Fabrication of Aligned Poly(L‐lactide) Fibers by Electrospinning and Drawing

A new target collector was designed for taking up aligned nanofibers by electrospinning. The collector consists of a rotor around which several fins were attached for winding electrospun filaments continuously in large amounts. The alignment of the nanofibers wound on the collector was affected by the electrospinning conditions, such as the needle‐to‐collector distance and the applied voltage, but not by the rotation speed of the collector. At a voltage of 0.5 kV · cm^?1, about 60% of the fibers were found to be aligned within an angle of ± 5° relative to the rotational direction of the collector. The fiber alignment was improved to 90% by drawing the fiber bundle 2–3 times at 110 °C. The drawing was also effective for crystal orientation of the fibers as revealed by WAXD. The drawn fibers show improved mechanical properties.

     

Crystalline and Conductive Poly(3‐hexylthiophene) Fibers

Intrinsically conducting polymer fibers are prepared from P3HT by melt spinning. High crystallinity is achieved by drawing the fibers after the spinning process, applying a draw ratio of 1:2. DSC and XRD measurements confirm the continuous increase of crystalline phases with drawing. For comparison, poly(ethylene terephthalate) fibers are coated with P3HT and drawn as well. Again, the drawing of the coated fiber results in a significant increase in crystallinity of the P3HT coating. The high amount of crystalline phases is associated with a dramatic increase in conductivity (350 S · cm^?1) after doping with FeCl₃ in nitromethane.

     

Methionine‐Containing Poly(amino acid) Hybrid Fibers via Self‐Assembly at Aqueous Interface

Summary: Using sulfonium groups to create a novel fiber material, methionine‐containing hybrid fibers were prepared from S‐methylated poly(L ‐methionine) and poly(L ‐lysine, L ‐methionine) solutions with gellan solution by polyion complex (PIC) formation via self‐assembly at the aqueous interface. The breaking strain of the PIC fibers were increased by incorporation of methionine residues into the poly(L ‐lysine). These findings may provide a new approach for preparing a wool‐like fiber in aqueous media using the synthetic water‐soluble methionine‐containing poly(amino acid)s.

SEM image of Met‐containing PIC fiber: (a) poly[Met¹⁹Met(SMe)⁸¹]‐gellan fiber (magnification, ×500).     

Unmodified and Modified Surface Sisal Fibers as Reinforcement of Phenolic and Lignophenolic Matrices Composites: Thermal Analyses of Fibers and Composites

Summary: The study and development of polymeric composite materials, especially using lignocellulosic fibers, have received increasing attention. This is interesting from the environmental and economical viewpoints as lignocellulosic fibers are obtained from renewable resources. This work aims to contribute to reduce the dependency on materials from nonrenewable sources, by utilizing natural fibers (sisal) as reinforcing agents and lignin (a polyphenolic macromolecule obtained from lignocellulosic materials) to partially substitute phenol in a phenol‐formaldehyde resin. Besides, it was intended to evaluate how modifications applied on sisal fibers influence their properties and those of the composites reinforced with them, mainly thermal properties. Sisal fibers were modified by either (i) mercerization (NaOH 10%), (ii) esterification (succinic anhydride), or (iii) ionized air treatment (discharge current of 5 mA). Composites were made by mould compression, of various sisal fibers in combination with either phenol‐formaldehyde or lignin‐phenol‐formaldehyde resins. Sisal fibers and composites were characterized by thermogravimetry (TG) and DSC to establish their thermal stability. Scanning electron microscopy (SEM) was used to investigate the morphology of unmodified and modified surface sisal fibers as well as the fractured composites surface. Dynamic mechanical thermoanalysis (DMTA) was used to examine the influence of temperature on the composite mechanical properties. The results obtained for sisal fiber‐reinforced phenolic and lignophenolic composites showed that the use of lignin as a partial substitute of phenol in phenolic resins in applications different from the traditional ones, as for instance in other than adhesives is feasible.

