The influence of pyrolysis on physical properties and microstructure of modified PAN fibers during carbonization

Modification of polyacrylonitrile (PAN) fibers with potassium permanganate has reduced the time required for stabilization and also improved the mechanical properties of the resulting carbon fibers. In this study, the effect of modification on the physical properties, microstructure, and elemental composition of fibers during the carbonization process was examined for the first time. The resulting carbon fibers developed from modified PAN fibers had a higher density, a greater stacking size (Lc), and a higher preferred orientation than those developed from unmodified PAN fibers. The carbon fibers developed from the modified PAN fibers also showed an improvement in tensile strength from 20 to 40%. These fibers showed a radial structure in the fracture surface and were somewhat different structurally in the cross section than were the carbon fibers developed from the original PAN fibers. A model for the structure of both carbon fibers is presented. The relationship between the formation of closed pores from open pores and the variety of cumulative pore area during the heat-treatment stage is also discussed.     

Processing,structure, and properties of gel spun PAN and PAN/CNT fibers and gel spun PAN based carbon fibers

Polyacrylonitrile (PAN) and PAN/carbon nanotube (PAN/CNT) fibers were manufactured through dry‐jet wet spinning and gel spinning. Fiber coagulation occurred in a solvent‐free or solvent/nonsolvent coagulation bath mixture with temperatures ranging from ?50 to 25°C. The effect of fiber processing conditions was studied to understand their effect on the as‐spun fiber cross‐sectional shape, as well as the as‐spun fiber morphology. Increased coagulation bath temperature and a higher concentration of solvent in the coagulation bath medium resulted in more circular fibers and smoother fiber surface. as‐spun fibers were then drawn to investigate the relationship between as‐spun fiber processing conditions and the drawn precursor fiber structure and mechanical properties. PAN precursor fiber tows were then stabilized and carbonized in a continuous process for the manufacture of PAN based carbon fibers. Carbon fibers with tensile strengths as high as 5.8 GPa and tensile modulus as high as 375 GPa were produced. The highest strength PAN based carbon fibers were manufactured from as‐spun fibers with an irregular cross‐sectional shape produced using a ?50°C methanol coagulation bath, and exhibited a 61% increase in carbon fiber tensile strength as compared to the carbon fibers manufactured with a circular cross‐section. POLYM. ENG. SCI., 55:2603–2614, 2015. © 2015 Society of Plastics Engineers     

Structural changes during the thermal stabilization of modified and original polyacrylonitrile precursors

A polyacrylonitrile (PAN) precursor fiber of a special grade for preparing carbon fibers was modified by the impregnation of an aqueous KMnO₄ solution. The effects of the modification on the lateral and morphology structure, related to the crystalline properties of both the precursors and preoxidized fibers, such as the orientation index, crystal size, and crystallinity index, were measured by wide‐angle X‐ray diffraction. For both modified and original PAN fibers, a comparative study of the changes of the elemental content during the process of preoxidation, the relations between the thermal stress and heat‐treatment temperature, and the effect of the modification on the skin/core structure of a preoxidized fiber were also introduced by the use of elemental analysis, optical microscopy, and so on. The modification of KMnO₄ was demonstrated to increase the density, increase the crystallinity index, increase the preferred orientation index, and decrease the crystal size for a modified precursor fiber and for a preoxidized fiber developed from a modified precursor fiber after a different heat‐treatment temperature. KMnO₄ also showed a catalytic action, accelerating the rate of preoxidation and reducing the time of thermal stabilization; this improved the homogenization of the cross‐section structure and led to an improvement in the tensile strength of 15–20% and an improvement in the elongation of 20–30% in the resulting carbon fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2047–2053, 2005     

聚丙烯腈纤维预氧化前处理研究进展

综述了前人在聚丙烯腈原丝预氧化前处理方面的研究成果,介绍了前处理的作用机理及作用效果。研究发现,聚丙烯腈原丝的改性处理可显著提高纤维的结构和性能,并影响原丝在预氧化过程中的热力学和动力学,进而影响最终碳纤维的质量。     

