10 results
Now showing1 - 10 of 10
- Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , A ferroelectric liquid crystal confined in cylindrical nanopores : reversible smectic layer buckling, enhanced light rotation and extremely fast electro-optically active Goldstone excitations(Royal Society of Chemistry (RSC), 2017-11-27); ; ; ; The orientational and translational order of a thermotropic ferroelectric liquid crystal (2MBOCBC) imbibed in self-organized, parallel, cylindrical pores with radii of 10, 15, or 20 nm in anodic aluminium oxide monoliths (AAO) are explored by high-resolution linear and circular optical birefringence as well as neutron diffraction texture analysis. The results are compared to experiments on the bulk system. The native oxidic pore walls do not provide a stable smectogen wall anchoring. By contrast, a polymeric wall grafting enforcing planar molecular anchoring results in a thermal-history independent formation of smectic C* helices and a reversible chevron-like layer buckling. An enhancement of the optical rotatory power by up to one order of magnitude of the confined compared to the bulk liquid crystal is traced to the pretransitional formation of helical structures at the smectic-A*-to-smectic-C* transformation. A linear electro-optical birefringence effect evidences collective fluctuations in the molecular tilt vector direction along the confined helical superstructures, i.e. the Goldstone phason excitations typical of the para-to-ferroelectric transition. Their relaxation frequencies increase with the square of the inverse pore radii as characteristic of plane-wave excitations and are two orders of magnitude larger than in the bulk, evidencing an exceptionally fast electro-optical functionality of the liquid-crystalline-AAO nanohybrids.Publicationtype: Journal ArticleScopus© Citations 25 397 533 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Chiral Phases of a Confined Cholesteric Liquid Crystal: Anchoring-Dependent Helical and Smectic Self-Assembly in Nanochannels(2016-06-02); ; ; ; Chiral liquid crystals (ChLCs) allow a fundamental insight into the interplay of molecular chirality and the formation of macroscopic, self-assembled helices. They also exhibit unique optical properties, in particular huge polarization rotation, which is employed in a wide range of photonic technologies. Here, we present a study of linear and circular optical birefringence in combination with X-ray diffraction experiments on an archetypical ChLC, i.e., the cholesteric ester CE6, confined in cylinders of mesoporous alumina and silica with distinct polymer surface graftings resulting in normal or tangential wall anchoring. The unconfined ChLC exhibits a discontinuous, first-order isotropic-to-chiral nematic (cholesteric) phase transition with the formation of double-twist helices and a discontinuous cholesteric-to-smectic A transition. The thermotropic behavior of the confined ChLC, explored in a channel radii range of 7-21 nm, deviates substantially from bulk behavior. There is no isotropic state. In contrast, a chiral paranematic phase with a preferred arrangement of the ChLC at the channel wall is found. For normal anchoring, a radial-escape structure evolves upon cooling. The phase transition to the smectic phase is completely suppressed. For tangential anchoring, a large optical activity indicates a continuous paranematic-to-cholesteric transition with double-twist helices aligned parallel to the long axes of the cylinders. Upon cooling, these helical structures, known as basic building blocks of blue ChLC phases, transform in a continuous manner to a cylinder-aligned smectic A phase.Publicationtype: Journal Article78 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Thermotropic interface and core relaxation dynamics of liquid crystals in silica glass nanochannels: A dielectric spectroscopy study(Royal Society of Chemistry (RSC), 2015-08); ; ; ; We report dielectric relaxation spectroscopy experiments on two rod-like liquid crystals of the cyanobiphenyl family (5CB and 6CB) confined in tubular nanochannels with 7 nm radius and 340 micrometer length in a monolithic, mesoporous silica membrane. The measurements were performed on composites for two distinct regimes of fractional filling: monolayer coverage at the pore walls and complete filling of the pores. For the layer coverage a slow surface relaxation dominates the dielectric properties. For the entirely filled channels the dielectric spectra are governed by two thermally-activated relaxation processes with considerably different relaxation rates: A slow relaxation in the interface layer next to the channel walls and a fast relaxation in the core region of the channel filling. The strengths and characteristic frequencies of both relaxation processes have been extracted and analysed as a function of temperature. Whereas the temperature dependence of the static capacitance reflects the