Micrograph of the impact fracture surface of phenolic composite reinforced with mercerized sisal fiber (500 X).     

Preparation of Nano‐Polyethylene Fibers and Floccules by Extrusion Polymerization Under Atmospheric Pressure Using the SBA‐15‐Supported Cp2ZrCl2 Catalytic System

Summary: Nano‐polyethylene fibers and floccules were prepared under atmospheric pressure via ethylene extrusion polymerization in suit, using the SBA‐15‐supported Cp₂ZrCl₂ catalytic system. The major morphology units in the samples were fibers and floccules. The diameter of the single nano‐fibers was 120–200 nm. The single nano‐fibers could aggregate to form fiber aggregates and bundles. The number of PE floccules increased with extension of polymerization time, while the melting point of PE with nano‐fibers was little higher than that of common polyethylene.

SEM micrograph of the nano‐polyethylene fibers produced at a polymerization time of 60 min: micro‐fibers and floccule surface morphologies.     

Comparison of the Effects of an Ionic Liquid and Triethylbenzylammonium Chloride on the Properties of Electrospun Fibers, 1 – Poly(lactic acid)

Improving the conductivity of electrospinning solutions is often achieved by adding small amounts of conductive additives. HMIMCl, a room temperature ionic liquid, and TEBAC, a quaternary ammonium salt, were added to polylactic acid in chloroform and their effects on solution properties, electrospinning, and fiber properties were investigated. Both additives increased the conductivity which decreased the fiber diameter, but differences were observed on the fiber dispersity and fiber morphology. The conductive solutions caused fiber backbuilding with aggregation and fiber fusion. Reasons for the differences in fiber diameter and fiber morphology are discussed.

     

Transcrystallinity in Surface Modified Aramid Fiber Reinforced Nylon 66 Composites

Aramid (kevlar‐49) fibers were surface treated by two different methods to induce roughness and then used to produce unidirectional nylon 66 based composites. The transcrystallinity generated around the treated fibers was characterized by SEM and polarized light microscopy and compared with the regular transcrystalline layers produced by pristine aramid under the same processing conditions. The treated fibers generated a double transcrystalline layer, the inner layer being thinner and more compact than the regular nylon 66 transcrystallinity. In addition, mechanical testing of the composites showed the longitudinal Young's modulus of the treated fiber composites to be significantly higher than the control in a wide range of fiber volume fractions.

Polarized light microscopy picture of double transcrystallinity in Br/NH₃ treated aramid fiber reinforced nylon 66.     

Structure Property Correlation of Thermally Treated Hemp Fiber

Summary: Hemp (Cannabis sativa L.) is an important ligno‐cellulosic raw material for the manufacture of cost‐effective environmentally friendly composite materials. Hemp plant samples of different initial condition (stem and bast fibers) were subjected to heating varying the temperature (from 160 to 260 °C) and the ambient heating environment (air and inert atmosphere). Weight measurements showed that all heat treatment resulted in a reduced weight of hemp. Those treated in air showed drastic decline in weight compared with those treated under nitrogen, especially at a temperature higher than 220 °C. Observation using optical and scanning microscope showed the possibilities of opening up of the fiber bundles in both heating environments. However, higher temperature and presence of air had a more severe effect on fibers and associated tissues compared to effects under nitrogen. Heat treatment at 220 °C under nitrogen seemed to provide enough fiber opening without affecting tissues of the fibers.

SEM micrograph of the cross‐section of hemp fiber heat treated in air environment.     

Ionized‐Air‐Treated Curaua Fibers as Reinforcement for Phenolic Matrices

Curaua fibers were treated with ionized air to improve the fiber/phenolic matrix adhesion. The treatment with ionized air did not change the thermal stability of the fibers. The impact strength increased with increase in the fiber treatment time. SEM micrographs of the fibers showed that the ionized air treatment led to separation of the fiber bundles. Treatment for 12 h also caused a partial degradation of the fibers, which prompted the matrix to transfer the load to a poorer reinforcing agent during impact, thereby decreasing the impact strength of the related composite. The composites reinforced with fibers treated with ionized air absorbed less water than those reinforced with untreated fibers.

