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.     

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     

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.     

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     

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.     

Fiber formation and properties of polyester/lignin blends

Thermotropic liquid crystalline polyesters with varied chemical structure are synthesized by melt transesterification polycondensation. They are employed as matrix for blends with lignin materials to obtain melt-spinnable precursors for carbon fibers. The lignin samples are carefully purified by fractionation, enzymatic removal of reducing sugars, and subsequent modification of the terminal OH groups. Effective melt blending is achieved with liquid-crystalline aromatic–aliphatic polyesters having melting ranges that match the softening temperature of the lignin fractions, which is necessary to prevent thermal decomposition of the lignin. Polyester/lignin blends are partially compatibilized, phase-separated materials. The polyester/lignin materials are melt-spun successfully. The fiber properties depend on the lignin purification process. X-ray scattering reveals that orientation in lignin-containing fibers is maintained. First experiments show that the fibers can be converted successfully to carbon fibers by thermal annealing procedures. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48257.     

Carbon Fibers Prepared from Melt Spun Peracylated Softwood Lignin: an Integrated Approach

Different softwood lignin O‐acyl derivatives, i.e., methacrylated, hexanoylated, benzoylated, methoxybenzoylated, and cinnamoylated lignin are synthesized and subjected to melt spinning. In the presence of spinning aids such as vanillin and ethylene glycol dimethacrylate, multifilament melt spinning is accomplished with spinning speeds up to 500 m min⁻¹, which allowed for realizing uniform precursor fibers 17 μm in diameter. Out of all acyl‐derivatives of softwood lignin investigated, cinnamoylated softwood lignin (CL) turned out to be superior in terms of processability. CL‐derived precursor fibers are oxidatively thermostabilized and then carbonized applying carbonization temperatures up to 2200 °C. Carbon fiber structure formation is followed in detail by wide‐angle X‐ray scattering and Raman spectroscopy. An orientation ≤53% and a d ₀₀₂ spacing of 0.353 nm is achieved. According to small angle X‐ray scattering, carbon fibers have a porosity of ≈38%. CL‐derived carbon fibers are also characterized in terms of mechanical properties. Tensile strengths up to 0.93 GPa (average 0.75 GPa) are obtained and follow Weibull statistics. Elastic moduli are ≤66.5 GPa (average 41.1 GPa).

     

Controlling lignin particle size for polymer blend applications

Softwood lignin produced by the LignoForce System^TM was physically processed using different milling approaches to ascertain effective and scalable means to yield micro to submicron particles of controllable and uniform size. Our work suggests that wet ball‐milling using a small milling medium is the most reliable method in terms of processing efficiency and particle‐size controllability. Controllable particle size reduction would permit lignin to be used as an effective filler in polymer blends. We show that wet‐milled lignin could, subsequently, be oven‐ or spray‐dried, and, subsequently, blended with, for instance, polypropylene (PP) through co‐extrusion. The spray‐drying method produced spherical lignin aggregates smaller and more uniform than oven‐dried ones. As a consequence, spray‐dried lignin demonstrated a more uniform distribution within the polymer melt, leading to noticeable improvement in the strain—or flexibility—of the lignin‐PP polymer blends. Furthermore, it is confirmed that the investigated drying methods had no effect on the thermal stability of the resulting lignin‐PP blends. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44669.     

Electrospinning of aqueous lignin/poly(ethylene oxide) complexes

Microfibers of kraft lignin blended with poly(ethylene oxide) (PEO) were produced by electrospinning of the solution of lignin and high molecular weight poly(ethylene oxide) (PEO) in alkaline water. Interactions between lignin and PEO in alkaline aqueous solutions create association complexes, which increases the viscosity of the solution. The effect of polymer concentration, PEO molecular weight, and storage time of solution before spinning on the morphology of the fibers was studied. It showed that after one day the viscosity dropped and fiber diameter decreased. Results from the solutions in alkaline water and N,N‐dimethylformamide (DMF) with different polymer concentrations were compared. The 7 wt % of (Lignin/PEO: 95/5 wt/wt) in alkaline aqueous solution was successfully spun and the ratio of PEO in lignin/PEO mixture could be further reduced. In comparison, higher concentrations were needed to prepare a spinning solution in DMF and fiber diameters were in a much smaller range. The final target of spinning lignin is to produce carbonized fibers. Fibers spun from aqueous solutions had lower PEO content, which is a big advantage for the carbonization process as it reduces the challenges regarding melting of the fibers or void creation during carbonization. Furthermore, the larger diameter of these fibers inhibits disintegration of the carbonized fibers, which happens due to the mass loss during the process. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41260.     

