From colloids in liquid crystals to colloidal liquid crystals

ABSTRACT

Liquid crystals in combination with nanoparticles are a fascinating topic of research, because of the wealth of aspects and questions to study. These range from simple effects of nanoparticles on phase transitions and phase diagrams, to the tuning of physical properties, adding of novel functionalities, all the way to the formation of spontaneous order by nanoparticles themselves and the possibilities that templating has for future materials design and applications. This article intends to provide a flavour of the multiplicity, variety and diversity that these thermotropic and lyotropic systems have to offer in the area of materials development, which we believe will become increasingly important, especially for switchable non-display applications and nanotechnology. It is not intended to provide a conclusive overview, which would be a presumptuous attempt considering the limited space available, but rather to place our own work into a wider context and to point out some more recent developments and trends in liquid crystal – nanoparticle dispersions.     

Application of the novel dynamic thermo-optical analysis for identification of the sequence of mesophases in thermotropic liquid crystal

Identification of mesophases using a polarising microscope is vital in the area of research and development of the liquid crystal (LC) materials, however, sometimes it is very difficult to distinguish one texture from another. Here, we propose a novel method allowing for the examination of thermotropic phase sequence in polymorphic LCs called dynamic thermo-optical analysis (DTOA). In the DTOA technique the LC subjected to the cooling process is simultaneously influenced by the electric field varying sinusoidally with time. It results in the dynamic changes in the light intensity passing through the layer of such LC observed under a polarised microscope and recorded by a charge-coupled device camera. The magnitude of the changes uniquely depends on the type of the mesophase. The subsequent numerical analysis of the recorded movie (performed with a help of the image-processing software) reveals the changes in the amplitude of the average intensity of the images of the respective textures, i.e. nematic, SmA, SmC, SmI, thereby allowing for their clear identification. Furthermore, the DTOA allows to distinguish easily the SmA from the SmC phase. The azobenzene-based LC known of rich sequence of mesophases has been used here to demonstrate the principle of the DTOA method.     

Monocyclic rod-type liquid crystals; 2,5-dialkanoyloxytropones and 5-alkanoyloxy-2-alkoxytropones

Two kinds of monocyclic troponoid mesogens, 2,5-dialkanoyloxytropones (4) and 5-alkanoyloxy2-alkoxytropones (5), were prepared. The former showed monotropic smectic A phases and the virtual isotropic liquid-smectic A transitions of the latter were determined by extrapolation of results in a binary phase diagram. Comparing the mesogenic properties between the tropones 4 and the 2-alkanoyloxy-5-alkoxytropones (1), the alkanoyloxy group at C-5 enhances both the melting points and the transition temperatures of the smectic A phases. From the comparison between 5 and 1, the alkanoyloxy group at C-2 lowers the melting points.     

Rheological properties of lyotropic liquid crystals encapsulating curcumin

This study constructed new curcumin-loaded lyotropic liquid crystals containing pharmaceutically accepted oil, and ethyl oleate (EtOL). Three liquid crystalline phases including lamellar, hexagonal, and cubic phases were identified by means of the polarized optical microscopy and rheology method. By analyzing the shear viscosity (η_0.1), the viscosity of curcumin-liquid crystals is smaller than those without curcumin. Dynamic rheological results show that: Dissolved curcumin in EtOL can make the elastic modulus of hexagonal and cubic phase increase compared with that without curcumin, while the elastic modulus of lamellar phase decreases. Dissolved curcumin in Brij 97 can lead to the decreasing of the elastic modulus for cubic and lamellar phases, whereas it has little influence on hexagonal phase. When the curcumin is solubilized in both EtOL and Brij 97, the elastic modus of hexagonal phase increase, the elastic modus of lamellar and cubic phases decrease compared with that without curcumin. Furthermore, three temperature turning points were identified by the change in the slope of tanδ (G″/G′) for curcumin-hexagonal liquid crystal. These studies might be a help to study the storage of drug carrier and in vitro release properties of lyotropic liquid crystals containing curcumin.     

