Recent advances in low‐cost carbon fiber manufacture from lignin

The confluence of two US energy policy mandates, the 2012 Corporate Average Fuel Economy Standards and Renewable Fuels Standard #2, provide the opportunity to examine the possibility of high‐value materials from lignin with increased depth. In this case, the desire to provide lighter, low‐cost materials for automobiles to reduce fuel consumption, and to improve the economics of biorefineries for fuel production, have led to an increased interest in low‐cost carbon fiber manufacture from lignin. For this review the authors provide the context of subject matter importance, a cost comparison of potential low‐cost carbon fibers, a brief review of historical work, a review of more recent work, and a limited technical discussion followed by recommendations for future directions. As the available material for review is limited, the author includes many references to publicly available government documents and reviewed proceedings that are generally difficult to locate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 713‐728, 2013     

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.     

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.     

Biodegradable baked foam made with chayotextle starch mixed with plantain flour and wood fiber

New renewable materials are needed to reduce petroleum‐based plastic packaging. The effect of plantain flour (PF) and wood fiber (WF) on the properties of starch‐based foams (SBFs) were investigated. The SBFs were characterized using physical, thermal, and mechanical methods to better understand the relationship between PF and WF concentration. Contact angle values showed that the addition of WF or PF increased the hydrophobic character of the SBFs. Also, the addition of PF increased the heat transfer resistance and density of the foams, while their solubility decreased. The values of tensile strength and Young's modulus increased with increasing concentrations of PF in the SBFs. However, the addition of PF and WF promoted a decrease on the elongation at break of the SBFs. An increase in concentration of PF also showed a decrease in water vapor permeability, and an increase in the thickness of the cell wall layer of the SBFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45565.     

Development of lignin carbon fibers: Evaluation of the carbonization process

The use of lignin as a renewable resource for the production of less‐expensive carbon fibers has in recent years attracted great interest. In order to develop the strength properties, the stabilization and carbonization processes have to be optimized. For this reason, the process parameters during carbonization have here been studied on stabilized lignin fibers in the temperature interval from 300 to 1300 °C. The effects of temperature, heating rate, and straining of fibers during carbonization on the strength properties of carbon fibers were investigated. The heating rate, in the range from 1 to 40 °C/min, was shown to have no effect on the property development of the fibers. During carbonization with no load applied to the fibers, a shrinkage of 20% was noted. Counteracting the shrinkage by imposing a load on the fibers during the carbonization resulted in fibers with a greater stiffness. The tensile strength was not, however, affected by this loading. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43965.     

Investigation of eco-friendly chemical treatments of apple pomace for producing high quality molded pulp biocomposite

Eco-friendly chemical treatments using citric acid (CA) and sodium bicarbonate were employed to remove pectin, hemicellulose, and extractives from apple pomace (AP) for improving AP fiber quality and maximizing its utilization in producing biocomposite boards with newspaper (NP) fibers (AP:NP ratio of 2:1) using molded pulp technique. CA treatment was further optimized at different pH and temperature and cellulose nanofiber (CNF, 0.15, 0.3% w/w pulp solids) was used as reinforcement agent to enhance mechanical property and water resistance of biocomposite boards. CA treatment improved AP fiber strength and cellulose content. AP treated by CA at pH 2.5 and 75°C with 0.15% CNF reinforcement produced AP/NP biocomposite board with high flexural strength, and dimension stability, and low density. Thermal analysis verified increased cellulose content, crystallinity, and thermal stability of CA treated AP fibers. This study provided new insight to improve fiber functionality and utilize AP for developing sustainable packaging.     