NMR a critical tool to study the production of carbon fiber from lignin

The structural changes occurring to hardwood Alcell™ lignin as a result of fiber devolatilization/extrusion, oxidative thermo-stabilization and carbonization are investigated in this study by solid-state and solution nuclear magnetic resonance (NMR) spectroscopy techniques. Solution based ¹H–¹³C correlation NMR of the un-spun Alcell™ lignin powder and extruded lignin fiber detected modest changes occurring due to fiber devolatilization/extrusion in the type and proportion of aliphatic side-chain carbons or monolignol inter-unit linkages. Molecular weight analysis by gel permeation chromatography (GPC), along with an additional ³¹P NMR method used to indicate changes in terminal hydroxyl functionality, suggest fiber devolatilization/extrusion causes both chain scission and condensation reactions. ¹H CRAMPS (combined rotation and multiple-pulse spectroscopy) and ¹³C cross-polarization/magic angle spinning (CP/MAS) spectra of extruded and stabilized lignin fibers indicate stabilization severely reduces the proportion of methoxy groups present, while also increasing the relative proportion of carbonyl and carboxyl-related structures, typically associated with cross-linking chemistries. ¹³C direct-polarization/magic angle spinning (DP/MAS) analysis of stabilized and carbonized fibers shows an increased relative amount of carbon–carbon bonds on aryl structures and a relative decrease of aryl ethers. DP/MAS dipolar dephasing experiments suggest that a majority of non-protonated carbons convert from carbonyl to aryl and condensed aryl structures during carbonization.     

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.     

Thermal properties and chemical changes in blend melt spinning of cellulose acetate butyrate and a novel cationic dyeable copolyester

A novel cationic dyeable copolyester (MCDP) containing purified terephthalate acid (PTA), ethylene glycol (EG), 2‐methyl‐1,3‐propanediol (MPD), and sodium‐5‐sulfo‐isophthalate (SIP) was synthesized via direct esterification method. The chemical structure of modified cationic dyeable polyester (MCPD) was confirmed by FTIR and ¹H‐NMR. The thermal properties of MCDP and cellulose acetate butyrate (CAB) blends with different blend ratios were investigated by DSC. The results revealed that MCDP and CAB were immiscible polymer blends, and the glass transition temperature of CAB in blend fibers was higher than that of CAB in blend chips because of the strengthening hydrogen bonding. The chemical changes of MCDP and CAB in blend melt spinning were analyzed. It was found that the thermal hydrolysis reaction of ester side groups of CAB occurred in blend melt spinning, which resulted in that the acid gas was produced and the hydroxyl group content of CAB was increased. Furthermore, the moisture absorption of blend fibers was improved about three times than pure MCDP fiber even after washing 30 times. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Melt‐spun polylactic acid fibers: Effect of cellulose nanowhiskers on processing and properties

Bio‐based continuous fibers were processed from polylactic acid (PLA) and cellulose nanowhiskers (CNWs) by melt spinning. Melt compounding of master batches of PLA with 10 wt % CNWs and pure PLA was carried out using a twin‐screw extruder in which compounded pellets containing 1 and 3 wt % of CNWs were generated for subsequent melt spinning. The microscopy studies showed that the fiber diameters were in the range of 90‐95 µm, and an increased surface roughness and aggregations in the fibers containing CNWs could be detected. The addition of the CNWs restricted the drawability of the fibers to a factor of 2 and did not affect the fiber stiffness or strength, but resulted in a significantly lower strain and slightly increased crystallinity. Furthermore, CNWs increased the thermal stability, creep resistance and reduction in thermal shrinkage of PLA fibers, possibly indicating a restriction of the polymer chain mobility due to the nanoscale additives. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of the addition of lubricant on the properties of poly(ether ether ketone) fibers

A high‐temperature lubricant genioplast pellets (GPPS) was used in order to improve the processing behavior of poly(ether ether ketone) (PEEK) resin and high‐performance PEEK fibers were produced by melt‐spinning. The rheological properties of spinning material, morphology, mechanical, and thermal properties of PEEK fibers were characterized by using a polymer capillary rheometer, scanning electron microscopy, single fiber electronic tensile strength tester, wide‐angle X‐ray diffraction and thermal gravimetric analyzer, respectively. The results indicated that the introduction of lubricant GPPS decreased the melting viscosity of PEEK resin and improved spinnability of PEEK resin without sacrificing its thermal properties. The filaments are cylindrical with smooth surface and uniform diameter. The optimized content of GPPS was determined to be 1.0 wt% by balancing the decreased torque and changes of the mechanical properties. The strength and modulus of PEEK fibers were 420 MPa and 3.6 GPa, respectively. This should be due to the improvement in spinnability, followed by the enhancements in the orientation and crystallization of PEEK fibers in the process of drawing and annealing. POLYM. ENG. SCI., 53:2254–2260, 2013. © 2013 Society of Plastics Engineers     

