Liquid Crystalline Morphology Research Articles

Phase Behavior and Ionic Conductivity of Blended, Ion-Condensed Electrolytes with Ordered Morphologies

In this study, the amphiphilic salt lithium trifluoromethanesulfonylimide octadecane (C18LiTFSI) was used as a basis to investigate the effects of anion density and cation coordination sites within blended electrolytes with strong ionic aggregation. C18LiTFSI was previously reported as a single-component, ion-condensed electrolyte with a wide layered liquid crystalline phase regime. Three additive molecules with varyingly sized polar sulfonyl groups attached to an octodecane-tail were synthesized and mixed with C18LiTFSI. The thermal properties, morphology, and ionic conductivity of the blended electrolytes were characterized. It was found that the blended electrolytes exhibited layered liquid crystalline morphology over a narrower temperature range than the pure salt, and the ionic conductivity of the blended liquid crystalline electrolytes were generally lower than that of the pure salt. Surprising, the additives were found to have the greatest effect on the bulk ionic conductivity of the semicrystalline phase of the electrolytes. Addition of minor fractions of methylsulfonyloctadecane to C18LiTFSI resulted in increases in conductivity of over two orders of magnitude at room temperature, while addition of ethylsulfonyloctadecane or isopropylsulfonyloctadecane with the larger head group resulted in decreased ionic conductivity over the entire composition space and temperature range investigated.

Formation of Self-Assembled Mesophases During Lipid Digestion.

Lipids play an important role in regulating bodily functions and providing a source of energy. Lipids enter the body primarily in the form of triglycerides in our diet. The gastrointestinal digestion of certain types of lipids has been shown to promote the self-assembly of lipid digestion products into highly ordered colloidal structures. The formation of these ordered colloidal structures, which often possess well-recognized liquid crystalline morphologies (or “mesophases”), is currently understood to impact the way nutrients are transported in the gut and absorbed. The formation of these liquid crystalline structures has also been of interest within the field of drug delivery, as it enables the encapsulation or solubilization of poorly water-soluble drugs in the aqueous environment of the gut enabling a means of absorption. This review summarizes the evidence for structure formation during the digestion of different lipid systems associated with foods, the techniques used to characterize them and provides areas of focus for advancing our understanding of this emerging field.

Thermotropic liquid crystalline copolyester fibers according to various heat treatment conditions

Thermotropic liquid crystal copolyester (TLCP) was synthesized using a melt polymerization method, with a molar ratio composition of 2,5-diethoxy terephthalic acid (ETA), hydroquinone (HQ), and p-hydroxybenzoic acid (HBA) of 1:1:3. TLCP exhibited nematic liquid crystalline mesophase and maintained nematic textures under all heat treatment conditions applied. The synthesized TLCP was processed into fibers using a capillary rheometer. The liquid crystalline mesophase, thermo-mechanical properties, and morphology of TLCP fibers obtained under various heat treatment conditions were investigated. The thermo-mechanical properties of the heat-treated fibers were improved compared to those of the as-spun fibers. The best results were obtained for TLCP fibers annealed at 230 °C for 9 h. The heat-treated fibers showed a well-developed microfiber morphology compared to the as-spun fibers. In the spun fibers, a skin–core morphology was observed regardless of the heat treatment conditions, and a well-developed fiber morphology better than the core area was observed in the skin area. The diameter of the fiber heat-treated at 230 °C for 9 h was approximately 60–110 nm.

Using Deposition Rate and Substrate Temperature to Manipulate Liquid Crystal-Like Order in a Vapor-Deposited Hexagonal Columnar Glass.

