Surface Porosity of Lignin/PP Blend Carbon Fibers

Abstract

The surface porosities of carbon fibers derived from the polymer blend fibers of hardwood kraft lignin, HKL and polypropylene, PP, were discussed using thermal analyses, FTIR, and nitrogen adsorption. HKL/PP carbon fibers were prepared by two‐step thermal processing, thermostabilization, and carbonization. During the thermostabilization process, pores are created by oxidative degradation of the PP component. After thermostabilization some crystalline and highly oxidized PP components remained in the blend fiber. These residual PP components were subsequently pyrolyzed during carbonization, and effectively created a porous structure in the resulting carbon fibers. N₂ adsorption tests of the porous carbon fibers revealed the same type of adsorption/desorption isotherms as for activated carbon fiber. The internal surface area of the HKL/PP = 62.5/37.5 carbon fibers was calculated to be 499 m² g^?1. This value was lower than that for commercial activated carbon, 745 m² g^?1. However, these porous lignin‐based carbon fibers were not activated carbon fibers, which could be relatively easily done through steam activation. Thus, the HKL/PP blend carbon fibers appear to be promising precursors for activated carbon fibers.     

Influence of pulp bleaching and compatibilizer selection on performance of pulp fiber reinforced PLA biocomposites

This article focuses on the effect of pulp bleaching and emerging commercial compatibilizers on physical performance of pulp fiber reinforced poly(lactic acid) (PLA) biocomposites. Industrially bleached and unbleached hardwood kraft pulp fibers are treated with several additive types, and compounded with PLA to fiber content of 30 wt %. After injection molding, the produced biocomposites are evaluated by their mechanical performance and fiber–matrix adhesion. For selected materials, fiber surface and fiber properties are reflected to composite performance by analyzing the compositions, dimensions, and lignin coverage of original fibers, as well as fiber dispersion and dimensions after melt processing. As a conclusion, unbleached kraft pulp fibers provide significant improvement in physical properties of PLA/pulp fiber composites. Of the screened compatibilizers, epoxidated linseed oil has a clear positive effect on performance when bleached kraft pulp fibers are used. The improvements correspond to enhanced fiber–matrix adhesion and differences in remaining fiber length distributions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47955.     

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.     

Kraft lignin/poly(ethylene oxide) blends: Effect of lignin structure on miscibility and hydrogen bonding

Blends of poly(ethylene oxide) (PEO) with softwood kraft lignin (SKL) were prepared by thermal blending. The miscibility behavior and hydrogen bonding of the blends were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The experimental results indicate that PEO was miscible with SKL, as shown by the existence of a single glass‐transition temperature over the entire composition range by DSC. In addition, a negative polymer–polymer interaction energy density was calculated on the basis of the melting point depression of PEO. The formation of strong intermolecular hydrogen bonding was detected by FTIR analysis. A comparison of the results obtained for the SKL/PEO blend system with those previously observed for a hardwood kraft lignin/PEO system revealed the existence of stronger hydrogen bonding within the SKL/PEO blends but weaker overall intermolecular interactions between components; this suggested that more than just hydrogen bonding was involved in the determination of the blend behavior in the kraft lignin/PEO blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1437–1444, 2005     

Characterization of soda hardwood lignin and the formation of lignin fibers by melt spinning

Lignin fibers were developed from a commercial available soda hardwood lignin (SHL) with a melt‐spinning approach. SHL showed spinnability to form the fine fibers when poly(ethylene oxide) was used as a plasticizer with lignin. The thermal properties of lignin provided valuable information to assist the processing steps of the lignin fiber formation. The guaiacyl/syringyl ratio in SHL was determined by ³¹P‐NMR because it had great influence on the thermal mobility of lignin. A suitable temperature profile for the melt spinning was predicted through rheological studies of lignin. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