Impact of co-doping concentration in copolymer network liquid crystals

ABSTRACT

The impact of varying the co-doping concentration of a mesogenic and a non-mesogenic monomer in the reactive mixtures used to create a copolymer network LCs was investigated. Use of copolymer has been found to improve the response properties in the obtained liquid crystal composites. The polymer network in the studied copolymer network LCs was examined by scanning electron microscopy and the response times in various samples were investigated. Samples were prepared with various reactive mixtures, each of which had a constant concentration of mesogenic monomer, various concentrations of non-mesogenic monomer, and the same amount of photoinitiator. These reactive mixtures were filled in home assembled test cells with planar alignment and then exposed to UV light. With increasing concentration of the non-mesogenic monomer, the response properties of the resulting copolymer network LC were improved. Usually, if the overall polymer content in a polymer network LC is increased, the threshold voltage is also increased. However, both threshold voltages and response times were lowered and the response properties were thus improved in the studied copolymer network LCs. This unexpected behavior could be traced back to inducing a grainy polymer morphology of the copolymer network by using a non-mesogenic monomer.     

Synthesis of novel and regioselectively mesogen-incorporated thermotropic liquid crystals from cellulose derivatives

Regioselectively mesogen-incorporated cellulose derivatives, in which the hydroxy group at C-6 is displaced by a bulky and rigid mesogenic group such as {4-[(4-methoxyphenoxy)carbonyl]phenoxy}acetate or [(4′-cyanobiphenyl-4-yl)oxy]acetate, and the C-2 and C-3 groups are displaced by octanoyl or lauroyl groups, were synthesized. Thermogravimetric and differential scanning calorimetric analyses of the final products, along with polarized optical microscopic observations, revealed that the obtained cellulose derivatives have a thermotropic liquid-crystalline nature and transition from the mesomorphic to the isotropic phase over a wide range of temperatures. These derivatives could be considered to be main-chain liquid-crystalline cellulosic polymers.     

The effect of voltage controlled orientation order of liquid crystals in non-acrylic polymer dispersed liquid crystals films

The nematic liquid crystals (LCs) are randomly dispersed material with random orientation order in polymer dispersed liquid crystal (PDLC) films. The LCs change their orientation from random to vertical as electric field is applied. This transformation of orientation order of nematic liquid crystals in the PDLC films is controlled by many factors operating simultaneously. For instance, some factors like the internal forces of attractions among the neighboring LC molecules, anchoring with polymeric matrix, ITO glass boundaries, and chemical structures of the materials are less studied. The learning of extent of vertical orientation of liquid crystal droplets in an electric field is essential to attain optimum electro optical properties of PDLCs. In this finding, bipolar and radial LCs droplets with random orientation have been observed in non-acrylic polymeric media. It is learned that with small increase of contents of external material, the extent of vertical orientation has been varied intensely. The extent of vertical orientation of LCs molecules increases as the contents of external non-acrylic polymeric material decreased. For this study, the orientations of LCs with respect to material type/contents, external applied force, and restoration of electric filed as hysteresis have been studied in details.     

Asymmetric N-heterocyclic carbene benzimidazolium salts and their silver(I) complexes: potential as ionic liquid crystals

The synthesis and characterisation of a homologous series of monodentate benzimidazolium salts, 1–4 and their mononuclear silver(I)–NHC (where NHC = N-heterocyclic carbene) complexes, 5–8, are reported. The benzimidazolium salts were prepared from the N-alkylation of 1-methyl-benzimidazole with alkyl halides of varying carbon chain lengths. The mono silver(I)-NHC complexes, 5–8, were prepared by the reaction of the benzimidazolium salts with Ag₂O. All the synthesised compounds were fully characterised by ¹H-nuclear magnetic resonance (¹H-NMR), ¹³C-NMR and fourier-transform infrared (FTIR) spectroscopy. The molecular structures of compounds 3·PF₆, 4·PF₆, 7 and 8 were elucidated through single-crystal X-ray diffraction analyses. We postulate that the attachment of long alkyl chains to the heterocyclic core of 1-methyl benzimidazole could induce mesophase formation. The liquid crystalline behaviour of the benzimidazolium salts was investigated by polarised optical microscope and differential scanning calorimetry. Salts 3 and 4 were found to be thermotropic liquid crystals which exhibited a smectic A phase. However, upon complexation with silver(I) ions, all the Ag(I)–NHC complexes are found to be non-mesogenic.     