Structure and properties of thermotropic liquid crystal polymer and poly(ethylene 2,6‐naphthalate) blend fibers

BACKGROUND: The melt blending of thermotropic liquid crystal polymers (TLCPs) using conventional thermoplastics has attracted much attention due to the improved strength and tensile modulus of the resulting polymer composites. Moreover, because of their low melt viscosity, the addition of small amounts of TLCPs can reduce the melt viscosity of polymer blends, thereby enhancing the processability. RESULTS: In this study, TLCP/poly(ethylene 2,6‐naphthalate) (PEN) blend fibers were prepared by melt blending and melt spinning to improve fiber performance and processability. The relation between the structure and the mechanical properties of TLCP/PEN blend fibers and the effect of annealing on these properties were also investigated. The mechanical properties of the blend fibers were improved by increasing the spinning speed and by adding TLCP. These properties of the blend fibers were also improved by annealing. The tensile strength of TLCP5/PEN spun at a spinning speed of 2.0 km h^?1 and annealed at 235 °C for 2 h was about three times higher than that of TLCP5/PEN spun at a spinning speed of 0.5 km h^?1. The double melting behavior observed in the annealed fibers depended on the annealing temperature and time. CONCLUSION: The improvement of the mechanical properties of the blend fibers with spinning speed, by adding TLCP and by annealing was attributed to an increase in crystallite size, an increase in the degree of crystallinity and an improvement in crystal perfection. The double melting behavior was influenced by the distribution in lamella thickness that occurred because of a melt‐reorganization process during differential scanning calorimetry scans. Copyright © 2007 Society of Chemical Industry     

Effect of lignin particles as a nucleating agent on crystallization of poly(3‐hydroxybutyrate)

The effect of lignin fine powder, as a new kind of nucleating agent, on the crystallization process of poly(3‐hydroxybutyrate) (PHB) was studied. The kinetics of both isothermal and nonisothermal crystallization processes from the melt for both pure PHB and PHB/lignin blend was studied by means of differential scanning calorimetry. Lignin shortened the crystallization half‐time t_1/2 for isothermal crystallization. The activation energy ΔE for PHB/lignin and pure PHB in the isothermal crystallization process was ?237.40 and ?131.22 kJ/mol, respectively, clearly indicating that the crystallization of the PHB/lignin blend was more favorable than that of pure PHB from a thermodynamic perspective. At the same time, according to polarized optical microscopy, the rate of spherulitic growth from the melt increased with the addition of lignin, which is ascribed to the reduction of surface fold energy σ_e, that is, σ_e is 59.2 × 10^?3 and 41.6 × 10^?3 J m^?2 for pure PHB and PHB/lignin, respectively. Polarized optical microscopy also showed that the spherulites found in PHB with lignin were smaller in size and greater in number than those found in pure PHB. The wide‐angle X‐ray diffraction indicated that an addition of lignin caused no change in the crystal structure and degree of crystallinity. These results indicated that lignin is a good nucleating agent for the crystallization of PHB. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2466–2474, 2004     

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.     

Influence of amorphous alkaline lignin on the crystallization behavior and thermal properties of bacterial polyester

Bacterial polyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and alkaline lignin composites were prepared via melt processing method, and the influence of amorphous lignin on the crystallization behavior and thermal properties of PHBV were investigated. It was found that dual melting peaks appeared in DSC curves of PHBV/lignin composites, while only one single peak existed in PHBV. The non‐isothermal crystallization process analyzed by Jeziorny method suggested that lignin changed the nucleation mode of composites and hindered the crystallization rate of PHBV. Data calculated from the results of WAXD demonstrated that lignin did not change the basic crystal structure of PHBV, but decreased the average size of the lamellar stacks. POM results confirmed that the effect of lignin on the crystallization behavior of PHBV carried out in two opposite way, namely the enhanced effect of nucleation and the hindered effect of growth. Besides, the thermal stability of composites was also decreased significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41325.     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005