effective (average) molecular ordering over the pore volume and is well described within a Landau-de Gennes theory, the extracted relaxation strengths of the slow and fast relaxation processes provide an access to distinct local molecular ordering mechanisms. The order parameter in the core region exhibits a bulk-like behaviour with a strong increase in the nematic ordering just below the paranematic-to-nematic transition temperature TPN and subsequent saturation during cooling. By contrast, the surface ordering evolves continuously with a kink near TPN. A comparison of the thermotropic behaviour of the monolayer with the complete filling reveals that the molecular order in the core region of the pore filling affects the order of the peripheral molecular layers at the wall.Publicationtype: Journal Article72 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , High-resolution dielectric study reveals pore-size-dependent orientational order of a discotic liquid crystal confined in tubular nanopores(2015-07-08); ; ; ; We report a high-resolution dielectric study on a pyrene-based discotic liquid crystal (DLC) in the bulk state and confined in parallel tubular nanopores of monolithic silica and alumina membranes. The positive dielectric anisotropy of the DLC molecule at low frequencies (in the quasistatic case) allows us to explore the thermotropic collective orientational order. A face-on arrangement of the molecular discs on the pore walls and a corresponding radial arrangement of the molecules is found. In contrast to the bulk, the isotropic-to-columnar transition of the confined DLC is continuous, shifts with decreasing pore diameter to lower temperatures, and exhibits a pronounced hysteresis between cooling and heating. These findings corroborate conclusions from previous neutron and x-ray-scattering experiments as well as optical birefringence measurements. Our study also indicates that the relative simple dielectric technique presented here is a quite efficient method in order to study the thermotropic orientational order of DLC-based nanocomposites.Publicationtype: Journal Article46 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Inhomogeneous relaxation dynamics and phase behaviour of a liquid crystal confined in a nanoporous solid(2015-04-28); ; ; We report filling-fraction dependent dielectric spectroscopy measurements on the relaxation dynamics of the rod-like nematogen 7CB condensed in 13 nm silica nanochannels. In the film-condensed regime, a slow interface relaxation dominates the dielectric spectra, whereas from the capillary-condensed state up to complete filling an additional, fast relaxation in the core of the channels is found. The temperature-dependence of the static capacitance, representative of the averaged, collective molecular orientational ordering, indicates a continuous, paranematic-to-nematic (P-N) transition, in contrast to the discontinuous bulk behaviour. It is well described by a Landau-de-Gennes free energy model for a phase transition in cylindrical confinement. The large tensile pressure of 10 MPa in the capillary-condensed state, resulting from the Young-Laplace pressure at highly curved liquid menisci, quantitatively accounts for a downward-shift of the P-N transition and an increased molecular mobility in comparison to the unstretched liquid state of the complete filling. The strengths of the slow and fast relaxations provide local information on the orientational order: the thermotropic behaviour in the core region is bulk-like, i.e. it is characterized by an abrupt onset of the nematic order at the P-N transition. By contrast, the interface ordering exhibits a continuous evolution at the P-N transition. Thus, the phase behaviour of the entirely filled liquid crystal-silica nanocomposite can be quantitatively described by a linear superposition of these distinct nematic order contributions.Publicationtype: Journal Article66 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Thermotropic orientational order of discotic liquid crystals in nanochannels: An optical polarimetry study and a Landau-de Gennes analysis(2014-07-07); ; ; ; 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. © The Royal Society of Chemistry 2014.Publicationtype: Journal Article33 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Paranematic-to-nematic ordering of a binary mixture of rodlike liquid crystals confined in cylindrical nanochannels(American Physical Society (APS), 2014-06-09); ; ; ; We explore the optical birefringence of the nematic binary mixtures 6CB1-x7CBx (0≤x≤1) embedded into parallel-aligned nanochannels of mesoporous alumina and silica membranes for channel radii of 3.4≤R≤21.0 nm. The results are compared with the bulk behavior and analyzed with a Landau-de Gennes model. Depending on the channel radius the nematic ordering in the cylindrical nanochannels evolves either discontinuously (subcritical regime, nematic