Wild Silkworm Cocoon Waste Conversion into Tough Regenerated Silk Fibers by Solution Spinning.

Wild silkworm silk fibers have garnered attention owing to their softness, natural color, lightweight, and excellent mechanical properties. Because most wild silkworm cocoons obtained are pierced or dirty after the eclosion process, it is difficult to reel the long filament from the pierced cocoons to use as textile materials. Therefore, damaged wild silkworm cocoons are typically removed during the industrial process. Artificial silk spinning has been developed to transform domesticated silkworm silk solutions into regenerated silk fibers. However, regenerated fibers derived from wild silkworm silk have not been reported. Here, we produced regenerated silk fibers using a dry-wet spinning method using a dope solution derived from wild silkworm silk cocoon wastes. These regenerated silk fibers have thick and uniform diameters, unlike native silk fibers, contributing to their usefulness for sterilization and handling in medical applications. Moreover, they exhibited the same level of mechanical strength as their native counterparts. The molecular orientation and crystallinity of the regenerated silk fibers were adjustable by the drawing process, enabling the realization of their various tensile properties. This study promotes the utilization of unused protein resources to produce mechanically stable and tough silk-based fibers.

Assessment of the anti-biofouling potentials of a copper iodide-doped nylon mesh.

We propose a copper iodide (CuI)-doped nylon mesh prepared using polyiodide ions as a precursor toward anti-biofouling polymer textile. The CuI-doped nylon mesh was subjected to the prevention of biofouling in marine environments. The attachment of the marine organisms was markedly inhibited on the CuI-doped nylon mesh surface until 249 days. Scanning electron microscopy-energy dispersive X-ray analysis indicated that copper compounds were maintained in the nylon mesh after the field experiment, although copper content in the nylon mesh was reduced. Therefore, the copper ions slowly dissolved from nylon mesh will contribute to the long-term prevention of biofouling. Furthermore, electron spin resonance analysis revealed the generation of reactive oxygen species (ROS) from CuI-doped nylon mesh after the field experiment. One of the possibilities for toxic action of copper ions will be the direct effect of Cu+ -induced ROS on biofilm forming on nylon mesh surface. The proposed polymer textile can be applied to fishing and aquafarming nets, mooring rope for ship, or silt fence to restrict polluted water in marine environments.

Toward "strong" green nanocomposites: polyvinyl alcohol reinforced with extremely oriented cellulose whiskers.

To exploit the maximum potential of cellulose whiskers (CWs), we report here for the first time the successful fabrication of nanocomposites reinforced with highly oriented CWs in a polymer matrix. The nanocomposites were prepared using polyvinyl alcohol (PVA) and a colloidal suspension of cotton-derived CWs. The macroscopically homogeneous PVA-CW suspensions were extruded into cold methanol to form gel fibers followed by a hot drawing. Compared to the neat PVA fiber, the as-spun fiber containing a small amount of CWs (5 wt % of solid PVA) showed higher drawability, leading to an extremely high orientation of CWs with the matrix PVA. The stress-transfer mechanism, a prime determining factor for high mechanical properties of nanocomposites, was studied by X-ray diffraction. The stress on the incorporated CWs was monitored by applying an in situ nondestructive load to the composite fibers. The applied stress to the whole sample was found to be effectively transferred to the CWs inside the composites, suggesting strong interfacial bonding between the filler and the matrix. Effective stress transfer to the oriented whiskers resulted in outstanding enhancement in mechanical properties of the nanocomposites.

Electrical conductivity of microwave heated polyaniline nanotubes and possible mechanism of microwave absorption by materials.

