Formation Of Liquid Crystalline Structure Research Articles

Reaction-induced liquid crystalline polybenzoxazine thermosets using aryl ester bonds as cross-linkages

ABSTRACT The increasing tendency to develop integration in electronic devices lead to the demand for thermally conductive polymeric materials. We offered a simple synthetic route to thermally conductive polybenzoxazine thermosets bearing liquid crystalline structures without the addition of any filler. Benzoxazine monomer of BZ-COOH was synthesized via Mannich reaction of p-hydroxy benzoic acid, p-formaldehyde, and dodecyl amine. After ring-opening polymerization of BZ-COOH, the obtained benzoxazine oligomer of OBZ-COOH was converted into acetoxy-bearing benzoxazine oligomer of OBZ-AC. Through self-crosslinking reaction of acetoxy group and carboxyl group in OBZ-AC using Zn(CH3COO)2 as a catalyst, the polybenzoxazine thermosets of OBZ-PES were produced. The liquid crystalline behavior of OBZ-AC was studied by POM, SAXS, and DSC. The results show that OBZ-AC formed the LC mesophase during isothermal and non-isothermal curing. The LC mesophase displays a layered arrangement of the smectic C phase. The formation mechanism is esterification reaction-induced. Owing to the formation of liquid crystalline structure, the TC of OBZ-PES is found to be 0.284 W/m. K, which is 21% and 16% greater than those of OBZ-COOH and OBZ-AC, respectively. In addition, the OBZ-PES shows excellent thermal performance. Its Tg(G”) is up to 269°C. Its 5% weight loss temperature (Td5) and 10% weight loss temperature (Td10) are 383°C and 410°C, respectively.

Solid-liquid equilibrium of free form of oil contaminants (3-MCPD and glycidol) in lipidic systems

Esters of 3-monochloropropane-1,2-diol (3-MCPD) and glycidol are reported vegetable fats and oils contaminants formed during processing. During digestion, esterified forms are hydrolyzed making the free forms, with high toxicity to human health, possibly available in the digestive system, which could depend, among other factors, on the phase condition stablished in the gastrointestinal tract between contaminants and lipids. Therefore, this work was aimed at evaluating the solid–liquid equilibrium (SLE) of binary and pseudobinary mixtures of fatty acids (palmitic, oleic and stearic), triacylglycerols (tripalmitin, triolein and tristearin) and a partial acylglycerols, with 3-MCPD and glycidol, by differential scanning calorimetry (DSC) and thermodynamic modeling with Margules 2 and 3 suffixes, UNIFAC and ideal models. Melting properties of the contaminants were determined by DSC thermograms, with microstructure micrographs and compared to some predictive group contribution models (GC). 14 complete SLE phase diagrams could be determined. Results showed that the lipid compounds had high affinity with the free contaminants with probably the formation of liquid crystalline structures and/or solid solutions. The Margules 3 suffixes model showed the best fit with the lowest average relative deviations, no higher than 1%, although the parameters probably incorporated the non-ideality promoted by the crystalline phase behavior. The formation of mesophases and/or solid solutions with very high melting temperature probably means a difficulty of separating the contaminants from the lipid matrix in which, on the other hand, could avoid separation process or affect (probably decreasing) their absorption during digestion.

Formation of liquid-crystalline structures in the bile salt-chitosan system and triggered release from lamellar phase bile salt-chitosan capsules.

Nanostructured capsules comprised of the anionic bile salt, sodium taurodeoxycholate (STDC), and the biocompatible cationic polymer, chitosan, were prepared to assess their potential as novel tailored release nanomaterials. For comparison, a previously studied system, sodium dodecyl sulfate (SDS), and polydiallyldimethylammonium chloride (polyDADMAC) was also investigated. Crossed-polarizing light microscopy (CPLM) and small-angle X-ray scattering (SAXS) identified the presence of lamellar and hexagonal phase at the surfactant-polymer interface of the respective systems. The hydrophobic and electrostatic interactions between the oppositely charged components were studied by varying temperature and salt concentration, respectively, and were found to influence the liquid-crystalline nanostructure formed. The hexagonal phase persisted at high temperatures, however the lamellar phase structure was lost above ca. 45 °C. Both mesophases were found to dissociate upon addition of 4% NaCl solution. The rate of release of the model hydrophilic drug, Rhodamine B (RhB), from the lamellar phase significantly increased in response to changes in the solution conditions studied, suggesting that modulating the drug release from these bile salt-chitosan capsules is readily achieved. In contrast, release from the hexagonal phase capsules had no appreciable response to the stimuli applied. These findings provide a platform for these oppositely charged surfactant and polymer systems to function as stimuli-responsive or sustained-release drug delivery systems.

