Potential of producing carbon fiber from biorefinery corn stover lignin with high ash content

The possibility of producing carbon fiber from an industrial corn stover lignin was investigated in the present study. As‐received, high‐ash containing lignin was subjected to methanol fractionation, acetylation, and thermal treatment prior to melt spinning and the changes in physiochemical and thermal properties were evaluated. Methanol fractionation removed most of the impurities in the raw lignin and also selectively removed the molecules with high melting points. However, neither methanol fractionation nor thermal treatment rendered melt‐spinnable precursors. The precursors were highly viscous and decomposed easily at low temperatures, attributed to the presence of H, G phenolic units, and abundant hydroxycinnamate groups in herbaceous lignin. A two‐step acetylation of methanol fractionated lignin greatly improved the mobility of lignin, while enhancing the thermal stability of the precursor during melt‐spinning. Fourier Transform Infrared and 2D‐NMR analysis showed that the contents of phenolic and aliphatic hydroxyls, as well as the hydroxycinnamates, decreased in the acetylated precursors. The optimum precursor was a partially acetylated lignin with a glass transition temperature of 85 °C. Upon oxidative stabilization and carbonization, the carbon fibers with an average tensile strength of 454 MPa and modulus of 62 GPa were obtained. The Raman spectroscopy showed the I_D/I_G ratio of the carbon fiber was 2.53. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45736.     

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.     

Bio-renewable precursor fibers from lignin/polylactide blends for conversion to carbon fibers

Lignin, a highly aromatic biopolymer extracted as a coproduct of wood pulping, was investigated as a suitable precursor for carbon fibers. Lignin was chemically modified and blended with poly(lactic acid) (PLA) biopolymer before melt spinning into lignin fibers. The chemical modification of raw lignin involved butyration to form ester functional groups in place of polar hydroxyl (–OH) groups, which enhanced the miscibility of lignin with PLA. Fine fibers were extracted and spooled continuously from lignin/PLA blends with an overall lignin concentration of 75 wt.%. The influence of chemical modification and physical blending of lignin with PLA on the resulting fiber was studied by analyzing the microstructure of the fibers using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The influence of blend composition on the phase behavior was studied by differential scanning calorimetry (DSC). The effect of composition on the mechanical properties was studied by tensile tests of the lignin/PLA blend fibers. The thermal stability and carbon yield of the blended fibers with different concentrations of lignin were characterized by thermogravimetric analysis (TGA). The microstructure analysis of carbon fibers produced from lignin/PLA blends revealed composition dependent microporous structures inside the fine fibers.     

A new softening agent for melt spinning of softwood kraft lignin

Kraft lignin obtained from the pulping of wood is an interesting new precursor material for carbon fiber production because of its high carbon content and ready availability. However, continuous spinning of softwood kraft lignin (SKL) has been impossible because of its insufficient softening characteristics and neat hardwood kraft lignin (HKL) has required extensive pretreatments to enable fiber formation. Softwood kraft lignin permeate (SKLP) and hardwood kraft lignin permeate (HKLP), fractionated by membrane filtration, were continuously melt spun into fibers. To improve the spinnability of SKL and HKL, HKLP was added as a softening agent. SKL‐ and HKL‐based fibers were obtained by adding 3–98 wt % HKLP. A suitable temperature range for spinning was 20–85°C above the T_g of the lignin samples, and this range gave a flawless appearance according to the SEM analysis. Smooth, homogeneous fibers of SKLP, HKLP, and SKL with HKLP were successfully processed into solid carbon fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Rheological and thermal properties of blends of modified poly(ethylene terephthalate) with p‐acetoxybenzoic acid and poly(butylene terephthalate)

Blending of thermotropic liquid crystalline polyesters (LCPs) with conventional polymers could result in materials that can be used as an alternative for short fiber‐reinforced thermoplastic composites, because of their low melt viscosity as well as their inherent high stiffness and strength, high use temperature, and excellent chemical resistance and low coefficient of expansion. In most of the blends was used LCP of 40 mol % of poly(ethylene terephthalate) (PET) and 60 mol % of p‐acetoxybenzoic acid (PABA). In this work, blends of several copolyesters having various PABA compositions from 10 to 70 mol % and poly(butylene terephthalate) (PBT) were prepared and their rheological and thermal properties were investigated. For convenience, the copolyesters were designated as PETA‐x, where x is the mol % of PABA. It was found that PET‐60 and PET‐70 copolyesters decreased the melt viscosity of PBT in the blends and those PBT/PETA‐60 and PBT/PETA‐70 blends showed different melt viscosity behaviors with the change in shear rate, while blends of PBT and PET‐x having less than 50 mol % of PABA exhibited totally different rheological behaviors. The blends of PBT with PETA‐50, PETA‐60, and PETA‐70 showed the morphology of multiple layers of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1797–1806, 1999     

