A study of the surface anchoring at a polymer/liquid crystal interface in the neighbourhood of the glass transition

Abstract

Recently, we have observed dramatic changes in the electro-optic properties of PDLC films composed of droplets of the liquid crystal E7 in a matrix of polyvinylformal (PVFM) in the vicinity of the glass transition temperature of the matrix. One plausible explanation for these changes is a decrease in the surface anchoring strength on passing through the glass transition. For this reason, we undertook a study of the surface anchoring strength between E7 and a thin film of PVFM using the technique of Yokoyama and van Sprang. To mimic the properties of the matrix more closely, we dissolved 20 per cent E7 liquid crystal into the PVFM film. The surface anchoring for this film was compared with that of a pure PVFM film. From these data, we observed no obvious changes in the surface anchoring on passing through the glass transition of the matrix. However, the incorporation of liquid crystal into the matrix did cause a decrease in the surface anchoring strength. We discuss the impact of these results on the interpretation of the PDLC electro-optic properties.     

Determination of the surface anchoring potential of a nematic in contact with a substrate

We have developed a method for determining the surface anchoring potential for nematics in contact with a substrate that provides director alignment. Our main result is that the surface torque and hence the anchoring potential may be determined from either dielectric or optical phase response of a nematic undergoing a Freedericksz transition. The method is based on the Frank-Oseen continuum theory, and makes no assumptions about the functional form of the potential. We have measured the surface anchoring potential of two types of substrate in contact with the nematic liquid crystal 4-n-pentyl-4′-cyanobiphenyl. The surfaces were ITO-coated float glass, coated either with obliquely evaporated SiO or a buffed polymer film. Comparison of the results obtained from capacitance and optical measurements provides an estimate of the goodness of the method.     

Weak surface anchoring energy of 4-cyano-4'-pentyl-1,1'-biphenyl on perfluoropolyether Langmuir-Blodgett films

Functional director alignment layers are needed for high performance liquid crystal displays (LCDs). Reported herein is a novel polymer material for LC alignment, namely, perfluoropolyether (PFPE), which exhibits a weak surface anchoring energy for bend deformation and is amenable to simple fabrication of grooved surfaces by soft lithography, a surface topography desired for multistable LCDs. Liquid crystal optical cells fabricated using Langmuir-Blodgett films of PFPE (of variable thickness) exhibited weak surface anchoring energies on the order of 10(-5) Jm2 for the nematic liquid crystal 4-cyano-4'-pentyl-1,1'-biphenyl with no dependence on film thickness.     

Effects of surface morphology on the anchoring and electrooptical dynamics of confined nanoscale liquid crystalline films

The orientation and dynamics of two 40-nm thick films of 4-n-pentyl-4'-cyanobiphenyl (5CB), a nematic liquid crystal, have been studied using step-scan Fourier transform infrared spectroscopy (FTIR). The films are confined in nanocavities bounded by an interdigitated electrode array (IDA) patterned on a zinc selenide (ZnSe) substrate. The effects of the ZnSe surface morphology (specifically, two variations of nanometer-scale corrugations obtained by mechanical polishing) on the initial ordering and reorientation dynamics of the electric-field-induced Freedericksz transition are presented here. The interaction of the 5CB with ZnSe surfaces bearing a spicular corrugation induces a homeotropic (surface normal) alignment of the film confined in the cavity. Alternately, when ZnSe is polished to generate fine grooves along the surface, a planar alignment is promoted in the liquid crystalline film. Time-resolved FTIR studies that enable the direct measurement of the rate constants for the electric-field-induced orientation and thermal relaxation reveal that the dynamic transitions of the two film structures are significantly different. These measurements quantitatively demonstrate the strong effects of surface morphology on the anchoring, order, and dynamics of liquid crystalline thin films.     

Influence of 4-cyano-4'-biphenylcarboxylic acid on the orientational ordering of cyanobiphenyl liquid crystals at chemically functionalized surfaces