In the course of experiments to perform deprotonation and carbonization of doped polyaniline (PANI) nanotubes (NTs) by irradiating directly 2.45 GHz microwave (MW) in our microwave heating system (MWHS), we have discovered that the PANI-NTs self heat by absorbing the MW but the temperature of the PANI-NTs stops rising around 300 degrees C in spite of the heightened MW power Furthermore, we have found that the MW irradiated PANI-NTs have transferred from electrical conductor to insulator depending on the temperature of the PANI-NTs. By measuring electron spin resonance (ESR) spectra of the MW heated PANI-NTs, the existence of the unpaired electrons is shown to have a strong correlation between the degree of MW absorption and the transition in the electrical conductivities. In order to deprotonate and carbonize further the PANI-NTs, we have performed heat treatment for the PANI-NTs up to a temperature (T(HT)) of about 1200 degrees C in the same MWHS using carbon fiber which self heats by absorbing MW. The chemical transformations in the PANI-NTs induced by the heat treatments are discussed by measuring the X-ray photoelectron spectroscopy (XPS) spectra. Finally, the temperature dependence of electrical conductivities of the PANI-NTs are measured in order to investigate the mechanism of electrical conduction of the heat treated PANI-NTs.

Non-woven fabrics of fine regenerated cellulose fibers prepared from ionic-liquid solution via wet type solution blow spinning.

A wet type solution blow spinning system with a water-mist coagulation chamber was developed to spin fine regenerated cellulose fibers from the non-volatile ionic liquid solvent 1-ethyl-3-methylimidazolium diethyl phosphate. The molecular weight distribution of cellulose, and the rheological properties and spinnability of its spinning solution were evaluated. Scanning electron microscope observations indicated that the fine water mist/vapor was important for efficient coagulation of the stretched solution jets. Under optimized spinning parameters, a non-woven fabric was obtained consisting of fine fibers with an average diameter of 0.98 ± 0.62 µm. The tensile strength of the samples was greatly influenced by the fabric structure formed upon regeneration of cellulose from solution. X-ray diffraction and polarized optical microscopy measurements revealed that the prepared cellulosic non-woven fabric was highly crystalline and had a well-defined molecular orientation, respectively, which might have contributed to the increased tensile strength.

Structural characteristics and properties of Bombyx mori silk fiber obtained by different artificial forcibly silking speeds.

To study the spinning condition of natural biopolymer silk, the silk fibers were directly acquired from Bombyx mori silkworm, N140 x C140 by a simple artificial forcibly silking method at the speed of 60, 120, 180 and 240 cm min(-1), respectively and its microstructure and physical properties were evaluated. The fine silk fibers (about 8 microm) were obtained at faster spinning speed, 240 cm min(-1). The tensile properties of silk fibers were remarkably increased with raising the forcibly spinning speeds. The beta-sheet structure contents of silk fibers obtained at higher speed were considerably increased. The fibers obtained by different spinning speeds exhibited a fairly similar X-ray crystallinity, while the degree of molecular orientation increased with decreasing the fiber diameter. The fine silk fibers obtained at higher speed (240 cm min(-1)) exhibited a slightly higher thermal stability, as shown by the upward shift of differential scanning calorimetry (DSC) decomposition temperature.

Outstanding reinforcing effect of highly oriented chitin whiskers in PVA nanocomposites.

To utilize the extreme reinforcing performance of chitin whiskers (ChWs), the current work was undertaken to fabricate nanocomposites embedded with highly uniaxial oriented ChWs into the matrix polymer. Fibers of poly(vinyl alcohol) (PVA)/ChWs were prepared by gel spinning and the fibers were subjected to a hot drawing to their maximal draw ratio. WAXD analysis revealed the very high orientation of ChWs in the PVA matrix. DSC measurements showed that, upon ChWs loadings, crystallinity of PVA increased and non-isothermal cooling crystallization peak of PVA shifted towards lower temperature, indicating the interaction of PVA with ChWs. Measurement of infrared dichroism suggested that the orientation of overall PVA chains increased with the increase in ChWs loading due to the possible dragging of PVA chains attached with ChWs during drawing, which resulted higher PVA crystallinity in the composites. The stress transfer in PVA/ChWs interface quantified by X-ray diffraction evidenced the strong adherence between the two. The stress transfer between PVA and ChWs interface, and higher PVA crystallinity induced by ChWs were reflected to the outstanding enhancement in mechanical- and anti-creep properties of nanocomposite fibers.

Mechanistic studies on the formation of silver nanowires by a hydrothermal method.

