Computer simulations of the interactions between liquid crystal molecules and polymer surfaces III. Use of pseudopotentials to represent the surface

Results are presented from atomistic computer simulations of single molecules of the liquid crystals 4-n-octyl-4'-cyanobiphenyl and 4-n-heptyl-2-fluorophenyl 4-octyloxybiphenyl-4'-carboxylate in contact with crystalline polymeric surfaces. The simulations were performed as part of a study of the nature of the alignment interactions in liquid crystal displays and other devices. In contrast to previous atomistic simulations of this type, the crystalline polymer surface was represented by a pseudopotential, effectively replacing the parallel array of polymer chains with a periodic corrugation. The use of a pseudopotential has two main advantages. Firstly, it allows an exploration of the general principles behind liquid crystal alignment on crystalline surfaces, free from the obscuring effect of specific chemical interactions. Secondly, it permits a significant saving in computer time compared with using a surface constructed from explicit atom-pair potentials. In the present work, the aligning capabilities of two simple sinusoidal pseudopotential functions were tested. In each case the wavelength and amplitude of the surface corrugations were varied. It was found that the degree of orientational order of liquid crystal molecules in contact with the surfaces increased with increasing amplitude and decreasing wavelength of the corrugations. Aspects of the two potentials were then combined to produce a pseudopotential designed to represent specific polymeric crystal surfaces. In this case, the (1 0 0) and (1 1 0) faces of polyethylene were modelled. Comparisons with earlier simulations employing atomistic surfaces indicate a good agreement between the orientation functions produced by the two methods. However, the pseudopotential approach uses significantly less computer time, allowing a more reliable determination of orientation within a given timescale.     

Computer simulations of the interactions between liquid crystal molecules and polymer surfaces III. Use of pseudopotentials to represent the surface

Results are presented from atomistic computer simulations of single molecules of the liquid crystals 4-n-octyl-4'-cyanobiphenyl and 4-n-heptyl-2-fluorophenyl 4-octyloxybiphenyl-4'-carboxylate in contact with crystalline polymeric surfaces. The simulations were performed as part of a study of the nature of the alignment interactions in liquid crystal displays and other devices. In contrast to previous atomistic simulations of this type, the crystalline polymer surface was represented by a pseudopotential, effectively replacing the parallel array of polymer chains with a periodic corrugation. The use of a pseudopotential has two main advantages. Firstly, it allows an exploration of the general principles behind liquid crystal alignment on crystalline surfaces, free from the obscuring effect of specific chemical interactions. Secondly, it permits a significant saving in computer time compared with using a surface constructed from explicit atom-pair potentials. In the present work, the aligning capabilities of two simple sinusoidal pseudopotential functions were tested. In each case the wavelength and amplitude of the surface corrugations were varied. It was found that the degree of orientational order of liquid crystal molecules in contact with the surfaces increased with increasing amplitude and decreasing wavelength of the corrugations. Aspects of the two potentials were then combined to produce a pseudopotential designed to represent specific polymeric crystal surfaces. In this case, the (1 0 0) and (1 1 0) faces of polyethylene were modelled. Comparisons with earlier simulations employing atomistic surfaces indicate a good agreement between the orientation functions produced by the two methods. However, the pseudopotential approach uses significantly less computer time, allowing a more reliable determination of orientation within a given timescale.     

Computer simulation of interactions between liquid crystal molecules and polymer surfaces I. Alignment of nematic and smectic A phases

Results are presented from computer simulations of liquid crystal molecules in contact with polymeric surfaces. These form part of a study of the complex alignment interactions which operate in liquid crystal displays. The liquid crystal molecules considered are 4-n-pentyl-4'-cyanobiphenyl (5CB) and 4-n-octyl-4'-cyanobiphenyl (8CB); the polymeric surfaces simulated were crystalline polyethylene, polypropylene, poly(vinyl alcohol) and Nylon 6. Additional simulations were performed using graphite as a substrate. Polyethylene, poly(vinyl alcohol) and Nylon 6 were all found to induce orientation of the 5CB and 8CB molecules parallel to the polymer chain axes, as would be expected from experimental studies. On the other hand, polypropylene induces many different orientations with no clear preference for either. No evidence was found for the alignment of 8CB molecules on graphite substrates, in disagreement both with experimental findings and the results from previous simulations. The nature of the alignment interactions and possible reasons for the observed discrepancies are discussed.     

