Confinement and orientational study at liquid crystal phase transitions

Abstract

We have studied the heat capacity of the thermotropic liquid crystal, octylcyanobiphenyl (8CB), confined to the nearly cylindrical, 0·2 μm diameter pores of Anopore membranes. Orientation of the nematic director within the pores can be controlled with surface treatment. It is known from NMR measurements that the nematic director is aligned parallel to the pore axis in the untreated membrane. A perpendicular alignment is obtained when the pore surface is treated with lecithin. The second order smectic A to nematic (S_A–N) and the weakly first order nematic to isotropic (N–I) phase transitions of 8CB were studied in these pores, for both director orientations, using an AC calorimetry technique. Effects on heat capacity amplitudes, transition temperature shifts, rounding and broadening of these phase transitions will be presented and contrasted with bulk measurements.     

Influence of cylindrical submicrometer confinement on the static and dynamic properties in nonyloxycyanobiphenyl (9OCB)

Broadband dielectric spectroscopy (10(2)-1.9 x 10(9) Hz) and specific heat measurements have been performed on nonyloxycyanobiphenyl (9OCB) in the isotropic (I), nematic (N), and smectic A (SmA) phases confined to 200 nm diameter parallel cylindrical pores of Anopore membranes. Untreated and HTBA-treated membranes have been found to obtain axial and radial confinements, respectively. However, structural or configurational transitions in untreated membranes have been reported to exist in the SmA-mesophase of 9OCB. Both confinements clearly affect the N-I and SmA-N phase transitions. In the axial confinement, the analysis of the specific heat and static dielectric permittivity data leads to a second order SmA-N phase transition, which is known to be weakly first order for bulk 9OCB. Dynamic dielectric measurements have accounted for the different molecular motions in both confinements. On both mesophases, either N or SmA, the relaxation processes in axial configuration are faster than in the bulk. However, in radial confinement, they are either equal or slower than in the bulk. Additionally, there are no differences in the energy barrier hindering the molecular motions between the axial and radial confinements and even in relation to bulk. Likewise, dielectric results suggest that the extension inside the pores of the surface pinned molecular layer (proved to be temperature-dependent) persists at high enough temperature as a residual-thin layer adjacent to the pore wall.     

Confinement and surface effects on the molecular dynamics of a nematic mixture investigated by dielectric relaxation spectroscopy

Broadband dielectric spectroscopy (10(-2)-10(9) Hz) was employed to investigate the molecular dynamics of the liquid crystalline mixture E7 confined in both untreated and lecithin-treated 20 nm Anopore membranes. Because E7 does not crystallize, it was possible to cover a temperature range of more than 200 K, providing an exhaustive dielectric characterization of a liquid crystal confined to Anopore membranes for the first time. In the nematic state, the tumbling (alpha-) and the delta-relaxation are observed, also under confinement conditions. The analysis of their relative intensities give that the orientation of the E7 molecules is preferentially axial in untreated but opposite radial in lecithin-treated pores. The radial alignment of the liquid crystals in the modified membrane is understood as a tail-to-tail conformation of E7 molecules imposed by the adsorbed lecithin molecules. The relaxation rate of the alpha-process is enhanced for E7 confined in native Anopore compared with the bulk and E7 in treated pores. This is interpreted as resulting from a less dense molecular packing of E7 in the middle of the pore compared to the bulk. In both untreated and treated membranes, the relaxation rate of the delta-process is higher than in the bulk, and the values of the respective Vogel-Fulcher-Tammann temperatures depend on the actual surface treatment. Additionally, a surface process, due to molecular fluctuations of molecules within an adsorbed layer at the pore wall, was detected.     

Dielectric properties of the nematic liquid crystal 4-n-pentyl-4'-cyanobiphenyl in porous membranes

Broadband dielectric spectroscopy (up to 10₉ H_z) is employed to study the molecular dynamics of the liquid crystal 4-n-pentyl-4'-cyanobiphenyl (5CB) in the free bulk phase and confined in cylindrical channels of Anopore membranes having a diameter of 0.2 μm and length of about 60 μm. The bulk samples of 5CB orient almost homeotropically between the untreated metal electrodes of the measurement set-up, and two relaxation processes are observed: the slower δ-relaxation is assigned to hindered rotation (180° flips) of the molecules around their molecular short axis, and a faster second process is attributed to the tumbling of the molecules about this axis. In the confined 5CB samples, the membrane pores align the nematic director axially or radially depending upon their surface preparation. Planar (axial) alignment is always found in untreated membranes, whereas radial alignment was achieved by treatment with decanoic acid. Consequently the director field is fixed perpendicular or parallel to the electric field and we are able to study each of the two relaxation processes separately by appropriate surface treatment of the pores. The frequencies of both processes are found to be unchanged with respect to the bulk phase. We extract the frequency dependence of the dielectric anisotropy δε from the dispersion curves of ε∥ and ε⊥. Two changes of sign of δε = (ε∥-ε⊥) are detected as predicted in the literature.     

