Processing,structure, and properties of gel spun PAN and PAN/CNT fibers and gel spun PAN based carbon fibers

Polyacrylonitrile (PAN) and PAN/carbon nanotube (PAN/CNT) fibers were manufactured through dry‐jet wet spinning and gel spinning. Fiber coagulation occurred in a solvent‐free or solvent/nonsolvent coagulation bath mixture with temperatures ranging from ?50 to 25°C. The effect of fiber processing conditions was studied to understand their effect on the as‐spun fiber cross‐sectional shape, as well as the as‐spun fiber morphology. Increased coagulation bath temperature and a higher concentration of solvent in the coagulation bath medium resulted in more circular fibers and smoother fiber surface. as‐spun fibers were then drawn to investigate the relationship between as‐spun fiber processing conditions and the drawn precursor fiber structure and mechanical properties. PAN precursor fiber tows were then stabilized and carbonized in a continuous process for the manufacture of PAN based carbon fibers. Carbon fibers with tensile strengths as high as 5.8 GPa and tensile modulus as high as 375 GPa were produced. The highest strength PAN based carbon fibers were manufactured from as‐spun fibers with an irregular cross‐sectional shape produced using a ?50°C methanol coagulation bath, and exhibited a 61% increase in carbon fiber tensile strength as compared to the carbon fibers manufactured with a circular cross‐section. POLYM. ENG. SCI., 55:2603–2614, 2015. © 2015 Society of Plastics Engineers     

Study of SiC fiber axial compressive behavior using tensile recoil measurement

SiC fibers have been widely investigated as reinforcements for advanced ceramic matrix composites owing to their excellent high-temperature properties. However, the axial compressive strength of SiC fibers has not been thoroughly studied. In this study, the compressive behavior of two SiC fiber types containing different compositions and thermal degradation were characterized by tensile recoil measurements. Results illustrated that the SiC fiber compressive strength was 30%–50% of its tensile strength, after heat treatment at 1200℃–1800℃ for 0.5 h in argon. The fiber compressive failure mechanism was studied, and a “shear-bending-cleavage” model was proposed for the recoil compression fracture of pristine SiC fibers. The average compressive and tensile strengths of the pristine SiC-II fiber were 1.37 and 3.08 GPa, respectively. After treatment at 1800℃ for 0.5 h in argon, the SiC-II fiber compressive strength decreased to 0.42 GPa, whereas the tensile strength reduced to 1.47 GPa. The mechanical properties of the fibers degraded after high-temperature treatment. This could be attributed to SiC grain coarsening and SiC_xO_y phase decomposition.     

Mechanical properties of individual electrospun polymer-nanotube composite nanofibers

Singlewalled carbon nanotube/polyvinylalcohol composite nanofibers were electro-spun onto a silicon surface pre-patterned with trenches. These nanofibers were prepared with different loadings of SWCNTs and had radii between 20 and 40 nm. Individual fiber sections were pinned across the trenches and laterally loaded by an AFM tip to yield mechanical response curves. A simple model was exploited to extract the tensile mechanical properties from the lateral force-displacement data. Depending on the fiber composition, the tensile modulus was found to be between 3 and 85 GPa. In addition we have prepared fibers with tensile strength of up to 2.6 GPa. Such optimised fibers break at strains of ∼4% and exhibit toughness of up to 27 MJ/m³.     

Fabrication of High Performance PET/TLCP Fibers through the Synergistic Interfacial Enhancement and Compatibilization of Functional 1D and 2D Carbon Nanomaterials

The maleic anhydride functionalized graphene oxide (GO-MA) is fabricated by an efficient and solvent-free Diels–Alder reaction. Polyethylene terephthalate (PET)/thermotropic liquid crystal polyester (TLCP), PET/TLCP/GO-MA, PET/TLCP/aminated multi-walled carbon nanotubes (MWCNTs-NH₂), and PET/TLCP/GO-MA/MWCNTs-NH₂ composite fibers are systematically melt-spun. The structure and compatibilizing effects of GO-MA and MWCNTs-NH₂ on the mechanical, thermal, and crystallization properties of the composite fibers are indicated. The non-isothermal crystallization kinetics and X-ray diffraction (XRD) data show that TLCP and nanofillers can change the crystalline morphology of PET. The mechanical properties of the fibers rise with increasing TLCP content. The tensile strength 929 MPa and modulus 17.5 GPa of the fibers with 7 wt% TLCP and 0.25 wt% nanofillers (0.1 wt% GO-MA and 0.15 wt% MWCNTs-NH₂) are significantly higher than those with 7 wt% TLCP (tensile strength 622 MPa and modulus 16.1 GPa) and even higher than those with 15% TLCP (tensile strength 836 MPa, and modulus 18.0 GPa). When the GO-MA and MWCNTs-NH₂ co-exist, the anti-dripping phenomenon is improved. Therefore, the TLCP, GO, and MWCNTs synergistically strengthens the mechanical properties. This is promising for the industrial fabrication of high-strength fibers.     

