Carbon fibers derived from wet‐spinning of equi‐component lignin/polyacrylonitrile blends

Equi‐component blends of polyacrylonitrile (PAN) and lignin, i.e., with a lignin content as large as 50 wt %, were successfully used as precursors to produce carbon fibers. Rheological measurements demonstrated that increasing lignin content in spinning solution reduced shear viscosity and normal stress, indicating a decrease of viscoelastic behavior. This was confirmed by Fourier transform infrared results that show no discernable chemical reaction or crosslinking between PAN and lignin in the solution. However, the resulting carbon fibers display a large I_D/I_G ratio (by Raman spectroscopy) indicating a larger disordered as compared to that from pure PAN. The macro‐voids in the lignin/PAN blend fibers typically generated during wet‐spinning were eliminated by adding lignin in the coagulant bath to counter‐balance the out‐diffusion of lignin. Carbon fibers resulting from lignin/PAN blends with 50 wt % lignin content displayed a tensile strength and modulus of 1.2 ± 0.1 and 130 ± 3 GPa, respectively, establishing that the equi‐component wet‐spun L/P‐based carbon fibers possessed tensile strength and modulus higher than 1 and 100 GPa. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45903.     

Effect of nanocrystalline cellulose addition on needleless alternating current electrospinning and properties of nanofibrous polyacrylonitrile meshes

Needleless alternating current (AC)‐electrospinning is capable of achieving high nanofiber generation rates while adding more flexibility to the process development when compared to common direct current (DC)‐electrospinning. However, AC‐electrospinning process may produce very different results than DC‐electrospinning when using the same precursors. This study demonstrated that stable AC‐electrospinning of uniform and mechanically strong polyacrylonitrile (PAN) nanofibrous meshes can be achieved at 30 ± 5 kV rms voltage when 0.75–6.0 wt % of nanocrystalline cellulose‐II with respect to PAN is added to a typical PAN precursor solution. Efficient generation (up to 2 g/h rate or 0.7 g h^?1 cm^?2 mass flux) of nanofibers with 250–500 nm fiber diameters has been observed when using flat fiber‐generating electrodes with diameters up to 25 mm. Depending on the amount of nanocellulose, nanofibrous nanocellulose/PAN meshes revealed large variations in tensile modulus (90–273 MPa) and yield strength (1.0–2.5 MPa), whereas the fiber diameter, air permeability, air resistance, mesh porosity, and water absorption were less affected. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45772.     

Structure and property changes of polyamide 6 during the gel‐spinning process

Polyamide 6 (PA6) gels were prepared by the dissolution of PA6 powder in formic acid with CaCl₂ as a complexing agent. The concentration of the polymer was 16% w/v. PA6 fibers were obtained through gel‐spinning, drawing, decomplexation, and heat‐setting processes. The structure and properties of the fibers at different stages were characterized with differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The experiment results indicate that the melting transition of the as‐spun fibers obtained by the extrusion of the PA6/CaCl₂/HCOOH solution into a coagulation bath through a die disappeared. A porous structure existed in the as‐spun fibers, which led to poor mechanical properties. Compared with the as‐spun fibers, the melting and glass‐transition temperatures of the decomplexed and drawn fibers retained their original values from PA6, the degree of crystallinity increased, the porous structure disappeared, and the mechanical properties were improved. The maximum modulus and tensile strength obtained from the drawn fibers in this study were 32.3 GPa and 530.5 MPa, respectively, at the maximum draw ratio of 10. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4449–4456, 2013     

Polyimide fibers prepared by a dry‐spinning process: Enhanced mechanical properties of fibers containing biphenyl units

Polyimide (PI) fibers with enhanced mechanical properties and high thermal and dimensional stability were prepared via a two‐step dry‐spinning process through the introduction of 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride (BPDA) containing biphenyl units into rigid homopolyimide of pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline. The attenuated total reflectance–Fourier transform infrared spectra results imply that the incorporated BPDA moieties accelerate the imidization process and increase the imidization degree (ID) of the precursor fibers; this was attributed to the increased molecular mobility of the polymer chains. Two‐dimensional wide‐angle X‐ray diffraction spectra indicated that the prepared PI fibers possessed a well‐defined crystal structure and polymer chains in the crystalline region were highly oriented along the fiber axis. The PI fiber, with the molar ratio of PMDA/BPDA being 7/3, showed optimum tensile strength and modulus values of 8.55 and 73.21 cN/dtex, respectively; these were attributed to the high IDs and molecular weights. Meanwhile, the PI fibers showed better dimensional stability than the commercial P84 fiber, and this is beneficial for its security applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43727.     

