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.     

Enhanced Thermal Stability and Electrochemical Performance of Polyacrylonitrile/Cellulose Acetate-Electrospun Fiber Membrane by Boehmite Nanoparticles: Application to High-Performance Lithium-Ion Batteries

In this study, polyacrylonitrile/cellulose acetate (PAN/CA) composite nanofiber membranes with different boehmite contents are prepared by electrospinning. The physical and electrochemical properties of the composite nanofiber membrane as a separator in lithium batteries are investigated. In contrast to commercial polypropylene membrane (PP), the nanocomposite fiber membrane has a 3D network structure, higher porosity, higher thermal stability, higher electrolyte absorptivity, higher ionic conductivity, and better cycling performance. The PAN/CA composite membrane with 12 wt% boehmite has the highest ionic conductivity (1.694 mS cm⁻¹); the specific discharge capacity is 160 mAh g⁻¹ at 0.2 C discharge density and the highest capacity retention rate is 99.3% after 100 cycles. The cycle rate at 2 C has a higher capacity retention rate (88.75%). These results indicate that the PAN/CA/AlOOH composite nanofiber membrane can be expected to replace the commercial polyolefin membrane and behave as a high-performance separator for lithium-ion batteries.     

Impact of lignin extraction methods on microstructure and mechanical properties of lignin‐based carbon fibers

In order to optimize the use of residues of enzymatic hydrolysis of corn stalk (REHCS) and explore the low‐cost and sustainable raw material substitute for carbon fibers, three types of lignin samples were extracted from REHCS by various extraction methods, and then they were converted into carbon fibers (CFs) by electrospinning, thermostabilization, and carbonization under the same process conditions. The microstructure and mechanical properties of the three types of carbonized fibers were different. The CFs from the ethanol organosolv lignin were actually smooth and brittle carbon films. The CFs from the formic acid/acetic acid organosolv lignin had microscopic pores, causing poor mechanical properties. Comparatively, the CFs from the alkaline lignin demonstrated preferable microstructure and mechanical properties. The reasons for the differences were analyzed by characterizing the lignin samples, precursor fibers, and resultant CFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45580.     

Potassium persulfate-mediated preparation of conducting polypyrrole/polyacrylonitrile composite fibers: Humidity and temperature-sensing properties

Conducting polypyrrole (PPy)/polyacrylonitrile (PAN) composite fibers were prepared by the polymerization of pyrrole in the presence of PAN fibers with potassium persulfate in an acidic aqueous solution. We obtained composite fibers containing concentrations of PPy as high as 1.14% and having surface resistivities as low as 0.6 kΩ/cm² by changing the polymerization parameters, including the temperature and concentrations of pyrrole and oxidant. The tensile strength of 10.02 N/m² and breaking elongation of 32.68% for the pure PAN fiber increased up to 10.45 N/m² and 33.23%, respectively, for the composite fiber containing 0.13% PPy. The change in the resistivity of the PPy/PAN composite fiber during heating–cooling cycles in the temperature range of +5 to 120°C was examined. Scanning electron microscopy and optical microscopy images of the composite fibers showed that the PPy coating was restricted to the surfaces of the PAN fibers. Surface resistivity measurements, Fourier transform infrared spectroscopy, and thermogravimetric analysis techniques were also used to characterize the composite fibers. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Development of multiwalled‐carbon‐nanotube‐welded carbon fibers and evaluation of the interfacial strength in epoxy composites

Multiwalled carbon nanotube (MWCNT)‐welded carbon fibers (CFs) were prepared by a three‐step process, which included polyacrylonitrile (PAN) coating, MWCNT absorption, and heat treatment. The structure of these materials was characterized by scanning electron microscopy, Fourier‐transform infrared spectroscopy, and Raman spectroscopy. The MWCNTs were uniformly assembled on the surface of the PAN‐coated CFs and welded by a PAN‐based carbon layer after heat treatment. The contact angle of the MWCNT‐welded CFs in the epoxy resins was 41.70°; this was 22.35% smaller than that of the unsized CFs. The interfacial shear strength (IFSS) of the MWCNT‐welded CF–epoxy composite was 83.15 MPa; this was 28.89% higher than that of the unsized CF–epoxy composite. The increase in the IFSS was attributed to the enhancement of adhesions between the CFs and polymer matrix through the welding of the MWCNTs on the CFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45027.     

Continuous and rapid stabilization of polyacrylonitrile fiber bundles assisted by atmospheric pressure plasma for fabricating large-tow carbon fibers

A bundle of carbon fibers (CFs) with 24,000 filaments was prepared using atmospheric pressure plasma and heat simultaneously for only 30 min, followed by the carbonization process. Conventional thermal stabilization process takes more than few hours to prevent the ignition of the polyacrylonitrile (PAN) fiber when large-tow PAN fibers are stabilized. The CFs produced using the plasma stabilization process had a tensile strength as high as 2.6 GPa. This strength level, which is slightly higher than that of CFs stabilized by the conventional process for 120 min, satisfies the demands in automobile applications. It is believed that the plasma-based stabilization process provides a potential solution not only for shortening the process time but also for providing continuous stabilization of large-tow carbon fibers.     

