Characterization of Langmuir-Blodgett films of a ferroelectric liquid crystal

Molecular orientation, structure, and phase transition behaviors in Langmuir-Blodgett (LB) and cast films of a ferroelectric liquid crystal of sec-butyl 6-(4-(nonyloxy)benzoyloxy)-2-naphthoate (FLC-1) are determined by ultraviolet (UV) spectroscopy, X-ray diffraction, and infrared (IR) spectroscopy. It is found that the orientation angle of chromophores theta in LB films is 41 degrees from the surface normal. The tilt angle of the chromophore changes at 56, 70, and 88 degrees C, respectively, which denotes the presence of phase transitions. Two kinds of layered or isomeric crystal structures of the LB films with layer spacings of 3 and 3.5 nm at room temperature have been found while the latter disappears above 45 degrees C, as confirmed by measurement of temperature-dependent IR spectra.     

Alignment of a nematic liquid crystal using substituted calixarene Langmuir-Blodgett films

The alignment of a nematic liquid crystal (5CB) induced by several substituted calixarene-based films is reported. Calixarene molecules consisting of four or six moieties and different substituents (acyl and azobenzene groups) were synthesized. Films of such molecules were deposited using a Langmuir-Blodgett technique onto glass plates and were characterized using atomic force microscopy. These treated plates were used to prepare liquid crystal cells, and the overall alignment studied. In the case of photosensitive molecules, photoinduced reorientation experiments were undertaken and are reported. It is shown that it is not important to have a large number of interacting sites on the surface to induce a reorientation of the liquid crystal.     

Self-screening of Langmuir-Blodgett films by a discotic micellar lyotropic liquid crystal

The influence of the surface treatment on the anisotropic part of the surface tension of a lyotropic discotic micellar nematic liquid crystal doped with ferrofluid is analysed. The treatment involves Langmuir-Blodgett (LB) films deposited on the glass substrates. Textural observations and phase-shift measurements of the transmitted light were carried out. A phenomenological model which allows calculation of the director average orientation in the bulk and at the surfaces is used for interpreting the experimental data. Our results show that the average director alignment depends on the concentration of the magnetic grains of ferrofluid at the glass surfaces. On the contrary, it is practically independent of the nature of the molecule deposited on the glass substrate. According to the model, the flat glass surface, independently of the treatment or the absence of any treatment, stabilizes onto itself a lamellar layer (or bilayer) formed by the amphiphilic molecules of the liquid crystal. This layer screens the effect of the LB film (or of the pure untreated substrate) on the alignment of the lyotropic nematic mesophase.     

Alignment of a nematic liquid crystal using substituted calixarene Langmuir-Blodgett films

The alignment of a nematic liquid crystal (5CB) induced by several substituted calixarene-based films is reported. Calixarene molecules consisting of four or six moieties and different substituents (acyl and azobenzene groups) were synthesized. Films of such molecules were deposited using a Langmuir-Blodgett technique onto glass plates and were characterized using atomic force microscopy. These treated plates were used to prepare liquid crystal cells, and the overall alignment studied. In the case of photosensitive molecules, photoinduced reorientation experiments were undertaken and are reported. It is shown that it is not important to have a large number of interacting sites on the surface to induce a reorientation of the liquid crystal.     

Phase-transitions in Langmuir-Blodgett and cast films of a ferroelectric liquid crystal.

Langmuir-Blodgett films and cast films of a ferroelectric liquid crystal of sec-butyl-6-(4-(nonyloxy)benzoyloxy)-2-naphthoate have been fabricated. Their thermal behavior was investigated using infrared spectroscopy at elevated temperature combined with principal component analysis. The result shows a new phase transition from smectic A to nematic phase, compared to the phase sequence obtained by polarizing optical microscopy. Another solid transition of different isomeric crystals was also found, which was confirmed by calorimetric measurement.     

X-ray investigations of Langmuir-Blodgett multilayer films of side-chain liquid crystal copolymers

X-ray reflectivity studies on Langmuir-Blodgett multilayer films of side-chain liquid crystal polymers are reported. The films have a high degree of lamellar order. The layer periodicity is independent of the type of monolayer deposition, implying a reorientation of the side group mesogens following the deposition process. X-ray reflectivity from thin films displays subsidiary maxima permitting a quantitative measure of the change in side-chain density between multilayer and monolayer. A unit cell density profile is calculated for thick films assuming a symmetric unit cell.     

