Thermo-chemical reactions occurring during the oxidative stabilization of electrospun polyacrylonitrile precursor nanofibers and the resulting structural conversions

Thermo-chemical reactions occurring during the oxidative stabilization of electrospun polyacrylonitrile (PAN) precursor nanofibers with diameters of approximately 300 nm were investigated as well as the resulting structural conversions, and the results were compared to those of conventional SAF 3K (Courtaulds) precursor fibers. The study revealed that: (1) the nitrile groups in the electrospun nanofibers possessed a higher reactivity than those in the SAF 3K fibers; (2) the macromolecules in the electrospun nanofibers predominantly underwent inter-molecular cyclization/crosslinking while those in the SAF 3K fibers underwent intra-molecular cyclization during the early stages of stabilization; and (3) under the same stabilization conditions, the structural conversion from linear macromolecules to aromatic ring/ladder structures in the electrospun nanofibers occurred faster and more thoroughly than in the SAF 3K fibers. These characteristics combined with other properties, including small diameter and high degree of structural perfection, suggest that electrospun PAN precursor nanofibers may be used to develop continuous nano-scale carbon fibers with superior mechanical strength, especially if the electrospun nanofibers could be further aligned and stretched.     

Development of carbon nanofibers from aligned electrospun polyacrylonitrile nanofiber bundles and characterization of their microstructural, electrical, and mechanical properties

Carbon nanofibers with diameters of 200-300 nm were developed through stabilization and carbonization of aligned electrospun polyacrylonitrile (PAN) nanofiber bundles. Prior to the oxidative stabilization in air, the electrospun PAN nanofiber bundle was tightly wrapped onto a glass rod, so that tension existed during the stabilization. We also investigated several carbonization procedures by varying final carbonization temperatures in the range from 1000 to 2200 °C. The study revealed that: (1) with increase of the final carbonization temperature, the carbon nanofibers became more graphitic and structurally ordered; (2) the carbon nanofiber bundles possessed anisotropic electrical conductivities, and the differences between the parallel and perpendicular directions to the bundle axes were over 20 times; and (3) the tensile strengths and Young's moduli of the prepared carbon nanofiber bundles were in the ranges of 300-600 MPa and 40-60 GPa, respectively.     

Structure and thermo-chemical properties of continuous bundles of aligned and stretched electrospun polyacrylonitrile precursor nanofibers collected in a flowing water bath

Continuous bundles of aligned and stretched electrospun polyacrylonitrile (PAN) precursor nanofibers were prepared in an attempt to develop carbon nanofibers with superior strength. The bundles were prepared through collection of electrospun nanofibers with a flowing water bath followed by stretching in water at 97 °C. Their morphologies, structures, and thermo-chemical properties were characterized by SEM, XRD, and DSC. The shrinkages in boiling water and the amounts of residual solvent were also measured. The results indicated that, the nanofibers in the bundles were uniform with smooth surfaces and small variations in diameters; after stretching the bundles by 4 times, the average fiber diameter was reduced to 56%, while the crystallinity of PAN was improved by 72%. The post-spinning stretching process facilitated the stabilization of PAN, as evidenced by the shift of the cyclization reaction to a lower temperature with smaller activation energy and larger enthalpy change. In comparison with the commonly adopted nanofiber collection method of a rotating drum, the flowing water bath method results in higher degree of uni-axial alignment and more desired structures of nanofibers.     

Fabrication and characterization of carbon nanofibers with a multiple tubular porous structure via electrospinning

Carbon nanofibers with a multiple tubular porous structure were prepared via electrospinning from a polymer blend solution of polyacrylonitrile (PAN) and polylactide (PLA) followed by carbonization. The electrospun composite nanofibers underwent pre-oxidization and carbonization, which selectively eliminated PLA phases and transformed the continuous PAN phase into carbon, thereby porous structure formed in the carbon nanofibers. The morphologies of as-spun, pre-oxidized and carbonized nanofibers were studied by scanning electron microscope (SEM) and transmission electron microscopy (TEM). It was found that carbon nanofibers with an average diameter about 250 nm and a multiple tubular porous structure were obtained. The chemical changes during thermal treatment were studied by Fourier transform infrared spectrometer (FTIR), Raman spectra, differential thermal analysis (DTA) and thermogravimetric analysis (TG). The results showed that PLA phases were effectively removed and the continuous PAN phase was completely carbonized. The obtained carbon nanofibers had more disordered non-graphitized structures than non-porous nanofibers.     