We investigate vapor-deposited glasses of a phenanthroperylene ester, known to form an equilibrium hexagonal columnar phase, and show that liquid crystal-like order can be manipulated by the choice of deposition rate and substrate temperature during deposition. We find that rate-temperature superposition (RTS)-the equivalence of lowering the deposition rate and increasing the substrate temperature-can be used to predict and control the molecular orientation in vapor-deposited glasses over a wide range of substrate temperatures (0.75-1.0 Tg). This work extends RTS to a new structural motif, hexagonal columnar liquid crystal order, which is being explored for organic electronic applications. By several metrics, including the apparent average face-to-face nearest-neighbor distance, physical vapor deposition (PVD) glasses of the phenanthroperylene ester are as ordered as the glass prepared by cooling the equilibrium liquid crystal. By other measures, the PVD glasses are less ordered than the cooled liquid crystal. We explain the difference in the maximum attainable order with the existence of a gradient in molecular mobility at the free surface of a liquid crystal and its impact upon different mechanisms of structural rearrangement. This free surface equilibration mechanism explains the success of the RTS principle and provides guidance regarding the types of order most readily enhanced by vapor deposition. This work extends the applicability of RTS to include molecular systems with a diverse range of higher-order liquid-crystalline morphologies that could be useful for new organic electronic applications.

Six-fold director field configuration in amyloid nematic and cholesteric phases

Chiral liquid crystals, or cholesteric phases, have been widely studied in the last decades, leading to fundamental advances and a multitude of applications and technologies. In general, the rich phenomenology of these systems depends directly on the molecular traits and conditions of the system, imposing precise symmetry to the resulting nematic field. By selecting amyloid fibrils as model filamentous chiral colloids, we report an unprecedented breadth of liquid crystalline morphologies, where up to six distinct configurations of the nematic field are observed under identical conditions. Amyloid-rich droplets show homogeneous, bipolar, radial, uniaxial chiral and radial chiral nematic fields, with additional parabolic focal conics in bulk. Variational and scaling theories allow rationalizing the experimental evidence as a subtle interplay between surface and bulk energies. Our experimental and theoretical findings deepen the understanding of chiral liquid crystals under confinement, opening to a more comprehensive exploitation of these systems in related functional materials.

Barrier properties and structure of liquid crystalline epoxy and its nanocomposites

There is ever increasing demand for a suitable sealant material to protect electronic devices, in particular, different displays. We present a new approach to generate a liquid processible material that possesses excellent barrier properties and flexibility that can be used for electronic encapsulation. The liquid processable material is based on liquid crystalline (LC) epoxy diglycidyl ether of 4, 4′-dihydroxy-α-methylstilbene (DGE-DHAMS or EDHAMS) and its nanocomposite comprising organo-modified montmorillonite clay. The best-achieved water vapor transmission rate is 4.5 g-mil/m2-day at ambient pressure, which is more than 20 times better than that of a conventional bisphenol A epoxy. The improved barrier performance comes from the reduction in the water diffusivity. The diffusivity in the liquid crystalline epoxy is 1.25 × 10−9 cm2/s, one order of magnitude lower than that of bisphenol A epoxy. The addition of 1 vol% of organoclay further reduces the diffusivity by 2 times. The cavity size of the free volume of the liquid crystalline epoxy is much smaller than that of conventional bisphenol A epoxy as measured by positron annihilation lifetime spectroscopy, suggesting that the improved barrier property originates from this reduced free volume cavity size. The free volume cavity size of the film with an addition of 1 vol% of an organically modified montmorillonite clay is similar to that of the liquid crystalline epoxy. We hypothesize that the additional barrier performance improvement by the nanoclay is due to its effect on the liquid crystalline phase morphology (reduced LC phase domain sizes) or the tortuosity effect of the high aspect ratio particles. The material also has excellent adhesion, optical transparency, and thermal stability.

Counterion-Regulated Dynamics of Water Confined in Lyotropic Liquid Crystalline Morphologies.

