tested concentration range of 0.5 to 2 wt.-% and hardly changed rheological behaviour. CB, CNT and TRGO induce electrical conductivity to their particular PBT composites by forming a conducting particle network within the polymer matrix. CNT reached the percolation threshold at the lowest concentration (<0.5 wt.-%), followed by TRGO (<1 wt.-%) and CB (<2 wt.-%). With the formation of a particle network, the flow behaviour of composites with CB, CNT and TRGO is affected, i.e., a flow limit occurs and the melt viscosity increases. The degree of influence of the carbon nanofillers on the rheological properties of PBT composites follows the same order as for electrical conductivity. Electrical and rheological results suggest an influence attributed to the particle dispersion, which is proposed to follow the order of EG<< CB<TRGO<CNT.
Polymeric membranes represent a cost- and energy efficient solution for gas separation. Recently superglassy polymers with high free volume outperform many conventional dense polymers in terms of gas permeability and selectivity. However, such polymers are prone to pronounced physical aging, resulting in a dramatic reduction in the gas permeability. Molecular mobility of polymer segments plays an important role in the physical aging and the gas transport performance of polymeric membranes. Molecular mobility and physical aging of a representative superglassy polynorbornene with very high gas permeability, PTCNSi2g, was monitored by using dielectric spectroscopy with state-of-the-art high-resolution analyzers. This work helps to shed some light on the structure−property relationship of superglassy polymers on a molecular level and to provide practical “design rules” for the development of high performance polymers for gas separation.
Polymeric membranes represent a cost- and energy efficient solution for gas separation. Recently superglassy polymers with high free volume outperform many conventional dense polymers in terms of gas permeability and selectivity. However, such materials with a high fractional free volume (FFV) are prone to pronounced physical aging. The initial microporous structures approach a denser state via local chain rearrangements which results in a dramatic reduction in the gas permeability. For the first time, dielectric spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate the molecular mobility and physical aging of two representative groups of superglassy polymers: PIMs (PIM-1 & PIM-EA-TB) and Si-containing polynobornenes (PTCNSi1 & PTCNSi2). The dielectric behavior of the solution-cast polymeric films was measured by isothermal frequency scans during the different heating cycles in a broad temperature range. Structural relaxation of the films was observed during the measurements. Multiple dielectric processes following Arrhenius behavior were observed for all the investigated polymers. Moreover, they all showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature especially for PIMs is explained in terms of the formation of local intermolecular agglomerated structures due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Polymers with intrinsic microporosity (PIMs) represent a novel, innovative class of materials with great potential in various applications from high-performance gas separation membranes to electronic devices. Here for the first time, for PIM-1, as the archetypal PIM, fast scanning calorimetry provides definitive evidence for a glass transition (Tg=715 K, heating rate 3·10^4 K/s) by decoupling the time-scales responsible for glass transition and decomposition. As the rigid molecular structure of PIM-1 prevents any conformational changes, small-scale bend and flex fluctuations must be considered the origin of its glass transition. This result has strong implications for the fundamental understanding of the glass transition and for the physical aging of PIMs and other complex polymers, both topical problems of materials science.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, the vibrational density of states (VDOS) for PIM-1, the prototypical polymer with intrinsic microporosity, is investigated by means of inelastic neutron scattering. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. For an annealed PIM-1 sample, the Boson peak shifts to higher frequencies in comparison to the un-annealed sample. These changes in the VDOS of the annealed PIM-1 sample are related to changes in the microporous structure as confirmed by X-ray scattering.