Enhancing the mechanical and thermal properties of polyacrylonitrile through blending with tea polyphenol

Several polyacrylonitrile (PAN)/tea polyphenol (TP) blends were prepared with various mixing weight ratios (percentage). With a commercial acrylonitrile–butadiene–styrene (ABS) as reference, the results show that the PAN/TP blends with 12.5 wt % TP had a better antiwear ability and similar hardness to those of ABS. All of the prepared PAN/TP blends showed a lower impact strength than the referenced ABS. However, some values were indeed higher than those reported for engineering materials in the literature, for example, polystyrenes and some ABS blends. Differential scanning calorimetry, differential thermogravimetry, and dynamic mechanical analysis indicated that the PAN/TP blends had enhanced the thermal stability compared to the pure PAN. Fourier transform infrared spectral analysis suggested that the H bonds increased in the PAN/TP blends. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40411.     

Effect of processing parameters of the continuous wet spinning system on the crystal phase of PVDF fibers

Poly(vinylidene difluoride) (PVDF) has been widely used in piezoelectric applications as films and nanofiber mats, but there are limited publications on piezoelectric wet‐spun fibers. In this work, PVDF fibers were prepared using the wet spinning method, and the processing parameters, including the drawing ratio and heat setting temperature, were controlled in the continuous wet spinning system to increase the β‐phase crystallinity of the fibers. In addition, the wet‐spun PVDF fibers were compressed by a rolling press to eliminate voids in the fibers. Then, the compressed PVDF fibers were poled to align the molecular dipoles. The crystal structures of the PVDF fibers were investigated using X‐ray diffraction and Fourier‐transform infrared spectroscopy. Single filament tensile tests were performed to measure the tensile strength of the fibers. The morphologies of the PVDF fibers with respect to the processing parameters were observed by scanning electron microscope (SEM) and polarization optical microscopy. The piezoelectric constant of the prepared PVDF fibers was then measured using a d₃₃ meter. The wet‐spun PVDF fibers showed the highest β‐phase and piezoelectric constants when the drawing ratio and heat setting temperature were 6 and 150 °C, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45712.     

Surface modification of polyimide fibers by novel alkaline–solvent hydrolysis to form high‐performance fiber‐reinforced composites

We modified polyimide (PI) fibers by a novel hydrolysis approach and fabricated PI‐fiber‐reinforced novolac resin (NR) composites with enhanced mechanical properties. We first used an alkaline–solvent mixture containing potassium hydroxide liquor and dimethylacetamide (DMAc) for the surface modification of the PI fibers. The results indicate that the surface roughness and structure of the PI fibers were controlled by the hydrolysis time and the content of DMAc. With the optimized hydrolysis conditions, the tensile modulus of modified PI fibers improved 15% without compromises in the fracture stress, fracture strain, or thermal stability. The interfacial shear strength between the modified PI fibers and NR increased 57%; this indicated a highly enhanced interfacial adhesion. Finally, the tensile and flexural strengths of the composites increased 72 and 53%, respectively. This research provides an effective method for the surface modification of PI fibers and expands their applications for high‐performance composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46595.     

Characteristics of wet‐spun and thermally treated poly acrylonitrile fibers

The performance of carbon fibers depends on the quality of the precursor and the conditions of the thermal treatment. In detail, for a PAN precursor fiber the viscosity of a spinning dope and the draw ratio during the spinning process needs to be considered. Through wet spinning, different types of PAN precursor fibers with defined spinning parameters, including solid content, solvent content in a bath, and especially draw ratio resulting in defined cross section diameters, were fabricated and analyzed with tensile tests, density investigations, SEM, TGA‐MS, FTIR, and XRD. The results show that the mechanical properties of the fibers correlate to crystallinity. The cross section diameter is strongly related to the morphology of the fibers after thermal treatment. By extending the postdrawing of PAN fibers high tenacities were obtained at the cost of the cross section shape. In addition, TGA measurements reveal trapped residues of the wet spinning process as well as show several chemical reactions takes place at the same time at different temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43698.     