Ecofriendly modification of acetosolv lignin from oil palm biomass for improvement of PMMA thermo‐oxidative properties

The environmentally friendly esterification of acetosolv lignin (AL), obtained from pressed oil palm mesocarp fibers, is described, for the improvement of thermo‐oxidative properties of poly(methyl methacrylate) (PMMA) films. Acetylation of AL was performed in ecofriendly conditions using acetic anhydride in the absence of catalysts. Acetylated acetosolv lignin (AAL) was successfully obtained in only 12 min with a solvent‐free and catalyst‐free microwave‐assisted procedure. Lignins were characterized by Fourier transform infrared spectroscopy, size exclusion chromatography, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC), confirming the efficacy of the methodology employed. AL and AAL as fillers in different concentrations (1% and 5%) were added to PMMA films. The thermal and mechanical properties of the lignin‐incorporated films were analyzed by TGA, DSC, and dynamic mechanical analysis (DMA). The films incorporated with lignin and acetylated lignin presented initial degradation temperature (T_onset) and onset oxidative temperature (OOT) values higher than pure PMMA films, contributing thus to an enhancement of thermo‐oxidative stability of PMMA. The DMA analyses showed that incorporation of AL or AAL increased the storage modulus (E′) of PMMA films, but did not affect their glass‐transition temperatures (T_g). The results indicate the potential use of oil palm mesocarp lignin to enhance the thermo‐oxidative properties of PMMA without compromising its mechanical response. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45498.     

Comparative characterization of degraded lignin polymer from the organosolv fractionation process with various catalysts and alcohols

Triploid poplar was fractionated using mild organosolv process, and detailed characteristic elucidation of the lignin obtained was performed to determine the effects of various chemicals (sodium hydroxide, triethylamine, and formic acid) and solvents (methanol, ethanol, n‐propanol, and n‐butanol). Both nondestructive techniques (e.g., NMR technology) and degradation methods (e.g., alkaline nitrobenzene oxidation) were performed to comparatively evaluate the structural degradation of lignin molecules. The addition of acidic and basic catalysts improved the purity of lignin by acid hydrolysis and the cleavage of the ester groups and other types of lignin–carbohydrate interactions formed by polyoses and lignin under the basic conditions. A certain amount of aryl alkyl ether linkages (β‐O‐4) was cleaved during the fractionation process, whereas other carbon–carbon linkages were resistant to degradation. The formation of new carbon–carbon bonds led to the lignin fraction with obviously higher molecular weight and thermal stability, resulting from the induced carbon cation under the acidic condition. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39673.     

Mechanical and thermal characterization of compression moulded polylactic acid natural fiber composites reinforced with hemp and lyocell fibers

This research evaluates the effects of PLA/PP blend ratio and Lyocell/hemp mixture ratio on the morphology, water absorption, mechanical and thermal properties of PLA‐based composites. The composites were fabricated with 30 mass % hemp using compression moulding. As a reference composites made from PP were also studied. Combining of hemp and Lyocell in PLA composite leads to the reduction of moisture absorption and can improve the impact, tensile, flexural properties when compared with PLA/hemp. Composite based on the PLA/PP blend‐matrix could not improve the tensile and flexural properties compared with PLA/hemp, however; the lighter composite with better impact properties was obtained. The crystallization temperature of the PLA‐PP/hemp increased compared with pure PLA. This result was also confirmed by the SEM micrographs. The moisture absorption of PLA‐PP/hemp was higher than PLA/hemp. Based on theoretical analysis of DMTA data, there was favorable adhesion in all composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40534.     

Effect of bone ash fillers on mechanical and thermal properties of biobased epoxy nanocomposites

In this study, the fabrication and characterization of bone ash filled biobased epoxy resin (Super SAP 100/1000, contains 37% biobased carbon content) nanocomposites are presented. Biosource bone ash was modified by size reduction and surface modification processes using a combination of ball milling and sonochemical techniques and characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The modified bone ash particles were incorporated into biobased epoxy with noncontact mixing process. The as-fabricated nanocomposites were characterized using various thermal and mechanical analyses. The nanocomposites showed significant improvement in flexural strength (41.25%) and modulus (34.56%) for 2 wt% filler loading. Dynamic mechanical analysis (DMA) results showed improvement in both storage modulus and loss modulus. Additionally, DMA results showed a slight reduction in glass transition temperature which also complies with differential scanning calorimetry results. Thermomechanical analysis results showed a reduction in the coefficient of thermal expansion. Thermogravimetric analysis results showed improved thermal stability at both onset of degradation and the major degradation. These enhanced thermal and mechanical performances of the epoxy nanocomposites allows them to be suitable for lightweight aerospace, automotive, and biomedical applications.     