ordering field σ<1/2) or continuously (overcritical regime, σ>1/2), but in both cases with a characteristic paranematic precursor behavior. The strength of the ordering field, imposed by the channel walls, and the magnitude of quenched disorder varies linearly with the mole fraction x and scales inversely proportionally with R for channel radii larger than 4 nm. The critical pore radius, Rc, separating a continuous from a discontinuous paranematic-to-nematic evolution varies linearly with x and differs negligibly between the silica and alumina membranes. We find no hints of preferred adsorption of one species at the channels walls. By contrast, a linear variation of the nematic-to-paranematic transition point TPN and of the nematic ordering field σ versus x suggests that the binary mixtures of cyanobiphenyls 6CB and 7CB keep their homogeneous bulk stoichiometry also in nanoconfinement, at least for channel diameters larger than ∼7 nm. © 2014 American Physical Society.Publicationtype: Journal ArticleScopus© Citations 33 41 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Molecular ordering of the discotic liquid crystal HAT6 confined in mesoporous solidsAn optical polarimetry study of the orientational order of a discotic liquid crystal (DLC), 2,3,6,7,10,11-hexakis(hexyloxy)triphenylene (HAT6), confined into parallel-aligned cylindrical nanochannels of mesoporous alumina, silica, and silicon membranes as a function of temperature and channel radius (3.4-21.0 nm) is presented. In contrast to the bulk state, the birefringence resulting from the confined discotic liquid crystal, exhibits a continuous temperature evolution and is positive indicating a dominating face-on (homeotropic) type molecular ordering with respect to the channel walls. Pronounced hysteresis effects observed in the experiment are traced to different nucleation sites of the low-temperature phase upon cooling and the high-temperature phase upon heating. Deviations from the Gibbs-Thomson scaling of the phase transition temperature for channel diameters below 10 nm are traced to splay distortions of the confined liquid crystal.Publicationtype: Journal Article24 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Thermotropic nematic order upon nano-capillary filling(American Physical Society (APS), 2013-04-05); ; ; Optical birefringence and light absorption measurements reveal four regimes for the thermotropic behavior of a nematogen liquid (7CB) upon sequential filling of parallel-aligned capillaries of 12 nm diameter in a monolithic, mesoporous silica membrane. No molecular reorientation is observed for the first adsorbed monolayer. In the film-condensed state (up to 1 nm thickness) a weak, continuous paranematic-to-nematic (P-N) transition is found, which is shifted by 10 K below the discontinuous bulk transition at TIN=305K. The capillary-condensed state exhibits a more pronounced, albeit still continuous P-N reordering, located 4 K below TIN. This shift vanishes abruptly on complete filling of the capillaries, which we tentatively trace to a 10 MPa tensile pressure release associated with the disappearance of concave menisci in the confined liquid.Publicationtype: Journal Article164 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Influence of nano confinement on nematic liquid crystals(American Physical Society (APS), 2012-08-10); ; ; We explore the nematic ordering of the rod-like liquid crystals 5CB and 6CB, embedded into parallel-aligned nanochannels in mesoporous silicon and silica membranes as a function of mean channel radius (4.7<=R <=8.3 nm), and thus geometrical confinement strength, by optical birefringence measurements in the infrared region. The orientational order inside the nanochannels results in an excess birefringence, which is proportional to the nematic order parameter. It evolves continuously upon cooling with a precursor behavior, typical of a paranematic state at high temperatures. These observations are compared with the bulk behavior and analyzed within a phenomenological model. Such an approach indicates that the strength of the nematic ordering fields sigma is beyond a critical threshold sigmac =1/2, that separates discontinuous from continuous paranematic-to-nematic behavior. In agreement with the predictions of the phenomenological approach a linear dependency of sigma on the inverse channel radius is found and we can infer therefrom the critical channel radii, Rc, separating continuous from discontinuous paranematic-to-isotropic behavior, for 5CB (12.1 nm) and 6CB (14.0 nm). Our analysis suggests that the tangential anchoring at the channel walls is of similar strength in mesoporous silicon and mesoporous silica membranes. A comparison with the bulk phase behavior reveals that the nematic order in nanoconfinement is significantly affected by channel wall roughness leading to a reduction of the effective nematic ordering.Publicationtype: Journal Article27