Inertial effects in rotating lyotropic liquid crystals

The orientation of the director of a lyotropic liquid crystal with negative anisotropy of the diamagnetic susceptibility is studied when the sample is spun at various speeds and angles from the magnetic field. Different behaviours is observed at low and high spinning speeds where the orientation is governed by the magnetic and the inertial torques, respectively. At intermediate frequencies it is possible to reach an equilibrium between these two torques. The evolution of this equilibrium with the average magnetic torque allows one to form a conclusion on the inertial nature of this effect.     

EPR anisotropy induced by a magnetic field in the smectic A phase of a mesogenic Cu(II) complex derived from a Schiff's base

The Q-band electron paramagnetic resonance (EPR) spectrum of the frozen smectic phase of the mesogenic compound bis[N -(4'-n-pentoxyphenyl)-4-n-decyloxysalicylaldiminate] copper(II) is studied. An anisotropic EPR spectrum is observed if freezing from the SmA phase is done in the presence of a magnetic field; the sample tends to orient with the director perpendicular to the magnetic field. The relative intensities of the EPR signal of this exchange coupled system are discussed in relation to the orientational distribution of the molecules. The results appear to be compatible with a biaxial magnetic susceptibility in the SmA phase. This suggests that an ordering of the short axes of the molecules in the plane perpendicular to the director in the SmA mesophase may take place.     

Inertial effects in rotating lyotropic liquid crystals

Abstract

The orientation of the director of a lyotropic liquid crystal with negative anisotropy of the diamagnetic susceptibility is studied when the sample is spun at various speeds and angles from the magnetic field. Different behaviours is observed at low and high spinning speeds where the orientation is governed by the magnetic and the inertial torques, respectively. At intermediate frequencies it is possible to reach an equilibrium between these two torques. The evolution of this equilibrium with the average magnetic torque allows one to form a conclusion on the inertial nature of this effect.     

Rotation in a magnetic field of nematic liquid crystalline samples with a negative anisotropy of their magnetic susceptibility

The behaviour of the mesophase directors when a sample with a negative anisotropy Deltachi in the magnetic susceptibility is rotated at a speed omega in a magnetic field B0 about an axis inclined at an angle beta is investigated by deuterium NMR spectroscopy. There are combinations of beta and omega which lead to the directors aligning along the spinning axis (stable region), and other combinations where the directors are either unaffected by the rotation, or have a timedependent distribution (unstable region). These two regions are separated by a line (the q line) whose position depends on beta and omegac DeltachiB02/2mu0gamma1, where gamma1 is a twist viscosity coefficient. Experiments on 4-n-propyl-4-cyanobicyclohexane (CCH3) are used to demonstrate how the q line, and hence omegac may be determined. Combining this result with a measurement of the anisotropy in the magnetic susceptibility, Deltachi, yields a value for gamma1.     

Simulation of EPR and time resolved EPR lineshapes in partially ordered glasses

Simulation of magnetic resonance spectra of probes in partially ordered glasses requires in principle a numerical integration on the full set of three Euler angles omega=(alpha beta gamma) from a laboratory fixed to a molecule fixed reference frame. It is shown that it is possible to manage efficiently this problem by using the algebraic properties of the Wigner matrix elements. This analysis is applied to time resolved EPR (TREPR) spectra of a series of bis-adducts of C60 in the ordered glass of a nematic liquid crystal solvent. A paramagnetic triplet state is created by light excitation and TREPR spectra are obtained with the external magnetic field set parallel or perpendicular to the director n of the mesophase. The preferred orientation in the mesophase of the triplet state zero field tensor is determined.     

Manipulation of the director in bicellar mesophases by sample spinning: a new tool for NMR spectroscopy.

It is shown that bicellar nematic liquid-crystalline phases can be oriented with the director (the normal to the bicellar plane) at an arbitrary angle to the applied magnetic field by sample rotation around one axis (variable-angle sample spinning) or around two axes successively (switched-angle spinning). This promises to open novel possibilities for NMR studies of bicelles and proteins incorporated into bicelles or dissolved in a solution containing bicelles, including the correlation of several orientations in a two-dimensional NMR experiment.     