High resolution transmission electron microscopy study on polyacrylonitrile/carbon nanotube based carbon fibers and the effect of structure development on the thermal and electrical conductivities

Polyacrylonitrile (PAN) and PAN/carbon nanotube (CNT) based carbon fibers at various CNT content have been processed and their structural development was investigated using high resolution transmission electron microscope (HR-TEM). In CNT containing carbon fibers, the CNTs act as templating agents for the graphitic carbon structure development in their vicinity at the carbonization temperature of 1450 °C, which is far below the graphitization temperature of PAN based carbon fiber (>2200 °C). The addition of 1 wt% CNT in the gel spun precursor fiber results in carbon fibers with a 68% higher thermal conductivity when compared to the control gel spun PAN based carbon fiber, and a 103% and 146% increase over commercially available IM7 and T300 carbon fibers, respectively. The electrical conductivity of the gel spun PAN/CNT based carbon fibers also showed improvement over the investigated commercially available carbon fibers. Increases in thermal and electrical conductivities are attributed to the formation of the highly ordered graphitic structure observed in the HR-TEM images. Direct observation of the graphitic structure, along with improved transport properties in the PAN/CNT based carbon fiber suggest new applications for these materials.     

Modification of polyacrylonitrile (PAN) carbon fiber precursor via post-spinning plasticization and stretching in dimethyl formamide (DMF)

This study investigates the possibility of using a post-spinning plasticization and stretching process to eliminate suspected property-limiting factors in polyacrylonitrile-based carbon fibers. This process was performed with the intention of removing surface defects (to improve tensile strength), attenuating fiber diameter (to promote more uniform heat treatment), and reducing molecular dipole interactions (to facilitate further molecular orientation). Among the various organic and inorganic solutions tested, treatment using aqueous dimethyl formamide (DMF) offered far and away the best properties and was therefore selected for further testing. Tested individually (as single filaments), fibers exposed to 80% DMF for 10 s gave the highest precursor values of elastic modulus (9.07 GPa) and tensile strength (675 MPa). While fibers treated in 80% DMF gave a 73% improvement in elastic modulus and a 53% improvement in tensile strength over as-received PAN, limitations in sample preparation and carbonization necessitated a reduction in DMF concentration (to 30%) to allow extraction of individual carbon fibers for tensile testing. Despite this compromise, results for fibers carbonized at 1000°C ultimately showed a 32% improvement in carbon fiber elastic modulus and a 14% improvement in carbon fiber tensile strength over regularly prepared carbon fibers. These results show that, to a certain extent, improvements in PAN precursor properties can translate to corresponding improvements in subsequently produced carbon fibers. Additional characterization using wide angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) suggests that these improvements are due in part to improved lateral order as well as the successful elimination of surface defects and prevention of skin-core formation.     

Characteristics of wet‐spun and thermally treated poly acrylonitrile fibers

The performance of carbon fibers depends on the quality of the precursor and the conditions of the thermal treatment. In detail, for a PAN precursor fiber the viscosity of a spinning dope and the draw ratio during the spinning process needs to be considered. Through wet spinning, different types of PAN precursor fibers with defined spinning parameters, including solid content, solvent content in a bath, and especially draw ratio resulting in defined cross section diameters, were fabricated and analyzed with tensile tests, density investigations, SEM, TGA‐MS, FTIR, and XRD. The results show that the mechanical properties of the fibers correlate to crystallinity. The cross section diameter is strongly related to the morphology of the fibers after thermal treatment. By extending the postdrawing of PAN fibers high tenacities were obtained at the cost of the cross section shape. In addition, TGA measurements reveal trapped residues of the wet spinning process as well as show several chemical reactions takes place at the same time at different temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43698.     