Determination of the Real Influence of the Addition of Four Thickening Agents in Creams Using Rheological Measurements

This study aimed to characterize different emulsions obtained by the addition of four thickening agents, using rheological measurements, beyond analyzing the emulsions by polarized light microscopy looking for liquid crystals on them. The addition of these four thickening agents did not modify the base emulsion rheology, only an improvement in the sensory of the formulation was verified. The polarized light microscopy showed the formation of liquid crystalline structures in all the formulations, thus, the thickening agents did not influence in this parameter too. However, the emulsions could be considered appropriated for cosmetic purposes, probably being highly physically stable.

Nematic Ion‐Clustomesogens from Surfactant‐Encapsulated Polyoxometalate Assemblies

AbstractThree surfactant‐encapsulated polyoxometalate (SEP) complexes were synthesized by grafting T‐shaped quaternary ammonium units onto the surface of K5BW12O40, K6SiW11O39Co, and Na10[Mn4(H2O)2(VW9O34)2]·34H2O. All the complexes possess shell–core structures, in which the peripheral mesogenic units adopt a lateral attachment. The bulk organization of the complexes with thermal stimulus was studied by polarized optical microscopy, differential scanning calorimetry, and X‐ray diffraction. The quaternary ammonium surfactant alone was found to form smectic structures, whereas the SEPs exhibited nematic characteristics. The detailed structural characterizations suggested the presence of a delicate synergy between the surfactants and polyoxometalates (POMs). The orientation of the mesogenic units was demonstrated to have a pivotal influence on the formation of liquid crystalline structures of the SEPs by comparison with the reported SEPs with head‐to‐tail attached mesogenic units. The clearing temperatures of the nematic complexes were found to be dependent on the number of peripheral surfactants. Finally, the magnetism of the polyoxometalates was proven to be well maintained in the liquid crystalline matrices, which allows the potential development of magnetically tunable liquid crystals bearing nematic structures.

Real Time Evolution of Liquid Crystalline Nanostructure during the Digestion of Formulation Lipids Using Synchrotron Small-Angle X-ray Scattering

The role of the digestion of lipids in facilitating absorption of poorly water-soluble compounds, such as vitamins, is not only an important nutritional issue but is increasingly being recognized as an important determinant in the effectiveness of lipid-based drug formulations. It has been known for some time that lipids often form complex liquid crystalline structures during digestion and that this may impact drug solubilization and absorption. However, until recently we have been unable to detect and characterize those structures in real time and have been limited in establishing the interplay between composition, digestion, and nanostructure. Here, we establish the use of an in vitro lipid digestion model used in conjunction with synchrotron small-angle X-ray scattering by first confirming its validity using known, nondigestible liquid crystalline systems, and then extend the model to study the real time evolution of nanostructure during the digestion of common formulation lipids. The formation of liquid crystalline structures from unstructured liquid formulations is discovered, and the kinetics of formation and dependence on composition is investigated.

Cellulose Acetate Sulfate as a Lyotropic Liquid Crystalline Polyelectrolyte: Synthesis, Properties, and Application

The optimal conditions of cellulose acetate sulfate (CAS) homogeneous synthesis with the yield of 94–98 wt.% have been determined. CAS was confirmed to have an even distribution of functional groups along the polymer chain. The polymer was characterized by an exceptionally high water solubility (up to 70 wt.%). The isothermal diagrams of its solubility in water-alcohol media have been obtained. CAS aqueous solutions stability, electrolytic, thermal, and viscous properties have been defined. The main hydrodynamic characteristics such as intrinsic viscosity, Huggins constant, and crossover concentration have been evaluated. The parameters of polymer chain thermodynamic rigidity have been calculated. The formation of liquid crystalline structures in concentrated CAS solutions has been confirmed. CAS was recommended to be used as a binder for the medicinal forms of activated carbon and carbon sorbent for water treatment, hydrophilic ointment foundation.

Strand-like phase separation in mixtures of xanthan gum with anionic polyelectrolytes

Binary aqueous mixtures of xanthan gum with anionic polyelectrolytes (alginate, polyacrylate, carboxymethylcellulose, λ-carrageenan, and low methoxyl pectin) exhibited phase separation above threshold concentrations of added polyelectrolyte. Dynamic oscillatory rheology showed that separation was associated with a large decrease in storage modulus, and when viewed under plane-polarised light, the dispersed phase exhibited a birefringent, strand-like morphology indicative of a liquid crystalline phase. At constant xanthan concentration, the strand thickness was inversely related to the viscosity of the added polyelectrolyte solution. Phase diagrams obtained for xanthan:alginate, and xanthan:carboxymethylcellulose mixtures showed that whilst the strands contained both xanthan and polyelectrolyte, the continuous phase was xanthan-free. Mixtures of xanthan gum with neutral polysaccharides (maltodextrin, methylcellulose) did not show phase separation, and separation was not observed when xanthan was replaced by scleroglucan a neutral polysaccharide which, like xanthan, adopts a stiff, helical structure in solution. The alginate concentration required to initiate phase separation was inversely related to alginate molecular weight, and was independent of the alginate mannuronate/guluronate ratio. Higher concentrations of alginate were required to elicit phase separation when the salt content of the mixture was increased. The results suggest that segregative phase separation, driven by repulsive interactions between polyelectrolytes, promotes the formation of liquid crystalline structures in the xanthan-rich domain. The consequence is that the decreased viscosity reported when xanthan solutions undergo liquid crystal formation, occurs at much lower xanthan concentrations, when in the presence of an anionic polyelectrolyte.