Probing the electric field alignment of a thermotropic liquid crystalline polymer by synchrotron radiation

The orientation of a cyclic side-chain thermotropic liquid crystalline material in an AC field was monitored in real-time using synchrotron radiation. Monitoring the realignment processes in the millisecond-to-minute time-scale was made possible by the high X-ray flux. Orientation parameters and response times were calculated as a function of temperature and frequency. Response times decreased exponentially with temperature due to a decrease in the viscosity. Very little dependence of the response time on frequency was observed, except at low temperatures, where a switch from homeotropic to planar alignment of the molecules was detected. This reorientation of the director was studied in real-time and the resulting complex diffraction patterns were due to equal but opposite director rotations from an alignment parallel to the applied electric field to an alignment perpendicular to the applied electric field. The orientation parameters were highest in the central portion of the mesophase temperature range. At temperatures near clearing, the net degree of orientation diminished. Cooling through the mesophase with an applied electric field resulted in much larger orientation parameters than could be obtained by aligning at a fixed temperature in the mesophase.     

Magnetohydrodynamic effects in nematic liquid crystals

The behaviour of a nematic liquid crystal when it is spun about an axis orthogonal to a magnetic field is predicted to be controlled by the critical angular velocity, ω_c. For spinning speeds below ω_c theory shows that the director makes an increasing angle with the field until at ω_c this angle is 45°. Above ω_c the director should rotate with an angular velocity slightly less than that of the sample. Observation in both regimes allows ω_c to be determined; since it depends on the ratio of the diamagnetic anisotropy to the rotational viscosity coefficient of the nematic, this ratio can be measured. However, an experimental investigation by Eastman et al. [1], suggests that the theoretical relationship between ω_c and this ratio may be in error by a factor of about four. We have reanalysed their data in an attempt to check this important claim and have found that there is in fact good agreement between theory and experiment.     

The elastic behaviour of liquid crystal dimers: an ESR investigation of their induced chiral nematic phases

We have attempted to investigate the dependence of the elastic behaviour of liquid crystal dimers on the parity of the spacer linking the two mesogenic groups by using an indirect method. In this the nematic phase formed by the dimers is converted to a chiral nematic by the addition of a chiral dopant. The uniform distribution of the director in the helical structure of the mesosphase is perturbed by the magnetic field of an ESR spectrometer. The extent of the field-induced perturbation is then determined from the appearance of the ESR spectrum of a nitroxide spin probe dissolved in the mesophase. The observed difference in the extent of the field-induced perturbation is analysed in terms of the higher orientational order of the even with respect to the odd dimer. However, the theoretical model fails to account for this difference in behaviour and a possible explanation is discussed.     

Optical microscopy and deuterium N.M.R. of non-ionic amphiphiles which exhibit thermotropic and aqueous lyotropic mesophases

Tetrabenzocyclododecatetraene (I) substituted with eight methoxy-mono-, di-, and triethyleneoxide side chains exhibit the same highly ordered thermotropic mesophase, M. In the methoxydiethyleneoxide (I-2), and methoxytriethyleneoxide (I-3) derivatives this mesophase is also lyotropic and can sustain (at room temperature) up to 40 wt per cent water. The homologue (I-2) exhibits at higher water content another lyomesophase, M_F, which is more fluid and nematic-like. Optical microscopy, differential scanning calorimetry and deuterium N.M.R. of both labelled (I-2) and water as well as of the water ¹⁷O were used to construct the (I-2)-water phase diagram and to characterize the various mesophases. It is found that both M and M_F are uniaxial with negative birefringence and negative anisotropic magnetic susceptibility. The M_F phase readily aligns in a magnetic field and is characterized by fast (∼ 10⁷ s^-1) reorientation of the mesogen molecules about the director. The M phase is apparently columnar, highly ordered and is not readily aligned by a magnetic field. The rate of molecular reorientation in this mesophase is much slower (∼ 10³ s^-1) compared with M_F.     

Electric-field driven director oscillations in a nematic liquid crystal: a NMR investigation

We have investigated the oscillatory behavior of the nematic director for 4-pentyl-4'-cyanobiphenyl (5CB) when it is subjected to a static magnetic field and a sinusoidal electric field. In these experiments the two fields were inclined at about 50 degrees and the frequency of the electric field was varied from several hertz to approximately 1000 Hz. The director orientation was measured using time-resolved deuterium NMR spectroscopy since this has the advantage of being able to determine the state of director alignment in the sample. In fact, for all of the frequencies studied the director is found to remain uniformly aligned. Since the diamagnetic and dielectric anisotropies are both positive the director oscillates in the plane formed by the two fields. These oscillations were observed to continue for many cycles, indicating that the coherence in the director orientation was not lost during this motion. The maximum and minimum angles made by the director with the magnetic field were determined, as a function of frequency, from the NMR spectrum averaged over many thousand cycles of the oscillations. At low frequencies (several hertz) these limiting angles are essentially independent of frequency but as the frequency increases the two angles approach each other and become equal at high frequencies, typically 1000 Hz. Our results are well explained by a hydrodynamic theory in which the sinusoidal time dependence of the electric field is included in the torque-balance equation. This analysis also shows that, for a range of frequencies between the high and low limits, these NMR experiments can give dynamic as well as static information concerning the nematic phase.     