Langmuir-Blodgett films as aligning layers for homeotropic alignment of liquid crystal molecules

The first single crystal structure of a Group VA halide salt with three equivalent long n-alkyl chains, benzyltrioctadecylammonium bromide (BzN18Br), is reported. It consists of alternating interdigitated and non-interdigitated regions of alkyl chains separated by ionic planes. Two chains per molecule are paired and extend to one side in a non-interdigitated region. The third chain is on the opposite side of the ionic plane and pairs intermolecularly to form an adjacent, interdigitated region. The thickness of two nearly extended molecules defines the bilayer unit-two ionic planes flanked by a region with intramolecularly paired chains and separated by an interdigitated chain region. Powder X-ray diffraction and optical microscopy data of liquid crystalline BzN18Br are consistent with an enantiotropic smectic A₂ (SmA₂) phase: the three n-alkyl chains of each molecule are projected from one side of an ionic plane, and head groups of neighbouring molecules are oriented head-to-head, in a non-interdigitated bilayer assembly. The structure of BzN18Br fills an important gap in our knowledge about the crystal packing of ammonium and phosphonium salts with one-four equivalent long n-alkyl chains. A comparison of their packing arrangements is made and the transitional nature of the BzN18Br structures is demonstrated. Although salts with one, two, or three long n-alkyl chains form SmA₂ phases, each is distinctive in its molecular packing. A large molecular reorganization accompanies the crystal-to-liquid crystal transition of BzN18Br.     

Alignment of liquid crystal and dichroic dye molecules in mixed Langmuir and Langmuir-Blodgett films

A study of dichroic dye-liquid crystal mixtures (guest-host systems) in monolayers formed at a gas-liquid interface (Langmuir films) and at a solid surface (Langmuir-Blodgett films) has been made. As a host 4- n -octyl-4'-cyanobiphenyl (8CB) or 4- n -pentyl-4"-cyano- p -terphenyl (5CT) were chosen, while three dichroic azo dyes with various molecular structures were used as guest species. The dyes were added to the liquid crystal matrices at a concentration corresponding to the whole range of molar fractions and the surface pressure-mean molecular area isotherms for Langmuir films were recorded. On the basis of the isotherms, conclusions about the molecular organization and the miscibility of the components in the ultrathin films were drawn. The Langmuir films were transferred onto the quartz plates at surface pressures below the collapse point. The polarized absorption spectra of the Langmuir-Blodgett films were recorded and information about the alignment and intermolecular interactions in the mixtures of the non-amphiphilic dichroic dyes and the liquid crystals with strongly polar terminal groups were obtained.     

Alignment of liquid crystal and dichroic dye molecules in mixed Langmuir and Langmuir-Blodgett films

A study of dichroic dye-liquid crystal mixtures (guest-host systems) in monolayers formed at a gas-liquid interface (Langmuir films) and at a solid surface (Langmuir-Blodgett films) has been made. As a host 4- n -octyl-4′-cyanobiphenyl (8CB) or 4- n -pentyl-4″-cyano- p -terphenyl (5CT) were chosen, while three dichroic azo dyes with various molecular structures were used as guest species. The dyes were added to the liquid crystal matrices at a concentration corresponding to the whole range of molar fractions and the surface pressure-mean molecular area isotherms for Langmuir films were recorded. On the basis of the isotherms, conclusions about the molecular organization and the miscibility of the components in the ultrathin films were drawn. The Langmuir films were transferred onto the quartz plates at surface pressures below the collapse point. The polarized absorption spectra of the Langmuir-Blodgett films were recorded and information about the alignment and intermolecular interactions in the mixtures of the non-amphiphilic dichroic dyes and the liquid crystals with strongly polar terminal groups were obtained.     

Investigation of alignment mechanism of liquid crystal on polyimide Langmuir-Blodgett films by scanning tunnelling microscopy

The homogeneous alignment of a liquid crystal material, 4'-n-octyl-4-cyanobiphenyl (8CB), was achieved by polyimide Langmuir-Blodgett (LB) films. Scanning electron microscopy and scanning tunnelling microscopy measurements show that the alignment of the polyimide LB films with a grooveless surface occurs due to the orientation of the polyimide chains. We directly observe 8CB monolayers on oriented polyimide LB films. We find that the monolayers form a two dimensional crystalline structure and the 8CB molecules are always aligned along the chain direction of the polyimide. The results show that the alignment of 8CB molecules arises by an epitaxial growth on the oriented polyimide LB films.     