Synthesis and material properties of elastomeric high molecular weight polycycloacetals derived from diglycerol and meso-erythritol

Copolymerizing glutaraldehyde with tetraols such as diglycerol, meso-erythritol, and pentaerythritol is particularly effective for forming very high molecular weight polycycloacetals (M_n up to 65,000 g/mol) with elastomeric properties and up to 70% biorenewable content by weight. Altering the tetraol monomer feed ratio provides control over the polycycloacetal's tensile properties. The polymerizations are high-yielding, readily scalable, and employ commercially available starting materials that are used without further purification. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48780.     

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     

Overmolded polylactide/jute-mat eco-composites: A new method to enhance the properties of natural fiber biodegradable composites

Environmentally friendly, biodegradable composites were prepared via overmolding of poly(lactic acid) (PLA) onto PLA/jute-mat, named as “ecosheets,” reinforced continuous fiber composite sheets. Film stacking procedure was used to prepare ecosheets via using a hot-press. The fiber orientation was changed as −45°/+45° and 0°/0°. −45°/+45° orientation exhibited higher properties as compared to 0°/0° for ecosheets; therefore, this construction was used to produce overmolded composites (OMCs). The mechanical tests showed that flexural modulus and strength of OMCs were improved in comparison to neat PLA. The dynamic mechanical analysis exhibited that the thermomechanical resistance of PLA was enhanced for OMCs. Scanning electron microscopy investigation showed that the jute/PLA interphase needs to be improved to further increase the properties. It was concluded that one of the biggest advantages of this novel technique was the increase of mechanical properties of PLA without altering the density. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48692.     

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     

Study on the effect of woven sisal fiber mat on mechanical and viscoelastic properties of petroleum based epoxy and bioresin modified toughened epoxy network

Sisal fiber reinforced biocomposites are developed using both unmodified petrol based epoxy and bioresin modified epoxy as base matrix. Two bioresins, epoxidized soybean oil and epoxy methyl soyate (EMS) are used to modify the epoxy matrix for effective toughening and subsequently two layers of sisal fiber mat are incorporated to improve the mechanical and thermomechanical properties. Higher strength and modulus of the EMS modified epoxy composites reveals good interfacial bonding of matrix with the fibers. Fracture toughness parameters K_IC and G_IC are determined and found to be enhanced significantly. Notched impact strength is found to be higher for unmodified epoxy composite, whereas elongation at break is found to be much higher for modified epoxy blend. Dynamic mechanical analysis shows an improvement in the storage modulus for bioresin toughened composites on the account stiffness imparted by fibers. Loss modulus is found to be higher for EMS modified epoxy composite because of strong fiber–matrix interfacial bonding. Loss tangent curves show a strong influence of bioresin on damping behavior of epoxy composite. Strong fiber–matrix interface is found in modified epoxy composite by scanning electron microscopic analysis. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42699.     

Effect of lignin esters on improving the thermal properties of poly(vinyl chloride)