We report two methods that involve tailoring of the chemical composition of the nematic liquid crystal 4-cyano-4'-pentylbiphenyl to achieve control over the orientational ordering of the liquid crystal on chemically functionalized surfaces. The first method involves the direct addition of 4-cyano-4'-biphenylcarboxylic acid to 4-cyano-4'-pentylbiphenyl. The second method involves exposure of 4-cyano-4'-pentylbiphenyl to ultraviolet light and photochemical generation of a range of products, including 4-cyano-4'-biphenylcarboxylic acid. The addition of the acid or exposure to ultraviolet light accelerated the rate at which the liquid crystal exhibited an orientational transition from planar to perpendicular (homeotropic) alignment on surfaces presenting ammonium groups. The appearance of the homeotropic orientation of the UV-treated 4-cyano-4'-pentylbiphenyl on ammonium-terminated surfaces was dependent on the thickness of the film of liquid crystal (13-50 mum), consistent with a dipolar coupling between the liquid crystal and the electric field associated with an electrical double layer generated at the ammonium surface. Although the addition of 4-cyano-4'-biphenylcarboxylic acid or UV treatment of the liquid crystal also promoted homeotropic orientations on surfaces presenting hydroxyl groups, the orientations of the UV-treated liquid crystal on the hydroxyl-terminated surface did not change with thickness of the film of liquid crystal in the manner observed on the ammonium-terminated surfaces. The latter result indicates that the mechanism leading to homeotropic anchoring on hydroxyl-terminated surfaces is distinct from that on ammonium-terminated surfaces. Measurements performed using polarization modulation infrared reflection-absorption spectroscopy suggest that hydrogen bonding between the 4-cyano-4'-biphenylcarboxylic acid and the hydroxyl-terminated surface is responsible for the homeotropic anchoring on the surface. Finally, the orientation of the liquid crystal on methyl-terminated surfaces was not influenced by the addition of 4-cyano-4'-biphenylcarboxylic acid nor UV treatment. These results illustrate how the chemical composition of liquid crystals can be manipulated to achieve control over their ordering on surfaces that possess chemical functionality relevant to the development of liquid crystal-based sensors and diagnostic tools. We illustrate the utility of this approach by using the tailored liquid crystal to amplify and optically transduce the presence of proteins arrayed on ammonium-terminated surfaces.     

Using measurements of anchoring energies of liquid crystals on surfaces to quantify proteins captured by immobilized ligands

We describe a simple optical method that employs measurement of the interaction energy of a liquid crystal (LC) with a surface (the so-called anchoring energy) to report proteins captured on surfaces through specific interactions with immobilized binding groups. To define the sensitivity and dynamic range of the response of the LC, we covalently immobilized a tyrosine-containing, 13-residue peptide sequence (Y1173) from the epidermal growth factor receptor/kinase (EGFR) at which autophosphorylation takes place and to which the adapter protein Shc binds. We determined that, on peptide-decorated (Y1173 or pY1173, where pY1173 is the corresponding phosphopeptide) surfaces incubated against anti-phosphotyrosine antibody, the anchoring energy of the LC decreased systematically from 4.4 to 1.4 microJ/m2 (with SEM=0.3 microJ/m2 for n=5) as the antibody concentration increased from 10 pM to 100 nM. Over the same range of antibody concentrations in solution and densities of immobilized peptides, independent ellipsometric measurements were not sufficiently sensitive to report the captured antibody (ellipsometric thicknesses were <0.1 nm). These results, when combined with control experiments reported in this article, provide the first demonstration of the use of anchoring energy measurements of LCs to report proteins captured by immobilized ligands on surfaces. The sensitivity and dynamic range of the methodology suggest that it may offer the basis of a simple yet broadly useful principle for reporting the interactions between proteins and other biomolecules that underlie complex and poorly understood chemical and biological events.     

Direct measurement of hydrophobic particle–bubble interactions in aqueous solutions by atomic force microscopy: Effect of particle hydrophobicity

Direct measurements of the interaction forces between a spherical silica particle and a small air bubble have been conducted in aqueous electrolyte solutions by using an atomic force microscope (AFM). The silica particle was hydrophobized with a silanating reagent, and the interaction forces were measured by using several particles with different surface hydrophobicities. In the measured force curves, a repulsive force was observed at large separation distances as the particle moved towards the bubble. The origin of the repulsive force was attributed to an electrostatic double-layer force because both the particle and bubble were negatively charged. After the repulsive force, an extremely long-range attractive force acted between the surfaces. These results indicate that the intervening thin water film between the particle and bubble rapidly collapsed, resulting in the particle penetrating the bubble.

The instability of the thin water film between the surfaces suggests the existence of an additional attractive force. By comparing the repulsive forces of the obtained force curves with the DLVO theory, the rupture thickness was estimated. The hydrophobicity of the particle did not significantly change the rupture thickness, whereas the pH of the solution is considered to be a critical factor.     

