Experimental study of the director pattern dynamics in the vicinity of the Fréedericksz twist geometry

We present an experimental study of the transient periodic structures appearing in the nematic director field in the magnetically induced reorientation of the director in the vicinity of the twist Fréedericksz geometry. Thin nematic samples (50?µm thick) were exposed to magnetic fields of variable intensity and orientation relative to the surface aligning direction of the sample. The director reorientation was induced by a rapid rotation of the sample in the static magnetic field producing a misalignment between the director and the magnetic field. The director field was optically monitored during the reorientation process and the transient periodic structures were characterized. Two types of periodic structures could be identified, namely bands and walls. Walls grow from bands close to the twist Fréedericksz geometry. The time dependence of the wave length and inclination of the periodic structures was obtained as a function of the magnetic field intensity and orientation relative to the surface aligning direction of the sample. The results for the bands are compared with the predictions of a model that we specifically developed to account for the non-orthogonal field orientations. It is seen that our model can account rather well for the experimental results considering that it uses only the field rotation time as adjustable parameter. All other model parameters are known.     

Two-dimensional Raman study of the submolecular, electric field-induced reorientation of a nematic liquid crystal

Two-dimensional Raman scattering is presented as a technique for the monitoring of electric field-induced, submolecular reorientation in liquid crystals. The motions of the flexible part and the rigid core of 4-pentyl-(4-cyanophenyl)cyclohexane (PCH5) are independently monitored in response to both step and oscillatory electric fields. Step voltage experiments show that the flexible group reorients before the rigid core. Also, oscillatory electric field experiments demonstrate that the flexible and rigid groups reorient asynchronously. In fact, at periodicities that are shorter than the bulk reorientation times, it is observed that the reorientation of the flexible part is amplified, while the motion of the rigid core is inhibited. The data suggest that the flexible group possesses a small, local dielectric anisotropy that can couple with the electric field to induce an independent, cooperative reorientation when the mobility of the rigid core is restricted.     

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.     

Molecular alignment and field-induced reorientation in a twisted nematic liquid crystal pi-cell

A twisted nematic pi-cell has been studied by optical transmission measurement, polarized Fourier-transform infrared (pFTIR) absorption spectroscopy, and Raman spectroscopy. Our pFTIR results suggest that the LC molecules undergo a restricted rotation about the molecular long axis. The rise and decay times of the optical response were found to be 6 ms and 1.6 ms, respectively. The switching dynamics of the twisted pi-cell was also studied using time-resolved Raman spectroscopy. A normal mode associated with the C-H out-of-plane wag on the LC core was found to be enhanced after the electric field was switched off. Our data show that LC molecules in the twisted pi-cell do not rotate like a rigid molecule during the field-induced reorientation process. The methods employed in this study have yielded valuable information about LC alignment and field-induced reorientation with respect to functional group specificity.     

Molecular alignment and field-induced reorientation in a twisted nematic liquid crystal pi-cell

A twisted nematic pi-cell has been studied by optical transmission measurement, polarized Fourier-transform infrared (pFTIR) absorption spectroscopy, and Raman spectroscopy. Our pFTIR results suggest that the LC molecules undergo a restricted rotation about the molecular long axis. The rise and decay times of the optical response were found to be 6 ms and 1.6 ms, respectively. The switching dynamics of the twisted pi-cell was also studied using time-resolved Raman spectroscopy. A normal mode associated with the C-H out-of-plane wag on the LC core was found to be enhanced after the electric field was switched off. Our data show that LC molecules in the twisted pi-cell do not rotate like a rigid molecule during the field-induced reorientation process. The methods employed in this study have yielded valuable information about LC alignment and field-induced reorientation with respect to functional group specificity.     

Computer simulation of elongated bipolar nematic droplets II. External field aligned normal to the droplet axis of symmetry

Numerical results from the modelling and computer simulation of the magnetic-induced director reorientation dynamics in elongated bipolar nematic droplets are presented in this paper. The magnetic field is applied normally to the droplet axis-of-symmetry direction, which is one possible scenario found in applications of polymer dispersed liquid crystal (PDLC) films. This case has not yet been studied numerically, and its understanding is far from complete. The model is composed of the Leslie-Ericksen and Frank continuum theories and is solved in two dimensions since bipolar nematic droplets exhibit mirror symmetry in certain planes. The numerical results replicate frequently reported experimental observations on the performance of PDLC films. These observations include the ubiquitous exponential increase followed by saturation in light transmittance as the external applied field increases, and the exponential increase (decrease) followed by saturation as time increases in the on (off)-state. Furthermore, in contrast to current understanding for both the on- and off-states, the model predicts that the directors in the centre (surface) region of the droplet exhibit a dead time (no dead time) before reorientation. The numerical results presented in this paper provide a better understanding of the director reorientation dynamics in elongated bipolar nematic droplets; this can be used to optimize the design and performance of devices using PDLC films.     