Comparison about the structure and properties of PAN‐based activated carbon hollow fibers pretreated with different compounds containing phosphorus

Polyacrylonitrile (PAN) hollow fibers were pretreated with five different compounds containing phosphorus, including ammonium dibasic phosphate, ammonium dihydrogen phosphate, triammonium phosphate, phosphoric acid, and metaphosphoric acid, and then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of different compounds containing phosphorus as pretreating agents on the properties and structure of the resultant oxidized hollow fibers, carbon hollow fibers, and activated carbon hollow fibers are discussed. Comparing the Brunaner‐Emmett‐Teller (BET) surface area of PAN‐activated carbon hollow fibers (ACHF) pretreated with five different compounds, ammonium dibasic phosphate > triammonium phosphate > ammonium dihydrogen phosphate > phosphoric acid > metaphosphoric acid, and the surface area of mesopores in PAN‐ACHF pretreated with ammonium dibasic phosphate reaches maximum, 174 m² g^?1. The adsorption ratio to mesomolecule adsorbate, VB₁₂, of PAN‐ACHF pretreated with ammonium dibasic phosphate also reaches maximum, 97.7 wt %. Moreover, the dominant pore sizes of PAN‐ACHF range from 2 to 5 nm in diameter. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 294–300, 2005     

The effects of carbonization temperature on the properties and structure of PAN‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate and then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of carbonization temperature of PAN hollow fiber precursor on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based carbon hollow fiber (PAN‐CHF) and PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the surface area of the PAN‐ACHF increased very remarkably, reaching 900 m² g^?1 when carbonization is 1000°C, and the adsorption ratios to creatinine and VB₁₂ of ACHF were much higher than those of CHF, especially to VB₁₂. The different adsorption ratios to two adsorbates including creatinine and VB₁₂ reflect the number of micropores and mesopores in PAN‐ACHF. The dominant pore sizes of mesopores in PAN‐ACHF are from 2 to 5 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2155–2160, 2005     

Rheology of polyacrylonitrile‐based precursor polymers produced from controlled (RAFT) and conventional polymerization: Its role in solution spinning

Polymer solutions in dimethyl sulfoxide (DMSO) as a solvent, made from reversible addition fragmentation chain transfer (RAFT)‐mediated polyacrylonitrile (RAFT^¥ PAN) terpolymer with molecular weight (MW) of 260,000 g/mol and dispersity (Ð) of 1.29, behave differently under applied shear stress than polymer solutions made from conventional PAN (Control PAN) with similar MW (258,000 g/mol) but Ð of 2.05 in the same solvent. The unique rheology of RAFT PAN is because of the reduced amount of high MW polymer fractions. Specifically, a 25% (w/v) polymer solution of RAFT PAN had a viscosity of 198 Pas while the equivalent control PAN polymer solution had a viscosity of 968 Pas at a shear rate of 1 s^?1. Also, RAFT PAN polymer solutions had a longer Newtonian plateau than control PAN polymer solutions. This exhibits more liquid character in RAFT PAN polymer solutions than control PAN polymer solutions at same temperature and concentration. In dynamic tests, RAFT PAN polymer solutions gelled slower than their equivalent control PAN polymer solutions because of their longer polymer chain relaxation times. Slow gelling and higher liquid character in RAFT PAN polymer solutions can result in obtaining stronger and finer precursor fibers during wet spinning. Since RAFT PAN polymer solutions exhibit low viscosity and higher liquid character when compared to its equivalent control PAN at same concentration and temperature, these can allow a wider working window for wet spinning and can also allow higher solid content in the polymer solutions that remain easy to wet spin. This is expected to lead to compact and finer fibers with less voids and higher strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44273.     

Effects of ammonium dibasic phosphate pretreatment time on the structure and properties of PAN‐based activated carbon hollow fibers

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate aqueous solution, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of pretreatment time of PAN hollow fibers in ammonium dibasic phosphate aqueous solution on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the Brunaner–Emmett–Teller (BET) surface area of the PAN‐ACHF and surface area of mesopores in the PAN‐ACHF increases and reaches 513 m² g^?1 and 66 m² g^?1 respectively, when the dipping time of PAN hollow fibers in ammonium dibasic phosphate aqueous solution is 30 min. The adsorptions to creatinine and VB₁₂ of PAN‐ACHF are much high, reach 95% and 86% respectively, when dipping time is 30 min. The dominant pore sizes of mesopores in PAN‐ACHF range from 2 nm to 5 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2448–2453, 2006     

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.     

