Molecular dynamics and strengthening of liquid-crystal polymers

The role of large-scale molecular motion in the self-organization and strengthening of liquid-crystal polymer fibers is discussed. It is shown that, at high temperatures, these objects are oriented liquid-crystal melts in which macromolecules remain extended but execute high-frequency conformational motions without leaving the tube approximately 20 Å in diameter. This large-scale motion is referred to as quasi-segmental motion. During annealing, the chains involved in quasi-segmental motion can accomplish longitudinal displacements (reptate) over considerable distances. It is this reptation that favors spontaneous self-organization and, consequently, strengthening of liquid-crystal polymer fibers upon heat treatment. The role played by the quasi-segmental motion of rigid macromolecules in the strengthening of polymers of different types is compared with the role played by the segmental motion of flexible chains in this process.     

Molecular mobility and strengthening of oriented liquid-crystal polymers

Broad-line proton magnetic resonance has been used to study cooperative mesophase molecular motion in the example of a fully-aromatic oriented liquid-crystal polymer Vectra A950. The molecular mobility is found to decrease as a result of heat treatment, which is considered to be the reason for a higher tensile (rupture) strength owing to an increase in the activation energy for the fracture process. Fiz. Tverd. Tela (St. Petersburg) 41, 859–861 (May 1999)     

Investigation of thermal influence on the bandgap properties of liquid-crystal photonic crystal fibers

We have analyzed the thermal influence on the bandgap properties of liquid-crystal photonic crystal fibers. The bandgap parameters which affect the transmission conditions have been investigated. It is observed that the photonic bandgap can be thermally tuned, i.e. the red or blue shift of the bandgap results from the temperature dependence of the refractive index of the liquid crystal. For the planar alignment of liquid-crystal filled cladding, the ordinary refractive index plays a major role in determining the bandgap properties; the extraordinary refractive index comes into influence while the ordinary refractive index is relatively constant of temperature. The analyses agree well with the experiments results.     

Kinetics of adhesive contact formation between thermoplastic melts and solid surfaces: Effect on bond strength

Formation of an adhesive contact between a polymer melt (or solution) and reinforcing fibers is considered from the viewpoint of kinetics. A two-stage model of this process has been proposed, and an expression for the interfacial bond strength as a function of time and temperature is derived. Experimental data on bond strength in adhesive joints between thermoplastic polymers and reinforcing fibers formed under various conditions were obtained, and the concept of activation energy was used to analyze them. Since the process is controlled by the stage having the larger activation energy, the adhesive contact formation between fibers and polymer solutions is governed by the rate of adhesive bonding, whereas that between fibers and polymer melts is governed by the rate of the melt spreading.     

Fabrication of continuous fiber-reinforced thermoplastic composites with structural gradient from sheath-core type bicomponent fibers

Sheath-core type bicomponent fibers of polypropylene (PP) as a sheath component and thermotropic liquid crystalline polymer (TLCP) as a core component were prepared by the highspeed melt spinning process. Continuous fiber reinforced thermoplastic composites, in which TLCP acts as a reinforcing fiber and PP as a matrix polymer, were fabricated by the compression molding of these fibers. In the melt spinning, the attainable highest take-up velocity of TLCP was improved by co-processing with PP. Tensile modulus and strength of the TLCP component in the PP/TLCP bicomponent fibers increased with an increase in the take-up velocity. Comparison of wide-angle X-ray diffraction patterns of starting bicomponent fibers and fabricated composites indicated that the orientation relaxation of TLCP did not occur in the compression molding process. Accordingly, the tensile modulus and strength of the PP/TLCP composites were similar to those of the bicomponent fibers. Continuous fiber reinforced thermoplastic composites with various types of fiber content distributions were fabricated from the bicomponent fibers in which sheath-core composition was changed gradually in the spinning process. In the three-point bending test, the composites with two different types of symmetric structural gradients, one with higher TLCP fiber content near the surfaces than in the center and the other with higher TLCP content in the center than near the surfaces, exhibited different flexural moduli even though the overall TLCP contents were comparable. In the three-point bending test of a composite with asymmetric structural gradient, the yielding behavior and maximum flexural load varied depending on the direction of load application although the initial flexural moduli were similar.     