Silver (Ag) nanowires were fabricated from silver chloride (AgCl) by the hydrothermal method. The successful formation of Ag nanowires relied on the low solubility of AgCl as a precursor and the structural change of glucose to polymer on the Ag nanowire (protective layer). The Ag(+) ion concentration in the reaction solution containing AgCl was initially low, but after a reaction time of over 12 h, Ag(+) gradually reduced to Ag metal. Transmission electron microscope, Raman spectrometery, and X-ray photoelectron spectroscopy revealed that the surface of the obtained Ag nanowires possessed a carbon-rich layer with a carboxyl group, and the Ag(+) ion coordinated with the carboxyl group of this layer. The difference in the surface-free energy of Ag crystals changed the crystal growth rate that impelled the anisotropic growth of the Ag particles. By examining various reaction conditions, it was determined that the ratio of Cl(-) to Ag(+), reaction temperature, and reaction time are important factors for successful preparation of Ag nanowires. Under the reaction condition that the molar ratio of Cl(-) to Ag(+) at 160 °C for 24 h is above equimolar concentration, uniform Ag nanowires were successfully prepared.

Physical properties and dyeability of silk fibers degummed with citric acid.

Silk fibers from Bombyx mori silkworm was degummed with different concentration of citric acid, and the physical properties and fine structure were investigated to elucidate the effects of citric acid treatment. The silk sericin removal percentage was almost 100% after degumming with 30% citric acid which resulted in a total weight loss of 25.4% in the silk fibers. The surface morphology of silk fiber degummed with citric acid was very smooth and fine, showed perfect degumming like traditional soap-alkali method. The tensile strength of silk fiber was increased after degumming with citric acid (507MPa), where as the traditional soap-alkali method causes to decrease the strength about half of the control silk fiber (250MPa). The molecular conformation estimated by Fourier transform infrared spectroscopy and the crystalline structure evaluated from X-ray diffraction curve stayed unchanged regardless of the degumming with citric acid and soap. The dye uptake percentage of silk fiber degummed with citric acid decreased slightly, about 4.2%. On the other hand, the dye uptake percentage of silk degummed with soap was higher which indicates the disordering of the molecular orientation of the laterally ordered structure, accompanied with the partial hydrolysis of silk fibroin molecules by the alkali action of soap. The thermal properties were greatly enhanced by soap and citric acid degumming agents. Dynamic mechanical thermal analysis showed silk degummed with citric acid is more stable in higher temperature than that of soap. With heating at above 300 degrees C, the silk degummed with citric acid shows an increase in storage modulus and an onset of tan delta peaks at 325 degrees C and the melt flow of the sample was inhibited. The degumming of silk fibers with citric acid is safe and the results obtained are quite promising as a basis for possible future industrial application.

[Peripheral venous stenoses of hemodialysis shunts: improved long-term patency rates with stent placement].

PURPOSE: The purpose of this study was to evaluate the effectiveness of endovascular stents placed in the peripheral veins of hemodialysis shunts. MATERIALS AND METHODS: 156 endovascular stents were placed in the peripheral veins of 155 hemodialysis shunts with 220 stenoses. Among these, 106 stenoses of 93 hemodialysis shunts had been treated by percutaneous transluminal angioplasty (PTA) before stent placement. RESULTS: The initial success rate was 97.7%. Primary radiologic patency rates of the stents at 6 months, 1 year, and 2 years were 69.8%, 49.1%, and 45.8%, respectively. Secondary radiologic patency rates at 1 year, 2 years, and 3 years were 94.0%, 91.8%, and 88.0%, respectively. Primary clinical patency rates at 6 months, 1 year, and 2 years were 64.4%, 43.4%, and 27.3%; while secondary clinical patency rates at 1 year, 2 years, and 3 years were 93.5%, 86.5%, and 73.4%, respectively. Radiologic and clinical primary patency rates of 106 stenoses and 93 hemodialysis shunts were significantly higher than those of PTA that had been performed before stents were placed. CONCLUSION: Stent placement for stenoses of the peripheral veins of hemodialysis shunts recurring in three months and treated by PTA alone can improve long-term patency.