Electrospinning of polyacrylonitrile nanofibers

Polyacrylonitrile (PAN) was electrospun in dimethylformamide as a function of electric field, solution flow rate, and polymer concentration (C). The fiber diameter increased with C and ranged from 30 nm to 3.0 μm. The fiber diameter increased with the flow rate and decreased when the electric field was increased by a change in the working distance; however, it did not change significantly when the electric field was varied by a change in the voltage at a given working distance. The fibers below about 350 nm diameter contained beads, whereas above this diameter, bead‐free fibers were obtained. For PAN with a molecular weight of 100,000 g/mol, the fiber diameter scaled as C^1.2 and C^7.5 at low (5.1–16.1 wt %) and high (17.5–22.1 wt %) C values, respectively. Both concentrations were in the semidilute entangled regime, where the specific viscosity scaled as C^4.4, consistent with De Gennes's scaling concepts. In the semidilute unentangled regime (0.5–3.1 wt %), where the viscosity scaled as C^1.3, microscopic or nanoscopic particles rather than fibers were obtained. Concentration‐ dependent electrospinning studies were also carried out for higher molecular weight PAN (250,000 and 700,00 g/mol). The results of these studies are also presented and discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1023–1029, 2006     

PIN/PAN聚合物基电解质膜的制备及性能

利用静电纺丝技术制备了聚吲哚/聚丙烯腈(PIN/PAN)聚合物基电解质膜,代替纸基铝空气电池中的纤维素纸(C-P),并应用于固态铝空气电池。探究了PIN含量对电解质膜离子电导率及吸液率的影响。采用SEM和FTIR对PIN/PAN聚合物基电解质膜表面形貌及化学组成进行分析。借助电化学工作站和电池测试系统,分析了电解质膜离子电导率及固态铝空气电池放电特性。结果表明,采用PIN/PAN聚合物基电解质膜可有效提升固态铝空气电池性能,在3 mA.cm_^-2、5 mA.cm_^-2、7 mA.cm_^-2电流密度下,放电时长比纸基铝空气电池分别提升了21%、27%、34%,且放电时长与电解质膜的吸液率及离子电导率相关。其中4%PIN/PAN聚合物基电解质膜离子电导率可达6.7×10_^-4 S.cm_^-1,同时对碱性溶液具有良好的吸附能力,吸液率最高可达496%,为纤维素纸的3.2倍。     

Efficient preparation of carbon fibers using plasma assisted stabilization

Carbon fibers (CFs) were prepared by the plasma-assisted stabilization (PAS) of polyacronitrile (PAN) fibers. PAS was found to be an efficient treatment for stabilizing the precursor fibers in terms of the time, cost and mechanical properties compared to conventional thermal stabilization (CTS). The efficient stabilization of PAN by a radio-frequency capacitive plasma discharge was confirmed using FT-IR and DSC. The tensile strength and modulus of CFs from PAS were superior to those of CFs from CTS. These results suggest that PAS is an efficient treatment for the manufacture of CFs, which can save time and energy.     

Effect of spinning conditions on the structure and properties of PAN fibers containing nano‐hydroxyapatite

Spinning conditions for nano‐hydroxyapatite‐containing precursor polyacrylonitrile (PAN) fibers have been developed and their effects on the structure and properties of nanocomposite PAN fibers have been assessed. The precursor PAN fibers prepared under the developed conditions are characterized by high strength, with their total pore content being at a level of 0.25 cm³/g. After carbonization, these fibers are designed for use as implants that support and stimulate the process of bone reconstruction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2881–2888, 2006     

Preparation of ultra-thin PAN-based activated carbon fibers with physical activation

This study elucidates the stabilization and activation in forming activated carbon fibers (ACFs) from ultra-thin polyacrylonitrile (PAN) fibers. The effect of stabilization time on the properties and structure of resultant stabilized fibers was investigated by thermal analysis, X-ray diffraction (XRD), elemental analysis, and scanning electron microscopy (SEM). Stabilization was optimized by the pyrolysis of ultra-thin PAN fibers in air atmosphere at 280°C for 15 min, and subsequent activation in steam at 1000°C for 0.75 to 15 min. Resultant ACFs were characterized by N₂ adsorption at 77 K to evaluate pore parameters, XRD to evaluate structure parameters, and field emission scanning electron microscopy (FESEM) to elucidate surface morphology. The produced ACFs had surface areas of 668–1408 m²/g and a micropore volume to total pore volume ratio from 78 to 88%. Experimental results demonstrate the surface area and micropore volume of 1408 m²/g and 0.687 cm³/g, respectively, following activation at 1000°C for 10 min. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The production of submicron diameter carbon fibers by the electrospinning of lignin