Computer simulation of interactions between liquid crystal molecules and polymer surfaces I. Alignment of nematic and smectic A phases

Results are presented from computer simulations of liquid crystal molecules in contact with polymeric surfaces. These form part of a study of the complex alignment interactions which operate in liquid crystal displays. The liquid crystal molecules considered are 4-n-pentyl-4'-cyanobiphenyl (5CB) and 4-n-octyl-4'-cyanobiphenyl (8CB); the polymeric surfaces simulated were crystalline polyethylene, polypropylene, poly(vinyl alcohol) and Nylon 6. Additional simulations were performed using graphite as a substrate. Polyethylene, poly(vinyl alcohol) and Nylon 6 were all found to induce orientation of the 5CB and 8CB molecules parallel to the polymer chain axes, as would be expected from experimental studies. On the other hand, polypropylene induces many different orientations with no clear preference for either. No evidence was found for the alignment of 8CB molecules on graphite substrates, in disagreement both with experimental findings and the results from previous simulations. The nature of the alignment interactions and possible reasons for the observed discrepancies are discussed.     

Aliphatic polyimides as alignment layers for surface stabilized ferroelectric smectic C liquid crystal cells

Eight aliphatic polyimides have been synthesized and tested as alignment layers for surface stabilized ferroelectic liquid crystals with a number of room temperature ferroelectric mixtures. The cone angles are used as a quantitative measure of the bistability obtained in these cells. The effect of the structure of the polyimides on the cone angles obtained is discussed. It is shown that the structure of the polymer alignment layer strongly influences the cone angle found between the relaxed states in a surface stabilized ferroelectric liquid crystal cell. Highly crystalline polymers give a larger cone angle than less crystalline homologues.     

Sixfold bond orientational properties of a model liquid crystal in the dimensional crossover of B phases: a computer simulation study

A wide range of NPT simulations of a bead necklace liquid crystal model in the crystal B, smectic B, smectic A, and nematic phases have been performed. Systems with up to 21 600 molecules have been studied to observe the behavior of slowly decaying spatial correlation functions. The pair correlation function and its in-plane restriction are consistent with a crystalline phase made of independent two-dimensional crystalline layers. Smectic B phase is studied by the bond orientational pair correlation functions g(6) and its extension g(6ext). The first reaches a constant value, which seems to rule out a classical hexatic phase. The latter shows a power-law decay within the layers: its typical decay exponent (eta(6ext)) is evaluated. Relationships between multiple harmonics of the C(6n) order parameter have been evaluated through the whole range of existence of B phases (crystalline and smectic): the extension to the crystalline phase holds and provides an excellent fit of the simulation data.     

Small angle X-ray scattering study of chiral side chain liquid crystalline polymers in 5CB and 8CB solvents

Small angle X-ray scattering was used to examine the new chiral side chain liquid crystalline polyacrylates (P_4M and P_11M) and their mixtures (2 wt %) in the low molar mass nematogenics 4'-n-pentyl-4-cyanobiphenyl (5CB) and 4'-octyl-4-cyanobiphenyl (8CB). Complementary data were obtained by polarizing optical microscopy. In agreement with previous studies, the mesophases of the bulk polymers show a dependence on the aliphatic spacers linking the mesogenic units to the polymer backbone. Chiral nematic and smectic A₁ phases were observed for the polyacrylates with four (P_4M) and eleven (P_11M) methylene units as spacers, respectively. In solution with 5CB and 8CB, P_4M exhibits an injected smectic phase, whereas P_11M maintains the smectic arrangement already observed in the bulk, with swollen smectic layers. In all the mixtures, layer stability was found to depend on the liquid crystal used as solvent, as well as on the temperature. At temperatures corresponding to the nematic 5CB and 8CB, the coexistence of two mesophases was observed in the mixtures. Moreover, with the liquid crystal solvents in the isotropic phase, microstructures suspended in the solvent matrix containing the liquid crystalline polymer in the smectic arrangement were detected.     

Small angle X-ray scattering study of chiral side chain liquid crystalline polymers in 5CB and 8CB solvents

Small angle X-ray scattering was used to examine the new chiral side chain liquid crystalline polyacrylates (P_4M and P_11M) and their mixtures (2?wt?%) in the low molar mass nematogenics 4′-n-pentyl-4-cyanobiphenyl (5CB) and 4′-octyl-4-cyanobiphenyl (8CB). Complementary data were obtained by polarizing optical microscopy. In agreement with previous studies, the mesophases of the bulk polymers show a dependence on the aliphatic spacers linking the mesogenic units to the polymer backbone. Chiral nematic and smectic A₁ phases were observed for the polyacrylates with four (P_4M) and eleven (P_11M) methylene units as spacers, respectively. In solution with 5CB and 8CB, P_4M exhibits an injected smectic phase, whereas P_11M maintains the smectic arrangement already observed in the bulk, with swollen smectic layers. In all the mixtures, layer stability was found to depend on the liquid crystal used as solvent, as well as on the temperature. At temperatures corresponding to the nematic 5CB and 8CB, the coexistence of two mesophases was observed in the mixtures. Moreover, with the liquid crystal solvents in the isotropic phase, microstructures suspended in the solvent matrix containing the liquid crystalline polymer in the smectic arrangement were detected.     