Sodium Borohydride as a Protective Agent for the Alkaline Treatment of Sisal Fibers for Polymer Composites

The vegetable fibers used for polymer matrix composites are usually treated to improve their adhesion with the matrix. The chemical treatment with sodium hydroxide (NaOH), although widely used, may damage the fiber surface structure, reducing its strength. The possibility of protecting vegetable fibers against alkaline chemical aggression by using hydride ions (H^–) was investigated in this work. Sisal fibers were modified by immersion in a NaOH aqueous solution (2, 5 and 10% wt/vol), with or without the addition of sodium borohydride (NaBH₄) (1% wt/vol), under variable conditions (immersion time and temperature). The effect of using NaBH₄ was investigated using fiber tensile and pull-out tests, critical length calculation, along with a Weibull statistical analysis. This agent was found to minimize sisal degradation under highly concentrated alkaline conditions in comparison with sisal treated with the pure NaOH solution. The results suggest the 5% wt/vol treatment for 60 min under room temperature in the presence of the hydride ions as the most suitable for sisal. This result may be extended to other vegetable fibers of similar composition and may promote their use in polymer composites.     

Specific features in the generation and motion of dislocations in heat-treated silicon wafers

The specific features in the generation and motion of dislocations in silicon single-crystal wafers after different heat treatments are investigated by the four-point bending technique. It is demonstrated that annealing of silicon single-crystal wafers at a temperature of 450°C leads to their substantial hardening as compared to the postgrowth state. The oxygen-containing precipitates and precipitate dislocation pileups formed in the silicon wafer bulk during multistage heat treatment are efficient heterogeneous nucleation sites of dislocations under the action of thermal or mechanical stresses. It is found that the multistage heat treatment of the silicon wafers under conditions providing the formation of an internal getter within their bulk results in considerable disordering of the wafer structure. The inference is made that the formation of the defect state in the crystal lattice of silicon and the strength characteristics of silicon wafers substantially depend on the temperature-time schedules of the low-temperature stage of multistage heat treatment.     

Deformation and instability of nematic drops in an external electric field

The behavior of nematic liquid-crystal drops freely suspended in an isotropic liquid polymer exposed to an external electric field was studied. A giant deformation was observed for the drop. As the field intensity increased, its equilibrium shape took the form of a prolate ellipsoid. The dependences of the shape and critical fields on the concentration of ions in the polymer liquid were established. A plausible theoretical explanation is suggested for the observed effect. The experimental dependence of drop size on the electric-field strength is analyzed, and the conditions for the loss of drop stability are determined.     

用小角X射线散射法研究CH2Cl2,CHCl3和CCl4对磷脂酰胆碱液晶态结构的影响机理

本文采用小角X射线散射法分别研究CH₂Cl₂,CHCl₃和CCl₄对磷脂酰胆碱液晶态结构的影响机理,通过比较得知,CH₂Cl₂,CHCl₃和CCl₄对磷脂酰胆碱液晶态结构影响的不同之处,主要是它们空间旋转电子云密度分布不同所致,空间旋转电子云密度分布呈球状或椭球状的物质都有使磷脂酰胆碱液晶形成片层六角形的机理,呈圆锥状的物质有诱发磷 关键词：     

小直径单芯液晶聚合物挤塑光缆抗张强度的影响因素分析

从理论上分析了0.5 mm以下小直径单芯液晶聚合物（LCP）光缆在成型过程中,影响光缆抗张强度的主要因素,这些因素主要包括熔融液晶聚合物的温度特性、模芯和模套的结构参数、模芯与模套之间的距离以及光纤的放线张力及其牵引速度等,介绍了各影响因素与光缆抗张强度之间的相互关系,深入分析了光缆加强层厚度与其抗张强度系数之间的相互关系。实验结果证明:小直径液晶聚合物抗张强度与其加强厚度并不存在理想的线性关系,且在一定直径范围内,小直径液晶聚合物光缆具有相同数值的最大抗张强度。     

Macromolecular composites of extruded thermotropic polymer sheets

Using two types of thermotropic liquid-crystal polymers, experimental results reconfirmed previous reports that the relaxation time of extruded liquid-crystal polymers is much longer than that of conventional polymers. The initial modulus and elongation of sheets extruded with liquidcrystal polymers were found to be strongly dependent on the gauge length. In addition, it was observed, for the first time, that the mechanical properties of the extruded thermotropic copolyesters follow the general equations for fiber-reinforced composites such that the angular dependence of the tensile strength of the extruded liquid-crystal polymeric sheets obeys the Tsai-Hill theory, while the angular dependence of the initial modulus follows the Lees equation. These results suggest that the highly oriented liquid-crystal domains may be considered as reinforcing fibers in the extruded articles, and their mechanical properties can be predicted using existing composite theories.     