High-performance poly(vinylidene fluoride)-polyamide 11/lithium niobate nanocomposites for the applications in air filtration

To overcome the fiber-spinning problem of poly(vinylidene fluoride) (PVDF) because of its high melt viscosity and rapid crystallization, polyamide 11 (PA11) with excellent melt spinning capability and good electret properties is incorporated to prepare blends by melt mixing. Their crystal structure, morphology, electrical polarization properties, and melt spinning performance are systematically characterized by various techniques. It is found that the incorporation of PA11 reduces the crystallinity of PVDF, increases its thermally stimulated discharge current, and reduces its viscosity. Therefore, the blends show much better melt spinning capability. For such blends, the addition of outstanding inorganic electret materials, lithium niobate (LiNbO₃, LN) nanoparticles is found to further improve the materials’ electret properties. Such a strategy is proved to be successful in melt spinning PVDF electrets into fine fibers, which is beneficial to their applications in air filtration and other related fields. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48957.     

Sustainable Polymers from Renewable Resources: Polymer Blends of Furan‐Based Polyesters

A series of blends of furan‐based green polyesters, for eco‐friendly packaging materials, are synthesized. Poly(ethylene 2,5‐furandicarboxylate) (PEF), poly(propylene 2,5‐furandicarboxylate) (PPF), and poly(butylene 2,5‐furandicarboxylate) (PBF) are synthesized by applying melt polycondensation. Blends of the above polyesters with 50/50 w/w composition as well as blends of furanoate/terephthalate (PPF/PPT) are also prepared. The glass temperature along with the crystallization and melting behaviors of melt quenched blends are studied aiming at understanding their dynamic state and miscibility. Based on their T_g and crystallization behavior, PEF/PPF shows dynamic homogeneity and miscibility whereas PPF/PBF and PEF/PBF exhibit partial miscibility and immiscibility, respectively. In an effort to dynamically homogenize the compounds, reactive blending is applied and the behavior of the resulting blends is monitored following quenching. A profound improvement in blend homogenization is observed with increasing melt mixing time for the PPF/PPT sample, evidenced by the single glass temperature and by the narrowing in liquid‐to‐glass regime. The obtained single glass temperature together with the suppressed tendency for crystallization with increasing mixing time are taken as evidences of dynamic and thermodynamic homogeneity.     

Thermal treatment of pyrolytic lignin and polyethylene terephthalate toward carbon fiber production

In this work, pyrolytic lignin (PL) was thermally co-treated with polyethylene terephthalate (PET) to produce carbon fiber precursor. The produced PL-PET precursors were thoroughly characterized and analyzed, and then being processed into carbon fiber. It was found that a novel precursor, rather than their physical blending, was formed by the thermal co-treatment, indicating there were strong interactions between PL and PET. The novel PL-PET precursors had enhanced thermal properties and rheological characteristics, therefore are more suitable for processing into better carbon fibers based on melt-spinning method. In this study, the precursor fibers derived from the co-treatment of PL and 5% PET were also stretched under tension during stabilization step to reduce the fiber diameter and improve molecular orientation. The resulting carbon fibers with an average diameter of 12.6 μm had the tensile strength of up to 1220 MPa. This work demonstrated that PET could be used to improve the processability and quality of lignin-based carbon fiber when it is chemically bonded with lignin-based precursor. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48843.     