Control of the anchoring behavior of polymer-dispersed liquid crystals: effect of branching in the side chains of polyacrylates

A temperature-driven anchoring transition in a polymer/nematic fluid composite that is far from the bulk nematic-isotropic transition temperature is reported. A series of poly(methylheptyl acrylates) were studied to probe the subtle effects of the side chain structure of the polymer on control of the anchoring. A polymer-dispersed liquid crystal film made from TL205 and 1-methylheptyl acrylate shows only planar anchoring over the temperature range studied, while the films made from TL205 and each of the other methylheptyl acrylates or n-heptyl acrylate show the homeotropic-to-planar anchoring transition at temperatures between 70 and 78 degrees C. An interfacial model is proposed in which the different conformation of the side chains is suggested as the cause for the dramatic difference in the observed anchoring behavior.     

Molecular bond formation between surfaces: anchoring and shearing effects

Specific molecular bonds between apposing surfaces play a central role in many biological structures and functions. They display a widely varying anchoring to the cell surface, and they are subject to forces that affect their binding characteristics due to their hydrodynamic environments. Here, we examine both anchoring and shearing aspects using simplified model systems aimed at gaining insight into the formation of a 2D bond collection under stress using two different surface anchors. The highly specific streptavidin-biotin molecular bond was chosen as the model receptor-ligand pair, and grafted colloids were used as model surfaces. To explore the role of the surface anchor, we grafted biotin onto the particle surface following two different approaches: first, the grafting was performed directly on the particle amine functions; second, a 35-nm-long PEG spacer was used. Hybrid particle classes were brought into contact in a homogeneous shear (between 200 s(-)(1) and 1200 s(-)(1)) using a cone plate geometry. The bond association and dissociation kinetics were given by the time course assemblage of hybrid particles into doublets. We observed saturating kinetics profiles that we interpreted as a linkage-breakage equilibrium, which yielded the on and off rates. We found that the biotin-PEG spacer was needed in order to observe significant binding at any shear rate. We also showed that only the number of collisions per unit time, generated by the shear, affected the on rate of the binding. Neither the exerted forces nor the collision lifetime had any effect. The off rate decreased with shear, possibly because of the shortening of the force duration, which results from the increasing shear rate.     

Effects of wetting and anchoring on capillary phenomena in a confined liquid crystal

A fluid of hard spherocylinders of length-to-breadth ratio L/D=5 confined between two identical planar, parallel walls--forming a pore of slit geometry--has been studied using a version of the Onsager density-functional theory. The walls impose an exclusion boundary condition over the particle's centers of mass, while at the same time favoring a particular anchoring at the walls, either parallel or perpendicular to the substrate. We observe the occurrence of a capillary transition, i.e., a phase transition associated with the formation of a nematic film inside the pore at a chemical potential different from micro(b)-the chemical potential at the bulk isotropic-nematic transition. This transition terminates at an Ising-type surface critical point. In line with previous studies based on the macroscopic Kelvin equation and the mesoscopic Landau-de Gennes approach, our microscopic model indicates that the capillary transition is greatly affected by the wetting and anchoring properties of the semi-infinite system, i.e., when the fluid is in contact with a single wall or, equivalently, the walls are at a very large distance. Specifically, in a situation where the walls are preferentially wetted by the nematic phase in the semi-infinite system, one has the standard scenario with the capillary transition taking place at chemical potentials less than micro(b) (capillary nematization transition or capillary ordering transition). By contrast, if the walls tend to orientationally disorder the fluid, the capillary transition may occur at chemical potentials larger than micro(b), in what may be called a capillary isotropization transition or capillary disordering transition. Moreover, the anchoring transition that occurs in the semi-infinite system may affect very decisively the confinement properties of the liquid crystal and the capillary transitions may become considerably more complicated.     

Influences of hydration force and elastic strain energy on the stability of solid film in a very thin solid-on-liquid structure

Since hydration forces become very strong at short range and are particularly important for determining the magnitude of the adhesion between two surfaces or interaction energy, the influences of the hydration force and elastic strain energy due to hydration-induced layering of liquid molecules close to a solid film surface on the stability of a solid film in a solid-on-liquid (SOL) nanostructure are studied in this paper. The liquid of this thin SOL structure is a kind of water solution. Since the surface forces play an important role in the structure, the total free energy change of SOL structures consists of the changes in the bulk elastic energy within the solid film, the surface energy at the solid-liquid interface and the solid-air interface, and highly nonlinear volumetric component associated with interfacial forces. The critical wavelength of one-dimensional undulation, the critical thickness of the solid film, and the critical thickness of the liquid layer are studied, and the stability regions of the solid film have been determined. Emphasis is placed on calculation of critical values, which are the basis of analyzing the stability of the very thin solid film.     