The dynamics of confined water is of fundamental and long-standing interest. In technologically important forms of confinement, such as proton-exchange membranes, electrostatic interactions with the confining matrix and counterions play significant roles on the properties of water. There has been recent interest on the dynamics of water confined to the lyotropic liquid crystalline (LLC) morphologies of Gemini dicarboxylate surfactants. These systems are exciting because the nature of confinement, for example, size and curvature of channels and surface functionality is dictated by the chemistry of the self-assembling surfactant molecules. Quasielastic neutron scattering experiments have shown an interesting dependence of the water self-diffusion constant, Dα, on the identity (denoted α) of the counterion: at high hydration, the magnitude of the water self-diffusion constant is in the order DTMA < DNa < DK, where TMA, Na, and K refer to tetramethyl ammonium, sodium, and potassium counterions, respectively. This sequence is similar to what is seen in bulk electrolyte solutions. At low hydrations, however, the order of water self-diffusion is different, that is, DNa < DTMA < DK. In this work, we present molecular dynamics simulations for the dynamics of water in the LLC phases of dicarboxylate Gemini surfactants. The simulations reproduce the trends seen in experiments. From an analysis of the trajectories, we hypothesize that two competing factors play a role: the volume accessible to the water molecules and the correlations between the water and the counterion. The excluded volume effect is the largest with TMA+, and the electrostatic correlation is the strongest with Na+. The observed trend is a result of which of these two effects is dominant at a given water to surfactant ratio.

A comprehensive review on poly(3-alkylthiophene)-based crystalline structures, protocols and electronic applications

Abstract Poly (3-alkylthiophenes) (P3ATs) particularly poly (3-hexylthiophene) (P3HT) have vigorous tendency to crystallize into the ordered morphologies, thereby reflect the efficient electrical and optical characteristics. Here, the remarkable crystalline structures of P3ATs comprising single crystals, nanofibers, nano/microwires, nanoribbons, micelles, nanowhiskers, thin films, spherulites, etc. are thoroughly reviewed. In each category, the principle aspects like preparation methodologies (e.g., self-seeding, shearing, electrospinning, self-organization, epitaxial solidification, etc.), micro/nanostructures, orientation and optical properties are meticulously brought into consideration. Applications of the ordered P3AT structures in solar cells, organic field-effect transistors, and sensors as well as the theoretical studies are also highlighted. Furthermore, the polymorphism, sol-gel, nanoparticles, liquid crystalline morphology, and two-dimensional sheets are reviewed.

Synthesis, liquid crystalline mesophases and morphologies of diblock copolymers composed of a poly(dimethylsiloxane) block and a nematic liquid crystalline block

ABSTRACTIn this study, a series of liquid crystalline diblock copolymers, composed of a soft poly(dimethylsiloxane) (PDMS) block with a defined length and a side-on liquid crystalline poly(3ʹʹ-acryloyloxypropyl 2,5-di(4ʹ-butyloxybenzoyloxy) benzoate) (P3ADBB) block with different lengths, are synthesised by the atom transfer radical polymerisation. The macromolecular structures, liquid crystalline properties and the microphase-separated morphologies of the diblock copolymer are investigated by 1H NMR, FT-IR, GPC, POM, DSC and TEM. The results show that the well-defined diblock copolymers (PDMSn-b-P3ADBBm) possess four different soft/rigid ratios (n = 58, m = 10, 25, 42, 66) and relatively narrow molecular distributions (PDI ≤ 1.30). P3ADBB blocks of the copolymers show nematic sub-phases, which are identical to the mesomorphic behaviour of the homopolymer P3ADBB. After being annealed at 90°C in a vacuum oven for 48 h, the copolymers form a lamellar morphology when m = 10 and morphologies of PDMS spheres embedded in P3ADBB matrix when m = 25, 42 and 66.

Liquid crystalline epoxy resin based on biphenyl mesogen: Thermal characterization

An epoxy monomer of 4,4′-diglycidyloxybiphenyl (BP) was synthesized and cured with a tetra-functional amine, sulfanilamide (SAA), to produce novel liquid crystalline epoxy resins (LCERs). The thermal properties, liquid crystalline morphologies, and cure behavior of the monomer were studied using differential scanning calorimetry, wide angle X-ray diffraction, and polarized optical microscopy. The effects of curing condition on the glass transition temperature, coefficient of thermal expansion, and dynamic mechanical properties of the resins were determined through thermomechanical analysis and dynamic mechanical analysis, respectively. The effects of cure condition on the formation of the liquid crystalline phase were also examined. The results show that BP is not a liquid crystalline epoxy monomer and an irreversible crystal transition exists in the temperature range of 120 °C–140 °C. The use of SAA results in the formation of a smectic liquid crystalline phase. Compared to the resins cured into an amorphous network, the LCERs exhibited a polydomain structure with individual liquid crystalline domain distributed in the resin matrix, which results in better thermomechanical properties.