Kinetics of Epoxy–Amine Curing Accompanied by the Formation of Liquid Crystalline Structure

AbstractThe curing of a mesomorphic epoxy has been studied by polarized light microscopy (PLM) and differential scanning calorimetry. PLM in combination with wide‐angle X‐ray diffraction proves the formation of a liquid crystalline (LC) structure. An advanced isoconversional method reveals that the formation of the LC structure is accompanied by a dramatic decrease in the effective activation from ∼60 to ∼10 kJ · mol−1. A kinetic model of the phenomenon has been discussed.The dependence of the activation energy on the extent of conversion for isothermal curing of the diglycidyl ether of 4,4′‐dihydroxybiphenyl/2,6‐diaminopyridine (diamonds) and DGEBA/2,6‐diaminopyridine (circles) systems.magnified imageThe dependence of the activation energy on the extent of conversion for isothermal curing of the diglycidyl ether of 4,4′‐dihydroxybiphenyl/2,6‐diaminopyridine (diamonds) and DGEBA/2,6‐diaminopyridine (circles) systems.

The effect of stoichiometry on the fracture toughness of a liquid crystalline epoxy

AbstractThe fracture toughness of a liquid crystalline epoxy was compared with that of a standard bisphenol‐A based epoxy to understand how both the liquid crystalline structure and the crosslink density affect fracture toughness. For the liquid crystalline epoxy, the liquid crystalline domain size decreased with increasing temperature of cure and away from the stoichiometric formulation. Quantitative fractography showed that there is a competition between the liquid crystalline domain structure and the stoichiometry in determining the fracture toughness. At some cure conditions the effect of the domains is dominant. When the cure conditions are adjusted to reduce the domain size, the domains become too small to affect the fracture toughness, and thus the effect of the stoichiometry is dominant. The result is that the formation of liquid crystalline structure only increases the fracture toughness relative to that of a traditional epoxy at and near the stoichiometric formulation.

Formation of Liquid-Crystalline Structure in the Process of Film Extrusion from Cellulose Diacetate

Abstract Liquid-crystalline (LC) polymer properties depend considerably on the chemical structure of the rigid and flexible parts of the macromolecular chains. The relation of these factors determines a complex of physical and chemical properties and thus the operating characteristics. Realization of the LC state within a temperature range which is required by processing and operating conditions is achieved by the synthesis of LC's of a certain structure. The formation of LC structures in cellulose diacetate by selection of plasticizer level and type is considered in this article. Plasticizer selection is determined by the ratio of the polymer specific cohesion energies and the specific cohesion energies of a combined plasticizer consisting of a true plasticizer with the addition of small amounts of a precipitator.

Formation of liquid crystalline phase of actin filament solutions and its dependence on filament length as studied by optical birefringence

We studied the formation and structure of liquid crystalline phase of F-actin solutions by polarized light photometry, assuming that a small domain of the liquid crystalline phase works as a linear retardation plate. Transmittance of polarized light due to the birefringence of liquid crystalline phase appeared above a threshold concentration of F-actin. The threshold increased with a decrease in filament length, which was regulated by calcium-activated gelsolin. The intensity increased linearly with increasing concentrations until it reached a stationary value. The deviation of optical axis direction of the putative retardation plate was estimated 7-15 degrees. These results indicate that:(a) the liquid crystalline phase is formed above a threshold concentration of F-actin; (b) the threshold is proportional to the inverse of filament length; (c) the ordered phase coexists with the isotropic one, increasing the volume fraction with increasing concentrations until all filaments take the liquid crystalline structure; (d) the filaments in liquid crystalline phase take a highly ordered array. These results can be attributed to the excluded volume effect of rod-like molecules on the formation of liquid crystalline structure.

Permeation of hydrocarbons through liquid surfactant membranes and formation of liquid crystalline structures

The separation of benzene from its mixture with heptane can be achieved by emulsifying the feed mixture to form an oil-in-water emulsion and then dispersing this emulsion in kerosene. At high agitation intensity a gel-like structure develops which prevents phase separation and thereby interferes with the overall mass transfer process. These gel-like structures have very high viscosities, and show rheopectic behaviour; polarising microscopic examination of these gel-like structures revealed the existence of liquid crystalline structures on the surface of the emulsion globules dispersed in kerosene. A possible mode of development of such liquid crystalline structures is presented, 1-Pentanol added to kerosene prevents gel formation and assists phase separation. Its action is explained on the basis of Winsor's theory of solubilization. Typical results for selectivity and benzene yield are presented.