Thermal behavior and morphological characteristics of cationic dyeable poly(ethylene terephthalate) (CD‐PET)/metallocene isotactic polypropylene (m‐iPP) conjugated fibers

Cationic dyeable poly(ethylene terephthalate) (CD‐PET) and metallocene isotactic polypropylene (m‐iPP) polymers were extruded (in the proportions of 75/25, 50/50, 25/75) from two melt twin‐screw extruders to prepare CD‐PET/m‐iPP (and m‐iPP/CD‐PET)‐conjugated fibers of the island‐in‐sea type. This study investigated the thermal behavior and mechanical and morphological characteristics of the conjugated fibers using DSC, TGA, WAXD, melting viscosity rheometer, density indicator, tenacity measurement, and a polarizing microscope. Melting behavior of CD‐PET/m‐iPP polyblended polymers exhibited negative‐deviation blends (NDB) and the 50/50 blend showed a minimum value of the melt viscosity. Experimental results of the DSC indicated CD‐PET and m‐iPP molecules formed a partial miscible system. The tenacity of CD‐PET/m‐iPP‐conjugated fibers decreased initially and then increased as the m‐iPP content increased. Crystallinities and densities of CD‐PET/m‐iPP‐conjugated fibers presented a linear relation with the blend ratio. On the morphological observation, it was revealed that the blends were in a dispersed phase structure. In this study, the CD‐PET microfibers were successfully produced with enhanced diameters (from 2.2 to 2.5 μm). Additionally, m‐iPP colored fibers (m‐iPP fibers covered with CD‐PET polymer) were also successfully prepared. Meanwhile, the presence of PP‐graft‐MA compatibilizer improved the tenacity considerably. Blends with 10 wt % compatibilizer exhibited maximum improvement in the tenacity for m‐iPP colored fibers. The dye exhaustions of various fabrics followed the order: m‐iPP colored fibers > conventional CD‐PET fibers > CD‐PET microfibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5396–5405, 2006     

Agricultural residue-derived lignin as the filler of polylactic acid composites and the effect of lignin purity on the composite performance

In this study, corn stover lignin with different purities was used as filler in polylactic acid (PLA) matrix. It was found that the impurity metals present in unpurified lignin can significantly affect the performance of the composites in terms of their thermal stability, rheological behavior, mechanical properties, and hydrophobicity. Among the PLA composites, the ones fabricated with the lignin containing 4% of impurities overall had the best thermal stability and tensile strength. From melt rheology analysis, it was also found that the presence of the impurity metals decreases the complex viscosity of the composites. It is suggested that the impurity metals acted as catalysts to promote the interaction between lignin and PLA, resulting in an improved compatibility between PLA and the filler. In the present study, mechanical properties and hydrophobicity of the composites were further improved by acetylating the lignin with the optimum content of impurities. Tensile strength of the composite with the acetylated lignin was comparable to that of pure PLA, whereas the modulus increased to as high as 2.75 GPa. Overall, the study showed that unpurified lignin could be used as filler to achieve similar or better performance than the composites made with highly purified lignin fillers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47915.     

Rheological behavior and morphological and interfacial properties of PLA/TPE blends

Rheological and interfacial tension data were employed to predict the morphology and thermal and mechanical properties of noncompatibilized and compatibilized poly(lactic acid) (PLA)/thermoplastic elastomer (TPE) blends. PLA was melt blended with thermoplastic polyurethane (TPU) and ethylene elastomer (EE) and compatibilized by ethylene–butyl acrylate–glycidyl methacrylate (EBG) in an internal mixer chamber. Both TPU and EE TPEs have higher viscosities than PLA, and the interfacial properties evaluated have revealed better adhesion between domains of PLA–TPU. The efficiency of the compatibilizer agent EBG depended on the TPE type inferred by modifications in the scanning electron microscopy images of PLA/TPE blends and by the Izod impact strength (improved by 23%). The EBG was more effective in the PLA/TPU blend. The TPEs and EBG did not affect the PLA thermal stability, and no thermal event was observed in the usual PLA extrusion and injection temperature range. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47962.     