Strong carbon nanofibers from electrospun polyacrylonitrile

Strong carbon nanofibers with diameters between 150 nm and 500 nm and lengths of the order of centimeters were realized from electrospun polyacrylonitrile (PAN). Their tensile strength reached a maximum at 1400 °C carbonization temperature, while the elastic modulus increased monotonically until 1700 °C. For most carbonization temperatures, both properties increased with reduced nanofiber diameter. The tensile strength and the elastic modulus, measured from individual nanofibers carbonized at 1400 °C, averaged 3.5 ± 0.6 GPa and 172 ± 40 GPa, respectively, while some nanofibers reached 2% ultimate strain and strengths over 4.5 GPa. The average tensile strength and elastic modulus of carbon nanofibers produced at 1400 °C were six and three times higher than in previous reports, respectively. These high mechanical property values were achieved for optimum electrospinning parameters yielding strong PAN nanofibers, and optimum stabilization and carbonization temperatures, which resulted in smooth carbon nanofiber surfaces and homogeneous nanofiber cross-sections, as opposed to a previously reported core–shell structure. Turbostratic carbon crystallites with average thickness increasing from 3 to 8 layers between 800 °C and 1700 °C improved the elastic modulus and the tensile strength but their large size, discontinuous form, and random orientation reduced the tensile strength at carbonization temperatures higher than 1400 °C.     

Investigation of post-spinning stretching process on morphological, structural, and mechanical properties of electrospun polyacrylonitrile copolymer nanofibers

Electrospun polyacrylonitrile (PAN) copolymer nanofibers with diameters of ∼0.3 μm were prepared as highly aligned bundles. The as-electrospun nanofiber bundles were then stretched in steam at ∼100 °C into 2, 3, and 4 times of the original lengths. Subsequently, characterizations and evaluations were carried out to understand morphological, structural, and mechanical properties using SEM, 2D WAXD, polarized FT−IR, DSC, and mechanical tester; and the results were compared to those of conventional PAN copolymer microfibers. The study revealed that: (1) the macromolecules in as-electrospun nanofibers were loosely oriented along fiber axes; although such an orientation was not high, a small extent of stretching could effectively improve the orientation and increase the crystallinity; (2) most of macromolecules in the crystalline phase of as-electrospun and stretched nanofibers possessed the zig-zag conformation instead of the helical conformation; and (3) the post-spinning stretching process could substantially improve mechanical properties of the nanofiber bundles. To the best of our knowledge, this study represented the first successful attempt to stretch electrospun nanofibers; and we envisioned that the highly aligned and stretched electrospun PAN copolymer nanofibers could be an innovative type of precursor for the development of continuous nano-scale carbon fibers with superior mechanical strength.     

Characterization on oxidative stabilization of polyacrylonitrile nanofibers prepared by electrospinning

Ultrafine polyacrylonitrile (PAN) fibers, as a precursor of carbon nanofibers, with diameters in the range of 220–760 nm were obtained by electrospinning of PAN solution using N,N-dimethyl formamide (DMF) as solvent. Morphology of the nanofibers for varying concentration and applied voltage was investigated by field emission scanning electron microscopy (FESEM). The thermal properties and structural changes during the oxidative stabilization process were primarily investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Fourier transform infrared (FT-IR) and Raman spectroscopy. The nanofiber diameters increase as the applied voltage is increased and they also increase with an increase in the concentration of the polymer solution. It was also concluded that the electrospun fibers displayed a very sharp exothermic peak at 297.34 °C. A transition temperature observed by FT-IR and Raman was approximately 300 °C, which was closely consistent with the results of DSC and TGA studies. It was also found that oxidative stabilization in air was accompanied by a change in color of nanofibers webs.     

Osteocompatibility characterization of polyacrylonitrile carbon nanofibers containing bioactive glass nanoparticles

A kind of composite carbon nanofibers (CNF) containing bioactive glass (BG) nanoparticles was produced for bone regeneration by a combination of electrospinning and sol–gel techniques. To produce the BG, compounds such as calcium nitrate, triethyl phosphate and tetraethyl orthosilicate were used as precursors and hydrolyzed to form a sol–gel solution, which was then added to a polyacrylonitrile (PAN) solution in N,N-dimethylformamide. The resulting mixture was electrospun to form PAN nanofibers containing the BG precursors. Upon oxidation and carbonization, the PAN nanofibers and BG precursors transformed into continuous CNF embedded with BG nanoparticles (CNF/BG). Through this fabrication technique, several CNF/BG composites were obtained by controlling the feeding ratios of the different precursors giving rise to BG nanoparticles with various compositions (i.e. containing 70–90 mol% of SiO₂ component). In vitro biomineralization in a simulated body fluid and co-culture with MC3T3-E1 osteoblasts studies were performed to evaluate the osteocompatibility of the CNF/BG nanoparticle composites. When compared to pure CNF, the CNF/BG composites showed an improved ability to promote the in vitro formation of apatite and MC3T3-E1 proliferation, which was found to be dependent upon the composition of BG nanoparticles.     

