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Phase transitions and molecular mobility of a discotic liquid crystal under nanoscale confinement
(2013)
The phase behavior and the molecular dynamics of a pyrene-based discotic liquid crystal when confined in nanoporous aluminum membranes with different pore sizes is studied by broadband dielectric spectroscopy and differential scanning calorimetry. In confinement the two phase transitions between plastic crystalline and hexagonal ordered phase at lower and from the latter to an isotropic state at higher temperatures are also observed, but two different phase structures close to the wall and in the pore center are evidenced by two peaks in the heat flow for the first time. While the former peak is independent of the pore size, the depression of the phase transition temperatures of the latter ones can be described by the GibbsThomson equation. With decreasing pore size for both phase transitions the transition enthalpies decrease. A critical pore size for phase transformation of about 20 nm is estimated from the pore size dependence of the transition enthalpies. Like for the bulk, an a-relaxation is also observed in confinement. At the phase transition its relaxation rates show a discontinuity from which a dielectric phase transition temperature can be extracted. For temperatures above and below the phase transition the temperature of the relaxation rate can be approximated by an Arrhenius equation. The pore size dependence of the estimated apparent activation energies is ascribed to the interplay between pore size and interaction effects. The cooperative nature of the underlying molecular dynamics is indicated by the occurrence of the well-known compensation law.
Hexakis(n-alkyloxy)triphenylene) (HATn) consisting of an aromatic triphenylene core and alkyl side chains are model discotic liquid crystal (DLC) systems forming a columnar mesophase. In the mesophase, the molecules of HATn self-assemble in columns, which has one-dimensional high charge carrier mobility along the columns. Here, a homologous series of HATn with different length of the alkyl chain (n = 5,6,8,10,12) is investigated using differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and advanced calorimetric techniques including fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). The investigation of the phase behavior was done utilizing DSC experiments and the influence of the alkyl chain length on the phase behavior was revealed. By the dielectric investigations probing the molecular mobility, a c-relaxation due to localized fluctuations as well as two glassy dynamics, the acore- and aalkyl-relaxation, were observed in the temperature range of the plastic crystalline phase. Moreover, the observed glassy dynamics were further studied employing advanced calorimetry. All observed relaxation processes are attributed to the possible specific molecular fluctuations and discussed in detail. From the results a transition at around n = 8 from a rigid constrained (n = 5,6) to a softer system (n = 10,12) was revealed with increasing alkyl chain length. A counterbalance of two competing effects of a polyethylene-like behavior of the alkyl chains in the intercolumnar domains and self-organized confinement is discussed in the context of a hindered glass transition.
Hexakis(n-alkyloxy)triphenylene) (HATn) consisting of an aromatic triphenylene core and alkyl side chains are model discotic liquid crystal (DLC) systems forming a columnar mesophase. In the mesophase, the molecules of HATn self-assemble in columns, which has one-dimensional high charge carrier mobility along the columns. Here, a homologous series of HATn with different length of the alkyl chain (n=5,6,8,10,12) is investigated using differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and advanced calorimetric techniques including fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). The investigation of the phase behavior was done utilizing DSC experiments and the influence of the alkyl chain length on the phase behavior was revealed. By the dielectric investigations a γ-relaxation due to localized fluctuations as well as two glassy dynamics the αcore and αalkyl relaxation were observed in the temperature range of the plastic crystalline phase. Moreover, the observed glassy dynamics were further studied employing advanced calorimetry. All observed relaxation processes are attributed to the possible specific molecular fluctuations and discussed in detail. From the results a transition at around n=8 from a rigid constrained (n=5,6) to a softer system (n=10,12) on a molecular lenght scale was revealed with increasing alkyl chain length. A counterbalance of two competing effects of a polyethylene like behavior of the alkyl chains in the intercolumnar domains and self-organized confinement is discussed in the context of a hindered glass transition. The results were confirmed by in- and quasielastic neutron scattering
The vibrational density of states of a series of homologous triphenylene-based discotic liquid crystals HATn (n = 5, 6, 8, 10, 12) depending on the length of the aliphatic side chain is investigated by means of inelastic neutron scattering. All studied materials have a plastic crystalline phase at low temperatures, followed by a hexagonally ordered liquid crystalline phase at higher temperatures and a quasi isotropic phase at the highest temperatures. The X-ray scattering pattern for the plastic crystalline phase of all materials shows a sharp Bragg reflection corresponding to the intercolumnar distance in the lower q-range and a peak at circa 17 nm-1 related to intracolumnar distances between the cores perpendicular to the columns as well as a broad amorphous halo related to the disordered structure of the methylene groups in the side chains in the higher q-range. The intercolumnar distance increases linearly with increasing chain length for the hexagonal columnar ordered liquid crystalline phase. A similar behaviour is assumed for the plastic crystalline phase. Besides n = 8 all materials under study exhibit a Boson peak. With increasing chain length, the frequency of the Boson peak decreases and its intensity increases. This can be explained by a self-organized confinement model. The peaks for n = 10, 12 are much narrower than for n = 5, 6 which might imply the transformation from a rigid system to a softer one with increasing chain length. Moreover the results can also be discussed in the framework of a transition from an uncorrelated to a correlated disorder with increasing n where n = 8 might be speculatively considered as a transitional state.