A small angle neutron scattering study of the conformation of a side chain liquid crystal poly(methacrylate) in the smectic C phase

The conformation of the backbone in the side chain liquid crystal polymer poly\[ omega (4-methoxybiphenyl-4-yloxy)butyl methacrylate] has been studied in the smectic C and nematic phases. Small angle neutron scattering experiments were performed on mixtures of molecules with perdeuteriated backbones and unlabelled molecules. The polymer is found to adopt an oblate conformation in the smectic C phase. The components of the radius of gyration parallel and perpendicular to the director are determined as a function of temperature from Guinier plots of the SANS data. The radii of gyration do not vary across the smectic phase and are found to be Rg,||=(27+/-1)A, Rg, =(42+/-1)A. These results are compared with recent SANS results for other side chain liquid crystal polymers.     

Polymer nanostructure development of fluorinated and aliphatic monoacrylates in smectic liquid crystals via photopolymerization

To develop viable polymer stabilized liquid crystal systems, it is crucial to understand the factors that affect polymer nanostructure evolution. This work examines the influence of the photopolymerization of aliphatic and fluorinated monoacrylate monomer within a room temperature smectic liquid crystal (LC). Additionally, the effect of LC order on polymerization kinetics, monomer and polymer organization, and the effect of the polymer on LC properties have been examined. Through this work, insight has been gained regarding the impact that the introduction of a fluorinated monoacrylate monomer has on polymerization kinetics, LC organization, and monomer/polymer segregation and organization within a polymer/LC system. Fluorinated moieties lower the surface energy of the monomer to enhance segregation between the smectic layers of the LC as compared with an analogous aliphatic monomer. Additionally, the enhanced segregation significantly increases the polymerization rate in the smectic phase and drives the continued segregation of the fluorinated polymer during and after polymerization. Fluorination also leads to the formation of an ordered polymer nanostructure if polymerized in ordered LC phases. This ordering is particularly evident when the fluorinated monomer is polymerized in the smectic phase in which the monomer is organized between the smectic layers of the LC. In addition, the ordered polymer structure found with the fluorinated monomer in the smectic phase leads to continued birefringence above the clearing point of the LC due to surface interactions between the LC and the ordered fluorinated polymer. The continued birefringence offers an exceptional opportunity to examine how factors such as polymer molecular mass and UV light intensity affect the overall polymer morphology of these polymer/LC systems. As the initiator concentration and UV light intensity are decreased, longer polymer chains form lattice-type morphologies; whereas, shorter polymer chains form smoother morphologies that more closely mirror the texture of the LC smectic phase.     

Polymer nanostructure development of fluorinated and aliphatic monoacrylates in smectic liquid crystals via photopolymerization

To develop viable polymer stabilized liquid crystal systems, it is crucial to understand the factors that affect polymer nanostructure evolution. This work examines the influence of the photopolymerization of aliphatic and fluorinated monoacrylate monomer within a room temperature smectic liquid crystal (LC). Additionally, the effect of LC order on polymerization kinetics, monomer and polymer organization, and the effect of the polymer on LC properties have been examined. Through this work, insight has been gained regarding the impact that the introduction of a fluorinated monoacrylate monomer has on polymerization kinetics, LC organization, and monomer/polymer segregation and organization within a polymer/LC system. Fluorinated moieties lower the surface energy of the monomer to enhance segregation between the smectic layers of the LC as compared with an analogous aliphatic monomer. Additionally, the enhanced segregation significantly increases the polymerization rate in the smectic phase and drives the continued segregation of the fluorinated polymer during and after polymerization. Fluorination also leads to the formation of an ordered polymer nanostructure if polymerized in ordered LC phases. This ordering is particularly evident when the fluorinated monomer is polymerized in the smectic phase in which the monomer is organized between the smectic layers of the LC. In addition, the ordered polymer structure found with the fluorinated monomer in the smectic phase leads to continued birefringence above the clearing point of the LC due to surface interactions between the LC and the ordered fluorinated polymer. The continued birefringence offers an exceptional opportunity to examine how factors such as polymer molecular mass and UV light intensity affect the overall polymer morphology of these polymer/LC systems. As the initiator concentration and UV light intensity are decreased, longer polymer chains form lattice-type morphologies; whereas, shorter polymer chains form smoother morphologies that more closely mirror the texture of the LC smectic phase.     