Electrospun polyimide nanofibers and their applications

Aromatic polyimides (PIs) are high-performance polymers with rigid heterocyclic imide rings and aromatic benzene rings in their macromolecular backbones. Owing to excellent mechanical properties and thermal stability, as well as readily adjustable molecular structures, PIs have been widely adopted for many applications related to electronics, aerospace, automobile, and other industries. In recent years, PI fibers prepared by electrospinning of polyamic acid (PAA) precursor nanofibers followed by imidization (commonly known as electrospun PI nanofibers) have attracted growing interests. Herein, the preparation, evaluation, and application of electrospun PI nanofibers are reviewed. PI polymers and the electrospinning technique are introduced first followed by the preparation of electrospun nanofibers of homo-PI, co-PI, blend-PI, and PI composite. Subsequently, the mechanical and thermal properties of electrospun PI nanofibers are presented; in particular, the mechanical properties of individual electrospun PI nanofibers are highlighted. Thereafter, various applications of electrospun PI nanofibers are outlined, including reinforcement of composites, Li-ion battery separators, fuel cell proton exchange membranes, sensors, microelectronics, high-temperature filtration media, super-hydrophobic PI nanofibers, and PI-based carbon nanofibers. In the final section of conclusions and perspectives, future research endeavors and high-value applications of electrospun PI nanofibers are discussed.     

Carbon nanonodules fewer than ten graphenes thick grown on aligned amorphous carbon nanofibers

A novel structure of carbon nanonodules containing fewer than 10 layers graphene has grown on amorphous carbon nanofibers by carbonization-induced self-assembly. It is found that a successive processes containing pre-oxidation in air at 220 °C and carbonization in a high vacuum (1 × 10⁻⁴ Pa) at 750 °C are necessary for the fabrication of the carbon nanonodules. Possible mechanism for the evolution of amorphous nanofibers to carbon nanonodules is presented. It is also found that the temperature of the collector during electrospinning of the fiber and the pressure of carbonization are critical factors for growth of the nanonodules. With these mechanisms, carbon nanonodules can be selectively grown on the prepared amorphous carbon nanofibers using pre-oxidation and carbonization of an electrospun glycerol–polyacrylonitrile fiber.     

High-throughput fabrication of carbonized electrospun polyacrylonitrile/poly(acrylic acid) nanofibers with additives for enhanced electrochemical sensing

Lightweight, polyacrylonitrile-derived electrodes with different additives were fabricated using high-throughput nozzle-free electrospinning. The electrospun precursor nanofibers (PNFs) containing iron oxide, gold nanoparticles, or reduced graphene oxide (rGO) were subjected to oxidative stabilization and carbonization to obtain a carbon-rich conductive nanofiber structure. Scanning electron microscopy showed that the carbon nanofibers contracted between 11 and 55% while the Fourier-transform infrared spectroscopy confirmed that the carbon nanofibers were thermally stable. Thermogravimetric and differential scanning calorimetry results revealed that the cross-linking of the chain molecules and cyclization were completed. Next, cyclic voltammetry results indicated that the electroactivity of the modified screen-printed carbon electrodes was decreased by 85% due to the presence of carbon glue. The modified device presented significant enhanced electrochemical responses with the inclusions of nanoparticles, with rGO showing a 2.13 times higher electroactive surface area, followed by iron oxide (two times) and gold nanoparticles (1.37 times) than the equivalent PNFs.     