Manufacture of carbon fibers from polyacrylonitrile precursors treated with CoSO4

Free‐radical solution copolymerization of itaconic acid and acrylonitrile was carried out in DMSO using azodiisobutyronitrile as an initiator, changing the feed rate of itaconic acid. The resulting polymerization solution was spun to form polyacrylonitrile (PAN) precursors of carbon fibers. The precursors were treated with a CoSO₄ aqueous solution on‐line. The structure and properties of untreated and treated PAN precursors and the resultant carbon fibers were characterized by SEM and TEM, a stabilization process, etc. It is suggested that CoSO₄ acts as a catalyst in the formation of a ladder structure and reduces the temperature of cyclization, and the carbon fibers developed from treated PAN fibers showed improvement in the tensile strength and the Young's modulus. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 153–158, 2002     

The effect of the side chain of acrylate comonomers on the orientation,pore-size distribution,and properties of polyacrylonitrile precursor and resulting carbon fiber

The side-chain size of acrylate comonomer in polyacrylonitrile (PAN) precursor markedly influences the microstructure of PAN fiber and its resulting carbon fiber. In this paper, we propose that the model of the crystal orientation of PAN precursor and its resulting carbon fiber can explain the effect of the side-chain size of acrylate comonomer on the orientation of PAN fiber and carbon fiber. When PAN precursor contains a larger side chain of comonomer, PAN precursor has the preferred crystal orientation and higher crystallinity and the orientation of its resulting carbon fiber unexpectedly decreases. This is because the larger the side chain is, the lower is the orientation of the amorphous region of PAN fiber; as a result, the average orientation after carbonization decreases. In the same mole fraction of comonomer, the carbon fiber based on PAN precursor with a smaller side chain of acrylate comonomer has better mechanical properties and higher yield.     

Effect of activation on boron nitride coating on carbon fiber

Boron nitride (BN) thin coating has been formed on the surface of chemically activated polyacrylonitrile (PAN) carbon fibers by dip coating method. The chemical activation of PAN fibers was carried out by two different chemicals, i.e. nitric acid (HNO₃) and silver nitrate (AgNO₃) solution. The chemical activation changes the surface properties, e.g. surface area and surface microstructure of the carbon fibers. These surface modifications ultimately influence properties of boron nitride coating on carbon fibers. The boron nitride coating on carbon fibers showed better crystallinity, strength and oxidation resistance when carbon fibers were activated by HNO₃. This improvement in strength and oxidation resistance is attributed to better crystallinity of boron nitride coating on HNO₃ activated PAN fibers.     

Oxidative stabilization of PAN/SWNT composite fiber

PAN/SWNT composite fibers have been spun with 0, 5, and 10 wt% single wall carbon nanotubes (SWNTs). Tensile fracture surfaces of polyacrylonitrile (PAN) fibers exhibited extensive fibrillation, while for PAN/SWNT composite fibers, tendency to fibrillate decreased with increasing SWNT content. The reinforcing effect of SWNTs on the oxidized polyacrylonitrile (PAN) fiber has been studied. At 10 wt% SWNTs, breaking strength, modulus, and strain to failure of the oxidized composite fiber increased by 100%, 160%, and 115%, respectively. Tensile fracture surfaces of thermally stabilized PAN and the PAN/SWNT fibers exhibited brittle behavior and well distributed SWNT ropes covered with the oxidized matrix can be observed in the tensile fracture surfaces of the fibers. No de-bonding has been observed between unoxidized or the oxidized PAN matrix and the nanotube ropes. Higher strain to failure of the oxidized composite fiber as compared to that of the oxidized control PAN fiber also suggests good adhesion/interaction between SWNT and the oxidized matrix. Thermal stresses generated on the composite fiber during the oxidation process were lower than those for the control fiber. The potential of PAN/SWNT composite fiber as the precursor material for the carbon fiber has been discussed.     