Computer simulation of elongated bipolar nematic droplets II. External field aligned normal to the droplet axis of symmetry

Numerical results from the modelling and computer simulation of the magnetic-induced director reorientation dynamics in elongated bipolar nematic droplets are presented in this paper. The magnetic field is applied normally to the droplet axis-of-symmetry direction, which is one possible scenario found in applications of polymer dispersed liquid crystal (PDLC) films. This case has not yet been studied numerically, and its understanding is far from complete. The model is composed of the Leslie-Ericksen and Frank continuum theories and is solved in two dimensions since bipolar nematic droplets exhibit mirror symmetry in certain planes. The numerical results replicate frequently reported experimental observations on the performance of PDLC films. These observations include the ubiquitous exponential increase followed by saturation in light transmittance as the external applied field increases, and the exponential increase (decrease) followed by saturation as time increases in the on (off)-state. Furthermore, in contrast to current understanding for both the on- and off-states, the model predicts that the directors in the centre (surface) region of the droplet exhibit a dead time (no dead time) before reorientation. The numerical results presented in this paper provide a better understanding of the director reorientation dynamics in elongated bipolar nematic droplets; this can be used to optimize the design and performance of devices using PDLC films.     

Simulation of reorientation dynamics in bipolar nematic droplets

A two-dimensional model composed of a synthesis of the Leslie-Ericksen continuumtheory of nematics and the Euler-Lagrange equation for surface director motion is used to study the magnetic-induced director reorientation dynamics confined in spherical bipolar droplets with viscoelastic surfaces. The magnetic field is restricted to the droplet axis of symmetry direction. The numerical results indicate that the surface viscosity and anchoring strength must be taken into account to describe accurately director reorientation dynamics in droplets. In addition, the numerical results replicate frequently reported experimental observations on the performance of polymer dispersed liquid crystal films. These observations include the familiar exponential increase followed by saturation in light transmittance as the external applied field increases, and the exponential increase (decrease) followed by saturation as time increases in the on (off) state. Furthermore, this model is able to predict precisely the relationships between the rise and decay times and the external applied field strength, and the fact that the switching field strength is inversely proportional to droplet size.     

Investigation of flexoelectric properties of a palladium-containing nematic liquid crystal, Azpac, and its mixtures with MBBA

Flexoelectricity of pure Azpac (an HOAB-palladium complex) was studied using planar nematic layers under an in-plane electric field. Longitudinal domains were observed with a period inversely proportional to the applied d.c. electric field. These domains were considered as a first experiment manifestation of the theoretical prediction of R. B. Meyer (1969) and their study has permitted the evaluation of the difference in flexo-coefficientse_1z - e_3x. Their appearance can also be followed for the non-complexed HOAB, using instant video-microscopy frames.

Mixtures of Azpac, up to 10wt%, and MBBA were oriented homeotropically and band flexoelectric deformations were observed, both in d.c. and in a.c. (1 to 1000 Hz) electric fields normal to the director. The dynamics of director reorientation were studied by the method of flexoelectric light modulation. A system comprising a He-Ne laser and a lock-in amplifier interfaced by a PC was developed. By operating this in a frequency sweep regime, viscoelastic spectra of director dynamics were recorded. These spectra were excited using a linear flexoelectric coupling mechanism. Breaks in the spectra were observed in the range 200 to 600 Hz, indicating a cross-over from bulk to surface dissipation of energy. For the first time, a surface viscosity of 2.6 × 10^-8Jsm^-2 was determined for MBBA homeotropically anchored on a DMOAP-coated glass surface.

In concentrations at low as 2.5 wt%, Azpac was found to cancel the bend flexo-coefficient of MBBA and at higher concentrations, a steep rise in the flexo-coefficient of the mixture was observed, but with an opposite sign. Thus, the application of Azpac as an effective additive for adjustment of the value and sign of the flexo-coefficient in flexoelectro-optic displays or light modulators could be suggested.     

Submolecular dynamics of amorphous polymers probed by two-dimensional infrared (2D IR) spectroscopy

Two-dimensional infrared (2D IR) spectroscopy was used to probe the submolecular dynamics of atactic polystyrene. 2D IR is a powerful analytical technique especially suited for the elucidation of localized motions of polymer segments. In 2D IR, a polymer sample is excited by a small-amplitude oscillatory strain at a frequency in the acoustic range. The fluctuation of IR dichroism signals resulting from the strain-induced reorientation of electric dipole-transition moments is monitored with a time-resolved spectrometer. Spectra defined by two independent wavenumber axes are constructed by applying a correlation analysis to such signals. The 2D spectra provide detailed information about the local dynamics of submolecular constituents of the system. From the sign of cross peaks in the synchronous 2D IR spectrum of glassy polystyrene, it is shown that the main-chain backbone of polystyrene reorients in the direction of applied strain. Cross peaks in an asynchronous 2D IR spectrum reveal highly localized reorientational motions of phenyl side groups occurring more or less independently of the main-chain realignment. In the glassy state, the phenyl ring tends to fold back along the main-chain, indicating that there exists a highly constrained local distortion of side groups during deformation.     