Gel-spinning and drawing of gelatin

Gelatin fibers can be prepared by the gel-spinning method using dimethyl sulfoxide as a solvent. The use of the method and the drawing in a gel state were effective in inducing segmental orientation in gelatin fiber. The fibers showed high values for the mechanical properties of tensile strength of 180 MPa and Young's modulus of 3.4 GPa.     

High-strength superparamagnetic composite fibers

The polymer composites of magnetic nanoparticles can be possibly used in a bulk form by preserving all the novel characteristics of magnetic nanoparticles such as superparamagnetic behavior. By introducing magnetic properties of Fe₃O₄ nanoparticles into polymer fibers, novel magnetic properties combine with the advantages of composite fibers such as light-weight and ease-of-use. Using dry-jet-wet fiber spinning technology, we have successfully fabricated iron oxide/polyacrylonitrile (Fe₃O₄/PAN) composite fibers with 10 wt% nanoparticle in the polymer matrix. Composite fiber with a diameter as small as 15 μm can achieve tensile strength and tensile modulus values as high as 630 MPa and 16 GPa, respectively. Superparamagnetic properties of Fe₃O₄ nanoparticles were preserved in the composite fibers with saturation magnetization at 80 emu/g and coercivity of 165 G.     

Effect of coagulation conditions on solvent diffusions and the structures and tensile properties of solution spun polyacrylonitrile fibers

Polyacrylonitrile (PAN) fibers were spun by solution spinning. In this work, two coagulation compositions, dimethyl sulfoxide (DMSO)/water and methanol, were used, and coagulation temperatures were varied from ?20 to 0 to 20 °C. The coagulation compositions and temperatures strongly affected the solvent diffusion processes, the structures of as‐spun fibers, and the tensile properties of final drawn fibers. When DMSO/water was used as coagulation bath, non‐solvent (water) diffused into PAN fibers and led to a quick PAN solidification. By comparison, when methanol was used as coagulation bath, no or minimal amount of methanol diffused inward to the fibers. The different solvent diffusion behaviors in DMSO/water and methanol baths led to different structures of as‐spun PAN fibers. It was observed that the tensile properties of final drawn fibers strongly depended on the coagulation conditions. When methanol was used as coagulation bath and the bath temperature was ?20 °C, PAN fibers was found to possess the best tensile properties, a tensile strength of 0.89 GPa and young modulus of 20.4 GPa. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44390.     

Strength degradation of alumina fiber: Irreversible phase transition after high-temperature treatment

The mechanical properties of alumina AF17-20 fiber after high-temperature treatment have been evaluated through tensile tests on single fiber and bundle. The tensile test on single fibers shows that the temperature has little effect on the elastic modulus of the fibers, which stables around 140 GPa. The test on bundles minimizes the personal errors thus giving a more reliable value of tensile strength. In general, as temperature increases, both the Weibull modulus and the tensile strength decrease gradually. De-sized fibers have the highest tensile strength, but inherent defects like pores still cause slight dispersion of the strength. Further, the strength maintains about 90% after treating below 1200 °C, and this insignificant decline is caused by the decrease of amorphous SiO₂ and the formation of aluminum silicate. In addition, the severe degradation in strength over 1200 °C is mainly attributed to the appearance and growth of mullite grains, which is only about 60% of the initial value.     

Biopitch-based general purpose carbon fibers: Processing and properties

Eucalyptus tar pitches are generated on a large scale in Brazil as by-products of the charcoal manufacturing industry. They present a macromolecular structure constituted mainly of phenolic, guaiacyl, and siringyl units common to lignin. The low aromaticity (60-70%), high O/C atomic ratios (0.20-0.27%), and large molar mass distribution are peculiar features which make biopitches behave far differently from fossil pitches. In the present work, eucalyptus tar pitches are evaluated as precursors of general purpose carbon fibers (GPCF) through a four-step process: pitch pre-treatment and melt spinning, and fiber stabilization and carbonization. Homogeneous isotropic fibers with a diameter of 27 μm were obtained. The fibers had an apparent density of 1.84 g/cm³, an electrical resistivity of 2 × 10⁻⁴ Ω m, a tensile strength of 130 MPa, and a tensile modulus of 14 GPa. Although the tensile properties advise against using the produced fibers as structural reinforcement, other properties give rise to different potential applications, as for example in the manufacture of activated carbon fibers or felts for electrical insulation.     