     

Preparation of Ultrafine Ethylene/Propylene/Diene Terpolymer Rubber Fibers by Coaxial Electrospinning

Elastomeric EPDM fibers with diameters of 200–400 nm are prepared by coaxial electrospinning of PVP/EPDM fibers, subsequent vulcanization of the polymers and finally removal of the outer PVP layer using ethanol. The initially applied PVP layer restricts the elastic recovery of the EPDM fibers. The crosslinking density of the EPDM fibers reaches 8.44 × 10^?5 mol · cm^?3. The original morphology of EPDM is preserved after removing the PVP layer. The ultrafine EPDM fibers are expected to be useful in many fields, such as brittle plastics toughening, as well as applications in extremely high or low temperatures.

     

Phenolic Thermoset Matrix Reinforced with Sugar Cane Bagasse Fibers: Attempt to Develop a New Fiber Surface Chemical Modification Involving Formation of Quinones Followed by Reaction with Furfuryl Alcohol

Summary: A new chemical modification of sugar cane bagasse fibers for phenolic thermoset composites is presented. It consists in creating quinones in the lignin portions of fiber and react them with furfuryl alcohol to create a coating around the fiber more compatible with the phenolic resins used to prepare polymeric matrix. Sodium periodate was used in suitable conditions to oxidize mainly phenolic syringyl and guaiacyl units of the lignin polymer to create quinones, which were characterized by UV‐visible diffuse reflectance spectroscopy by comparison with model compounds. The reactivity of furfuryl alcohol (FA) with fibers was greatly enhanced after they were oxidized: 13% weight percent gain compared to 2% without oxidation. Chemical analysis of unmodified and FA‐modified fibers have shown an important degradation of hemicelluloses and a slight one of cellulose which almost maintains its crystallinity. A 25% decrease of strength and length properties of the fibers after FA chemical treatment was measured by dynamic mechanical analysis. The lignin‐like proportion of the fiber was greatly enhanced after the FA‐treatment. This was confirmed by thermal analysis, DSC, and TGA experiments, on unmodified and FA‐modified fibers. SEM analysis of the fibers and of phenolic composites with modified fibers have confirmed the FA grafting and shown a better compatibility at the interface between the chemically modified fibers and the phenolic matrix. Nevertheless, the chemical treatment of the fibers decreased the impact strength of the composite, which could be caused by the fiber damage suffered during the chemical modification and for the more intense adhesion at the interface, which in some cases decrease somewhat the impact strength.

Cross photomicrography of FA‐modified sugar cane bagasse fiber (600×).     

A Study on the Relationship Between the Crystal Structure and Hard Elasticity of PVDF Fibers

Summary: Poly(vinylidene fluoride) (PVDF) fibers were prepared by melt-spinning process. The crystal structure of annealed PVDF fibers was characterized by wide- and small-angle X-ray diffraction (WAXD and SAXD) and scanning electron microscopy (SEM). Crystalline reflections of c-axis orientation of annealed PVDF fibers were illustrated by WAXD pattern. The stacked lamellar structure aligned in the direction normal to the fiber axis was found in SAXD pattern and the d-spacing of the lamellae was 13.4 nm. Such lamellar structure was supported by SEM micrographs as well. The elastic recovery of annealed PVDF fibers was above 80% from 50% extension, which was much higher than that of unannealed fibers on the first cycle. The initial elastic modulus of annealed fibers reached to a value of 3.5 GPa. The morphological and mechanical properties, all indicated that the annealed PVDF fibers had the characteristic of hard elasticity. A typical stress-strain curve at a very low strain rate indicated the deformation of crystal lamellae in the fibers and a suggested structural deformation mechanism detailed the characteristics of hard elasticity.