To improve the thermal stability of poly(vinyl chloride) (PVC) and the utilization of lignin (L), different L esters were added to PVC to produce the plates with enhanced thermal stabilities. The properties and structures of the L ester–PVC plates and the properties of the L esters and their mixtures with PVC were analyzed by universal mechanical testing, static thermal stability testing, thermogravimetry–Fourier transform infrared (FTIR) spectroscopy, UV–visible spectroscopy, FTIR spectroscopy, scanning electron microscopy, and differential scanning calorimetry. The results show that L improved the thermal stability of PVC, but the mechanical properties were substantially deteriorated. Proper esterification of L improved the thermal stabilities and mechanical properties of the plates. Noncyclic anhydride acetylated L–PVC plates possessed good static and dynamic thermal stabilities and mechanical properties. The PVC plates incorporated with the L esters with a degree of esterification of around 40% exhibited the best combination properties. Maleated L–PVC plates had good dynamic thermal stability and mechanical properties but poor static thermal stability. The opposite properties were found for succinylated L–PVC plates. The differences in the properties of different L ester–PVC plates were attributed to the different abilities of L esters to capture free radicals, the crosslinking reaction between L esters and PVC, and their compatibility. Different properties of the L esters indicated their different applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47176.     

Preparation and performance of nanoparticle-reinforced chitosan proton-exchange membranes for fuel-cell applications

In this study, we incorporated commercially available p-toluene sulfonic acid coated boehmite nanofillers (commercially known as OS₁) into the chitosan (CS) matrix to fabricate CS–OS₁ nanocomposite membranes with a high proton conductivity for fuel-cell applications. These nanocomposite membranes were characterized by Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction analysis, scanning electron microscopy, and thermogravimetric analysis. Their mechanical properties, water uptake, ion-exchange capacity, and proton conductivity were also determined. The results show that the incorporation of OS₁ to CS chains can inhibit the mobility of CS chains and, hence, enhance the thermal stability and mechanical properties of CS–OS₁ nanocomposite membranes. The composite membrane with 5 wt % OS₁ showed a proton conductivity of 0.032 S/cm; this was almost equal to that of commercially available Nafion 117. We concluded that CS–OS₁ nanocomposite membranes have potential for fuel-cell applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46904.     

Development and characterization of flax fiber reinforced biocomposite using flaxseed oil‐based bio‐resin

In this study, acrylated epoxidized flaxseed oil (AEFO) resin is synthesized from flaxseed oil, and flax fiber reinforced AEFO biocomposites is produced via a vacuum‐assisted resin transfer molding technique. Different amounts of flax fiber and styrene are added to the resin to improve its mechanical and physical properties. Both flax fiber and styrene improve the mechanical properties of these biocomposites, but the flexural strength decreases with an increase in styrene content. The mass increase during water absorption testing is less than 1.5% (w/w) for all of the AEFO‐based biocomposites. The density of the AEFO resin is 1.166 g/cm³, which increases to 1.191 g/cm³ when reinforced with 10% (w/w) flax fiber. The flax fiber reinforced AEFO‐based biocomposites have a maximum tensile strength of 31.4 ± 1.2 MPa and Young's modulus of 520 ± 31 MPa. These biocomposites also have a maximum flexural strength of 64.5 ± 2.3 MPa and a flexural modulus of 2.98 ± 0.12 GPa. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41807.     

Morphologies of electrospun fibers of lignin in poly(ethylene oxide)/N,N‐dimethylformamide

The effects of polyethylene oxide (PEO) molecular weight (Mv), and volume fraction ( ) on the morphology of electrospun sulfur free softwood lignin nanofibers were investigated. Small amounts of PEO were used during preparations of the solutions to aid the electrospinning process. It was found that tripling the PEO volume fraction resulted in a transition from semi‐dilute un‐entangled to semi‐dilute entangled solutions. Conversely, the solution remained in the semi‐dilute un‐entangled regime as the molecular weight was increased by five times. The effects of molecular weight and volume fraction of PEO both on entanglement density and fiber morphology were unified by scaling PEO viscosities as a function of . We investigated and discussed conditions that would produce smooth fibers and conditions that would produce fibers with beads. In the case of beads‐on‐a‐string formation, bead widths remained constant regardless of the molecular weight and concentration of PEO, but the bead length changed. Additionally, we observed a decrease in the diameter of the fibers and the dimension of beads (length and width of beads) with an increase in the electric field used for electrospinning. The aspect ratio of beads increased with increases to both the electric field and the PEO molecular weight or concentration. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44172.