Engineered Anisotropic Fluids of Rare‐Earth Nanomaterials

The self‐assembly of inorganic nanoparticles into well‐ordered structures in the absence of solvents is generally hindered by van der Waals forces, leading to random aggregates between them. To address the problem, we functionalized rigid rare‐earth (RE) nanoparticles with a layer of flexible polymers by electrostatic complexation. Consequently, an ordered and solvent‐free liquid crystal (LC) state of RE nanoparticles was realized. The RE nanomaterials including nanospheres, nanorods, nanodiscs, microprisms, and nanowires all show a typical nematic LC phase with one‐dimensional orientational order, while their microstructures strongly depend on the particles’ shape and size. Interestingly, the solvent‐free thermotropic LCs possess an extremely wide temperature range from ?40 °C to 200 °C. The intrinsic ordering and fluidity endow anisotropic luminescence properties in the system of shearing‐aligned RE LCs, offering potential applications in anisotropic optical micro‐devices.     

Synthesis and Characterization of a Soluble Polyimide Containing a Photoreactive 4‐Styrylpyridine Derivative as the Side Group

An aromatic polyimide bearing photoreactive 4‐(2‐(4‐oxyethylenyloxyphenyl)vinyl)pyridine side groups was synthesized and characterized. The polymer is stable up to 300°C and soluble in organic solvents, giving thin films in good quality. When exposed to UV light, it reorients favorably with an angle of 98° with respect to the electric vector of linearly polarized UV light. UV‐exposed films align liquid‐crystals (LCs) homogeneously along the preferential orientation of the polymer chains on the surface. The pretilt angle of the LCs is 0.32–0.92°, depending on the exposure dose and annealing. LC alignment is retained up to 210°C. Based on the optical retardation behavior and spectroscopic measurements, a photoalignment mechanism is proposed.     

Synthesis and properties of organic–inorganic hybrid liquid crystal gels

Organic–inorganic hybrid liquid crystal (LC) gels have been synthesised by the thiol-ene reaction of a multifunctional cyclic siloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (TVMCTS) and alkane dithiols, 1,6-hexanedithiol (HDT) or 1,9-decanedithiol (DDT), in LC matrices, 4-cyano-4?-pentylbiphenyl (5CB) or 4′-n-octyl-4-cyano-biphenyl (8CB). The LC gels were prepared in an isotropic phase at 70°C or mesophases at 25°C using radical initiators. The phase transition temperatures from a mesophase to an isotropic phase of the resulting gels were lower than those of the original LCs. The gels containing 8CB (8CB gels) prepared at 25°C showed two phase transitions: smectic-to-nematic and nematic-to-isotropic transitions. By contrast, the 8CB gels synthesised in the isotropic phase showed only one phase transition from smectic phase directly to isotropic phase. Reaction conversions in the LC gels prepared at 70°C were higher than that in the gels prepared at 25°C. Scanning microscopic light scattering analysis of the LC gels cleared homogeneous small size mesh with a small amount of large defect. Polarisation micrographs of the LC gels showed framed optical textures derived from the LC molecules at room temperature. The LC gels containing more than 90 wt% of LC showed electro-optic response.     

Synthesis and properties of photoalignable aromatic polyesters containing phenylenediacrylate units in their backbones and n‐alkyl moieties in their side groups

A series of poly[oxy(4‐n‐alkyl‐3,5‐benzoate)oxy‐1,4‐phenylenediacryloyl]s (PPDA‐CnBZ polymers) with high molecular weights was synthesized. These polymers exhibit excellent solubility in some common organic solvents and produce good quality films using conventional spin‐casting and drying processes. The polymers are thermally stable up to 357–362 °C in a nitrogen atmosphere; their glass transition temperatures are greater than 121 °C. The photoreactions and photoalignments of the polymers were investigated using ultraviolet‐visible and infrared spectroscopy, and their liquid crystal (LC) alignment properties were examined. The phenylenediacrylate (PDA) chromophores in the polyesters were found to mainly undergo photocyclization upon ultraviolet light irradiation. Irradiation of the polyester films with linearly polarized ultraviolet light (LPUVL) induces preferential orientation of the polymer main chains, while the unreacted PDA chromophores are aligned along the direction perpendicular to the electric vector of the LPUVL. All the films irradiated with LPUVL were found to align LCs in a direction perpendicular to the electric vector of the LPUVL. Moreover, these LC alignments persisted even on irradiated films annealed at temperatures up to 210 °C, which is much higher than the glass transition temperatures of the polyesters. These LC alignment characteristics are due to the anisotropic interactions of the LC molecules with the oriented polymer chains and with the unreacted PDA chromophores. LC alignments on the polyester film surfaces have homeotropic to homogeneous characteristics, depending on the length of the n‐alkyl side group, providing strong evidence that the n‐alkyl side groups of the polyesters play a critical role in determining the pretilt angles of the LCs. The LC pretilt angles were also found to be influenced by the thermal annealing history of the irradiated films. In summary, the excellent properties of the PPDA‐CnBZ polymers make them promising candidate materials for use as LC alignment layers in advanced LC display devices. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1322–1334, 2004     

