Hierarchically controlled helical graphite films prepared from iodine-doped helical polyacetylene films using morphology-retaining carbonization.

One-handed helical graphite films with a hierarchically controlled morphology were prepared from iodine-doped helical polyacetylene (H-PA) films using the recently developed morphology-retaining carbonization method. Results from scanning electron microscopy indicate that the hierarchical helical morphology of the H-PA film remains unchanged even after carbonization at 800 °C. The weight loss of the film due to carbonization was very small; only 10-29% of the weight of the film before doping was lost. Furthermore, the graphite film prepared by subsequent heating at 2600 °C retained the same morphology as that of the original H-PA film and that of the helical carbon film prepared at 800 °C. The screwed direction, twisted degree, and vertical or horizontal alignment of the helical graphite film were well controlled by changing the helical sense, helical pitch, and orientation state of the chiral nematic liquid crystal (N*-LC) used as an asymmetric LC reaction field. X-ray diffraction and Raman scattering measurements showed that graphitic crystallization proceeds in the carbon film during heat treatment at 2600 °C. Transmission electron microscopy measurements indicate that ultrasonication of the helical graphite film in ethanol for several hours gives rise to a single helical graphite fibril. The profound potentiality of the present graphite films is exemplified in their electrical properties. The horizontally aligned helical graphite film exhibits an enhancement in electrical conductivity and an evolution of electrical anisotropy in which conductivity parallel to the helical axis of the fibril bundle is higher than that perpendicular to the axis.

Helical carbon and graphitic films prepared from iodine-doped helical polyacetylene film using morphology-retaining carbonization.

In this communication, we report a novel preparation of the helical carbon nanofibril-fabricated thin film from the iodine-doped filmy helical polyacetylene through a carbonization process. Carbonization of the helical polyacetylene films by way of iodine doping is found to afford carbon and graphitic films completely preserving morphologies and even helical nanofibril structures.

Tubular-shaped nanocarbons prepared from polyaniline synthesized by a self-assembly process and their electrical conductivity.

A tubular-shaped polyaniline less than 5 microm in length and 170 nm in outer diameter was synthesized by a self-assembly process using D-camphorsulfonic acid as a dopant. A tubular-shaped nanocarbon was prepared from the tubular-shaped polyaniline by means of pyrolysis at 1000 degrees C in argon gas. The structural and electrical properties of the resultant tubular-shaped nanocarbons were investigated using Raman scattering spectrum, X-ray diffraction measurements, scanning and transmission electron microscopes, and a low resistivity meter. The tubular-shaped nanocarbons are very short in length and are an amorphous state. The short length and amorphous tubular-shaped nanocarbon were crystallized to some extent by heat-treatment at 2600 degrees C. The tubular-shaped nanocarbons mentioned in this work are appropriate for mass production, compared to the well-known multi-walled carbon nanotubes. The electrical conductively of the tubular-shaped polyaniline was remarkably improved by the carbonization and was enhanced by the heat-treatment.

Preparation of 2D Carbon Materials by Chemical Carbonization of Cellulosic Materials to Avoid Thermal Decomposition.

Cellulosic materials, including regenerated cellulose, are promising precursors for a variety of carbon materials. However, thermal decomposition, typically accompanying carbonization at high temperatures, hinders cellulosic materials from being efficiently carbonized (i.e., very low carbon yields). Herein, this study presents a new and efficient method for the preparation of porous 2D carbon materials from sheet-like cellulosic materials, such as papers and fabrics, involving a catalyzed chemical reaction at high temperatures without thermal decomposition. Thus, cellulosic materials are treated with sulfonic acid solutions and significantly dehydrated at high temperatures via evaporation of water. As a result, black materials are obtained at a weight near the theoretical carbon content of cellulose and remain in the carbonized materials. The as-obtained porous 2D carbon materials are flexible and suitable for a wide range of applications such as in electrodes and gas absorbents.

Entanglement-free fibrils of aligned polyacetylene films that produce single nanofibers.

An aligned polyacetylene (PA) film was synthesized in a macroscopically-aligned nematic liquid crystal (N-LC) solvent using a gravity-flow method. Long and single nanofibers of less than 100 nm in radius were successfully prepared by ultrasonication of the aligned PA film immersed in ethanol. The usual PA film was synthesized in an isotropic solvent, such as toluene, only yielding short and non-dispersed fibers after the ultrasonication due to the entangled fibril morphology. Entanglement-free fibrils of the aligned PA were well-separated into single fibrils through ultrasonication, even without a surfactant.

Highly twisted helical polyacetylene with morphology free from the bundle of fibrils synthesized in chiral nematic liquid crystal reaction field.

We synthesized novel axially chiral binaphthyl derivatives with highly twisting powers by substituting phenylcyclohexyl (PCH) mesogenic moieties into 2,2' positions or 2,2',6,6' positions of binaphthyl rings. The di- and tetrasubstituted binaphthyl derivatives, abbreviated as D-1 and D-2, respectively, were adopted as chiral dopants to induce chiral nematic liquid crystals (N*-LCs) available for synthesis of helical polyacetylene. The helical twisting power (betaM) of D-2 was 449 microm(-1), which was ca. 2.6 times larger than that of D-1 (171 microm(-1)). We prepared two kinds of induced N*-LCs with 5 microm and 270 nm in helical pitch by adding the chiral dopants D-1 and D-2 into the host N-LCs, respectively. The helical polyacetylene synthesized in the N*-LC containing D-2 exhibited highly screwed fibrils, but not a bundle of fibrils. This result is in quite contrast to the usual fibril morphology, where the screwed fibrils are gathered to form the bundle of fibrils, as observed in the helical polyacetylene synthesized in the N*-LC containing a chiral dopant with moderate helical twisting power, such as D-1. It is of keen interest that the helical pitch (270 nm) of the N*-LC including D-2 is much smaller than the diameter (ca. 1 microm) of the bundle of fibrils, which should depress the formation of the bundle of fibrils. The morphology free from the bundle of fibrils might enable us to evaluate more precisely intrinsic electromagnetic properties of a single screwed fibril of helical polyacetylene.

Synthesis of helical polyacetylene in chiral nematic liquid crystals using crown ether type binaphthyl derivatives as chiral dopants.

A series of crown ether type binaphthyl derivatives (CEBDs) were synthesized and used as chiral dopants to induce chiral nematic (N*) liquid crystals (LCs). The twisting powers of the CEBDs for phenylcyclohexane (PCH)-derived nematic LCs were evaluated. It was found that the twisting powers of the CEBDs increased with decreasing ring size of the crown ether. Helical polyacetylenes were synthesized in the N*-LCs induced by the CEBDs. The relationship between the morphology of the helical polyacetylene and the helical structure of the N*-LC was investigated. The result showed that the interdistance between the fibril bundles of the helical polyacetylene was equal to a half-helical pitch of the N*-LC and the screw direction of the polyacetylene fibrils was opposite to that of the N*-LC.