Banded texture decoration of disclinations in a main chain thermotropic aromatic copolyester observed by optical microscopy

A new method for the study of texture and director patterns in a main chain thermotropic aromatic copolyester with a flexible spacer is described, whereby the molecular chain or director orientation of the nematic mesophase becomes decorated by the formation of a banded texture during quenching, without being subjected to a shear. The pattern of the decorated banded texture may be observed directly by polarizing optical microscopy, revealing the complete texture of molecular chain orientation across the whole specimen. The molecular director orientation lies perpendicular to the long axis of the bands. Various types of disclination, including an inversion wall, in the nematic mesophase of a thermotropic aromatic copolyester have been observed. This decorating technique is particularly suited for non-crystallizable main chain liquid crystalline polymers, where the lamellar decoration technique fails.     

Thermotropic homopolyesters. IV. Study of fiber formation

We report a melt spinning and viscosity study of two semiflexible homopolyesters containing both rigid and flexible segments in the repeating unit. Single filaments of the polyesters formed from 4,4′-diacetoxybiphenyl and azelaic acid (PB7) and sebacic acid (PB8), and from 4′-hydroxyphenyl-4-hydroxycinnamate and azelaic acid (C7), were spun at temperatures between 205 and 255°C. The temperature dependence of the Newtonian melt viscosity of PB7 and C7 was investigated, and a range of molecular weights was studied for PB7. The spinning parameters, fiber characteristics, and viscosity-temperature behavior are related to the type of mesophase formed. The mechanical properties of fibers spun from both the nematic and smectic phases of these semiflexible chain polymers were poor. Increasing the polymer molecular weight or extrusion rate only afforded a modest improvement in fiber properties. Most polymers could not be spun at temperatures corresponding to the existence of the single mesophase. Hence the low viscosity typical of the nematic mesophase is not necessarily an advantage in fiber formation from the melt. It appears from these results that this type of polyester does not possess adequate chain extension to develop ultrahigh-modulus properties. The director, which describes the local orientation of molecules within the mesophase, may undergo more frequent variations than is the case for rigid chain polyesters. Mechanisms relevant to flexible polymers may contribute to the development of orientation for this class of nematogenic melts.     

Linear analysis of pattern formation in nematics in oblique magnetic fields

The dynamics of nematic director field reorientation in non-Freedericksz geometries, after a magnetic field H is applied at an oblique angle relatively to the initial homogeneous director n 0 ( H not normal to n 0), is studied considering a magnetic reorientation driven by hydrodynamic instabilities (with backflow). This study is carried out for bounded samples between two parallel plates with planar boundary conditions and with rigid anchoring. Linear stability and wave vector selection analysis predict that, when the angle of the magnetic to the initial director field is increased, for a given magnetic field intensity, two transitions from a homogeneous to a transient distorted director field reorientation can occur: a transition at a first critical angle to an aperiodic distorted director field and a transition at a second critical angle to a periodic distorted director field. It is shown that the periodic mode is cut off at a higher reduced field when the magnetic field acts away from the normal direction.     

Director reorientation in nematics studied by microwave dielectrometry

A new experimental method is presented which is a useful approach in studying the reorientational dynamics in liquid crystals by means of dielectric measurements at microwave frequencies. The theoretical model is developed to describe the motion of the director when it is driven by two orthogonal electric or magnetic fields. A specific set up for the experimental apparatus is described. Experiments in fairly good agreement with the theoretical model are given for a nematic mesophase at different temperatures and field values. The capabilities of the method in monitoring the slow reorientational properties of collective molecular motions in liquid crystals are demonstrated. Possible refinements of the experimental apparatus to allow more quantitative measurements of the different physical parameters of anisotropic media are indicated.     