Molecular dynamics simulations of water droplets on polymer surfaces

Molecular dynamics simulations were used to study the wetting of polymer surfaces with water. Contact angles of water droplets on crystalline and two amorphous polyethylene (PE) and poly(vinyl chloride) (PVC) surfaces were extracted from atomistic simulations. Crystalline surfaces were produced by duplicating the unit cell of an experimental crystal structure, and amorphous surfaces by pressing the bulk polymer step by step at elevated temperature between two repulsive grid surfaces to a target density. Different-sized water droplets on the crystalline PE surface revealed a slightly positive line tension on the order of 10(-12)-10(-11) N, whereas droplets on crystalline PVC did not yield a definite line tension. Microscopic contact angles produced by the simple point charge (SPC) water model were mostly a few degrees smaller than those produced by the extended SPC model, which, as the model with lowest bulk energy, presents an upper boundary for contact angles. The macroscopic contact angle for the SPC model was 94 degrees on crystalline PVC and 113 degrees on crystalline PE. Amorphicity of the surface increased the water contact angle on PE but decreased it on PVC, for both water models. If the simulated contact angles on crystalline and amorphous surfaces are combined in proportion to the crystallinity of the polymer in question, simulated values in relatively good agreement with measured values are obtained.     

The influence of layer curvature on switching in ferroelectric B2 phases of liquid crystals having bent-shape molecules

In the B₂ phase of liquid crystalline compounds with bent-shape molecules ferroelectric switching can occur either by molecular rotation on the cone or by rotation of the molecule about its long axis (so-called chirality flipping), or by both mechanisms simultaneously. When the smectic layers of the B₂ phase are non-deformed and parallel the rotation of molecules under an external electric field occurs readily on the surface of the cone, while rotation around the long molecular axis is hindered by an energy barrier. Imposed deformation of smectic layers leads to interaction between local layer curvatures and molecular orientation, which results in the energy barrier hindering the molecular rotation by a cone. For appropriate constants describing this interaction the energy barrier can be so high that chirality flipping becomes the principal switching mode. An increase in the electric field can eliminate layer curvature, and therefore the energy barrier, so that switching with molecular rotation on the cone becomes possible. In the present contribution these mechanisms of switching are discussed and the influence of layer curvature on the switching mode is demonstrated.     

Mimicking the behaviour of rigid rod molecules. Smectic H liquid crystals from amphiphilic quaternary ammonium salts

The effect of secondary hydrogen-bonding interactions on the crystalline and liquid crystalline phases of quaternary ammonium salts functionalised with a carboxylic group attached at the polar head through a decyl spacer of a homologous series of N-alkyl-N-carboxydecyl-N,N-dimethylammonium bromides was investigated by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction. The low-temperature crystal phases were found to have a lamellar structure in which the ammonium bromide groups are arranged within the layers in two distinct planes, alternately separated by single layers of alkyl chains and double layers of carboxydecyl chains coupled through the carboxyl end groups. At higher temperatures, although these molecules were made from soft flexible chains, smectic H mesophases were identified. The smectic layers were found to be formed by the same two ionic planes alternately separated by the alkyl and carboxydecyl sub-layers. The smectic structure was compared with the three-dimensional positional order observed in the smectic T phase of dihydroxyl functionalised quaternary ammonium salts already described in the literature.     

Direct observation of the main-chain conformation of a combined liquid-crystal polymer

The conformation of the main-chain (backbone) of a combined main-chain/side-chain liquid crystalline polymer has been qualitatively determined by small angle neutron scattering in the oriented nematic, the smectic A and the smectic C phases. The polymer backbone presents only a weak anisotropy, of prolate shape, in the nematic and the smectic C phases. A stronger reorientation of the backbones in the direction of the applied magnetic field is measured for the S_A phase. However, this anisotropy remains small compared to the stretching of a main-chain liquid crystal polymer and the smectic structure results apparently from side-chain ordering. On the other hand, hydrodynamic measurements show that the combined polymer, in solvent, is as flexible as a polystyrene chain. This result is compatible with an explanation for the weak observed anisotropy.     