Preparation of high-strength poly(vinyl alcohol) fibers by crosslinking wet spinning

High-strength poly(vinyl alcohol) (PVA) fiber was obtained by the crosslinking wet-spinning technique, which is an improved technique of the conventional non-crosslinked type wet-spinning of PVA. High tensile strength as well as high Young's modulus was achieved by introduction of the borate ion-aided crosslinks during the coagulation process. The drawability of the as-spun fiber greatly depends on the fiber thickness. The thinner the fiber, the higher the drawability. Since thinner fiber is subject to a very high shear rate on extrusion, the crosslinks introduced are believed to maintain topological memory of the oriented chains, which have a low density of entanglements. This allows drawing the fiber to a higher draw ratio. The strength and Young's modulus of the resultant highly drawn PVA fiber were achieved to be 22 g/d (2.3 GPa) and 430 g/d (50 GPa), respectively. The mechanism of the spinning was discussed and the spinning condition was carefully examined in order to optimize the final mechanical properties of the PVA fibers.     

High strength and high modulus carbon fibers

Carbon fibers have been processed from gel spun polyacrylonitrile copolymer on a continuous carbonization line at Georgia Tech (GT) with a tensile strength in the range of 5.5–5.8 GPa, and tensile modulus in the range of 354–375 GPa. This combination of strength and modulus is the highest for any continuous fiber reported to date, and the gel spinning route provides a pathway for further improvements in strength and modulus for mass production of carbon fibers. At short gauge length, fiber tensile strength was as high as 12.1 GPa, which is the highest value ever reported for a PAN based carbon fiber. Structure analysis shows random flaws of about 2 nm size, which results in limiting tensile strength of higher than 20 GPa. Inter-planar turbostratic graphite shear modulus in high strength carbon fibers is 30 GPa, while in graphite the corresponding value is only 4 GPa.     

Structural evaluation and mechanical property of boron nitride fibers during melt‐drawn fabrication process

Boron nitride (BN) fibers were fabricated on a large scale through the melt‐drawn technique from low‐cost boric acid, NH₃, and N₂. Evolution of structure and properties of BN fibers during the fabrication process was studied by Fourier transform infrared (FT‐IR), X‐ray diffraction (XRD), scanning electron microscope (SEM), and X‐ray photoelectron spectroscopy (XPS). The mechanical properties of BN fibers were tested and analyzed. The results shown that both the mechanical properties and the crystallinity of BN fibers slightly increased with the temperature from 450 to 850°C, due to the combination of the fused‐B₃N₃. For BN fibers heat‐treated at 850 or 1000°C, the tensile strength (σ^R) and elastic modulus (E) were strongly increased because of the increase in crystallization of the BN phase. The meso‐hexagonal BN fibers with a diameter of 5.0 μm were fabricated at 1750°C, of which the tensile strength (σ^R) and elastic modulus (E) are 1200 MPa and 85 GPa, respectively. BN fibers with excellent mechanical properties and proper diameters were obtained by nitriding of green fibers during their conversion into ceramic.     

High-performance polypropylene film prepared from reactor powders having different characteristics

Ultra-high molecular weight isotactic polypropylene (UHMW-iPP) reactor powders have been successfully ultra drawn below melting temperature (T_m) by a combination of calendar rolling and tensile drawing techniques. Two UHMW-iPP reactor powders having different MWs were synthesized by using the same Ziegler-Natta catalyst system at 70 °C in hexane. The resultant tensile properties increased with increasing draw ratio, due to orientation-crystallization during tensile draw, which was indicated by DSC and WAXD measurements. The film drawn under optimum conditions exhibited the maximum tensile modulus of ∼25 GPa, independent of sample MW, corresponding to 70% of the ultimate modulus of iPP crystal. However, the higher maximum tensile strength of ∼1.0 GPa was achieved for the reactor powder having the higher MW, which is three times as high as those of commercial high-strength iPP tapes. Such a fact that high performances have been achieved by processing from reactor powder state below T_m implies that crystallization with less entanglement occurs during polymerization. When drawability and resultant properties were compared among different iPP reactor powders prepared under different conditions, it was clarified that they were predominantly affected by not only MW but also by the reactor powder morphology, especially surface smoothness.     