Cyclic loading to 50% extension of annealed PVDF fibers.     

Harnessing the Melting Peculiarities of Ultra‐High Molecular Weight Polyethylene Fibers for the Processing of Compacted Fiber Composites

Summary: Compacted fiber composites offer unique properties due to their lack of an extraneous matrix. The conditions of processing ultra‐high molecular weight polyethylene (UHMWPE) fibers were simulated in a heated pressure cell. In situ X‐ray diffraction measurements were used to follow the relevant transitions and the changes in the degree of crystallinity during melting and crystallization. The results strongly support the suggestion that the hexagonal crystal phase, in which the chain conformation is extremely mobile on the segmental level, constitutes the physical basis of compaction technologies for processing UHMWPE fibers into a single‐polymer composite. This report suggests that using a pseudo‐phase diagram outlining the occurrence of different phases during slow heating and the degree of crystallinity can provide valuable insight into the technological parameters relevant for optimal processing conditions.

Degree of crystallinity as a function of pressure and temperature in a region relevant to compaction processes.     

Processing,Structure, and Properties of PAN/MWNT Composite Fibers

Conventional dry‐jet wet fiber spinning techniques were used to fabricate continuous PAN/MWNT composite fibers with up to 20 wt.‐% nanotube loading. PAN at the MWNT interface exhibited lower solubility under thermodynamically favorable conditions than in bulk PAN, indicating good interfacial interaction. Due to the PAN/MWNT interaction at the interface, thermal shrinkage decreases with increasing MWNT loading (5 to 20 wt.‐%). For high MWNT loadings, PAN/MWNT composite fiber at 15 wt.‐% MWNT loading showed an axial electrical conductivity of 1.24 S · m^?1. For all loadings, PAN/MWNT composite fibers exhibited higher tensile moduli than theoretically predicted by rule‐of‐mixture calculations, suggesting good reinforcement of the PAN by MWNT.

     

Structural,Electrical, Mechanical,and Thermal Properties of Electrospun Poly(lactic acid)/Polyaniline Blend Fibers

Conducting electrospun fiber mats based on PLA and PAni blends were obtained with average diameter values between 87 and 1 006 nm with PAni quantities from 0 to 5.6 wt.‐%. Structural characteristics of fiber mats were compared to cast films with the same amount of PAni and studied by SEM, SAXS, and AFM. Thermal properties of fiber mats and cast films were compared by DSC analyses. Mechanical properties of fiber mats were also evaluated. It was found that electrospinning process governs the crystal structure of the fibers and strongly affects fiber properties. New properties of PLA/PAni blends are reported due to the size fiber reduction.

     

The Effect of Silane Coupling Agents on the Viscoelastic Properties of Rubber Biocomposites

Summary: This paper deals with the dynamic mechanical study of sisal/oil palm hybrid fiber reinforced natural rubber composites (at frequency 1 Hz) with reference to the role of silane coupling agents. Composites were prepared using sisal and oil palm fibers subjected to chemical modifications with different types of silane coupling agents. The silanes used were Silane F8261 [1,1,2,2‐perfluorooctyl triethoxy silane], Silane A1100 [γ‐aminopropyltriethoxy silane] and Silane A151 [vinyl triethoxy silane]. It was observed that for treated composites, storage modulus and loss modulus increased while the damping property was found to decrease. Maximum E' was exhibited by the composite prepared from fibers treated with silane F8261 and minimum by composites containing fibers treated with silane A151. This was attributed to the reduced moisture absorbing capacity of chemically modified fibers leading to improved wetting. This in turn produced a strong interfacial interface giving rise to a much stiffer composite with higher modulus. Surface characterization of treated and untreated sisal fibers by XPS showed the presence of numerous elements on the surface of the fiber. Scanning electron micrographs of tensile fracture surfaces of treated and untreated composites demonstrated better fiber–matrix bonding for the treated composites.