Synthesis and thermotropic liquid-crystalline properties of N-alkylpyridinium bromides substituted with a terphenylene moiety

Molecules containing a terphenylene core, two alkyl chains and a pyridinium ring associated with its bromine counterion were synthesised and their liquid crystalline properties were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The results were compared with those of chemical intermediates, which also develop a liquid crystalline behaviour. Both intermediates and pyridinium salts showed a rich polymorphism at temperatures ranging from around 100 to 200°C and 115 to 220°C, respectively. X-ray results indicate that both intermediates and pyridinium salts develop tilted smectic mesophases with molecules stacked in single and double layers, respectively. The tilt angle of some of these compounds decreases so markedly upon cooling that molecules attain almost an orthogonal position. The stacking of molecules in the smectic layers was explained in terms of the mutual repulsion interactions between the terphenylene core, the alkyl chains and the ionic species (the pyridinium ring associated with its counterion) and it was proposed that the π–π interactions between the long aromatic cores counterbalance the strong forces between the ionic species, leading to a full segregation of these molecular parts in periodic sublayers. A molecular arrangement model is proposed for these salts.     

Liquid crystalline 3-, 4- and 6-armed star molecules based on nitromethane-trispropanol or pentaerythritol without mesogen spacers

Some molecules of unusual shape and apparently non-linear geometry, with mesogens tied directly to a central unit (for example, tetrahedral pentaerythritol), have been investigated for liquid crystalline behaviour. It was found that these three-, four- and six-armed 'star' molecules generated liquid crystalline mesophases, which were characterized by DSC, optical microscopy and X-ray diffraction. The temperature ranges of the fluid mesophases for the thermotropic compounds were above 158°C for the three-armed molecules and above 219°C for the four-and six-armed 'stars'. All the liquid crystalline compounds exhibited a smectic phase, which appears to be smectic A, with the molecules in their fully extended conformations within the layers. Some of the compounds also had a smectic phase of higher order or a nematic phase.     

Effect of smectogenicity of the ionic groups on the thermotropic liquid crystalline behavior of pyridinium and poly(4-vinylpyridinium) salts quaternized with mesogenic groups

In order to demonstrate the important smectic power of the ionic functions present in mesogenic molecules, a series of N-alkylpyridinium bromides ω-substituted with (4-cyanobiphenylyl)oxy or [4-(2-methyl-1-butoxy)biphenylyl]oxy mesogenic group and their analogous 4-vinylpyridinium polymers were synthesized and characterized. The liquid crystalline behavior was studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. Smectic mesophases, namely A, B, and E, were identified for the low molecular weight compounds, whereas smectic A and E mesophases were identified for the analogous polymers. Both structures were found to be very similar. They consist of single layers of upright molecules laterally arranged head-to-tail; the polymer backbone is inserted in between the layers. The monolayer smectic ordering observed in spite of the presence of the interacting cyano and chiral groups demonstrates the prevailing effect of the electrical interactions upon the structural organization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2569–2577, 1997     

Effects of polymer surface structures on liquid crystal alignment studied with molecular dynamics simulations

Effects of polymer surface structures on surface alignment of liquid crystal molecules were studied by comparison with our previous results of molecular dynamics simulations. An adsorption-related liquid crystal molecule alignment on the packed polyimide surface was found in the simulation study. In this article, we first compared the alignment on a sparse polyimide surface with the previous results of the packed polyimide surface to see effects of polymer surface density. The excluded volume effect with the polyimide domain edges additionally contributed to alignment of the liquid crystal molecules on the sparse surface, and resulted in a similar alignment structure (i.e. alignment direction and tilt angle) to the packed cases. Secondly, we made similar simulations by changing the polymer from a polyimide to a polyamide with similar polymer chain density. Differences between the corresponding packed polyimide case were found mainly in the energetics (the polyamide had about two thirds of the adsorption energy of the liquid crystal molecule as the polyimide did). The alignment structures were not so different.     

Pretilt angle measurements on smectic A cells with chevron and tilted bookshelf layer structures

We have measured the pretilt angle induced by rubbed polymer films in a smectic A and in a nematic liquid crystalline medium using an optical phase retardation method. The pretilt angle was found to depend on the liquid crystalline phase (smectic A versus nematic) and on the smectic layer structure (chevron versus tilted-bookshelf). The occurrence of the different smectic layer structures was verified by X-ray diffraction measurements. The effect of the applied rubbing energy on the pretilt angle obtained is measured.