Photoalignment of liquid crystals by a covalently attached self-assembled ultrathin film

In this paper, the polyanion-containing cinnamoyl group (PACSS-CF3) was self-assembled with diazoresin (DR) to form a kind of stable covalent ultrathin film by irradiation with 365?nm UV light. The photoalignment properties of the DR/PACSS-CF₃ covalent film were investigated. The covalent film was found to have anisotropy after irradiation by 297?nm linearly polarised ultraviolet light (LPUVL), and could induce uniform alignment of liquid crystals (LCs). The pretilt angle of the LC was 2.5°. The stability of the film was enhanced by the covalent bonds. The films were thermally stable to 180°C. Polarised UV-Vis spectroscopy was utilised to investigate the photochemical process of the covalent film. It was found that cinnamoyl moieties parallel to the polarisation direction of the LPUVL were consumed by the photoreaction faster than those perpendicular to the polarisation direction. It can be concluded that the selective photoreaction induced the anisotropy of the films. The anisotropic films induced the homogeneous alignment of LC.     

Determination of solvatochromic solvent polarity parameters for the characterisation of some nematic liquid crystal in anisotropic and isotropic phases

Characterisation of liquid crystals (LCs) as solvents is needed, to obtain the polarity and solvatochromic polarity parameters of these media. Polarity parameters demonstrate the effects of LC media on the photo-physical behaviour of solute molecules in an anisotropic medium. The practical limitations in determining solvent polarity scale parameters for LCs can overcome the overlapping absorption band of LCs and solvent-sensitive standard compounds or their insolubility in LCs. In this work, we report Kamlet–Abboud–Taft polarity functions of some nematic LCs in different temperatures and phases, isotropic and anisotropic, with the solvatochromic method, using the Reichardt's dye and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio)-phenolate standard probe. In addition, a new azo and coumarin dye were used as probes to obtain some solvatochromic polarity parameters. Finally, a new polarity parameter, the LC anisotropic matrix, is introduced.     

Biphenyl-based liquid crystals for elevated temperature processing with polymers

Due to the limited thermal stability of current commercially available liquid crystals (LCs), the incorporation into polymer composites through standard processing techniques, such as melt coextrusion, has been hindered. Motivated by this dilemma, a series of smectic B liquid crystalline structures based on the 4,4?-alkyl substituted biphenyl moiety were synthesised through conventional methodologies and probed for their thermal stability and LC properties. Degradation temperatures were found to increase with increasing aliphatic chain length – up to 295 °C for C16 substituted structures, which is well above the processing temperatures of commercial polymers. Additionally, all compounds were found to be liquid crystalline in nature with crystal-to-smectic B transition temperatures ranging from 49.8 °C to 91.4 °C. Thermal stability, phase separation, and compatibility of LC/polystyrene composites were also examined. Less than 10% of 15A15 LC by weight in polystyrene exhibited good polymer miscibility, while phase separation occurred at loads higher than 15% by weight. We foresee the use of these LCs in applications that require elevated processing conditions to produce materials with enhanced mechanical or gas barrier properties.     

