Effect of the Fiber Diameter of Polyamide 11 Nanofibers on Their Internal Molecular Orientation and Properties.

Herein, the effect of the diameter of polyamide 11 nanofibers (PA11 NFs) on their internal structures as well as thermal and mechanical properties is investigated. Aligned PA11 NFs with diameters ranging from 109 to 462 nm are prepared by the single-component solvent electrospinning of different PA11/1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) solutions (4-8 wt%) and subsequently characterized. Owing to the similar hydrogen bond formation within the NFs during electrospinning, all prepared NFs have δ'-phase crystals with similar crystallinities and crystallite sizes. However, the orientation of the δ'-phase crystals is disrupted in NFs with diameters less than 200 nm, due to the rapid solidification during electrospinning. The δ'-phase crystals are the most highly oriented within NFs having a fiber diameter of ≈300 nm, and the corresponding NF sheets exhibit the highest mechanical strength. A single PA11 NF with a fiber diameter of ≈300 nm also exhibits a good piezoelectric response (piezoelectric coefficient d33 = 2.1 pm V-1 ).

Verification of the Influence of Processing History through Comparing High-Speed Melt Spinning Behavior of Virgin and Recycled Polypropylene.

A 'model' material of recycled polypropylene (PP) was prepared through the injection molding process, and the effect of processing history on the polymer characteristics was investigated through the high-speed melt spinning of virgin and recycled PP. On-line measurement of the thinning behavior of the spin-line revealed the downstream shift of solidification point for the recycled PP at the take-up velocity of 1.0 km/min, indicating the suppression of flow-induced crystallization. The difference was not clear at higher take-up velocities of up to 5 km/min. For any identical take-up velocity, no clear difference in the stress-strain curves and birefringence of the fibers from virgin and recycled PP could be observed, whereas the detailed investigation on the variation of relative amount of c-axis and a*-axis oriented crystals in the fibers prepared at varied take-up velocities suggested the deterioration of flow-induced crystallization at 1.0 km/min. It was speculated that the processing history induced the lowering of the entanglement density, which affected the melt spinning and crystallization behavior. An undistinguishable difference between the virgin and recycled PP at increased take-up velocities suggested the existence of an optimum elongational strain rate for the detection of the different states of molecular entanglement.

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.

Preparation of Perfluorosulfonated Ionomer Nanofibers by Solution Blow Spinning.

In this work, we report the preparation of high-purity perfluorosulfonated ionomer (Nafion) nanofibers (NFs) via solution blow spinning (SBS). Fiber formation in solution jet spinning is strongly dependent on the structure of the spinning solution. Upon adding a small amount of poly(ethyleneoxide) (PEO) as a spinning aid to Nafion dispersion, most of the highly ordered Nafion aggregate disappeared, allowing the stable production of bead-free and smooth high-purity NFs (Nafion/PEO = 99/1) by SBS. The microstructure of the blowspun Nafion NFs differed from that of electrospun NFs. In the blowspun NFs, incomplete microphase separation between hydrophilic (ionic) and hydrophobic domains was observed, but the crystallization of CF2-CF2 chains was enhanced owing to the high extensional strain rate and rapid solidification during SBS. These findings provide fundamental information for the preparation and characterization of blowspun Nafion NFs.

Melt-Spun Fibers from Bio-Based Polyester-Fiber Structure Development in High-Speed Melt Spinning of Poly(ethylene 2,5-furandicarboxylate) (PEF).

Poly(ethylene 2,5-furandicarboxylate) (PEF) is regarded as a bio-based alternative or complementary polyester for the widely used fossil resource-based polyester, poly(ethylene terephthalate) (PET). High-speed melt spinning of PEF of low and high molecular weight (L-PEF, H-PEF) was conducted, and the structure and properties of the resultant as-spun fibers were investigated. The occurrence of orientation-induced crystallization was confirmed for the H-PEF at the take-up velocity of 6.0 km/min, the highest speed for producing PET fibers in the industry. Molecular orientation and crystallinity of the as-spun fibers increased with the increase of take-up velocity, where the H-PEF fibers always showed a higher degree of structural development than the L-PEF fibers. The tensile modulus of the high-speed spun H-PEF fibers was relatively low at 5 GPa, whereas a sufficiently high tensile strength of approximately 500 MPa was measured. These values are adequately high for the application in the general semi-engineering fiber field.

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.