Miscibility and properties of completely biodegradable blends of poly(propylene carbonate) and poly(butylene succinate)

Completely biodegradable blends of poly (propylene carbonate) (PPC) and poly(butylene succinate) (PBS) were melt‐prepared and then compression‐molded. The miscibilities of the two aliphatic polyesters, that is, PPC and PBS, were investigated by dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The static mechanical properties, thermal behaviors, crystalline behavior, and melt flowability of the blends were also studied. Static tensile tests showed that the yield strength and the strength at break increased remarkably up to 30.7 and 46.3 MPa, respectively, with the incorporation of PBS. The good ductility of the blends was maintained in view of the large elongation at break. SEM observation revealed a two‐phase structure with good interfacial adhesion. The immiscibility of the two components was verified by the two independent glass‐transition temperatures obtained from DMA tests. Moreover, thermogravimetric measurements indicated that the thermal decomposition temperatures (T_?5% and T_?10%) of the PPC/PBS blends increased dramatically by 30–60°C when compared with PPC matrix. The melt flow indices of the blends showed that the introduction of PBS improved the melt flowability of the blends. The blending of PPC with PBS provided a practical way to develop completely biodegradable blends with applicable comprehensive properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of nanofillers as reinforcement agents for lignin composite fibers

Biobased nanocomposites and composite fibers were prepared from organosolv lignin/organoclay mixtures by mechanical mixing and subsequent melt intercalation. Two organically‐modified montmorillonite (MMT) clays with different ammonium cations were used. The effect of organoclay varying from 1 to 10 wt % on the mechanical and thermal properties of the nanocomposites was studied. Thermal analysis revealed an increased in T_g for the nanocomposites as compared with the original organosolv lignin. For both organoclays, lignin intercalation into the silicate layers was observed using X‐ray diffraction (XRD). The intercalated hybrids exhibited a substantial increase in tensile strength and melt processability. In the case of organoclay Cloisite 30B, X‐ray analysis indicates the possibility of complete exfoliation at 1 wt % organoclay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation on structure and characteristics of alpaca-based wet-spun polyacrylonitrile composite fibers by utilizing natural textile waste

The composite alpaca/acrylic fibers were auspiciously produced through a wet spinning technique to reduce the consumption of petroleum-based polyacrylonitrile (PAN) and to enhance the thermal stability and moisture properties of the fibers. The waste alpaca fibers were converted into powder using a mechanical milling method without applying any chemicals. Alpaca powders were then blended with the PAN dope solution in different weight ratios of alpaca: PAN (10:90, 20:80, and 30:70) to wet spin the composite fibers. The Fourier transform infrared spectroscopy showed that all the composite fibers possess the functional groups of both alpaca and PAN. The nuclear magnetic resonance spectroscopy confirmed the presence of typical carbonyl carbon (CO) and nitrile carbon (C≡N) peaks of protein and PAN, respectively. The differential scanning calorimetry and thermogravimetric analysis revealed the enhanced thermal stability of alpaca/PAN composite fibers. The moisture properties of the composite fibers were subsequently found to increase with the incorporation of alpaca, more than three times that of pure PAN fibers. These results revealed a potential green pathway to producing composite acrylic fibers with improved thermal and moisture properties by applying textile waste materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48370.     

Chemical modification of unsaturated polyesters influence of polyester's structure on thermal and viscoelastic properties of low styrene content copolymers

In this study, the chemical modification of unsaturated polyesters and the influence of polyester's structure on thermal and viscoelastic properties have been presented. The structure of unsaturated polyesters obtained in polycondensation of cyclohex‐4‐ene‐1,2‐dicarboxylic anhydride (THPA), maleic anhydride and only one suitable symmetrical glycol: ethylene glycol or 1,4‐butanediol (BDO) or 1,6‐hexanediol has been modified by peracetic acid. The selective oxidation of unsaturated polyesters conducted in mild time and temperature conditions was a successful and effective method to prepare new materials/unsaturated epoxy polyesters/containing epoxy groups in cycloaliphatic rings and carbon–carbon double bonds in polyester chain. The unsaturated epoxy polyesters were capable of both copolymerization with vinyl monomer and polyaddition reactions with suitable curing agent. Therefore, they were successfully used as a component of low styrene content copolymers. As was confirmed by DSC, DMA, and TGA analyses, polyester's structure had significant influence on thermal and viscoelastic properties of styrene copolymers. The properties of styrene copolymers prepared from unsaturated epoxy polyesters were considerably better compared with those obtained for styrene copolymers from unsaturated polyesters.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Alfa fiber/polypropylene composites: Influence of fiber extraction method and chemical treatments