Relationship between surface anchoring strength and surface ordering on weakly rubbed polyimide surfaces

We have investigated the relationship between the polar anchoring strength and surface ordering in a nematic liquid crystal on two kinds of weakly rubbed polyimide (PI) surfaces. The polar anchoring strength of 5CB on weakly rubbed PI surfaces, both with and without side chains, increases with rubbing strength and with decreasing temperature. The surface order parameter of 5CB on these surfaces increases with rubbing strength, suggesting that the polar anchoring strength on rubbed PI surfaces is related to the surface order parameter.     

Relationship between surface anchoring strength and surface ordering on weakly rubbed polyimide surfaces

We have investigated the relationship between the polar anchoring strength and surface ordering in a nematic liquid crystal on two kinds of weakly rubbed polyimide (PI) surfaces. The polar anchoring strength of 5CB on weakly rubbed PI surfaces, both with and without side chains, increases with rubbing strength and with decreasing temperature. The surface order parameter of 5CB on these surfaces increases with rubbing strength, suggesting that the polar anchoring strength on rubbed PI surfaces is related to the surface order parameter.     

Orientational transition in the cholesteric layer induced by electrically controlled ionic modification of the surface anchoring

A reorientation of cholesteric liquid crystal with a large helix pitch induced by the electrically controlled ionic modification of the surface anchoring has been studied. In initial state, the cholesteric helix is untwisted completely owing to the normal surface anchoring specified by the cations adsorbed at the substrates. As a result, the homeotropic director configuration is observed within the cell. Under the action of DC electric field, one of the substrates becomes free from the layer of surface active cations, therefore, setting the planar surface anchoring. The latter, in turn, leads to the formation of the hybrid chiral structure. The threshold value and dynamic parameters have been estimated for this process as well as the range of control voltages, which do not allow the electrohydrodynamic instabilities. The twisted hybrid director configuration observed in the experiment has been analysed by means of the simulation of polarisation change of light propagating through the cholesteric layer with asymmetric (planar and homeotropic) surface anchoring on the cell substrates.     

Electro-optical effects of anchoring transition in polymer dispersed liquid crystal films

Two groups of polymer dispersed liquid crystal films have been studied, one with a fixed cell thickness but varying liquid crystal (LC) concentrations and the other with a fixed LC concentration but varying cell thicknesses. A sudden decrease in transmittance with increasing temperature was observed for films whose LC domain sizes were comparable to their cell thicknesses. In particular, spontaneous alignment of LC directors was observed below ∼20°C when LC domains were formed spanning the space between upper and lower indium tin oxide-coated glass substrates. With increasing temperature, this axially aligned homeotropic configuration changed gradually into homogeneous configurations. We believe that the sudden decrease in transmittance originated from the anchoring transition at the glass substrates and polymer walls. In addition, it has been found that the intensity of ultra violet irradiation has a strong effect on the director configuration of LC domains, and that the cure temperature affects the anchoring transition temperature significantly.     

Surface excitations involving headgroup conformations and molecular protrusions. a monte carlo study of surface forces.

The force between two parallel zwitterionic surfaces has been calculated using Monte Carlo computer simulations. The zwitterions are modelled as two oppositely charged hard spheres joined by a string of length L with parameters chosen to mimic a phospholipid system. All centers interact by a homogeneous Coulomb interaction and by a hard sphere exclusion. The anchoring of the negative centers to the surfaces has been treated within two different models. They were either anchored by a parabolic potential or by a protrusion potential, i.e., a potential proportional to the distance between the center and the surface. The latter model gives a more realistic picture of the interaction between amphiphilic surfaces in aqueous solution but here only repulsive forces could be calculated. The first model also allowed the calculation of attractive forces.For distances D between the surfaces, as defined by the location of the negative centers, that are larger than 2L there is an attractive force of the classical van der Waals type. When, on the other hand, D < 2L a strong repulsive force appears, which in the limit D ⪡ 2L is analogous to a double layer force.Recently it was suggested (Israelachvili and Wennerström, Langmuir, 6 (1990) 873 ) that the repulsive so called hydration force observed for biological lipid systems has its origin in confinements of surface excitations induced by a second surface. Here we demonstrate how this mechanism works in a particular microscopic model of the surface and we show that it gives an important contribution to the total force. Although still simplistic several qualitative features of the force in the phospholipid systems are reproduced in the calculations. For example, a reduction of the size of the charged centers leads to a decrease in the repulsive force. This mimics the observed difference between phosphatidyl choline and phosphatidyl ethanolamine.     