Lignin fibers with and without platinum were synthesized in a single step by electrospinning of lignin/ethanol/platinum acetyl acetonate and lignin/ethanol solutions, respectively. The fibers obtained were stabilized in air at low temperature to avoid fiber fusion during the subsequent carbonization process. The effect of the carbonization temperature (600-1000 °C) on surface chemistry, morphology, textural properties, and oxidation resistance of the final carbon fibers was studied. The carbonization process decreased the oxygen content of the fibers, increasing the carbon and surface platinum proportion and producing a well developed microporous structure. Carbon fibers with and without platinum with apparent surface areas of 1178 and 1195 m²/g, respectively, and micropore volumes of around 0.52 cm³/g were obtained. The diameter of the carbon fibers obtained is in the range of 400 nm to 1 μm. Carbon fibers with surface platinum of 0.6% in weight were obtained. The carbon fibers with and without platinum showed high oxidation resistance despite their highly developed porous structure.     

Raman spectra and staging of intercalated graphite fibers

Raman spectra of graphite fibers intercalated with K, Rb and Cs are reported. X-Ray diffraction is used to characterize the fibers with respect to staging. We report results mainly for GY70, a highly graphitic commercially available fiber, which is polyacrylonitrile (PAN) based, and some results on UC4104B, a pitch-based fiber. These two fibers have different structures; ideally the GY70 consists of graphite layers parallel to the fiber surface, while UC4104B has graphite planes perpendicular to the surface. X-Ray diffraction, using the Debye-Scherrer method, shows that these fibers stage, though compounds of mixed stages are generally obtained. Our Raman results, which are sensitive to the staging within an optical skin depth, show for the alakli metal donor-intercalated fibers the 560 cm_?1 line characteristic of stage 1 compounds, the E_2g2 bounding layer mode characteristic of stage 2, as well as the interior and bounding layer splitting of the E_2g2 mode, observed in high stage intercalated graphite. In addition, a Raman line near 1355 cm^?1 is observed, characteristic of less ordered graphites.     

Investigation of polyacrylonitrile solution inhomogeneity by dynamic light scattering

Dynamic light scattering (DLS) has been used to quantify nanoscale heterogeneity in the industrially significant polyacrylonitrile (PAN) polymer solution. The heterogeneity in polymer solution, traced by the ratio of amplitudes of the slow to fast mode, is observed to be related to various parameters, such as molecular weight of the polymer, the type of co‐monomer, processing time, concentration of the solution, and the choice of the solvents. It has been identified that low molecular weight PAN homopolymer have the least heterogeneity issues. Amongst the chosen co‐polymers for this study, similar degree of heterogeneity was observed at concentration slightly above the critical concentration at which the polymer chains begin to overlap. Whereas, at higher concentration, PAN‐methacrylic acid (4 wt%) copolymer showed the least heterogeneity issue. The aggregate diffusion coefficient of PAN‐methacrylic acid (4 wt%) copolymer solution in dimethylformamide (DMF) and N,N‐dimethylacetamide (DMAc) are respectively determined to be ～1.6 × 10^?12 cm²/s and ～1.6 × 10^?13 cm²/s, which results in an estimated aggregate size of 9 nm and 90 nm. POLYM. ENG. SCI., 55:1403–1407, 2015. © 2015 Society of Plastics Engineers     

Graft polymerization of acrylonitrile onto wheat straw

Acrylonitrile was graft polymerized onto ground, water-washed wheat straw using Fe²⁺-H₂O₂ as initiator. Reaction conditions were selected to minimize homopolymer formation and maximize the amount of polyacrylonitrile (PAN) grafted to straw. Polymerizations typically yielded straw-g-PAN containing 30–35% PAN. A two-step fractionation scheme was developed for determining the relative amounts of PAN grafted to cellulose, hemicellulose, and lignin. This scheme involved (1) delignification of straw-g-PAN with sodium chlorite followed by removal of lignin-grafted PAN by extraction with dimethylformamide (DMF), and (2) hydrolysis of the hemicellulose component with 1 N trifluoroacetic acid followed by DMF extraction of hemicellulose-grafted PAN. Product remaining after these two treatments was assumed to be cellulose-g-PAN. When relative amounts of PAN grafted to cellulose, hemicellulose, and lignin were compared with relative percentages of these components present in wheat straw, the percentage of total PAN grafted to lignin was less than its relative percentage in straw, whereas that grafted to hemicellulose was considerably more. Although the use of Ce⁴⁺ as initiator gave little or no polymer with whole, water-washed straw, grafted polymerization occurred when delignified straw was used as substrate. Relative amounts of PAN grafted to cellulose and hemicellulose were not greatly different from those observed with Fe²⁺-H₂O₂ initiation onto whole straw.