Investigation of alignment mechanism of liquid crystal on polyimide Langmuir-Blodgett films by scanning tunnelling microscopy

Abstract

The homogeneous alignment of a liquid crystal material, 4′-n-octyl-4-cyanobiphenyl (8CB), was achieved by polyimide Langmuir-Blodgett (LB) films. Scanning electron microscopy and scanning tunnelling microscopy measurements show that the alignment of the polyimide LB films with a grooveless surface occurs due to the orientation of the polyimide chains. We directly observe 8CB monolayers on oriented polyimide LB films. We find that the monolayers form a two dimensional crystalline structure and the 8CB molecules are always aligned along the chain direction of the polyimide. The results show that the alignment of 8CB molecules arises by an epitaxial growth on the oriented polyimide LB films.     

Spontaneous polarization and electro-optic behaviour of a ferroelectric liquid crystal cell fabricated with polyimide Langmuir-Blodgett films

The spontaneous polarization and electro-optic response of ferroelectric liquid crystals (FLCs) were investigated in a cell fabricated with a polyimide alignment layer coated by the Langmuir-Blodgett method. The surface properties of the cured polyimide layers were monitored by contact angle measurement, and by FTIR spectroscopy and AFM for the orientation and surface roughness, respectively. The apparent spontaneous polarization of an FLC determined in a practical sandwich-cell depended on various conditions such as cell thickness, cooling rate from the smectic A to chiral smectic C phase, and deposition pressure. Electro-optic response and decay times of FLCs were also measured. Furthermore, the ions in the FLC mixture reduced the magnitude of the effective electric field, but had no effect at high frequency.     

Spectroscopic studies of Langmuir-Blodgett films of 3,4,9,10-tetra(heptyloxycarbonyl)perylene and its mixtures with a liquid crystal

Langmuir (L) and Langmuir-Blodgett (LB) films of 3,4,9,10-tetra(heptyloxycarbonyl)perylene and its binary mixtures with 4-octyl-4'-cyanobiphenyl (8CB) and 4-pentyl-4'-cyano-p-terphenyl (5CT) have been studied. On the basis of the surface pressure-mean molecular area isotherms of L films, the alignment of the molecules on the air-water interface has been estimated. The L films were transferred onto quartz plates at surface pressures below the collapse point. The absorption and fluorescence spectra of LB films, obtained using unpolarized and linearly polarized light, were recorded. The results obtained have led to conclusions on the arrangement of the dye and liquid crystal molecules on the air-solid substrate interface. The fluorescence spectra revealed the formation of excited dimers in LB films.     

Instabilities of nematic liquid crystal films

We discuss instabilities exhibited by free surface nematic liquid crystal (NLC) films of nanoscale thickness deposited on solid substrates, with a focus on surface instabilities that lead to dewetting. Such instabilities have been discussed extensively; however, there is still no consensus regarding the interpretation of experimental results, appropriate modeling approaches, or instability mechanisms. Instabilities of thin NLC free surface films are related to a wider class of problems involving dewetting of non-Newtonian fluids. For nanoscale films, the substrate–film interaction, often modeled by a suitable disjoining pressure, becomes relevant. For NLCs, one can extend the formulation to include the elastic energy of the NLC film, leading to an ‘effective’ disjoining pressure, playing an important role in instability development. Focusing on thin film modeling within the framework of the long-wave asymptotic model, we discuss various instability mechanisms and outline problems where new research is needed.     

Studies on the additive performance of liquid crystal blended polyacrylate in lubricating oil

Homopolymer of decyl acrylate (D) was synthesised, characterised (Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR)) and evaluated for its additive performance as antiwear (AW), pour point depressant (PPD) and viscosity modifier (VM). Physical blends of the polymer were also made with three different types of liquid crystals (each containing three samples), evaluated and the results were compared. The study indicated that additive performances (AW, VM and PPD) of the blended composites were much better in comparison to the homopolymer of polydecyl acrylates.     