Molecular ordering in microconfined liquid crystals: An infrared linear dichroism study

The molecular arrangement of 5CB confined within the cylindrical pores of Anopore membranes was characterized by means of the IR-order parameter obtained from linear dichroism measurements of selected IR absorption bands. The treatment of the experimental data includes a local field correction extended to the twisted nematic configuration, yielding order parameters increased by about 30% in comparison with the uncorrected data. The nematic director of 5CB aligns along the pore axes, whereas in lecithin coated Anopore channels, the local nematic director is oriented approximately radially due to the perpendicular anchoring of the 5CB molecules at the pore wall. Doping of 5CB with the chiral agent CB15 yields local nematic directors tilted with respect to the pore axes. The average tilt angle increases up to about 40° at a fraction of CB15, x_cb15 = 0.25 (w/w). These results are discussed in terms of the conical helicoidal and alternatively the radially twisted axial arrangement of the LC molecules within submicrometer cylindrical cavities.     

Molecular ordering in microconfined liquid crystals: An infrared linear dichroism study

Abstract

The molecular arrangement of 5CB confined within the cylindrical pores of Anopore membranes was characterized by means of the IR-order parameter obtained from linear dichroism measurements of selected IR absorption bands. The treatment of the experimental data includes a local field correction extended to the twisted nematic configuration, yielding order parameters increased by about 30% in comparison with the uncorrected data. The nematic director of 5CB aligns along the pore axes, whereas in lecithin coated Anopore channels, the local nematic director is oriented approximately radially due to the perpendicular anchoring of the 5CB molecules at the pore wall. Doping of 5CB with the chiral agent CB15 yields local nematic directors tilted with respect to the pore axes. The average tilt angle increases up to about 40° at a fraction of CB15, x _cb15 = 0.25 (w/w). These results are discussed in terms of the conical helicoidal and alternatively the radially twisted axial arrangement of the LC molecules within submicrometer cylindrical cavities.     

The effect of surface treatment on the alignment and phase transition of a polypeptide liquid crystal

Poly(γ-benzyl-L-glutamate) (PBLG), was utilized as a surface coating agent in order to obtain parallel molecular orientation in thin layers of PBLG liquid-crystalline solutions confined between coated surfaces. It was found that in a thickness range much larger than the cholesteric pitch value, the texture was predominantly planar cholesteric. At film thickness comparable or smaller than the pitch, isotropic spherulites developed from a homeotropic nematic phase. Because of the coupling between the solution concentration and nematic director, as well as large differences in the elastic moduli of PBLG liquid-crystalline solutions, the long-range intermolecular interaction was unfavorable. Competition between parallel orientation induced by the surface coating of PBLG and inherent perpendicular orientation induced by PBLG molecules in the bulk would favor a short-range helix-coil transition mechanism, which results into a reentrant isotropic phase.     

Role of the linear elastic term in the spatial derivatives of the nematic director in a 1D geometry

The role of the linear elastic term in the spatial derivatives of the nematic director on the director field is analysed. We consider a nematic sample in the shape of a slab, confined by two surfaces treated to induce homeotropic alignment. It is shown that this term can be responsible for spontaneous Fréedericksz transitions. The connection between the linear term and the flexoelectric contribution, associated with a surface field, to the bulk energy density, is discussed. The importance of dielectric anisotropy on the spontaneous Fréedericksz transition is also investigated.     

Anchoring of a nematic liquid crystal on a wettability gradient

We have studied the anchoring of the nematic liquid crystal 5CB (4'-n-pentyl-4-cyanobiphenyl) as a function of the surface wettability, thickness of the liquid crystal layer, and temperature by measuring the birefringence of a hybrid aligned nematic cell where the nematic material was confined between octadecyltriethoxysilane-treated glass surfaces, with one surface linearly varying in its hydrophobicity. A homeotropic-to-tilted anchoring transition was observed as a function of the lateral distance along the hydrophobicity gradient, typically in a region corresponding to a water contact angle of approximately 64 degrees. The effect of the nematic layer thickness was measured simultaneously by preparing a wedge cell where the thickness varied along the direction perpendicular to the wettability. The detailed behavior of the onset of birefringence was found to be consistent with a dual-easy-axis model that predicts a discontinuous anchoring transition from homeotropic to planar. The anchoring was independent of temperature, except within 1 degrees C of the nematic-to-isotropic transition temperature (T(NI)). As the temperature approached T(NI), the tendency for planar anchoring gradually increased relative to that for homeotropic anchoring.     