熔纺Kraft硬木木质素基活性炭纤维的活化工艺及性能研究

以熔融纺丝制备的Kraft硬木木质素纤维(HKL)为原料,经炭化得到木质素基炭纤维(HKL-CF),再采用水蒸气活化法制备了活性炭纤维(HKL-ACF),通过红外光谱仪和扫描电镜研究了水蒸气活化对活性炭纤维化学结构和表面形貌的影响,采用全自动物理吸附仪、X射线衍射仪和拉曼光谱仪等研究了活化时间、活化温度和活化水蒸气流量对所制备活性炭纤维的比表面积、孔结构和微晶结构的影响规律。研究表明,水蒸气活化处理提高了活性炭纤维中的C—O和C＝C结构含量;随着活化时间的延长,活性炭纤维的比表面积增大,且随活化温度和水蒸气流量的提高呈现出先增大后减小的趋势;晶粒尺寸随着活化时间和温度的提高,逐渐变小,纤维表面的石墨化程度随活化时间的增加,逐渐变大;活化温度800 ℃,活化时间4 h,水蒸气流量1 mL/min下制备的活性炭纤维的BET比表面积最高可达2 081.34 m²/g,总孔容最大为1.60 cm³/g。     

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.     

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.     

Novel applications of lignin in composite materials

Some exploratory work was done to look at novel applications, such as filler use and comonomers, for lignin in thermosetting unsaturated polyesters and vinyl esters. The solubility of different lignins (pine kraft, hardwood, ethoxylated, and maleinated) was determined in different resin systems (acrylated epoxidized soybean oil, hydroxylated soybean oil, soy oil monoglyceride, and a commercial vinyl ester) to give an idea of the compatibility of lignin with the resin systems that were used. Further, the use of lignin as a filler was studied. An increase in the glass‐transition temperature was noticed, and the modulus at 20°C decreased because of the plasticizing effect of lignin. The lignin was modified to improve its effect on the matrix properties by adding double bond functionality, thus making it possible to incorporate the lignin molecule in the resin through free‐radical polymerization. Modified lignin was introduced in several resins by a reaction with maleic anhydride and epoxidized soybean oil and was tested for its effect on the solubility, glass‐transition temperature, and modulus. This modification improved the solubility of lignin in styrene‐containing resins, as well as the chemical incorporation of lignin in the resin. Moreover, lignin was used to treat the surfaces of natural hemp fibers to utilize lignin's natural affinity for cellulosic fibers. The idea was to cure the surface defects on the natural fibers and increase the bonding strength between the resin and fiber. An optimum improvement was noticed that depended on the amount of lignin covering the fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 323–331, 2002     

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).

     

Mechanical characterization and application of Weibull statistics to the strength of softwood lignin‐based carbon fibers

Mechanical characterization of the first generation of softwood kraft lignin‐based carbon fibers (CF) was carried out. The single‐fiber tensile tests of filaments with different diameters and length were performed to evaluate stiffness and strength of carbon fibers. The average mechanical properties were measured as follows: tensile strength of approximately 300 MPa, the elastic modulus of 30 GPa and a strain at failure within interval of 0.7–1.2%. The fiber strength data was evaluated by the two‐parameter Weibull statistics and parameters of this distribution were obtained. Although strength of the produced fibers is still significantly lower than that of commercially available, the experimental results and predictions based on Weibull statistics show a fairly good fit. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3689–3697, 2013     

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.     

Lignin‐based carbon fibers: Accelerated stabilization of lignin fibers in the presence of hydrogen chloride

Organosolv switchgrass lignin (SGL) and hardwood lignin (HWL) polymers are used as precursors to prepare low cost carbon fibers (CFs). Lignin powder and fiber samples are stabilized and carbonized at different conditions to investigate the effect of HCl on thermal‐oxidative stabilization time, mass yield, fiber diameter, and mechanical properties. The results show that HCl can accelerate stabilization and reduce the stabilization time from many hours to 75 min for the SGL fibers, and to 35 min for the HWL fiber. The rate of rapid stabilization in HCl/air is at least four times faster than conventional stabilization in air. The CFs prepared with two different stabilization methods have almost the same strength and modulus, but higher carbon yield is obtained with the rapid stabilization due to a short time of oxidation. Pores and defects observed on the surface and the cross‐section of the CFs across all stabilization conditions contribute to low fiber strength. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45507.     