UV tuning of the electro-optical and morphology properties in polymer-dispersed liquid crystals

Polymer-dispersed liquid crystal (PDLC) films operating in reverse mode are transparent electro-optical devices, which can be turned into an opaque state by application of a suitable electric field. The effect was investigated of different UV powers, used during the polymerization process, on the electro-optical and morphology properties of PDLCs, working in reverse mode operation. Films were obtained by UV polymerization of mixtures of a low molecular weight nematic liquid crystal and a photopolymerizable liquid crystal monomer, homeotropically aligned by rough conductive surfaces. The electro-optical and morphology properties of samples were related to the polymerization conditions. Samples polymerized by lower UV powers exhibited “polymer ball” morphology and an electro-optical response due to the liquid crystal director reorientation, whereas samples obtained at higher UV powers showed a “Swiss cheese” morphology and an electro-optical response due to dynamic scattering. In addition, we observed by conductivity and IR measurements that UV exposure induces a degradation of the nematic liquid crystal.     

Correlation between Ferromagnetic Layer Easy Axis and the Tilt Angle of Self Assembled Chiral Molecules

The spin–spin interactions between chiral molecules and ferromagnetic metals were found to be strongly affected by the chiral induced spin selectivity effect. Previous works unraveled two complementary phenomena: magnetization reorientation of ferromagnetic thin film upon adsorption of chiral molecules and different interaction rate of opposite enantiomers with a magnetic substrate. These phenomena were all observed when the easy axis of the ferromagnet was out of plane. In this work, the effects of the ferromagnetic easy axis direction, on both the chiral molecular monolayer tilt angle and the magnetization reorientation of the magnetic substrate, are studied using magnetic force microscopy. We have also studied the effect of an applied external magnetic field during the adsorption process. Our results show a clear correlation between the ferromagnetic layer easy axis direction and the tilt angle of the bonded molecules. This tilt angle was found to be larger for an in plane easy axis as compared to an out of plane easy axis. Adsorption under external magnetic field shows that magnetization reorientation occurs also after the adsorption event. These findings show that the interaction between chiral molecules and ferromagnetic layers stabilizes the magnetic reorientation, even after the adsorption, and strongly depends on the anisotropy of the magnetic substrate. This unique behavior is important for developing enantiomer separation techniques using magnetic substrates.     

Photoinduced optical anisotropy in films of photochromic liquid crystalline polymers

The light-induced modification of the optical properties of photochromic liquid crystalline (side-group) polymers (LCPs) containing azobenzene moieties was studied. Films of such polymers were irradiated with unpolarized and linearly polarized light. Unpolarized irradiation results in a modification of the order parameter, whereas the director orientation remains constant. The light-induced disturbance of the supramolecular order is strongly dependent on the structure of the polymer. A correlation with the enthalpic stability of the liquid crystalline phases is given. Linearly polarized irradiation causes a modification of the order parameter and a reorientation of the side-groups towards a direction perpendicular to the electric vector of the actinic light. This reorientation process is caused by an angular-dependent photoselection within the steady state of the photoisomerization of the azobenzene units. The amount and kinetic of the reorientation differ considerably as a function of certain structural features of the polymers, such as the content of photochromic moieties and the lengths of the spacer chains between the polymeric backbone and the rod-like moieties. It is shown that under certain circumstances the angular-dependent photoselection process may cause a reorientation of the non-photochromic moieties by a cooperative process. The result is a light-induced rotation of the optical axis of the LCP and thus an efficient modification of the birefringent and dichroic properties. This effect can be used in optical data storage.     

Field-induced alignment of the nematic director: studies of nuclear magnetic resonance spectral oscillations in the limit of fast director rotation

Time-resolved NMR spectroscopy is a powerful method to investigate field-induced rotation of the director in a nematic liquid crystal. The method requires that the director does not rotate significantly during the acquisition of the free induction decay and hence the NMR spectrum. We have extended the method to systems where this is not the case and the observed NMR spectra are now found to contain novel oscillatory features. To understand these oscillations, we have developed a model combining both director and spin dynamics. In addition to increasing the information content of the time-resolved NMR spectra, it also proves possible to determine the field-induced relaxation time from a single spectrum.     