Synthesis of thermotropic liquid crystal polyimide and its properties

Thermotropic liquid crystal polyimide which has neither an ester linkage nor a carbonate linkage was prepared by the polymerization of 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA) and 1,3-bis[4-(4′-aminophenoxy)cumyl)]benzene (BACB). This polyimide shows the liquid crystal phase at 549-593 K. Mixing this liquid crystal polyimide or copolymerizing BACB decreases the melt viscosity of the thermoplastic polyimide (Aurum). © 1994 John Wiley & Sons, Inc.     

溶致液晶的结构及应用研究进展

本文评述了溶致液晶的相态和结构以及其相态随浓度变化的特点，并着重介绍了溶致液晶在新型纳米材料全盛中的应用，在生物医学中的应用，在化学反应中的催化作用，以及在工业中的作用。     

Synthesis and characterization of a trefoil-shaped liquid crystal based on 1,3,5-triazine with carbazole groups

A trefoil-shaped liquid crystal containing an aromatic hetero-nucleus has been synthesized by the reaction of cyanuric chloride with 3,6-didecanoyl carbazole (DDC). The molecular structure was characterized by ¹H NMR and ¹³C NMR spectroscopy, mass spectroscopy and elemental analysis. The core consists of 1,3,5-triazine directly linked to three carbazole groups. The trefoil-shaped conformation is suggested by molecular modelling. The mesophase was investigated using DSC, X-ray diffraction and polarizing optical microscopy. The X-ray diffraction pattern of a sample cooled slowly from the isotropic state showed sharp peaks in the small angle and wide angle regions implying the existence of a columnar phase with interand intra-columnar ordering. An unusual reticular texture similar to a cholesteric texture was observed.     

Influence of low concentration silver nanoparticles on the electrical and electro-optical parameters of nematic liquid crystals

Thermodynamical, optical, dielectric and electro-optical characterisation of nematic liquid crystals (LCs) and silver nanoparticle (NP) composites have been carried out. Transition temperatures of pure and composites systems have been measured. Thermodynamical studies suggest increase of clearing temperature of the composite material as compared to the pure material. Threshold voltage for switching from bright to dark state and splay elastic constant of the pure and composite materials have been determined. From frequency dependence of dielectric measurements, permittivity, loss, relaxation frequency and dielectric strength of flip-flop mechanism of LC molecules in the nematic phase have been calculated. Dielectric properties of composites have been explained in reference of Maier and Meier theory. The effects of doping of NPs on dielectric and electro-optic properties of LC-NP composites have been discussed.     

Synthesis and properties of liquid crystalline polyurethanes

1,4-Bis(p-hydroxybenzoate)phenylene was prepared using 1,4-bis(trimethylsiloxy)benzene and p-hydroxybenzoyl chloride as starting materials. A series of novel 1,4-bis(p-hydroxyalkoxybenzoate)phenylene were synthesized by reaction of 1,4-bis(p-hydroxybenzoate) phenylene with 3-brompropanol and 4-bromobutanol, respectively. The liquid crystal polyurethanes were prepared by 1,4-bis(p-hydroxyalkoxybenzoate)phenylene with MDI (p-methylene diphenylenediisocyanate) and 2,4-TDI(2,4-toluenediisocyanate), respectively. The thermotropic properties, the melting point (T _m) and the isotropization temperature (T _i) of the synthesized polyurethanes were characterized by DSC, IR and POM. It showed that all of the polyurethane polymers exhibited thermotropic liquid crystalline properties between 144°C and 260°C. The transition temperature (T _m and T _i) decreased with an increase in the length of the methylene spacer. __________ Translated from Journal of Qingdao University of Science and Technology, 2006, 27(1) (in Chinese)     

Electrical orientation behaviour of a nematic liquid crystal with negative dielectric anisotropy above the microelectrodes

Factors for the electrical orientation on interdigitated microelectrodes deposited on a substrate, a microdielectrometric sensor (or a sensor), were discussed experimentally using a model nematic liquid crystal with negative dielectric anisotropy. The electrical orientation behaviour of the nematic liquid crystal was investigated using microdielectrometry and polarised optical microscopy. The experimental results were discussed in relation to electric-field line, surface topology, anchoring of the liquid crystalline molecules to the microelectrodes, and transversal rotation of a rode-like molecule of the liquid crystal with negative dielectric anisotropy.     