Critical behavior and scaling relationships at the SmA(d)-N and N-I transitions in nonyloxycyanobiphenyl (9OCB)

Different kind of measurements were performed on the liquid crystal nonyloxycyanobiphenyl (9OCB) to carry out a study of the molecular dynamics in the smectic A (SmA), nematic (N), and isotropic (I) phases as well as an exhaustive analysis of both the SmA-to-N and N-to-I phase transitions. For the dynamic study, broadband dielectric spectroscopy (102 to 1.8 x 109 Hz) was used. Two orientations (parallel and perpendicular) of the molecular director with regard to the probing electric field were investigated. From this study, the static dielectric permittivity was obtained in both alignments and, in addition, the molecular motions that contribute to each one were discussed. The static dielectric data together with specific heat and volumetric determinations were analyzed, proving that both phase transitions are weakly first order, displaying a nearly tricritical behavior. However, the width of metastable regions seems to be dependent on the physical magnitude, although specific heat and volumetric determinations allow for comparable results. It should be noticed that the temperature derivative of the static dielectric permittivity, specific heat, and isobaric thermal expansion coefficient data derived from volumetric determinations are related to each other by scaling relationships.     

Pulsed gradient NMR study of anisotropic surfactant diffusion in the caesium perfluoro octanoate/D2O system

We use pulsed field gradient ¹⁹F NMR to measure the diffusion coefficients of surfactant molecules in the isotropic and lamellar phases of the caesium perfluoro octanoate (CsPFO)/D₂O system. An aligned lamellar sample is created by cooling through the nematic phase in the presence of a 1·4 T magnetic field. The director in the lamellar phase does not respond to ordinary field strengths, thus the aligned sample can be rotated clockwise or counterclockwise to place the director at a magic angle, where measurement of diffusion coefficients becomes possible. From a pair of so-obtained coefficients, we derive the principal values of the diffusion tensor corresponding to the directions parallel and perpendicular to the director (D_⊥ and D_⊥). We found D_∥ to be at least 20 times D_∥ a much larger anisotropy than is seen in electrical conductivity and water diffusion in similar systems. These results are compared to electrical conductivity, water and dye diffusion measurements.     

Dielectric relaxation in bulk and cylindrically confined octylcyanobiphenyl (8CB)

The dielectric relaxation spectrum over the frequency range 10² to 1.8×10⁹ Hz of 4-octyl-4'-cyanobiphenyl, 8CB, in bulk and confined to 200 nm diameter cylindrical pores is reported. We used matrices with parallel cylindrical pores, obtaining different alignments of the molecular director depending on the treatment. Results show that there are two relaxations in the isotropic phase and in the mesophases for parallel alignment and three for perpendicular alignment. The molecular origin of theses modes and the effect of the confinement on their dynamics are discussed. To compare properly the results for bulk and confined 8CB, a re-scaling of the experimental data is proposed.     

Preliminary Communications. Micellar phases formed by a solution of l-serine hydrochloride decylester and orthophosphoric acid

Polarizing microscope studies showed that the isotropic solution composed of l-serine hydrochloride decylester and orthophosphoric acid forms micellar cholesteric, nematic and lamellar phases, whereas the solution of the optically inactive ester gives micellar nematic and lamellar phases. The phase transitions were tentatively assigned as the result of two concurrent reactions at which ortho-phosphoserine hydrochloride decylester and orthophosphoric acid monodecylester are produced. Dilution of the optically active and the optically inactive lamellar phases with water gave a cholesteric and a nematic phase, respectively. The nematic director is aligned perpendicular to the glass plate, whereas that of the cholesteric phase is aligned parallel.     

Evidence for a tilted smectic phase in Anopore membranes by dielectric spectroscopy

Collective relaxation processes are completely undetectable in a ferroelectric liquid crystal confined in porous Anopore membranes, as a result of perfect orientation of the smectic layers perpendicular both to the long axis of the pores and the direction of the measuring electric field. In the ferroelectric liquid crystal - Anopore composite only one relaxation process, assigned to rotation of the molecule around the molecular short axis, appears throughout all smectic phases. The temperature dependence of the relaxation frequency and of the dielectric strength of this process also shows no irregularity at the point of polarization sign reversal. The temperature dependence of the relaxation frequency follows the Arrhenius law with an activation energy slightly higher in the ferroelectric SmC* phase. Analysis of the non-linear changes of temperature dependence of the dielectric strength at the SmA-SmC* phase transition enables one to obtain the temperature dependence of the tilt angle of the molecules in the SmC* phase in the Anopore membrane. Dielectric measurements confirm the existence of the tilted smectic phase in Anopore cylindrical channels with no tilt anomaly at the point of polarization sign reversal.     