Liquid crystalline and ion-conducting properties of mesogenic dendron–coil-dendron copolymers: characterization of LC phases using normalized conductivity

We synthesized three dendron–coil-dendron block copolymers consisting of ionophilic poly(ethylene oxide) (PEO) coils and mesogenic dendrons with four octadecyl peripheries via stepwise click reactions. The obtained polymers were doped with lithium triflate, whose concentration per ethylene oxide unit was 0.05. As characterized by optical polarized microscopy (POM) and X-ray scattering techniques, polymer 1 with the shortest PEO coil (Mn = 2000 g mol−1) did not show the liquid crystalline (LC) phase, while its ionic sample (1-Li+) exhibited a hexagonal columnar LC phase. On the other hand, 2 and 3 (with PEOs of Mn = 4000 and 8000 g mol−1, respectively) displayed identical LC morphologies to 2-Li+ and 3-Li+, respectively, although the phase transition temperatures increased upon salt doping. For 2 and 2-Li+, gyroid and lamellar LC phases were observed with increasing temperature, while 3 and 3-Li+ showed only a lamellar LC phase. The observed ion-transporting behavior was strongly dependent upon the connectivity of ion-conducting domain structures. The investigation of the morphology–conductivity correlation using a normalized conductivity (σ* = σ/f, where σ and f are the original conductivity and the PEO volume fraction) indicated that the 3-D gyroid LC phase showed the highest value, while the lowest conductivity was found in the 1-D columnar structure at identical temperatures. Additionally, the gyroid to lamellar phase transition temperature of 2-Li+ could be determined by the σ*, which was consistent with the X-ray data. Consequently, the results can be explained by the fact that the ionic pathway becomes complicated when going from higher to lower dimensional structures in polygrain samples.

Preclusion of nano scale self-assembly in block-selective non-aqueous solvents for rod–coil and coil–rod–coil macromolecular surfactants based on perylene tetracarboxylic diimide

Self-assembly of amphiphilic molecules ranging from simple surfactants to block copolymers in a solvent depends on one part of the molecule (one block in block copolymers) being soluble, and the other not. The aggregation of the insoluble segment in the block-selective solvent leads to the self assembly. In this paper, we describe a system of amphiphilic rod–coil and coil–rod–coil molecules, which do not show self assembly in block-selective non-aqueous solvents. We prepared rod–coil molecules based on hydrophilic propylene oxide/ethylene oxide copolymer (PO–EO copolymer) (Jeffamine®) as the flexible segment and photo-conducting large aromatic perylenediimide (PTCDI) as the rod. PO–EO copolymer was attached either to one side of PTCDI (MJ–PTCDI) or both sides (DJ–PTCDI). The former can be considered an inverse macromolecular surfactant, since the tail is hydrophilic and the head is hydrophobic. The DJ–PTCDI is a pseudo Gemini surfactant. Because of the presence of the chromophore, UV–Vis and fluorescent spectra could be used to study the self assembly of these amphiphilic rod coil polymers in solution. PTCDI forms π-interaction mediated aggregates in aqueous solution and these are H-stacked in MJ–PTCDI and J-stacked in DJ–PTCDI. Variable temperature UV and NMR spectra show that the assembly is stable over a large temperature range in water. The aggregates are also stable up to a pH of 12. However, when a non-aqueous solvent is used, no aggregation occurs. This is attributed to the “solvation” of the π-system of the PTCDI. With the addition of water, such solvation seems to be interrupted and aggregation occurs when water becomes a major component. We find that the mole percentage of the aggregates in acetone/water mixtures increases almost linearly with the concentration of water, providing a route to control the extent of aggregation of the chromophores. Due to the long, waxy PO–EO copolymer, MJ–PTCDI and DJ–PTCDI do not show liquid crystalline behavior or nanorod morphology, which were seen with short side chains. The optical microscopy of the bulk material shows aggregated crystals of PTCDI in the waxy matrix, showing that even in the presence of PO–EO copolymer, the molecular assembly of PTCDI takes place in the bulk. Secondary assembly was seen, in that upon ageing of the aqueous solutions, the drop cast films show that the spherical aggregates one-dimensionally coalesced into long fibers. Although UV–Vis spectra indicated no aggregation in non-aqueous solvents, drop-cast films of these solutions show needle-like aggregates and Lego-like assemblies.