Surface forces measurements of spin-coated cellulose thin films with different crystallinity

A systematic study of the surface forces between a cellulose sphere and cellulose thin films of varying crystallinity has been conducted as a function of ionic strength and pH. Semicrystalline cellulose II surfaces and amorphous cellulose films were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose I nanocrystals. These preparation methods produced thin, smooth films suitable for surface forces measurements. The interaction with the cellulose I was monotonically repulsive at pH 3.5, 5.8, and 8.5 and at 0.1, 1, and 10 mM ionic strengths. This was attributed to the presence of strongly ionizable sulfur-containing groups on the cellulose nanocrystal surfaces. The amorphous film typically showed a steric interaction up to 100 nm away from the interface that was independent of the solution conditions. A range of surface forces were successfully measured on the semicrystalline cellulose II films; attractive and repulsive regimes were observed, depending on pH and ionic strength, and were interpreted in terms of van der Waals and electrostatic interactions. Clearly, the forces acting near cellulose surfaces are very dependent on the way the cellulose surface has been prepared.     

Fluidity of water confined down to subnanometer films

A surface force balance with extremely high sensitivity and resolution for measuring shear forces across thin films has been used to investigate directly the dynamic properties of salt-free water (so-called conductivity water) in a gap between two atomically smooth solid surfaces. Our results reveal that no shear stress can be sustained by water (within our resolution and shear rates) down to films of thickness D = D0 = 0.0 +/- 0.3 nm. At short range (D < 3.5 +/- 1 nm), an attractive van der Waals (vdW) force between the surfaces causes a jump into a flat adhesive contact at D0, at which the surfaces rigidly couple. Analysis of the jump behavior reveals that the viscosity of water remains within a factor of 3 or so of its bulk value down to D0. This contrasts sharply with the case of confined nonassociating liquids, whose effective viscosity increases by many orders of magnitude at film thicknesses lower than about five to eight monolayers. We attribute this to the fundamentally different mechanisms of solidification of organic liquids and of water. In the former case, the density increase induced in the films by the confinement promotes solidification, while, in the case of water, such densification (due to vdW attraction between the liquid molecules and the confining walls), in agreement with bulk behavior, suppresses the tendency of the water to solidify.     

Surface anchoring of nematic liquid crystal 8OCB on a DMOAP-silanated glass surface

Dynamic light scattering spectroscopy has been used to determine the temperature dependence of the anchoring strength of the nematic liquid crystal 8OCB on DMOAP-silanated glass surfaces inducing homeotropic alignment. Wedge-type glass cells with known thickness profile starting from 150 nm to several microns have been used in the experiments. The relaxation rates of the nematic fluctuations with the wave vector perpendicular to the confining surfaces have been measured as a function of the cell thickness. Fitting of the thickness dependence of the relaxation rate allows for straightforward determination of the surface extrapolation length and therefore also the strength of the surface anchoring, which is 1×10^-4 J m^-2. The overall experimental accuracy of the experiments is discussed.     

AFM measurements of forces between silica surfaces

Interaction forces and adhesion between a silica sphere and a flat silica surface in aqueous electrolyte solutions were investigated by atomic force microscopy. The forces were measured as a function of surface separation, pH and NaCl concentration as the surfaces were approaching each other. The adhesion force was determined upon retraction with respect to pH, NaCl concentration and contact time. The magnitude of the long range repulsive force was decreasing with decreasing pH. A short range repulsive force was observed at pH = 2, but no long range repulsive forces were observed at this pH. Force measurements showed that adhesion of silica surfaces in water was obstructed by short and long range repulsive forces. Adhesion was enhanced when both the long and the short range repulsive force was mitigated. A maximum adhesion force of 7.8 mN/m was measured at pH = 12.5 when the short range force vanished and the long range repulsive force was reduced by increasing the NaCl concentration. At pH = 12.5, the work of adhesion was calculated to be 1.2 mJ/m² according to the Derjaguin–Muller–Toporov (DMT) model. Adhesion energy was much less at pH = 2 (0.3 mJ/m²) due to persistive short range repulsion.