Alkali treatment of jute fibers: Relationship between structure and mechanical properties

The mechanical properties of tossa jute fibers were improved by using NaOH treatment process to improve the mechanical properties of composites materials. Shrinkage of fibers during this process has significant effects to the fiber structure, as well as to the mechanical fiber properties, such as tensile strength and modulus. Isometric NaOH‐treated jute yarns (20 min at 20°C in 25% NaOH solution) lead to an increase in yarn tensile strength and modulus of ∼ 120% and 150%, respectively. These changes in mechanical properties are affected by modifying the fiber structure, basically via the crystallinity ratio, degree of polymerization, and orientation (Hermans factor). Structure–property relationships, developed for cellulosic man‐made fibers, were used with a high correlation factor to describe the behavior of the jute fiber yarns. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 623–629, 1999     

Effects of the coagulation temperature on the properties of wet‐spun poly(vinyl alcohol)–graphene oxide fibers

Graphene oxide (GO) as a positive reinforcement filler was dispersed into a poly(vinyl alcohol) (PVA) dope and wet‐spun into composite fibers. The effects of two EtOH coagulation baths maintained at ?5 and 25 °C, respectively, on the morphology, structure, and mechanical properties of the composite fibers were investigated. The results show that gel spinning at ?5 °C led to a relatively large shrinkage ratio, thin diameter, and low porosity of the as‐spun fibers. Simultaneously, the low coagulation temperature also greatly contributed to the formation and preservation of the liquid‐crystalline phase of the GO sheets and interrupted the crystalline zone of PVA less. As a result, either the tenacity or the elongation at break of the fibers spun at ?5 °C was higher than those of the fibers spun through a coagulation bath at 25 °C. In particular, 1 wt % GO showed the highest reinforcement effects among all of the wet‐spun composite fibers. Hence, controlling the gelling–demixing process at a low temperature will provide more instructive insights for tailoring functional industrial textiles with excellent mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45463.     

Structural,mechanical, and thermal properties of 3D printed L‐CNC/acrylonitrile butadiene styrene nanocomposites

3D printing has been extensively applied in human‐related activities, and therefore the 3D printed nanocomposites became more popular and important in end‐use products. In the present study, we use lignin‐coated cellulose nanocrystal (L‐CNC) to reinforce 3D printed acrylonitrile butadiene styrene (ABS) and explore the effect of L‐CNC on the structural, mechanical, and thermal properties of 3D printed L‐CNC/ABS nanocomposites. The results indicate that the addition of L‐CNC foams the ABS and decreases the density of 3D printed L‐CNC/ABS nanocomposites. However, the tensile modulus and storage modulus increase by adding 4% L‐CNC. The thermal stability of 3D printed L‐CNC/ABS nanocomposites is also significantly improved as indicated by an increase in the maximum degradation temperature. The morphology of the nanocomposites reveals good dispersion and interfacial adhesion between L‐CNC and ABS. The finding indicates that the 3D printed nanocomposites become lighter and stiffer with addition of L‐CNC, which will have great potential to be applied in end‐use products. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45082.     

Single fiber peel test to assess ultra high molecular weight polyethylene fiber mesostructure interactions

In this work, a variable angle, single fiber peel test is developed to analyze the effects of fiber structure on the mixed mode failure within ultra high molecular weight polyethylene fibers. The Mode I and Mode II peel energy release rates are quantified and the effects of fiber meso/nanostructure on these modes are examined. Comparison of the load‐extension curves from the peel test with in‐situ video, and post‐mortem analysis using high‐resolution microscopy techniques indicates that Mode I and Mode II splitting are both significantly influenced by the deformation of nanoscale fibrils within a mesoscale network. The fibrils in the network are placed in tension across the peel/shear interface resulting in elevated values of peel energy release rates with an increasing number of engaged fibrils. The number of engaged fibrils is shown to increase with decreasing peel angle and increasing Mode II failure contribution. A bi‐linear mixed‐mode failure criterion is established. The results, and analysis of the fiber structure are discussed in context of their implications for load pathways in the fiber. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46156.     