Determination of polarity parameters for liquid crystals using solvatochromic method in anisotropic and isotropic phases

The use of liquid crystals (LCs) as anisotropic solvents is desired for various potential applications and usually for other organic and inorganic compounds. In this work, solvent polarity parameters are obtained using a spectroscopic method for four LCs with a range of high and low dielectric anisotropy (?ε). Solvatochromic polarity parameters for these LCs were defined via Kamlet–Abboud–Taft polarity functions characterizing different temperatures and phases, isotropic and anisotropic, and using the Reichardt’s dye and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio) phenolate standard probe. The investigated polarity parameters reveal the effects of LC media on the photo-physical behaviour of solute molecules in isotropic and anisotropic media. Subsequently, a new LC polarity parameter (Z_o) is introduced as an overall matrix anisotropy polarity parameter to characterize variation between isotropic and anisotropic phases. The values of Z_o are sorted from higher to lower dielectric anisotropies (?ε).     

Unidirectional Alignment of Surface-Grafted ZnO Nanorods in Micrometer-Thick Cells Using Low-Molecular-Weight Liquid Crystals

Inorganic nanomaterials such as nanotubes and nanorods have attracted great attention due to their anisotropic properties. Although the alignment control of inorganic nanomaterials is key to the development of functional devices utilizing their fascinating properties, there is still difficulty in achieving uniform alignment over a large area with a micrometer thickness. To overcome this problem, we focused on liquid crystals (LCs) to promote the alignment of anisotropic nanomaterials, taking advantage of the cooperative motion of LCs. We present the uniform, one-dimensional alignment of ZnO nanorods along the direction of LCs in micrometer-thick cells by grafting nematic LC polymers from the nanorod surfaces to provide miscibility with the host LCs. Polarized optical microscopy and polarized UV–visible absorption spectroscopy revealed the unidirectional alignment of nematic LC polymer-grafted ZnO nanorods parallel to the nematic host LCs.     

Charge-transfer interaction in liquid-crystalline materials and their application to photonics

Photochemical phase transition of push-pull type azobenzene liquid crystal (LC), which contains both an electron donor and an acceptor in both ends of the azobenzene moiety, has been explored. Polymer azobenzene LCs were prepared, which show nematic (N) LC behavior in the trans form while no LC phase in the cis isomer. Photoirradiation of a very thin film of the azobenzene LCs (∼ 200 nm) in the trans form resulted in disappearance of the N phase due to transcis photoisomerization of each mesogen, and the N phase recovered quickly when the irradiated sample was kept in the dark because of cis-trans thermal isomerization and reorientation of trans-azobenzenes. Time-resolved measurements by the use of a laser pulse (355 nm; 10 ns FWHM) revealed that the N to isotropic (I) phase transition took place in 200 μs. The thermal I-N phase transition of the push-pull type azobenzene LC occurred in 800 ms at 135 °C. This response is faster by one order of magnitude than the response of azobenzene LCs without charge-transfer interaction.     

Electro-optical and dielectric study of multi-walled carbon nanotube doped polymer dispersed liquid crystal films

The self-organising property of nematic liquid crystals (LCs) was used to align multi-walled carbon nanotubes (MWCNT) dispersed in them. MWCNT not only well integrate in the matrix but also, even at very low concentration, have a detectable effect on the LC properties that can be very attractive for display applications. In the present work, MWCNT were doped (0–0.5% wt/wt) in two different types of LCs. These MWCNT doped polymer dispersed LC (CPDLC) films were studied comprehensively using fundamental techniques. Polarising optical microscope (POM) and scanning electron microscope (SEM) techniques used for morphological study reveal that the LC droplet size remains unchanged with increase in MWCNT concentration. The electro-optical (EO) study performed by increasing voltage in steps of 10 V up to 100 V at an optimised frequency of 200 Hz and at temperature 25°C shows that the low MWCNT concentration films show good optical response than the higher one. The dielectric behaviour of CPDLC films in the frequency range 20 Hz to 20 MHz was investigated using precision impedance analyser. The obtained data were modelled with Debye and Cole-Cole methods to calculate relaxation time and distribution parameter (α). The zero value of α indicates Debye type relaxation processes.     