Ultradrawing above the static melting temperature of ultra-high molecular weight isotactic poly(1-butene) having low ductility in the crystalline state

Ultra-high molecular weight isotactic poly(1-butene) (UHMW-PB1) melt-grown crystal (MGC) films were drawn using the PIN drawing technique. Although the UHMW-PB1 MGC films had poor ductility in the crystalline state, they were ultradrawable in the molten state above the static melting temperature (T_m). The drawability of the MGC films was strongly influenced by the draw temperature, the sample thickness, and the contact time between the metal heater and sample, and it increased with decreasing sample thickness. The maximum draw ratio (DR_max) was nearly constant when the sample thickness was less than 100 μm at a given draw temperature. The contact time between the metal heater and sample needed to draw continuously in the molten state was at least 0.1 s. The ductility increased rapidly above 130 °C, reaching a maximum at 200 °C, and decreased at higher temperatures. A DR_max of 170 was achieved at 200 °C under optimum conditions. The efficiency of the drawing, based on the Herman crystalline orientation function (f_c) and tensile properties versus DR, was lower for films drawn at higher temperatures. The highest f_c of 0.996, tensile modulus of 14 GPa, and strength of 900 MPa were obtained by ultradrawing with DR = 50 at 155 °C. This modulus corresponded to 58% of the X-ray crystal modulus (24 GPa), whereas the modulus of PB1 films drawn in the crystalline state corresponded to only 12–13% (3 GPa) of the theoretical crystal modulus.     

In situ transmission electron microscope tensile testing reveals structure–property relationships in carbon nanofibers

Tensile tests were performed on carbon nanofibers in situ a transmission electron microscope (TEM) using a microelectromechanical system (MEMS) tensile testing device. The carbon nanofibers tested in this study were produced via the electrospinning of polyacrylonitrile (PAN) into fibers, which are subsequently stabilized in an oxygen environment at 270 °C and carbonized in nitrogen at 800 °C. To investigate the relationship between the fiber molecular structure, diameter, and mechanical properties, nanofibers with diameters ranging from ∼100 to 300 nm were mounted onto a MEMS device using nanomanipulation inside the chamber of a Scanning Electron Microscope, and subsequently tested in tension in situ a TEM. The results show the dependence of strength and modulus on diameter, with a maximum modulus of 262 GPa and strength of 7.3 GPa measured for a 108 nm diameter fiber. In particular, through TEM evaluation of the structure of each individual nanofiber immediately prior to testing, we elucidate a dependence of mechanical properties on the molecular orientation of the graphitic structure: the strength and stiffness of the fibers increases with a higher degree of orientation of the 0 0 2 graphitic planes along the fiber axis, which coincides with decreasing fiber diameter.     

Mechanical properties and microstructure of poly(ethylene terephthalate) microfiber prepared by carbon dioxide laser heating

We determined that a poly(ethylene terephthalate) microfiber was easily obtained by irradiating a carbon dioxide laser to an annealed fiber. The annealed fiber was prepared by zone drawing and zone annealing. First, an original fiber was zone drawn at a drawing temperature of 90°C under an applied tension of 4.9 MPa, and the zone‐drawn fiber was subsequently zone annealed at 150°C under 50.9 MPa. The zone‐annealed fiber had a degree of crystallinity of 48%, a birefringence of 218.9 × 10^?3, tensile modulus of 18.8 GPa, and tensile strength of 0.88 GPa. The microfiber prepared by laser heating the zone‐annealed fiber had a diameter of 1.5 μm, birefringence of 172.8 × 10^?3, tensile modulus of 17.6 GPa, and tensile strength of 1.01 GPa. The draw ratio estimated from the diameter was 9165 times; such a high draw ratio has thus far not been achievable by any conventional drawing method. Microfibers may be made more easily by laser heating than by conventional technologies such as conjugate spinning. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1955–1958, 2003     