Scheme of interaction of silanes with cellulosic fibers.     

Surface Modification of Poly(vinyl alcohol) Fibers

The surfaces of PVA fibers prepared by in situ fibrillation were modified by first crosslinking using glyoxal and then attaching cationic and anionic groups by grafting. Crosslinking prior to modification was beneficial in minimizing the solubility of the fibers in the aqueous medium in which they were modified. Heterogeneous modification techniques were employed so that fiber properties could be preserved. PAA and PDMC were grafted from the PVA microfibrils using the KPS/NaS₂O₃ redox initiating system. Grafting was confirmed by FTIR and NMR spectroscopy. The modified PVA fibers were also analyzed by DSC, TGA, and SEM.

     

Strongly Photosensitive and Fluorescent F8T2 Electrospun Fibers

Electrospun fibers of poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐bithiophene] (F8T2) with exceptional electro‐optical performance are obtained. The I/T characteristics measured in fibers with 7–15 µm diameter and 1 mm length show a semiconductor behavior; their thermal activation energy is 0.5 eV and the dark conductivity at RT is 5 × 10^?9 (Ω cm)^?1. Besides exhibiting a photosensitivity of about 60 under white light illumination with a light power intensity of 25 mW · cm^?2, the fibers also attain RT photoluminescence in the cyan, yellow, and red wavelength range under ultraviolet, blue, and green light excitation, respectively. Optical microscope images of F8T2 reveal homogeneous electrospun fibers, which are in good agreement with the uniformly radial fluorescence observed.

     

On the Role of Extensional Flow in Morphology and Property Modifications of MWCNT/Polyamide‐Based Fibers

Unfilled and MWCNT‐filled PA fibers are prepared and the effect of the extensional flow on their mechanical performance and morphological variations is investigated. Morphological analyses using SEM, TEM, and SAXS suggest a stronger orientation of the MWCNTs along the fiber direction with increasing extensional flow. A particular MWCNT bundle formation in the PA drawn nanocomposite fibers is observed for the first time, and a pull‐out of the central nanotube in some bundles is noted. The maintenance of the “shish‐kebab” structure upon extensional flow is responsible for the mechanical improvements and dimensional stability in MWCNT‐filled PA fibers.

     

Ultrafine Electrospun Polyamide‐6 Fibers: Effects of Solvent System and Emitting Electrode Polarity on Morphology and Average Fiber Diameter

Summary: In the present contribution, polyamide‐6 (PA‐6) solutions were prepared in various pure and mixed‐solvent systems and later electrospun with the polarity of the emitting electrode being either positive or negative. The PA‐6 concentration in the as‐prepared solutions was fixed at 32% w/v. Some of the solution properties, i.e., shear viscosity, surface tension, and conductivity, were measured. Irrespective of the polarity of the emitting electrode, only the electrospinning of PA‐6 solution in formic acid (85 wt.‐% aqueous solution) produced uniform electrospun fibers, while solutions of PA‐6 in m‐cresol or sulfuric acid (either 20 or 40 wt.‐% aqueous solution) did not. In the mixed‐solvent systems, formic acid (85 wt.‐% aqueous solution) was blended with m‐cresol, sulfuric acid (either 20 or 40 wt.‐% aqueous solution), acetic acid, or ethanol in the compositional range of 10–40 vol.‐% (based on the amount of the minor solvent). Generally, the average fiber diameter increased with increasing amount of the minor solvent or liquid. Interestingly, the diameters of the fibers obtained under the negative electrode polarity were larger than those obtained under the positive one.

Optical images of electrospun fibers from solutions of polyamide‐6 in a mixed solvent of 85 wt.‐% formic acid and 20 vol.‐% m‐cresol under positive (left) and negative (right) electrode polarity.