Development of Stereocomplex Crystal of Polylactide in High-Speed Melt Spinning and Subsequent Drawing and Annealing Processes

High-speed melt spinning of racemate polylactide (r-PLA), which is a blend of equal amounts of poly(l-lactide) and poly(d-lactide) molecules, was performed up to the take-up velocity of 7.5 km/min. In the fiber structure analysis, particular attention was paid to the formation of stereocomplex crystals, because this crystal form has a melting temperature about 60° higher than the homocrystals. It was found that highly oriented and highly crystallized fibers containing the α-form and stereocomplex crystals were obtained when the take-up velocity exceeded about 4 km/min. The amount of stereocomplex crystal was higher under the spinning conditions of higher take-up velocity, lower throughput rate, and lower extrusion temperature. Under these conditions, higher tensile stress can be applied to the spinning line, and therefore, the orientation-induced crystallization is promoted. Annealing of the fibers obtained at high-take-up velocities, such as 6 km/min, which already have the crystalline structure with a certain amount of stereocomplex crystal, at a temperature between the melting temperatures of α-form and stereocomplex crystals, yielded the fiber structure mainly consisting of highly oriented stereocomplex crystal. The annealed fibers showed fairly high mechanical properties and good thermal stability.     

Improvement of the Mechanical Properties of Poly(Glycolic Acid) Fibers Through Control of Molecular Entanglements in the Melt Spinning Process

Abstract

To improve the mechanical properties of poly(glycolic acid) (PGA) fibers prepared by the direct spin-drawing process, the concept of “melt structure control” was introduced. A heating chamber was installed in the vicinity of the spinning head and a low take-up velocity in the melt spinning process was adopted to reduce the Deborah number in the spin-line. As a result, improvement of the toughness of as-spun fibers prepared by the melt-spinning process was accomplished, and the drawn fibers of high-strength and high-toughness were obtained by applying an additional in-line drawing process. Entanglement density reduction in the melt spinning process was found to be suppressed by installing a heating chamber as well as by lowering the take-up velocity. Through the matching of the true stress versus true strain curves of in-line drawn fibers by shifting the curves along the true-strain axis, the network draw ratio of the drawn fibers was estimated and the master curves for individual spinning conditions were prepared. The master curves were found to show steeper increases from lower true-strains for the lower Deborah number conditions, whereas the increases in birefringence and strength of the drawn fibers proceeded from the lower network draw ratios.     

Preparation and electrical properties of cobalt-containing carbon fibers

Carbon fibers with inclusions of cobalt nanoclusters are prepared by heat treatment of carboxylated cellulose containing cobalt cations. The influence of the heat treatment conditions on the structuring of the carbon matrix and cobalt clusters, the magnetization hysteresis loop, the temperature dependence of the conductivity, and the magnetoresistance is investigated. It is established that the cobalt-containing carbon fibers heat treated at T _M =700 and 900°C possess superparamagnetic and ferromagnetic properties, respectively. It is shown that fibers heat treated under different conditions are characterized by different conduction mechanisms and can exhibit anisotropic and giant magnetoresistances and also the effects associated with the influence of magnetic field on the processes of weak localization and spin-orbit scattering.     

Retrieval of order parameters of a monolayer of liquid-crystal droplets with weak anchoring

An optical method is proposed for extracting the order parameters of single-layer polymer-dispersed liquid-crystal film (monolayer) containing bipolar liquid-crystal droplets under weak anchoring conditions. The method is based on an analysis of the coherent transmittance of a monolayer irradiated with a normally incident linearly polarized plane wave. The method is used to retrieve the order parameter of a spherical liquid-crystal droplet and the order parameter of a monolayer consisting of such droplets as functions of the applied electric field. The effect of inaccuracy of the input values of monolayer parameters on the error of retrieval of the order parameters is examined. The method can be used to determine the refractive index of the polymer binder, as well as other parameters of the film. It provides a tool for solving the inverse scattering problem with field-dependent or field-independent droplet order parameter.     

An Overview of Mechanical Strength of Optical Fiber Fusion Splices: Examples of Fractographic Analysis of Break Causes

The theory and phenomena of mechanical strength of fusion splices are reviewed. An emphasis is placed on fractographic analysis of break causes. A variety of useful examples of splice breaks resulting from surface mechanical damage, various types of contamination, re-deposition of silica particles/thermal shock, and devitrification are shown. Special strength reduction issues related to emerging new splice types and splicing techniques, such as arc fusion splicing of heat sensitive fibers, prolonged pre- and post-heat treatment (for reducing splice losses of dissimilar fiber splices), and fire polishing, are discussed.     