Effect of spinning conditions on the mechanical properties of polyacrylonitrile fibers modified with carbon nanotubes

Carbon nanotubes (CNTs) were used to modify polyacrylonitrile (PAN) polymer. The PAN/CNT composite fibers were spun from dimethylformamide solutions containing different types of CNTs. The effect of nanotube addition to the fiber precursor on the resulting mechanical properties is discussed. In this study, we examined the relationship of the rheological properties of PAN spinning solutions containing various types of CNTs and the tensile strength of the resulting PAN fibers. The presence of CNTs in the PAN spinning solution enhanced its deformability during the drawing stage. This effect resulted in a higher tensile strength in the fibers containing nanotubes, as compared to the pure fibers. The use of a three‐stage drawing process resulted in a significant increase in the tensile strength of PAN fibers modified with multiwalled nanotubes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of polypropylene blends with excellent low‐temperature toughness and balanced toughness‐rigidity by a combination of EPR and SEEPS

To overcome serious rigidity depression of rubber‐toughened plastics and fabricate a rigidity‐toughness balanced thermoplastic, a combination of styrene‐[ethylene‐(ethylene‐propylene)]‐styrene block copolymer (SEEPS) and ethylene‐propylene rubber (EPR) was used to toughen polypropylene. The dynamic mechanical properties, crystallization and melting behavior, and mechanical properties of polypropylene (PP)/EPR/SEEPS blends were studied in detail. The results show that the combination of SEEPS and EPR can achieve the tremendous improvement of low‐temperature toughness without significant strength and rigidity loss. Dynamic mechanical properties and phase morphology results demonstrate that there is a good interfacial strength and increased loss of compound rubber phase comprised of EPR component and EP domain of SEEPS. Compared with PP/EPR binary blends, although neither glass transition temperature (T_g) of the rubber phase nor T_g of PP matrix in PP/EPR/SEEPS blends decreases, the brittle‐tough transition temperature (T_bd) of PP/EPR/SEEPS blends decreases, indicating that the increased interfacial interaction between PP matrix and compound rubber phase is also an effective approach to decrease T_bd of the blends so as to improve low‐temperature toughness. The balance between rigidity and toughness of PP/EPR/SEEPS blends is ascribed to the synergistic effect of EPR and SEEPS on toughening PP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45714.     

Determination of the minimum sample size for a reliable strength measurement of talc‐filled polypropylene fibers

Accurate determination of mechanical properties plays an important role to comment on improvement in the mechanical properties of particle‐filled PP fibers. However, the existing standards are not totally suitable for reliable strength determination of particle‐filled PP fibers. In the framework of this study, microsized talc particle‐filled PP fibers were produced with different talc ratio and tensile strength measurements were performed with various gage lengths. Statistical Akaike Information Criterion analysis shows that strength distribution of talc‐filled PP fibers is best characterized by Weibull distribution function. It is reported that, the gage length has almost no influence of Weibull parameters of pure PP fibers while strong effects on Weibull parameters of talc‐filled PP fibers. It is shown that if the tensile strength of talc‐filled PP fibers is to be measured, at least 50 samples, which is more than value suggested by existing standard, should be used for a reliable determination of Weibull parameters. Therefore, the main aim of this study is to question the feasibility of minimum sample size suggested by the existing ASTM D3822 standard for reliable strength measurement of talc filled PP fibers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44083.     

Use of short isobornyl methacrylate building blocks to improve the heat and oil resistance of thermoplastic elastomers via RAFT emulsion polymerization

Triblock copolymer (TCP)‐based thermoplastic elastomers (TPEs) were designed via reversible addition–fragmentation chain‐transfer emulsion polymerization. Short isobornyl methacrylate (IM) building blocks in the two ends of molecular chain were incorporated to guarantee the mechanical properties of the TPEs at high temperature (i.e., heat resistance) because of the high glass‐transition temperature (T_g) of poly(isobornyl methacrylate) (PIM; ～180 °C). The microphase separation, tensile properties at different temperatures, dynamic mechanical properties, oil resistance, and thermal stability of the TPEs were extensively characterized. The TPEs had distinct microphase separation with a wide inter‐T_g interval (150–185 °C). The tensile strength and elongation at break of the TPEs decreased with increasing temperature from 25 to 100 °C because of the reduced interactions in the phase domain. Even so, the TPEs had a high elongation at break beyond 200% and little change in the tensile strength even at 100 °C together with a wide quasi‐platform stage between the T_g values in dynamic mechanical analysis; this indicated good heat resistance. Meanwhile, the TPEs had an enhanced oil resistance and a thermal stability higher than 300 °C. These TCP‐based TPEs with heat and oil resistance broaden the application potential in practical fields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45379.     