On the characterization and spinning of an organic‐purified lignin toward the manufacture of low‐cost carbon fiber

A Kraft hardwood lignin (HWL) and an organic‐purified hardwood lignin (HWL‐OP) were evaluated as potential precursors for the production of low‐cost carbon fibers. It was found that the unpurified HWL exhibited poor spinnability while the HWL‐OP exhibited excellent spinnability characteristics. Fibers of various diameters were obtained from the HWL‐OP. Thermostabilization studies showed that oxidative stabilization can only be used to convert HWL‐OP‐based fibers into carbon fibers if extremely low heating rates are applied. Carbonized lignin‐based fibers had tensile strength of 0.51 GPa and tensile modulus of 28.6 GPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Cold-setting wood adhesives from kraft hardwood lignin

The model compound used in this study, for hardwood kraft lignin, 3,5-dimethoxy-4-hydroxyphenyl ethane, was successfully hydroxymethylated at the position meta to the aromatic hydroxy group. The consequent expectation that kraft hardwood lignin syringyl units can, under optimum conditions, also be hydroxymethylated to a substantial extent was confirmed in the present work and made it possible to cross-link the kraft hardwood lignin to yield polymeric products that could be used as adhesives. © 1994 John Wiley & Sons, Inc.     

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.     

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.     

Preparation of nanostructured porous carbon composite fibers from ferrum alginate fibers

Nano‐microstructured porous carbon composite fibers (Fe₂O₃@C/FeO@C/Fe@C) were synthesized by the thermal decomposition of ferrum alginate fibers. The ferrum alginate fiber precursors were prepared by wet spinning, and calcined at 300–1000°C in high purity nitrogen. The resulting composite fibers consist of carbon coated Fe₂O₃/FeO/Fe nanoparticles and porous carbon fibers. All the prepared nanostructures were investigated using thermal gravimetry, X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, transmission electron microscope (TEM), and nitrogen adsorption–desorption isotherm. The results show that there are five stages in the decomposition process of the ferrum alginate fibers. Transitions between the five stages are affected by the decomposition temperature. XRD results show that maghemite (Fe₂O₃), wüstite (FeO), martensite (Fe) nanoparticles were formed at 300–500°C, 600–700°C, 800–1000°C, respectively. Scanning electron microscopy and TEM results indicate that the composite fibers consist of nanoparticles and porous carbon. The diameter of the nanosized particles increased from 100 to 500 nm with increasing reaction temperature. The nitrogen adsorption–desorption results also show that the composite fibers have a micro‐ and mesoporous structure. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Identifying breach mechanism during air-gap spinning of lignin–cellulose ionic-liquid solutions

To be able to produce highly oriented and strong fibers from polymer solutions, a high elongational rate during the fiber-forming process is necessary. In the air-gap spinning process, a high elongational rate is realized by employing a high draw ratio, the ratio between take-up and extrusion velocity. Air-gap spinning of lignin–cellulose ionic-liquid solutions renders fibers that are promising to use as carbon fiber precursors. To further improve their mechanical properties, the polymer orientation should be maximized. However, achieving high draw ratios is limited by spinning instabilities that occur at high elongational rates. The aim of this experimental study is to understand the link between solution properties and the critical draw ratio during air-gap spinning. A maximum critical draw ratio with respect to temperature is found. Two mechanisms that limit the critical draw ratio are proposed, cohesive breach and draw resonance, the latter identified from high-speed videos. The two mechanisms clearly correlate with different temperature regions. The results from this work are not only of value for future work within the studied system but also for the design of air-gap spinning processes in general. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47800.