Rotational reorientation of the director in twisted nematic liquid-crystal cells

The orientational relaxation of the director to its equilibrium orientation under electric, elastic, and viscous torques arising in twisted nematic liquid-crystal cells is investigated. It is shown that the relaxation time of the director depends strongly on the external electric field strength and weakly on the energy of anchoring of liquid-crystal molecules to the surfaces of the cell. The relaxation time of the director anomalously increases in electric fields close to the Fréedericksz threshold. It is established that, at specific strengths of the external electric field, the relaxation can occur in the form of traveling waves propagating from one edge to the other edge of the twisted nematic liquid-crystal cell. The calculations of the relaxation processes in the vicinity of the nematic-smectic A phase transition temperature demonstrate that the distortion of the director field is uniform over the entire cross section of the liquid-crystal cell and does not depend on the strength of anchoring of the liquid-crystal molecules to the surfaces of the cell.     

Ribbon-to-fiber transformation in the process of spinning of carbon-nanotube dispersion

We describe a phenomenon of ribbon-to-fiber transformation observed in the process of spinning of single wall carbon nanotubes dispersed in polymer solutions. In the process of spinning, a gel-like ribbon comprised of nanotube bundles bound by polymer is withdrawn from a solvent bath. We show that upon crossing the liquid-air interface, the ribbon may either retain its flat shape or fold into a compact hairlike fiber. The ribbon-to-fiber transformation is caused by the capillary action of the liquid meniscus embracing the ribbon. Only sufficiently stiff ribbons can withhold the capillary compression. The critical conditions of folding, as well as the number of folds in the contractive ribbon, depend on the ribbon width, its flexural rigidity, and the solvent surface tension. We show that the ribbon rigidity can be efficiently modulated by varying the solvent composition, allowing us to control the pore structure of carbon-nanotube fibers.     

Preparation of High-Quality Polyacrylonitrile Precursors for Carbon Fibers Through a High Drawing Ratio in the Coagulation Bath During a Dry-Jet Wet Spinning Process

Excellent poly(acrylonitrile-co-itaconic acid) (99/1) (PAI) nascent fibers, which have an important role in preparing high-quality precursors for carbon fibers, were prepared by a dry-jet wet spinning process. Their structures were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and an ultrasound solvent etching method, as well their properties being determined by a strength and extension meter and a fineness meter, both designed specifically for fibers. When a high drawing ratio, over 300%, was applied to the fibers in the dry-jet wet spinning coagulation bath, the molecular chains were easy to orient and regularly arrange, resulting in the relative crystallinity, crystal size and amorphous orientation degree of the nascent fibers being improved. The fibrils with large diameter were formed, increasing the bulk density with the overall porosity and pore numbers decreasing. Therefore, the nascent fibers had smaller diameters, higher strength, higher rupture elongation and smaller coefficients of variation. The optimum high performance PAI precursor fibers, with 0.59dtex in titer, 7.51cN/dtex in tensile strength, 7.9% in rupture elongation and the final carbon fiber with 5.54GPa in tensile strength, were obtained through a post-spinning treatment in which they were subjected to a high coagulation bath draw ratio and carbonization.     

Thermal and electrical conductivity of poly(l-lactide)/multiwalled carbon nanotube nanocomposites

Multiwalled carbon nanotubes (MWCNTs) are considered to be the ideal reinforcing agent for high-strength polymer composites, because of their fantastic mechanical strength, high electrical and thermal conductivity and high aspect ratio. Polymer/MWCNTs composites are easily molded, and the resulting shaped plastic articles have a perfect surface appearance compared with polymer composites made using usual carbon or glass fibers. Good interfacial adhesion between the MWCNTs and the polymer matrix is essential for efficient load transfer in the composite. The ultrahigh strength polymer composites demand the uniform dispersion of the MWCNTs in the polymer matrix without their aggregation and the good miscibility between MWCNT and polymer matrix. This approach can also be applied to biodegradable synthetic aliphatic polyesters such as poly(l-lactide) (PLLA), which has received a great deal of attention due to environmental concerns. In this study, PLLA was melt-compounded with MWCNTs. A high degree of dispersion of the MWCNTs in the composites was obtained by grafting PLLA onto the MWCNTs (PLLA-g-MWCNTs). After oxidizing the MWCNTs by treating them with strong acids, they were reacted with l-lactide to produce the PLLA-g-MWCNTs. The mechanical properties of the PLLA/PLLA-g-MWCNT composite were higher than those of the PLLA/MWCNT composite. The electrical conductivity of the composites was determined by measuring the volume resistivity, which is a value of the resistance expressed in a unit volume by two-probe method. The thermal diffusivity and heat capacity of composites was measured by laser flash method, and the effects of modification of the MWCNT in PLLA matrix are discussed.