Encapsulation of CoS nanoparticles in PAN electrospun nanofibers: Effective and reusable catalyst for ammonia borane hydrolysis and dyes photodegradation

In this study, the effective cobalt sulfide NPs were successfully encapsulated inside polyacrylonitrile (PAN) electrospun nanofibers. Typically, the solid NPs were in-situ synthesized by addition of ammonium sulfide drops to PAN/cobalt acetate solution. Electrospinning of the obtained colloid led to obtain good morphology polymeric nanofibers containing CoS NPs. Complete sheathing of the active nanoparticles did not affect their catalytic activity as the prepared mats revealed high performance toward hydrogen release from ammonia borane hydrolysis. Moreover, as a photocatalyst, a mat containing 2 wt% CoS could catalyze oxidation of methylene blue dye to be completely eliminated within 15 min. Furthermore, the introduced nanofibers photocatalytically enhanced complete degradation of the methyl red dye within relatively short time. The experimental results indicated that the optimum CoS content is 2 wt%, more increase in the concentration of the solid NPs leads to particles aggregation and consequently decrease the surface area. Beside the good activity obtained, the introduced immobilization strategy is considered an acceptable methodology to overcome the secondary pollution of the nanostructural photocatalysts because of the easy separation feasibility.     

Formation and characterization of core-sheath nanofibers through electrospinning and surface-initiated polymerization

Novel core-sheath nanofibers, composed of polyacrylonitrile (PAN) core and polypyrrole (PPy) sheath with clear boundary between them, were fabricated by electrospinning PAN/FeCl₃·6H₂O bicomponent nanofibers and the subsequent surface-initiated polymerization in a pyrrole-containing solution. By adjusting the concentration of FeCl₃·6H₂O, the surface morphology of PPy sheath changed from isolated agglomerates or clusters to relatively uniform thin-film structure. Thermal properties of PAN-PPy core-sheath nanofibers were also characterized. Results indicated that the PPy sheath played a role of inhibitor and retarded the complex chemical reactions of PAN during the carbonization process.     

Influence of iron (III) acetylacetonate on structure and electrical conductivity of Fe3O4/carbon composite nanofibers

Fe₃O₄/carbon composite nanofibers were prepared by electrospinning polyacrylonitrile (PAN), iron (III) acetylacetonate (AAI) and dimethyl formamide (DMF) compound solutions, followed by stabilization and carbonization processes. Emphasis was put on the influence of AAI on reactions during stabilization and carbonization. The effect of Fe₃O₄ on catalytic graphitization and electrical conductivity was also studied. Experimental results show that AAI has participated in the reactions and structural changes of PAN during stabilization and carbonization, and is evidenced to promote the processes. Fe₃O₄ nanoparticles exhibit catalytic effect on carbonization process that promote graphitization by a catalytic effect at low AAI content and inhibit the formation of graphitized layers when AAI content is excessive. Therefore, there exists an optimum AAI content (C_o) where composite nanofibers show the maximum graphitization degree and electrical conductivity. With proper amount of AAI addition, Fe₃O₄/carbon composite nanofibers showing high graphite degree and electrical conductivity could be achieved.     

Preparation and characterization of electrospun Ag/polyacrylonitrile composite nanofibers

Novel composite nanofibers consisting of Ag nanoparticles and polyacrylonitrile (PAN) were fabricated successfully. The Raman properties of these Ag/PAN nanofibers were studied at low temperatures, which showed good Raman characteristics. In the process, a PAN solution containing Ag ions was directly electrospun to obtain nanofiber films containing Ag ions, and the Ag ions of resulting composite nanofibers were reduced to Ag nanoparticles in N₂H₅OH aqueous solution. Then, we treated Ag/PAN composite nanofibers at 100 °C, 200 °C, 400 and 600 °C, respectively. The Ag/PAN nanocomposite film was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) patterns and surface-enhanced Raman scattering (SERS) spectroscopy.     

Electrospinning of polyacrylonitrile solutions containing diluted sodiumthiocyanate

The effect of NaSCN salt on the spinnability of polyacrylonitrile (PAN) solutions, its resulting morphology, mechanical property, and the flame resistance of the resulting electrospun nanofibers were studied. The intent was to develop a method to produce nanosized carbon fiber precursors with good properties. Electrospun PAN nanofibers from 9.7–9.9 wt% PAN/sodiumthiocyanate (NaSCN) (aq)/Dimethylformamide (DMF) solutions with 1.0–2.9 wt% NaSCN (aq), and 10–15 wt% PAN/DMF solutions without salt exhibited good spinnability and morphology with no beading in the range of applied voltage (18–20 kV) and take‐up velocity (9.8–12.3 m/s). The relatively high take‐up velocity produced good yarn alignment. The diameter distributions of the PAN nanofibers containing the NaSCN salt were narrower than those of the PAN/DMF nanofibers without the salt. It was determined that the maximum content of salt for production of electrospun PAN nanofibers with good morphology was below 3.8 wt% (40 wt% based on PAN). The salt concentration can positively influence on the narrow diameter distributions of the resulting electrospun fibers. Also, it could be confirmed that the salt effect on mechanical property and flame resistance of electrospun PAN nanofibers. In particular, the elongation of the PAN nanofiber with 2.9 wt% NaSCN (aq) was significantly increased as much as 186% compared with that of 10 wt% PAN nanofiber without the salt. The flame resistance and mechanical properties of the stabilized PAN nanofibers with NaSCN (aq) increased after oxidization process. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Processing and characterization of carbon nanofibers obtained from PAN/lignin blends processed by electrospinning