Structure and properties of the smectic phase in a mesogenic complex of copper with a schiff base

The structural arrangement and the structure of the mesogenic copper compound {C₇H₁₅O-C₆H₃(O)CH-C₆H₄OC₈H₁₇}₂Cu(II) were investigated in the dilute solution, the isotropic melt, the mesophase, and the crystalline state by ESR in conjunction with calorimetry and polarization microscopy. The complex exhibits smectic polymorphism with the following transitions: K 415 S_C 430 S_A 438 I. It was found by ESR that the complexes in the solution and in the isotropic melt have a square-planar trans configuration. In the mesophase part the planar molecules undergo tetrahedral distortion; the planar molecules form the smectic phase, while the distorted molecules are concentrated into microscopic isotropic drops, i.e., the system becomes heterogeneous in the mesophase. In the S_A S_C transition the mesophase is oriented anomalously in the magnetic field (compared with the diamagnetic analogs) with the director orthogonal to the direction of the field.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 3, pp. 370–375, May–June, 1988.     

Proton field-cycling nuclear magnetic resonance relaxometry in the smectic A mesophase of thermotropic cyanobiphenyls: Effects of sonication

Proton field-cycling nuclear magnetic resonance relaxometry is used to study the spin-lattice relaxation dispersion of selected standard smectic A liquid crystals at different temperatures. Relaxation features at both, in the presence and absence of a monochromatic ultrasonic field are considered. We show that the laboratory-frame spin-lattice relaxation time is mainly governed by translational diffusion. Order director fluctuations (ODF) are less important while rotational diffusion seems to be only relevant near the clearing point. Our study suggests that sonication enhances the ODF contribution in the SmA mesophase. Within the framework of the approach we have outlined, different features associated with the ODF mechanism can be investigated.     

Using switched angle spinning to simplify NMR spectra of strongly oriented samples

This contribution describes a method that manipulates the alignment director of a liquid crystalline sample to obtain anisotropic magnetic interaction parameters, such as dipolar coupling, in an oriented liquid crystalline sample. By changing the axis of rotation with respect to the applied magnetic field in a spinning liquid crystalline sample, the dipolar couplings present in a normally complex strong coupling spectrum are scaled to a simple weak coupling spectrum. This simplified weak coupling spectrum is then correlated with the isotropic chemical shift in a switched angle spinning (SAS) two-dimensional (2D) experiment. This dipolar-isotropic 2D correlation was also observed for the case where the couplings are scaled to a degree where the spectrum approaches strong coupling. The SAS 2D correlation of C(6)F(5)Cl in the nematic liquid crystal I52 was obtained by first evolving at an angle close to the magic angle (54.7 degrees ) and then directly detecting at the magic angle. The SAS method provides a 2D correlation where the weak coupling pairs are revealed as cross-peaks in the indirect dimension separated by the isotropic chemical shifts in the direct dimension. Additionally, by using a more complex SAS method which involves three changes of the spinning axis, the solidlike spinning sideband patterns were correlated with the isotropic chemical shifts in a 2D experiment. These techniques are expected to enhance the interpretation and assignment of anisotropic magnetic interactions including dipolar couplings for molecules dissolved in oriented liquid crystalline phases.     

Orientational Behaviour of the Nematic Director upon Macroscopic Rotation at the Magic Angle

The ¹⁹F N.M.R. spectrum of 1,2,2,2-tetrachloro-l,l-difluoroethane has been studied in the nematic liquid crystal ZLI1167 (Merck) upon rotation at the magic angle. The director of the liquid crystal is oriented perpendicular to the spinning axis when the angle between the rotation axis and the magnetic field is less than the magic angle and parallel when this angle is more than the magic angle. It is shown that exactly at the magic angle the spectrum corresponds to a frequency modulated powder pattern. This powder pattern leads to an understanding of the orientational behaviour of the director when a nematic is spun at the magic angle.     

Proton NMR investigation of a hydrogen-bonded liquid crystal gel

Proton NMR is employed to determine director distributions in a hydrogen-bonded liquid crystal gel in the presence of a magnetic field. The samples consist of the mesogen 8CB mixed with small percentages of gelator, which forms a hydrogen-bonded network when the sample is cooled below the gelation point in the isotropic liquid. Since the gelation occurs above the clearing point, a non-oriented random director configuration is frozen in. The configuration of the hydrogen-bonded network is found to be isotropic. It fixes a preferential random local orientation of the nematic director, even in the presence of an external magnetic field of a few Tesla. The NMR spectra of the samples give information on orientation and order in such systems. A simple model for the director field is provided.