Effect of resin modifiers on the structural properties of epoxy resins

Thermomechanical, mechanical and fracture mechanical properties of modified epoxy resins with two different modifiers are investigated. Carboxyl‐terminated butadiene‐acrylonitrile (CTBN) is used as toughening agent and hexanediole diglycidyl ether (HDDGE) as reactive diluent. Both modifiers are admixed in contents from 0 up to 100 phr (parts per hundred resin) and exhibit flexibilizing and toughening qualities. The glass transition temperature is strongly depressed by the admixed reactive diluent, whereas the tensile modulus exhibits greater dependency on the toughening agent contents. The tensile strength and strain at break values are higher for the formulations with diluent compared to resins with toughening agent. Up to a content of 45 phr both modified systems exhibit comparable fracture toughness values. Only the toughened systems comprise increasing values for modifier amounts higher than 45 phr. For the formulation with both modifiers (toughening agent and diluent) a significantly higher toughness but a reduced glass transition temperature was obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45348.     

Effects of 4,4′‐diaminodiphenyl ether on the structures and properties of isocyanate‐based polyimide foams

A series of thermal insulation, acoustic absorption isocyanate‐based lightweight polyimide (PI) foams with 4,4′‐diaminodiphenyl ether (ODA) units were prepared from polyaryl polymethylene isocyanate (PAPI) and the esterification solution derived from pyromellitic dianhydride (PMDA) and ODA. The structures and properties of the PI foams prepared with different molar ratio of ODA/PMDA were investigated in detail. The results show that the ODA units have great influence on the foam properties. With the increase of the ODA units, the density decreases firstly and then increases. When the molar ratio of ODA/PMDA is 3/10, the foam reaches the minimum density (13.7 kg/m³). Moreover, with increasing the ODA units, the acoustic absorption properties increase firstly and then decrease owing to the variation of the average cell diameter of the PI foams. All PI foams show excellent thermal stability, and the 5% and 10% weight loss temperature are in the range of 250–270 °C and 295–310 °C, respectively. In addition, the PI foams present low thermal conductivity and thermal diffusivity. Furthermore, the mechanical property was also evaluated and the compressive strength of the PI foams is in the range of 33.0–45.7 kPa. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46029.     

Processing–morphology–property relationships of polypropylene–graphene nanoplatelets nanocomposites

Polypropylene (PP) nanocomposites reinforced with graphene nanoplatelets (GNPs) were prepared via melt extrusion. A special sheet die containing with two shunt plates was designed. The relationships among the flow field of the special die, exfoliation, and dispersion morphology of the GNPs in PP and the macroscopic properties of the nanocomposites were analyzed. Flow field simulation results show that the die with shunt plates provided a high shear stress, high pressure, and high velocity. The differential scanning calorimetry, X‐ray scattering, and electron microscopy results reveal that the nanocomposites prepared by the die with the shunt plates had higher crystallinity values and higher exfoliation degrees of GNPs. The orientation of the GNPs parallel with the extrusion direction was also observed. The nanocomposites prepared by the die with shunt plates showed a higher electrical volume conductivity, thermal conductivity, and tensile properties. This indicated that the high shear stress exfoliated the GNPs effectively to a thinner layer and then enhanced the electrical, thermal, and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44486.     

Preparation and characterization of high‐performance poly(ether ether ketone) fibers with improved spinnability based on thermotropic liquid crystalline poly(aryl ether ketone) copolymer

High‐performance poly(ether ether ketone) (PEEK) fibers were prepared by melt‐spinning in the presence of thermotropic liquid crystalline poly(aryl ether ketone) copolymer (FPAEKLCP). The rheological and mechanical properties, birefringence, orientation, and crystallization of the resulting PEEK/FPAEKLCP fibers were characterized by using a melt flow indexer, capillary rheometer, single fiber electronic tensile strength tester, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD), respectively. The results indicate that the melt viscosity of PEEK significantly reduced by introducing FPAEKLCP, followed by the improvements in the spinnability and the quality of as‐spun fibers. The tensile properties of PEEK/FPAEKLCP fibers mainly depend on the content of FPAEKLCP, drawing temperature, drawing ratio, and annealing processes. Moreover, the tensile strength and modulus of PEEK/FPAEKLCP fibers are obviously higher than those of neat PEEK fibers under the same processing conditions. This should be attributed to an enhancement in the orientation and crystallization of PEEK compounded with FPAEKLCP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1406‐1414, 2013