Development of ferroelectric liquid crystals with low birefringence

We propose an approach for development of ferroelectric liquid crystals (FLC) with low birefringence Δn. Two basic principles have been used to get lowering of Δn: selection of molecules with short chains of conjugation as components for achiral matrix and averaging of local refractive indices by FLC helical structure. FLC mixtures with low birefringence (0.07 < Δn < 0.10 at wavelength 589.3 nm of sodium line) were elaborated and investigated. They consist of an achiral matrix including both nematic and smectic liquid crystal components and of phenylpyrimidine derivatives as chiral dopants. The materials developed can be used for all basic electro-optical FLC modes such as surface stabilised FLC (SSFLC), deformed helix ferroelectrics (DHF) and electrically suppressed helix (ESH). The mixtures developed allow to reduce the FLC cells chromatic retardance variation due to the weaker birefringence dispersion as compared with the known FLC materials to date.     

Nematic liquid crystals in frequency and amplitude modulated electric fields

In this paper we study peculiarities of behaviour of a nematic liquid crystal (NLC) in an electric field consisting of two harmonics with different amplitudes and frequencies. The most interesting result is the experimental observation of high frequency, stabilization of a low frequency electrohydrodynamic instability in the NLC. A method of measurement of the one frequency instability threshold has been proposed. The beating regime of the two frequency electric field was also studied. The theory developed provides an explanation for all the experimental results.     

Electrochemical polymerization of aniline in the SDS/n‐C5H11OH/H2SO4(aq) lyotropic liquid crystal

Electrochemical polymerization of aniline was performed by the method of ultramicroelectrode cyclic voltammetry in the lamellar liquid crystal and hexagonal liquid crystal of SDS/n‐C₅H₁₁OH/H₂SO₄(aq) system. The results indicate that the electrochemical polymerization of aniline can be catalyzed by the SDS/n‐C₅H₁₁OH/H₂SO₄(aq) lyotropic liquid crystal. The polymerization potential of aniline is smaller in the lyotropic liquid crystal system than that in the 0.10 mol L?1 sulfuric acid solution. The catalytic efficiency and polymerization rate of aniline increase with the n‐pentanol content, but decrease with the increase of the SDS content or [PhNH₂/H₂SO₄(aq)] content. Moreover, the catalytic efficiency of the lamellar liquid crystal exceeds that of the hexagonal liquid crystal in the SDS/n‐C₅H₁₁OH/H₂SO₄(aq) system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2388–2394, 2006     

Synthesis and characterization of novel epoxy monomers and liquid crystal thermosets

Four new epoxy monomers have been synthesized and characterized as part of a program to prepare novel liquid crystal thermoset (LCT) materials. Three of the new epoxy monomers contained a biphenyl mesogen and were not liquid crystalline (LC). The remaining epoxy monomer, which contained a 1,4-dibenzoyloxybenzene mesogen, was synthesized in an overall yield of 30% and displayed a broad (83°C) nematic liquid crystalline phase. The new liquid crystalline epoxy monomer was cured at 120°C and postcured at 175°C with a stoichiometric amount of 1,4-phenylenediamine. The thermal transitions of the resulting LCT were studied by differential scanning calorimetry (DSC), polarized light optical microscopy (POM), thermomechanical analysis (TMA), and wide angle x-ray diffraction (WAXD) as a function of cure time and temperature. A process characterization diagram was constructed which shows that LCTs based on this new LC monomer can be processed in the liquid crystalline phase over a broad range of times and temperatures. Qualitative agreement with previous epoxy LCT results was found, as LCT's with smectic phases and without clearing temperatures were observed at long cure times (high crosslink densities), whereas nematic phases with clearing temperatures predominated in networks at short cure times (low crosslink densities). © 1993 John Wiley & Sons, Inc.     

Synthesis and mesomorphic properties of three- and four-ring liquid crystals containing cyclohexyl,phenyl and pyridyl units

Two series of 4-(3-alkoxycarbonylpyridyl-6-ethynyl)phenyl trans-4-n-alkylcyclohexylcarboxylates and 4-(3-alkoxycarbonylpyridyl-6-ethynyl)phenyl 4-(trans-4-n-alkylcyclohexyl)benzoates have been prepared. Their mesmorphic properties were observed and measured by polarizing optical microscopy and differential scanning calorimetry. The relationship between structures and properties is discussed, showing that the ferroelectric phase can be observed when chiral terminal chains exist.