The effect of polymerizable surfactants on morphology and electro-optical of PDLCs films based on epoxy acrylate system

Polymer dispersed liquid crystals (PDLCs) have been extensively studied for various excellent electro-optical applications. The anchoring interaction of liquid crystals (LCs) molecules on the surface of the polymer cavity surrounding an LCs droplet has a crucial effect on the electro-optical performance of the PDLCs. The effect of polymerizable surfactants on the electro-optical properties of PDLCs films was studied in detail. The active double bonds were polymerized with prepolymer to stabilize the performance of polymer matrix. The experimental results showed that polymerizable surfactants could effectively reduce the driving voltage. The speed of polymerization was monitored by real-time transmittance. The electro-optical properties of PDLC films were measured by Polarimeter (PerkinElmer Model 341). The driving electric field was reduced from 3.9 V/μm to about 2.8 V/μm for doping undec-10-enoic acid at curing temperature 80?°C. The surfactants containing polymerizable functional groups, polarity, and alkyl chain weakened the surface anchoring between LCs droplets and polymer interface. The morphologies of PDLCs films were also investigated by polarizing optical microscopy (POM) and Fourier transform infrared (FTIR) images. The LC droplets were encapsulated by polymerizable surfactant according to FTIR images.     

ZnO/liquid crystalline nanohybrids: from properties in solution to anisotropic growth

Branched thermotropic liquid crystals (LCs) were successfully used as stabilizers for the synthesis of isotropic photoluminescent ZnO nanoparticles (NPs) in solution. (1)H?NMR spectroscopy and differential scanning calorimetry experiments demonstrate the existence of specific interactions between the LC and both the ZnO precursor and ZnO NPs. This offers the possibility for some branched molecules to act as structurally ordered hosts for the anisotropic growth of ZnO NPs.     

UV-driven switching of chain orientation and liquid crystal alignment in nanoscale thin films of a novel polyimide bearing stilbene moieties in the backbone

A novel photosensitive polyimide, poly(4,4'-stilbenylene 4,4'-oxidiphthalimide) (ODPA-Stilbene PSPI) was newly synthesized. The most surprising feature of this PSPI is that the PSPI films irradiated with linear polarized ultraviolet light (LPUVL) can favorably induce a unidirectional alignment of liquid crystals (LCs) in contact with the film surface and further switch the director of the unidirectionally aligned LCs from a perpendicular direction to a parallel direction with respect to the polarization direction of LPUVL by simply controlling the exposure dose in the irradiation process. These LPUVL-irradiated films were found to provide high anchoring energy to LCs, always giving very stable, homogeneous cells with unidirectionally aligned LCs regardless of the LC alignment directions. In the films, the PSPI polymer chains were found to undergo favorably unidirectional orientation via a specific orientation sequence of the polymer chain segments led by the directionally selective trans-cis photoisomerization of the stilbene chromophore units in the backbone induced by LPUVL exposure. Such unidirectionally oriented polymer chains of the films induce alignment of the LCs along the orientation direction of the polymer chains via favorable anisotropic molecular interactions between the oriented polymer chain segments and the LC molecules. In addition, the PSPI has an excellent film formation processibility; good quality PSPI thin films with a smooth surface are easily produced by simple spin-coating of the soluble poly(amic acid) precursor and subsequent thermal imidization process. In summary, this new PSPI is the promising LC alignment layer candidate with rubbing-free processing for the production of advanced LC display devices, including LC display televisions with large display areas.     

Phase diagrams of liquid-crystal binary systems of lanthanum(III) laurate with some divalent metal laurates

Phase equilibria in binary systems of lanthanum(III) laurate with laurates of divalent metals (lead, cadmium, zinc, and cobalt) are studied at temperatures from 0 to 350°C using differential thermal analysis (DTA) and polythermal polarized-light microscopy. Continuous or terminal smectic A liquid-crystal (LC) solutions are found to form in all systems. The temperature-concentration fields of formation of ionic LCs and glasses are determined.     

Helical Carbon and Graphite Films Prepared from Helical Poly(3,4‐ethylenedioxythiophene) Films Synthesized by Electrochemical Polymerization in Chiral Nematic Liquid Crystals

Helical carbon and graphite films from helical poly(3,4‐ethylenedioxythiophene) (H‐PEDOT) films synthesized through electrochemical polymerization in a chiral nematic liquid‐crystal (N*‐LC) field are prepared. The microscope investigations showed that the H‐PEDOT film synthesized in the N*‐LC has large domains of one‐handed spiral morphology consisting of fibril bundles. The H‐PEDOT films exhibited distinct Cotton effects in circular dichroism spectra. The highly twisted N*‐LC with a helical pitch of smaller than 1 μm produced the H‐PEDOT film with a highly ordered morphology. The spiral morphologies with left‐ and right‐handed screws were observed for the carbon films prepared from the H‐PEDOT films at 800 °C and were well correlated with the textures and helical pitches of the N*‐LCs. The spiral morphologies of the precursors were also retained even in the graphite films prepared from the helical carbon films at 2600 °C.     