Thermal properties and vibrational density of states of a nanoconfined discotic liquid crystal
(2014)
Neutron scattering is employed to investigate the vibrational density of states (VDOS) of the discotic liquid crystal 2,3,6,7,10,11-hexakis[hexyloxy] triphenylene (HAT6) confined to the pores of alumina oxide membranes with different pore sizes. Additionally, the phase transitions were studied by differential scanning calorimetry. The transitions were observed down to the smallest pore size. The decrease of the transition enthalpies versus inverse pore size for both transitions implies an increase of the amount of disordered amorphous material. By extrapolation of its pore size dependence, a critical pore diameter for structure formation of 17 nm is estimated. Similar to the bulk, excess contributions to the VDOS (Boson peak) are also observed for confined HAT6. The Boson peak gains in intensity and shifts to lower frequencies with decreasing pore diameter. This is discussed in the framework of a softening of HAT6 induced by the confinement due to a less-developed plastic crystalline state inside the pores compared to the bulk.
Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3–22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau–de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.
In der Praxis kann Fäulnis in Holzkonstruktionen
ein großes Problem darstellen. Ein Fäulnisbefall
kann zu einer Schädigung in der Gesamtkonstruktion
führen. Zusammen mit der TU Berlin wurden an der
Bundesanstalt für Materialforschung und -prüfung (BAM)
Versuche mit Ultraschallecho zur Detektion von Bauteilrückwänden
und verdeckten Hohlstellen durchgeführt.
Hierbei werden Sender und Empfänger auf einer Bauteilseite
angekoppelt, was eine große Anwendungsvielfalt
ermöglicht. Im Rahmen der Versuche an der BAM wurden
zylindrische Longitudinalwellenprüfköpfe in Zweikopftechnik
mit 100 kHz angeregt und an den Probekörpern mit
verschiedenen Koppelmitteln angekoppelt. Die Messergebnisse
wurden graphisch als B-Bilder dargestellt und ausgewertet.
Dabei zeigte sich, dass die Rückwand der fehlerfreien
Probekörper klar geortet wird und eingebrachte Hohlstellen
besonders gut detektiert werden können.
Die Ortung von schlaffer Bewehrung in Beton erfolgt routinemäßig mit bildgebenden Radar- oder Wirbelstromverfahren. Die Anwendung dieser Verfahren ist aber begrenzt, wenn es sich um die Ortung tiefliegender Bewehrung (ab ca. 30 cm) oder um jungen Beton handelt. Grund ist die Schwächung der Radarpulse durch oberflächennahe Bewehrung oder durch die Betonfeuchte. Das bildgebende Ultraschallechoverfahren bietet den Vorteil, dass die Ultraschallpulse in diesen Fällen eine wesentlich höhere Eindringtiefe erreichen.
Im vorliegenden Beitrag wird eine Fallstudie vorgestellt, bei der mehrlagig eingebrachte Bewehrungseisen in einer nur einseitig zugänglichen 60 cm dicken Betonplatte geortet werden sollten, um eine Kernbohrung ohne Verkanten der Bohrkrone durchzuführen.
Zur Ortung der Bewehrung wurde das Ultraschallechoverfahren mitScherwellen der Mittenfrequenz 50 kHz mit einem automatisch arbeitenden Bauwerksscanner eingesetzt. Aus den flächig aufgenommenen Messdaten wurde mit der Rekonstruktionsrechnung nach dem Prinzip der synthetischen Apertur (SAFT, Synthetic Aperture Focusing Technique) die Position der Bewehrungseisen bildhaft ortsgenau dargestellt. Dies gelingt mit einer Auswertungsoption, bei der die Phase der reflektierten Ultraschallpulse ermittelt und farbcodiert dargestellt wird (Phasenauswertung). Damit lassen sich Reflexionen der Bewehrung eindeutig von eventuellen Fehlstellen oder Rückwandechos unterscheiden.
In- and quasielastic neutron scattering is employed to investigate both the vibrational density of states and the molecular dynamics of two homologous discotic liquid crystals (DLC) with different length of the alkyl side chain based on a triphenylene derivate. For both compounds characteristic low frequency excess contributions to the vibrational density of states are found. Therefore it is concluded that these liquid crystals show a glass-like behaviour. Elastic scans further show that in these materials a rich molecular dynamics takes place.