Alfa fiber/polypropylene composites were manufactured using twin-screw extrusion. Fibers were extracted using alkaline and steam explosion methods. Three chemical treatments were also applied to the alkaline-extracted fibers: stearic acid (SA), and potassium permanganate dissolved in water (KW) and in acetone (KA). Finally, thermal annealing was applied to the composites. The results indicate that composites with steam-exploded fibers had a significantly higher melt flow index than composites with alkaline-extracted fibers. Moreover, the incorporation of fibers into the matrix increased the Young's modulus, where the optimum results were obtained utilizing the alkaline-extracted fibers. Both extraction methods also significantly decreased the water uptake, especially the steam explosion. The three chemical treatments increased the melt flow index and conversely decreased the tensile strength and Young's modulus. In addition, KW treatment decreased the water uptake. Finally, thermal annealing increased the tensile strength and Young's modulus of composites with SA-treated fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47392.     

Preparation of PBT/POE-g-GMA/PP ternary blends with good rigidity–toughness balance by core–shell particles

Compared with poly(butylene terephthalate)/glycidyl methacrylate grafted poly(ethylene–octene) (PBT/POE-g-GMA) binary blends, supertough PBT-based ternary blends with little rigidity loss were successfully obtained by adding rigid polypropylene (PP) into PBT/POE-g-GMA blends to construct core–shell particles during melt blending. The effects of PP content and type on the phase morphology and mechanical properties of the blends were systematically investigated. Theoretical predictions and scanning electron microscopy observation showed that a core–shell structure was formed in PBT matrix with PP as the core and POE-g-GMA as the shell. The mechanical property tests showed that POE-g-GMA and PP had significant synergistic toughening effect. When PP with high melt flow index (H-PP) was used, PBT/POE-g-GMA/H-PP (70/15/15) blends possessed the highest Izod notched impact strength, which was 1.9-fold compared with PBT/POE-g-GMA (70/30) binary blends, while the tensile performance loss was little. The essential work of fracture tests was performed to evaluate the fracture resistance of different samples. The results demonstrated that PBT/POE-g-GMA/PP ternary blends possessed much better resistance to crack propagation than PBT/POE-g-GMA binary blends. The decrease of interparticle distance and the fibrillation of core–shell particles activated intense matrix shear yielding, which was the reason for the high crack resistance of ternary blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48872.     

Study of the Processing and Mechanical Properties of In Situ Composite Materials of Thermoplastics with Thermotropic Liquid Crystalline Polymers

By blending thermoplastics (TPs)—polycarbonate (PC) and polyethersulfone (PES)—with thermotropic liquid crystalline polymers (TLCPs)—KU9221 and KU9231—and then extruding the blends to form fibers, the in situ reinforcing characteristics were studied. The injection experiment of blends was compared with the extrusion experiment. According to the experimental results, in situ reinforcing characteristics of these processes were analyzed theoretically. These researches have come to some important conclusions. TLCP domains can be transformed to form fibers that are oriented in the direction of flow during processing; these TLCP microfibers result in improved mechanical properties of the TP/TLCP blends. The extruding flow is more effective in orienting TLCP domains and results in better in situ reinforcement than that of injection molding, and the extruded fibers have better mechanical properties. The mechanical properties of the blend fibers are improved greatly with increasing tensile ratio of melt drawing and the content of TLCPs.     

Shell–core structured carbon fibers via melt spinning of petroleum- and wood-processing waste blends

In the last decades, carbon fibers with light weight and high strength have experienced the largely increased uses in various industrial applications. However, their expected uses in the automotive industry and building are largely limited because of their high production cost. Herein, we have demonstrated an effective method of making low cost carbon fibers via the melt spinning of petroleum-processing residue (pyrolyzed fuel oil, PFO)/lignin blends. Careful selection of tetrahydrofuran as the solvent to dissolve both PFO and lignin was made to optimize the miscible blend. The melt spinnable blend with a softening point of 260–280 °C exhibited good spinning ability at 280 °C. The plasticizing function of PFO allowed the highly cross linked lignin-based pitch to have high fluidity in the melt spinning process. Based on detailed TEM observations, the thermally treated fiber prepared at 2800 °C exhibited a shell–core structure, consisting of a highly crystalline surface from PFO and an amorphous disordered core from lignin. Such a crystalline surface structure gave rise to a high modulus value (up to 100 GPa) to the prepared carbon fibers.