Synthesis of lamellar mesoporous silica materials using LCs as templates

The study focuses on the synthesis of mesoporous silica materials using liquid crystals (LCs) formed in an aqueous mixture of cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium dodecyl sulfate (SDS) as templates and tetrathoxysilane (TEOS) as precursor. For this purpose, the phase behavior and range of LC areas were determined at different temperatures, concentrations, and ratios of CTAB/SDS. It was found that LCs became denser with the increased of concentration of surfactants. The mesoporous materials were synthesized using LCs as templates at various temperatures, surfactant concentrations, and pH values. The mesoporous samples were characterized using SEM and nitrogen sorption analysis. The research results showed that the structure of synthesized samples were lamellar and their surface areas increased significantly with the increase of temperature in the temperature range of LCs, reaching about 900?m²/g at 60°C. The surfactant concentrations affect the thickness of pore wall and thereby the specific surface area of products. The specific surface area and the order of mesoporous sample increased gradually with the decrease of pH.     

Nanocrystalline LaYSrO films for liquid-crystal alignment via a solution process

The alignment of liquid crystals (LCs) has been widely studied to enable their use in high-quality displays. In addition to the deposition of an alignment layer, an alignment process to orient the LCs is also required. To accomplish self-alignment and to simplify the fabrication process, many alternatives have been proposed, including the doping of nanoparticles or organic/inorganic composites into LCs or the use of special treatments, such as ultra-violet (UV) irradiation or imprinting. However, an additional treatment is required to achieve proper LC orientation. Herein, we demonstrate the fabrication of an aligned LaYSrO (LYSO) via a solution process. Using this technique, we have generated a simple manufacturing method that eliminates the alignment process, and we have found that the quality of the LC cell is comparable to that of polyimide-rubbed films. The mechanisms of the film formation and the LC alignment were elucidated with a nanocrystalline LYSO film. In comparison with LCs, the nanocrystal is sufficiently large so that order in the LCs is induced along the direction of the nanocrystal. This approach allows for the fabrication of LC displays that meet specific goals such as high performance with a simple fabrication process.     

Palladium nanoparticles supported on gum arabic as a reusable catalyst for solvent-free Mizoroki-Heck reaction

Palladium nanoparticles (2–8 nm) supported on gum arabic has been prepared under green conditions in water. Gum arabic has been used as both support and reducing agent. These nanoparticles have been characterized by UV–Vis, XRD and EDX spectra as well as SEM and TEM images. The nanoparticles have been applied as the catalyst in Mizoroki-Heck reaction of different aryl halides (I, Br, Cl) with butyl acrylate in the presence of n-Pr₃N under solvent-free conditions at 140 °C. The reusability of the catalyst was also checked for five consecutive runs.     

Investigation of the formation of nickel and cobalt nanoparticles upon thermal decomposition of Ni,Al-and Co,Al-layered double hydroxides pillared with complexes [Ni(edta)]<Superscript>2−</Superscript> and [Co(edta)]<Superscript>2−</Superscript>

Double layered hydroxides [M_0.7Al(OH)_3.6] [M(edta)]_0.4·nH₂O (M,Al-M(edta), M = Ni, Co) containing nickel or cobalt edta complexes in the interlayer space were obtained for the first time. Vacuum thermal decomposition of these compounds results in the formation of metal nanoparticles dispersed in an amorphous matrix. Thermal decomposition products were studied by powder X-ray diffraction and ferromagnetic resonance technique. The scheme of structural rearrangements occurring during heating was derived from the data obtained. According to this scheme, below 200°C the interlayer and absorbed water escapes, and at 200–325°C metal-hydroxide layers undergo dehydration. At higher temperatures organic fragment of the complex suffers destruction to yield metal. It is shown that thermal decomposition of Ni, Al-Ni(edta) at 325–340°C gives isotropic nickel nanoparticles, while at higher temperatures the metal consists of a mixture of isotropic and anisotropic particles. Isotropic particles of β-Co formed at 350°C and above are of size 3–4 nm, no anisotropic particles being observed.