Strain-induced director reorientation in nematic liquid single crystal elastomers

The strain-induced director reorientation process in nematic liquid single crystal elastomers is investigated for the case of an arbitrary angle between the original director and the external stress axis. If the mechanical stress is applied perpendicular to the original director axis, the reorientation process sets in at a threshold strain. The mesogens are realigning ‘clockwise’ or ‘counter-clockwise’ towards the axis of external stress, simultaniously the monodomain structure is distorted and a periodic pattern formation is observed. If the mechanical stress is applied obliquely with respect to the original director axis, a uniform director reorientation is obtained with retention of the monodomain structure. No threshold strain is observed for this process. The existence of a threshold strain in the case of a perpendicular arrangement of the director to the external stress axis can be understood as a consequence of the distortion of the monodomain structure.     

Peculiarities of electric field alignment of nonlinear optical chromophores incorporated into thin film polymer matrix

The electric field poling process of free-standing films of poly(methyl methacrylate) (PMMA) matrix doped with the nonlinear optical compound 4-(dimethylamino)-4'-nitrostilbene (DMANS) was investigated by molecular simulation methods. The influence of the vacuum/bulk interfacial regions on static and dynamic properties, including the glass transition temperature T_g and the field-induced chromophore reorientation, was studied by employing films of three different thicknesses and by comparison with previous work on the bulk system. The interfacial region, defined as the region, where the local density increases from zero to the bulk density, is about 2 nm wide, independent of the film thickness. T_g decreases with decreasing film thickness, in accord with previous experimental work and theoretical predictions. The resistance against field-induced chromophore reorientation in the liquid state is found to increase strongly with the film thickness.     

Structure and internal dynamics of a side chain liquid crystalline polymer in various phases by molecular dynamics simulations: a step towards coarse graining

Side chain liquid crystalline polymer with relatively long spacer was modeled on a semiatomistic level and studied in different liquid crystalline phases with the aid of molecular dynamics simulations. Well equilibrated isotropic, polydomain smectic and monodomain smectic phases were studied for their structural and dynamic properties. Particular emphasis was given to the analysis on a coarse-grained level, where backbones, side chains, and mesogens were considered in terms of their equivalent ellipsoids. The authors found that the liquid crystalline phase had a minor influence on the metrics of these objects but affected essentially their translational and orientational order. In the monodomain smectic phase, mesogens, backbones, and side chains are confined spatially. Their diffusion and shape dynamics are frozen along the mesogen director (the one-dimensional solidification) and the reorientation times increase by one to one-and-half orders of magnitude. In this phase, besides obvious orientational order of mesogens and side chains, a stable detectable order of the backbones was also observed. The backbone director is confined in the plane perpendicular to the mesogen director and constantly changes its orientation within this plane. The backbone diffusion in these planes is of the same range as in the polydomain smectic phase at the same temperature. A detailed analysis of the process of field-induced growth of the smectic phase was performed. The study revealed properties of liquid crystalline polymers that may enable their future fully coarse-grained modeling.     

Computer simulation of elongated bipolar nematic droplets 1. External field aligned parallel to the droplet axis of symmetry

The magnetically-induced transient nematic director reorientation dynamics, confined in elongated bipolar droplets, is studied in this paper. Numerical results are obtained by solving the Leslie-Ericksen continuum theory in ellipses. The aspect ratio is varied to determine the effect of droplet shape on director reorientation dynamics. The magnetic field is restricted to the droplet axis of symmetry direction, which has not yet been studied but is fundamentally important in polymer dispersed liquid crystal (PDLC) film operation. The numerical results replicate frequently-reported experimental observations on the performance of PDLC films. These observations include the familiar exponential increases followed by saturation in light transmittance as the external applied field increases and the exponential increase (decrease) followed by saturation as time increases in the on- (off-) state. In addition, the experimental observation that switching field strength increases while decay time decreases as the droplet becomes more elongated, are also exhibited by the numerical results.     

Computer simulation of elongated bipolar nematic droplets 1. External field aligned parallel to the droplet axis of symmetry

The magnetically-induced transient nematic director reorientation dynamics, confined in elongated bipolar droplets, is studied in this paper. Numerical results are obtained by solving the Leslie-Ericksen continuum theory in ellipses. The aspect ratio is varied to determine the effect of droplet shape on director reorientation dynamics. The magnetic field is restricted to the droplet axis of symmetry direction, which has not yet been studied but is fundamentally important in polymer dispersed liquid crystal (PDLC) film operation. The numerical results replicate frequently-reported experimental observations on the performance of PDLC films. These observations include the familiar exponential increases followed by saturation in light transmittance as the external applied field increases and the exponential increase (decrease) followed by saturation as time increases in the on- (off-) state. In addition, the experimental observation that switching field strength increases while decay time decreases as the droplet becomes more elongated, are also exhibited by the numerical results.