Spontaneous bulk organization of molecular assemblers based on aliphatic polyether and/or poly(benzyl ether) dendrons

Hybrid self-assemblers based upon dendritic building blocks such as aliphatic polyether and/or poly(benzyl ether) dendrons can be prepared by a combination of physically different flexible linear and rigid discotic segments. The unconventional self-assemblers organize into various bulk liquid crystalline morphologies, which can be used as a versatile platform for ion-conducting materials.

Formation of Intermicellar-Chained and Cylindrical Micellar Networks From an Amphiphilic Rod−Coil Block Copolymer: Poly(n-hexyl isocyanate)-block-poly(2-vinylpyridine)

Morphologies of the poly(n-hexyl isocyanate)-block-poly(2-vinylpyridine) (PHIC-b-P2VP, fP2VP=0.3) amphiphilic rod-coil block copolymer were studied in rod-selective chloroform (CHCl3), both-block-soluble tetrahydrofuran (THF), and CHCl3/THF mixed solvent systems. Spherical, solid micelles with a P2VP core and PHIC shell were formed in CHCl3, whereas a microphase-separated liquid crystalline morphology was prominent in the presence of THF. In the CHCl3/THF mixed solvent system, a unique long-range intermicellar-chained network (v/v=7/3) and a more evolved cylindrical micellar network (v/v=3/7) were remarkably formed, respectively. PHIC-b-P2VP network nanostructures were used as a template for the in situ synthesis of Au nanoparticles (8 nm) selectively within the functional P2VP core domains.

Metallosupramolecular Side-Chain Polymers and Polyelectrolyte- Metallosupramolecular Surfactant Complexes

We report on the columnar liquid-crystalline morphologies adopted by a series of polymeric supramolecular complexes in which alkoxy dendron side-chains were attached to the polymer backbone via either metal−ligand coordination or a combined metal−ligand coordination plus ionic complexation approach.

A New Level of Hierarchical Structure Control by Use of Supramolecular Self‐Assembled Dendronized Block Copolymers

Complexation of dendronized block copolymers with sulfate alkyl tails forms unprecedented hierarchically ordered bulk structures, including rectangular-in-lamellar, tetragonal-in-lamellar, hexagonal-in-lamellar and lamellar-in-lamellar. These novel liquid-crystalline morphologies, which can be designed at low length scales in these systems, are expected to provide final materials with not only unprecedented structural complexity, but also tunable physical properties.

Surface-induced morphology and free-energy pathways in breakup of a nematic liquid crystalline cylinder

We compute the surface-induced morphology and the free-energy pathways as a cylindrical liquid crystalline filament with preferred homeotropic (orthogonal) interface orientation passes through a sequence of growing sinusoidal perturbations and breaks up into droplets. Liquid crystalline morphology is determined using a simulated annealing algorithm [R. K. Goyal and M. M. Denn, Phys. Rev. E, 75, 021704 (2007)] to minimize the Oseen-Frank free energy. A first-order morphological transition with a finite energy barrier is required when the perturbation amplitude exceeds a critical value, and it is possible that progress towards breakup will be kinetically trapped in a varicose cylindrical shape. This result may be related to the apparent kinetic trapping of dispersed nematic 4'-octyl-4-biphenylcarbonitrile in a gel state reported by Inn and Denn [J. Rheol., 49, 887 (2005)].