Evidence for a tilted smectic phase in Anopore membranes by dielectric spectroscopy

Collective relaxation processes are completely undetectable in a ferroelectric liquid crystal confined in porous Anopore membranes, as a result of perfect orientation of the smectic layers perpendicular both to the long axis of the pores and the direction of the measuring electric field. In the ferroelectric liquid crystal – Anopore composite only one relaxation process, assigned to rotation of the molecule around the molecular short axis, appears throughout all smectic phases. The temperature dependence of the relaxation frequency and of the dielectric strength of this process also shows no irregularity at the point of polarization sign reversal. The temperature dependence of the relaxation frequency follows the Arrhenius law with an activation energy slightly higher in the ferroelectric SmC* phase. Analysis of the non‐linear changes of temperature dependence of the dielectric strength at the SmA–SmC* phase transition enables one to obtain the temperature dependence of the tilt angle of the molecules in the SmC* phase in the Anopore membrane. Dielectric measurements confirm the existence of the tilted smectic phase in Anopore cylindrical channels with no tilt anomaly at the point of polarization sign reversal.     

Anisotropic diffusion of elongated and aligned polymer chains in a nematic solvent

The translational diffusion constant, D, of a polymer solute in a single-domain, nematic liquid crystal solvent (5CB) is measured in directions parallel and perpendicular to the nematic director using a fluorescence two-beam, cross-correlation technique. The solute under investigation is the stiff, conjugated polymer, MEH-PPV. The ratio D parallel/D perpendicular) of diffusion constants (parallel and perpendicular to the director) is observed to be 1.9 +/- 0.3. This is surprisingly small considering that MEH-PPV is known to be both elongated and highly aligned along the liquid crystal director of 5CB. We therefore argue that the structural order parameter of the solvent governs the anisotropy of the diffusion of the solute.     

Orientation of chromonic liquid crystals by topographic linear channels: multi-stable alignment and tactoid structure

We study the alignment behaviour of the chromonic liquid crystal phases of sunset yellow (SSY)/water, disodium cromoglycate (DSCG)/water and their mixtures when confined in cells by polymer films topographically imprinted with linear channels of 250 nm width, depth and spacing. A variety of novel alignment effects are generated by contact with such a patterned surface, as follows. Nematic DSCG and nematic SSY at low concentration and their nematic mixtures orient with the long axes of stacked chromonic aggregates on average parallel to the channels, that is, with the molecular planes normal to the channel axis. These oriented nematics exhibit isotropic/nematic tactoids aligned with their major axes along the channels. Two geometries of the tactoids, elliptic cylinder and rectangular cuboid with hemi cylindrical ends are observed. Additionally, a transition of DSCG tactoids from a three-dimensional (3D) director configuration to a two-dimensional one is observed when the tactoids on one surface of a cell touch the other surface of the cell. In SSY solutions of sufficiently high concentration, multi-stable alignment is found, including preferential in-plane orientation of the director parallel to, perpendicular to and 45° rotated from the channels.     

Effects of a transverse electric field in nematics: Induced biaxiality and the bend Fréedericksz transition

We have studied the effects of a transverse electric field on director fluctuations in the nematic liquid crystal 5CB (4-n-pentyl-4′-cyanobiphenyl) in the bend Fréedericksz geometry. The sample was homeotropically aligned by surface treatment of the glass cell walls and an additional magnetic field was applied perpendicular to the walls. An electric field was then applied parallel to the walls; below the bend Fréedericksz transition, director fluctuations parallel to the electric field are enhanced. This field-induced biaxiality was observed and studied by monitoring the intensity of light transmitted by the sample placed between crossed polarizers. Landau theory for 5CB predicts the electric field induced bend transition to be first order. Our observations of the transmitted intensity are consistent with this prediction. We have also observed that this transition is to a modulated rather than to a uniform phase.     

Broadband dielectric studies of weakly polar and non-polar liquid crystals

Complex dielectric permittivities, for two orientations of the director n, parallel (E || n) and perpendicular (E ⊥ n) to the probing electric field E, of the weakly polar liquid crystals (LCs) 4,4'-dihexylazoxybenzene (D6AOB) and 4,4'-diheptylazoxybenzene (D7AOB) as well as the non-polar LC diheptylazobenzene (D7AB) have been measured in the frequency range 75 kHz to 1 GHz. The measurements were performed in the nematic, smectic and isotropic phases of the LCs. The dielectric anisotropies Δε (=ε_||-ε_⊥) obtained from the values of dielectric permittivities at 100 kHz in the nematic phase were found to increase with decreasing temperature. However, for the DnAOBs, the Δε values are somewhat smaller than that for D7AB which does not have a permanent dipole moment. In the nematic phase two molecular relaxation processes were observed for both DnAOBs in each of the orientations—parallel and perpendicular. The four processes merge into two separate processes in the isotropic phase. For D7AB no orientational relaxations were observed in the experimental frequency range.