Blankets based on blends with different PAN/lignin ratios (10 and 50% wt. of lignin) were processed via electrospinning. Then, the blankets obtained were thermally treated in order to produce samples of carbon nanofibers. The thermo-oxidative stabilization parameters were defined based on a 2³-factorial design. The samples, after stabilization, were analyzed by differential scanning calorimetry (DSC), thermogravimetry (TGA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR) techniques. Based on the results, the best parameters for the stabilization of electrospun, blankets were selected, and subsequently, the most adequate carbonization parameters were established to obtain the carbon blankets. The carbonized blankets were characterized for electrical conductivity by impedance spectroscopy, chemical structure (Raman and FT-IR spectroscopies), crystallographic ordering by X-ray diffraction (XRD), and morphology (SEM). The results showed the feasibility of producing carbon blankets based on PAN/lignin blends. However, carbonized blankets showed low carbon yield (10–56%) and a decrease of up to 70% in fiber diameter. XRD and Raman spectroscopy showed that the structural ordering of carbon blankets presents different values according to the heat treatment parameters used (45–57%) and a poorly ordered structure, indicated by the ID/IG ratio.     

Study of electrospun polyacrylonitrile fibers with porous and ultrafine nanofibril structures: Effect of stabilization treatment on the resulting carbonized structure

Electrospun polyacrylonitrile (PAN)-based carbon nanofibers (CNFs) with high surface area have been of promising interest because of their potential for applications in various fields, especially energy devices. In this study, PAN nanofibers with porous and ultrafine nanofiber structures were prepared by electrospinning PAN/poly(vinyl pyrrolidone) (PVP) immiscible solutions and then selectively removing the PVP component from the electrospun PAN/PVP bicomponent nanofibers. The chemical reaction and microstructure of the PAN fibers with porous and ultrafine nanofibril structures in the stabilization process were investigated. The results revealed the effects of PAN fibers with porous and ultrafine nanofibril structures on the crosslinking reaction, microstructure, and morphology during the stabilization process. According to the in situ Fourier transform infrared spectroscopy results, the intermolecular and intramolecular reactions of the nitrile group for the PAN fibers with ultrafine nanofibril structures exhibited slower reaction rates than those for the neat PAN fibers during stepwise and isothermal heating. Selecting a good stabilization temperature for ultrafine PAN-crosslinked nanofibrils can enhance the surface area and carbonized structure of CNFs. The possible applications of CNFs with porous and ultrafine nanofibril structures in supercapacitors were also evaluated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48218.     

Preparation and characterization of multiwalled carbon nanotubes/polyacrylonitrile nanofibers

Multiwalled carbon nanotube/Polyacrylonitrile (MWNT/PAN) composite nanofibers were prepared by electrospinning technique, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC₆H₄-NH₂) groups onto the sidewall. The diameter range of the PAN nanofibers was 400-100 ± 50 nm. The beads formation was also observed when the amounts of MWNTs were increased in the PAN solution. The bead formation in F-MWNT/PAN composite nanofibers was less as compared to P-MWNT/PAN. The MWNTs were embedded within nanofibers and were well oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The mechanical and thermal properties of the PAN nanofibers were improved by the incorporation of MWNTs.     

静电纺丝制备聚丙烯腈纳米纤维及其预氧化

利用聚丙烯腈／二甲基甲酰胺纺丝溶液由静电纺丝制备了聚丙烯腈纳米纤维,纳米纤维的直径在220～760nm。随着聚合物溶液浓度和纺丝施加电压的升高,纳米纤维的直径变大。采用热分析和热重分析研究了纳米纤维的热性能,还用红外光谱对纳米纤维预氧化过程分子化学结构的变化进行了表征,结果表明,纳米纤维有一个很尖锐的放热峰,是聚丙烯腈均聚物典型的放热峰。随着预氧化温度的升高,纤维的内部分子结构发生了变化,表现在红外光谱上最突出的是C≡N在2243～2241cm^-1峰的降低,以及C—H在1684cm^-1峰的降低。