Supramolecular routes towards liquid crystalline side-chain polymers.

Supramolecular attachment of mesogenic or non-mesogenic side chains to polymer backbones can result in the formation of liquid crystalline morphologies. The various parameters that can be tuned in order to achieve these morphologies, such as the type of non-covalent bonding chemistry (hydrogen bonding, ionic bonding, metal coordination, π-π interactions), the polymeric template architecture, and the side chain structure and properties, are reviewed in what follows, with emphasis placed on the role these parameters play in the determination of the final material morphologies and properties.

Spacer Length Controlled Oblique-Columnar to Lamello-Columnar Mesophase Transition in Liquid Crystalline DNA−Discotic Cationic Lipid Complexes

Asymmetric triphenylene imidazolium salts with spacer lengths of C5, C8, and C11 were successfully synthesized. DNA complexation with these cationic discotic lipids was achieved by mixing DNA and triphenylene imidazolium salts in aqueous solutions. The molecular composition of the complexes in the bulk was quantitatively determined using Fourier transform infrared (FTIR) spectroscopy; the ratio of negative phosphate groups to positive imidazolium salt ranged from 1.4 to 2.0 for different discotic cationic lipids. The columnar liquid crystalline morphology was characterized by polarized light microscopy, X-ray diffraction (XRD), and transmission electron microscopy. When the spacer length of the triphenylene imidazolium salts increased from C5 to C8 and C11, a morphological transition from an oblique-columnar (Colo) phase to lamello-columnar (ColL) phases was observed. From detailed XRD results, the face-to-face interdisk spacing in a triphenylene column (0.35 nm) was similar to the period of hydrogen-bonded pairs in DNA (0.34 nm), suggesting a 1:1 complexation between the phosphate group and the imidazolium salt. The higher phosphate/imidazolium salt ratio (1.4−2.0) determined by FTIR suggested that the DNA chains were partially complexed due to rapid precipitation of the complexes upon mixing the two components in aqueous solutions. The columnar stacking of the triphenylene discotic molecules destroyed the helical conformation in the double-strand DNA, as evidenced by a circular dichroism study. When the semirigid DNA molecules were replaced with flexible total RNA, columnar liquid crystalline self-assembly of the triphenylene molecules in the complexes disappeared, and only a lamellar morphology with random discotic triphenylenes sandwiched between neighboring RNA layers was observed.

Effect of pyridazine structure on thin-film polymerization and phase behavior of thermotropic liquid crystalline copolyesters

An intensive study has been conducted to compare the effects of malei hydrazine (MH) and hydroquinone (HQ) on the liquid crystallinity and phase transition behavior in the ABA/HQ/TFTA and ABA/MH/TFTA copolyesters (p-acetoxybenzoic acid (ABA) and tetrafluoroterephthalic acid (TFTA)). These two copolyesters were prepared by thin-film polymerization and characterized by differential scanning calorimetry (DSC), polarizing light microscope (PLM), wide-angle X-ray diffraction (WAXD), as well as Cerius2 computational simulation. Characterization and comparison of the liquid crystalline (LC) evolution and morphology changes of HQ moiety with corresponding MH moiety suggest that ABA/MH/TFTA system is energetically favorable to mesophase formation than ABA/HQ/TFTA system. When the films are quenched, a surface microcrack decoration is observed in both systems. Both systems, which have the persistence ratio larger than 6.42, satisfy the minimum requirement for the LC formation by molecular science software. The ABA/MH/TFTA film exhibits only one single peak transition. However, two distinct transitions have been observed in the ABA/HQ/TFTA system. The average Avrami exponent, n, is ∼1.2, and PLM and WAXD results suggest mesophase transition in ABA/MH/TFTA film. As reflected by the results obtained from PLM, WAXD, and DSC studies, the phase transition is confirmed as crystal → nematic → isotropic in ABA/HQ/TFTA copolyester. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2230–2242, 2005