Laser-Assisted Melt Electrospinning of Poly(L-lactide-co-ε-caprolactone): Analyses on Processing Behavior and Characteristics of Prepared Fibers.

The laser-assisted melt electrospinning (LES) method was utilized for the preparation of poly(L-lactide-co-ε-caprolactone) (PLCL) fibers. During the process, a carbon dioxide laser was irradiated, and voltage was applied to the raw fiber of PLCL. In situ observation of fiber formation behavior revealed that only a single jet was formed from the swelling region under the conditions of low laser power and applied voltage and feeding rate, whereas multiple jets and shots were produced with increases in these parameters. The formation of multiple jets resulted in the preparation of thinner fibers, and under the optimum condition, an average fiber diameter of 0.77 µm and its coefficient of variation of 17% was achieved without the formation of shots. The estimation of tension and stress profiles in the spin-line was also carried out based on the result of in situ observation and the consideration that the forces originated from surface tension, electricity, air friction, and inertia. The higher peak values of tension and stress appearing near the apex of the swelling region corresponded to the formation of thinner fibers for the condition of single-jet ejection. Analyses of the molecular orientation and crystallization of as-spun fibers revealed the formation of a wide variation of higher order structure depending on the spinning conditions.

Planar or Biaxial Stretching of Poly(ethylene terephthalate) Fiber Webs Prepared by Laser-Electrospinning.

In this work, laser-heated electrospinning (LES) process using carbon dioxide laser was explored as an eco-friendly method for producing ultrafine fibers. To enhance the thinning of fibers and the formation of fiber structure, planar or equibiaxial stretching and subsequent annealing processes were applied to poly(ethylene terephthalate) (PET) fiber webs prepared by LES. The structure and properties of the obtained webs were investigated. Ultrafine fiber webs with an average diameter of approximately 1 µm and a coefficient of variation of 20-25% were obtained when the stretch ratios in the MD (machine direction) × TD (transverse direction) were 3 × 1 and 3 × 3 for the planar and equibiaxial stretching, respectively. In the wide-angle X-ray diffraction analysis of the web samples, preferential orientation of crystalline c-axis were confirmed along the MD for planar stretching and only along the web plane for equibiaxial stretching, which was in contrast to the stretching of film samples, where additional preferential orientation of benzene ring along the film plane proceeded. The results obtained suggest that PET fiber webs fabricated through LES and subsequent planar or biaxial stretching processes have potential for a wide variety of applications, such as packaging and battery separator materials.

Bamboo Charcoal/Poly(L-lactide) Fiber Webs Prepared Using Laser-Heated Melt Electrospinning.

Although several studies have reported that the addition of bamboo charcoal (BC) to polylactide (PLA) enhances the properties of PLA, to date, no study has been reported on the fabrication of ultrafine BC/poly(L-lactide) (PLLA) webs via electrospinning. Therefore, ultrafine fiber webs of PLLA and BC/PLLA were prepared using PLLA and BC/PLLA raw fibers via a novel laser electrospinning method. Ultrafine PLLA and BC/PLLA fibers with average diameters of approximately 1 µm and coefficients of variation of 13-23 and 20-46% were obtained. Via wide-angle X-ray diffraction (WAXD) analysis, highly oriented crystals were detected in the raw fibers; however, WAXD patterns of both PLLA and BC/PLLA webs implied an amorphous structure of PLLA. Polarizing microscopy images revealed that the webs comprised ultrafine fibers with uniform diameters and wide variations in birefringence. Temperature-modulated differential scanning calorimetry measurements indicated that the degree of order of the crystals in the fibers was lower and the molecules in the fibers had higher mobilities than those in the raw fibers. Transmittance of BC/PLLA webs with an area density of 2.6 mg/cm2 suggested that the addition of BC improved UV-shielding efficiencies.

Structure and Properties of Poly(ethylene terephthalate) Fiber Webs Prepared via Laser-Electrospinning and Subsequent Annealing Processes.

Melt-electrospinning is an eco-friendly method for producing ultra-fine fibers without using any solvent. We prepared webs of poly(ethylene terephthalate) (PET) through melt-electrospinning using CO2 laser irradiation for heating. The PET webs comprised ultra-fine fibers of uniform diameter (average fiber diameter = 1.66 µm, coefficient of variation = 19%). The co-existence of fibers with high and low molecular orientation was confirmed through birefringence measurements. Although the level of high orientation corresponded to that of commercial highly oriented yarn, crystalline diffraction was not observed in the wide-angle X-ray diffraction (WAXD) analysis of the webs. The crystallinity of the webs was estimated using differential scanning calorimetry (DSC). The fibers with higher birefringence did not exhibit any cold crystallization peak. After annealing the web at 116 °C for 5 min, a further increase in the birefringence of the fibers with higher orientation was observed. The WAXD results revealed that the annealed webs showed crystalline diffraction peaks with the orientation of the c-axis along the fiber axis. In summary, the formation of fibers with a unique non-crystalline structure with extremely high orientation was confirmed.

Smectic C to cubic phase transition of 4'-n-docosyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-22) and alternating-current electric field effect.

Smectic C (SmC) to cubic (Cub) phase transition behavior of 4'-n-docosyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-22) and alternating-current (AC) electric field effect on the SmC phase were examined. The most important and unexpected finding is that even at a temperature 8 K below the zero-field SmC to Cub phase transition temperature (T(SmC-Cub) approximately 408 K) determined previously for the compound and without field, the Cub phase growth occurs, after a very long induction period of several hours. The X-ray diffraction measurements revealed the formation of an Im3m-type Cub phase at the temperature. It is suggested that the "true" transition temperature, which is difficult to determine precisely, exists around 396 K. The time-dependence of the Cub phase growth both without field and under field was analyzed using the well-known Avrami equation, implying the nucleation and growth mechanism mainly operating in the SmC to Cub phase transformation. The fact uncovered is that between 408 and 396 K, the SmC to Cub transformation is virtually prohibited by the strongly limited nucleation. It is concluded that the effect of the electric field on the transition is to promote the nucleation of the Cub phase in the temperature region where the Cub phase is potentially more stable than the precursory SmC phase.

Electric field-induced cubic phase in 4'-n-docosyloxy-3'-nitrobiphenyl-4-carboxylic acid.

We examine the influence of an alternating-current electric field on the lamellar smectic C (SmC) phase of 4'-n-docosyloxy-3'-nitrobiphenyl-4-carboxylic acid, and the formation of a field-induced cubic (Cub) phase with optical isotropy was observed for the first time. The induction was realized down to a temperature 10 K below the zero-field SmC to Cub phase transition temperature (TSmC-Cub). The formation of the induced Cub phase gave rise to a gradual increase of the shear storage modulus, and the modulus recovered quickly in response to the removal of the field, which is of interest as future applications to the stress transferring device.