Development and application of triglyceride-based polymers and composites

Triglyceride oils derived from plants have been used to synthesize several different monomers for use in structural applications. These monomers have been found to form polymers with a wide range of physical properties. They exhibit tensile moduli in the 1–2 GPa range and glass transition temperatures in the range 70–120 °C, depending on the particular monomer and the resin composition. Composite materials were manufactured utilizing these resins and produced a variety of durable and strong materials. At low glass fiber content (35 wt %), composites produced from acrylated epoxidized soybean oil by resin transfer molding displayed a tensile modulus of 5.2 GPa, a flexural modulus of 9 GPa, a tensile strength of 129 MPa, and flexural strength of 206 MPa. At higher fiber contents (50 wt %) composites produced from acrylated epoxidized soybean oil displayed tensile and compression moduli of 24.8 GPa each, and tensile and compressive strengths of 463.2 and 302.6 MPa, respectively. In addition to glass fibers, natural fibers such as flax and hemp were used. Hemp composites of 20% fiber content displayed a tensile strength of 35 MPa and a tensile modulus of 4.4 GPa. The flexural modulus was ∼2.6 GPa and the flexural strength was in the range 35.7–51.3 MPa, depending on the test conditions. The flax composite materials had tensile and flexural strengths in the ranges 20–30 and 45–65 MPa, respectively. The properties exhibited by both the natural- and synthetic fiber-reinforced composites can be combined through the production of “hybrid” composites. These materials combine the low cost of natural fibers with the high performance of synthetic fibers. Their properties lie between those displayed by the all-glass and all-natural composites. Characterization of the polymer properties also presents opportunities for improvement through genetic engineering technology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 703–723, 2001     

Lignin-based carbon fibers for composite fiber applications

Carbon fibers have been produced for the first time from a commercially available kraft lignin, without any chemical modification, by thermal spinning followed by carbonization. A fusible lignin with excellent spinnability to form a fine filament was produced with a thermal pretreatment under vacuum. Blending the lignin with poly(ethylene oxide) (PEO) further facilitated fiber spinning, but at PEO levels greater than 5%, the blends could not be stabilized without the individual fibers fusing together. Carbon fibers produced had an over-all yield of 45%. The tensile strength and modulus increased with decreasing fiber diameter, and are comparable to those of much smaller diameter carbon fibers produced from phenolated exploded lignins. In view of the mechanical properties, tensile 400–550 MPa and modulus 30–60 GPa, kraft lignin should be further investigated as a precursor for general grade carbon fibers.     

Superstructure and mechanical properties of poly(L-lactic acid) microfibers prepared by CO2 laser-thinning

Poly(L-lactic acid) (PLLA) microfibers were obtained by a carbon dioxide (CO₂) laser-thinning method. A laser-thinning apparatus used to continuously prepare microfibers was developed in our laboratory; it consisted of spools supplying and winding the fibers, a continuous-wave CO₂-laser emitter, a system supplying the fibers, and a traverse. The laser-thinning apparatus produced PLLA microfibers in the range of 100-800 m min⁻¹. The diameter of the microfibers decreased as the winding speed increased, and the birefringence increased as the winding speed increased. When microfibers, obtained through the laser irradiation (at a laser power of 8.0 W cm⁻²) of the original fiber supplied at 0.4 m min⁻¹, were wound at 800 m min⁻¹, they had a diameter of 1.37 μm and a birefringence of 24.1×10⁻³. The draw ratio calculated from the supplying and winding speeds was 2000×. The degree of crystal orientation increased with increasing the winding speed. Scanning electron microscopy showed that the microfibers obtained with the laser-thinning apparatus had smooth surfaces not roughened by laser ablation that were uniform in diameter. The PLLA microfiber, which was obtained under an optimum condition, had a Young's modulus of 5.8 GPa and tensile strength of 0.75 GPa.     

Solid‐state polymerization of melt‐spun poly(ethylene terephthalate) fibers and their tensile properties

The production of high modulus and high strength poly(ethylene terephthalate) fibers was examined by using commercially available melt‐spun fibers with normal molecular weight (intrinsic viscosity = 0.6 dL/g). First, molecular weight of as‐spun fibers was increased up to 2.20 dL/g by a solid‐state polymerization, keeping the original shape of as‐spun fibers. Second, the polymerized as‐spun fibers were drawn by a conventional tensile drawing. The achieved tensile modulus and strength of as‐drawn fibers (without heat setting) were 20.0 and 1.1 GPa, respectively. A heat setting was carried out for the as‐drawn fibers. Tensile properties of the treated fibers were greatly affected by the condition of the heat setting. This was related to the increase of sample crystallinity and molecular degradation during the treatments. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1791–1797, 2007