Liquid crystal orientation by holographic phase gratings recorded on photosensitive Langmuir-Blodgett films

Holographic gratings were recorded on photosensitive Langmuir-Blodgett films characterized by UV spectroscopy, birefringence measurements and atomic force microscopy. Different polarizations of Ar laser writing beams create particular patterns of chromophore orientation in the diffraction spots. The gratings were shown to orient a nematic liquid crystal with the director parallel to the axes of the chromophores predetermined by film irradiation. In the case of the sp grating (recorded with laser beams polarized perpendicular to each other), two equivalent easy directions for the liquid crystal orientations at 90degree with respect to each other were observed; that is a quasi-bistable anchoring interface had been prepared. Measurements of the pretilt angles theta1s and anchoring energy Ws of 5CB on different holographic gratings show that this orientation technique is very promising for display technology.     

Fluorescence behaviour of cyanobiphenyl liquid crystal molecules in liquid crystal/polymer composite films

The fluorescence behaviour of the liquid crystal, 4-cyano-4-pentylbiphenyl (5CB), in composite thin films prepared by the photopolymerization of 5CB/diacrylate mixtures, was investigated by means of three different excitation methods, in which the total-internal-reflection or surface-limited excitation method was used for analysis of the fluorescence from an ultra-thin interface layer ( 100nm) in contact with the substrate surface, whereas the fluorescence from the interior bulk was analysed by the through-film excitation method. It was found that intensity ratios of the monomer and excimer emissions of 5CB are significantly lower in the interface layer than in the interior bulk, depending upon photopolymerization conditions as well as upon the structures of the diacrylates used. Scanning electron microscopic observations and light-scattering measurements of some typical composite films showed possible relationships between morphological features and fluorescence characteristics depending upon the diacrylate structures and polymerization conditions. The different fluorescence behaviour has been discussed in terms of differences in mobility and/or aggregation degrees of 5CB molecules arising from dominant molecular interactions with the substrate and polymer surfaces.     

Influence of the liquid crystal behaviour on the Langmuir and Langmuir-Blodgett film supramolecular architecture of an ionic liquid crystal

Novel fluorescent poly(2-(acetoacetoxy)ethyl methacrylate)(PAAEMA) latexes have been synthesized by miniemulsion polymerization employing a polymeric costabilizer. Nanoscale aggregates of macromolecules bearing β-dicarbonyl are formed in the prepared latex particles. Ammonia and the β-dicarbonyl aggregates assemble a supramolecular complex, which exhibits strong visible fluorescence under UV light. The formation of the complex is confirmed by the characteristic absorption peak located at about 275 nm in UV-Vis spectra. The absorption spectrum has been found to be applicable for ammonia detection. Atomic Force Microscopy (AFM) studies of surface morphology reveal that gas-sensing properties of the PAAEMA thin films involve the reversible absorption and desorption of ammonia. PAAEMA thin films are sensitive to ammonia gas and have a short response time of 80s when exposed to 54 ppm of ammonia gas concentration.     

Polyoxometalate monolayers in Langmuir-Blodgett films

Langmuir and Langmuir-Blodgett (LB) films of a variety of polyoxometalates of different shapes, sizes, and charges were prepared by taking advantage of the adsorption properties of these polyanions on a positively charged monolayer of an organic surfactant spread on water. Three different aspects were investigated. 1) The electrochemical and electrochromic properties of LB films containing the easily reducible polyoxoanion [P2Mo18O62]6-. Absorbance changes of these LB films deposited onto an ITO substrate have been induced by repeated switching of the applied potential. These changes are due to the formation of the colored reduced forms of the polyanion. Coloration and bleaching of the LB film occur very quickly and are reversible. 2) The preparation of LB films based on magnetic polyoxometalates, such as the Keggin anions, [CoW12O40]6- and [SiMn(OH2)W11O39]6-, or containing magnetic clusters of increasing nuclearities such as [Co4(H2O)2(PW9O34)2]10- and [Co4(H2O)2(P2W15O62)2]16- based on a Co4O16 ferromagnetic cluster, and the polyoxometalates [Co9(OH)3(H2O)6(HPO4)2(PW9O34)3]16- and [Ni9(OH)3-(H2O)6(HPO4)2(PW9O34)3]16- based on a nonanuclear M9O36 cluster. 3) The preparation of LB films of the giant heteropolyoxomolybdate, [Na3(NH4)12][Mo57Fe6(NO)6O174(OH)3-(H2O)24]76 H2O.