The index of dry‐jet wet spinning for polyacrylonitrile precursor fibers

A new spinning index for a PAN precursor fiber is proposed that includes the viscosity of a spinning dope, the thermodynamic affinity, and the draw ratio during the spinning process. Through dry‐jet wet spinning, six types of PAN precursor fibers with different spinning parameters, including solid content, solvent content in a bath, and draw ratio, were fabricated and analyzed with tensile tests, SEM, and XRD. The results show that the spinning index can reflect the mechanical properties of the fibers but is less indicative of crystallinity. Hence, the current spinning index is recommended for use as an indicator for the mechanical properties of PAN precursor fibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41265.     

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.     

Investigating the jet stretch in the wet spinning of PAN fiber

The jet stretch of wet‐spun PAN fiber and its effects on the cross‐section shape and properties of fibers were investigated for the PAN‐DMSO‐H₂O system. Evidently, the spinning parameters, such as dope temperature, bath concentration, and bath temperature, influenced the jet stretch. Also, under uniform conditions, the postdrawing ratio changed as well as that of jet stretch. When coagulation temperature was 35°C simultaneously with bath concentration of 70%, jet stretch impacted obviously the cross‐section shapes of PAN fiber, but had little effect when the temperature was below 10°C or above 70°C. As the jet stretch ratio increased, the crystallinity, crystal size, sonic orientation, and mechanical properties of the as‐spun fiber changed rapidly to a major value for jet stretch ratio of 0.9 where the cross section of as‐spun fiber was circular. With further increasing of jet stretch ratio, the properties changed slightly but the fiber shape was not circular. The results indicated that appropriate jet stretch, under milder formation conditions in wet‐spinning, could result in the higher postdrawing ratio and circular profile of PAN fiber, which were helpful to produce round PAN precursor with minor titer and perfect properties for carbon fiber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Electrospun magnetic carbon composite fibers: Synthesis and electromagnetic wave absorption characteristics

Electrospun polyacrylonitrile (PAN)‐based carbon composite fibers embedded with magnetic nanoparticles have been developed as materials for electromagnetic wave absorption. The nanocomposite fibers were prepared by electrospinning from a dispersion of magnetite (Fe₃O₄) nanoparticles stabilized by L ‐glutamic acid in a solution of PAN and N, N‐dimethyl formamide. The Fe₃O₄‐embedded PAN nanofibers were stabilized at 270°C in air and carbonized at 800°C in nitrogen. The Fe₃O₄ nanoparticles were crystalline with a particle size of about 7 nm, most of which was reduced to Fe₃C with agglomerates of up to 50 nm diameter in the carbon fibers. The carbon morphology was mostly disordered, but exhibited a layered graphitic structure in the vicinity of the nanoparticles. The carbon composite fiber exhibited ferromagnetic behavior, and the induced magnetic saturation per unit mass of fibers increased with increasing Fe₃O₄ content in the precursor. The complex relative dielectric permittivity was tuned by adjusting the amount of Fe₃O₄ in the carbon fiber precursor. With increasing Fe₃O₄ content, good electromagnetic wave absorption characteristics were observed below 6 GHz, even for samples with fiber loadings as low as 5 wt %. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of spinning conditions on the mechanical properties of polyacrylonitrile fibers modified with carbon nanotubes

Carbon nanotubes (CNTs) were used to modify polyacrylonitrile (PAN) polymer. The PAN/CNT composite fibers were spun from dimethylformamide solutions containing different types of CNTs. The effect of nanotube addition to the fiber precursor on the resulting mechanical properties is discussed. In this study, we examined the relationship of the rheological properties of PAN spinning solutions containing various types of CNTs and the tensile strength of the resulting PAN fibers. The presence of CNTs in the PAN spinning solution enhanced its deformability during the drawing stage. This effect resulted in a higher tensile strength in the fibers containing nanotubes, as compared to the pure fibers. The use of a three‐stage drawing process resulted in a significant increase in the tensile strength of PAN fibers modified with multiwalled nanotubes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

熔融纺丝工艺制备碳纤维原丝

聚丙烯腈基碳纤维的制备主要采用溶液纺丝方法,生产过程需要溶剂回收,工艺流程长,因此制造成本高。笔者主要介绍了聚丙烯腈基碳纤维的制备工艺概况,特别介绍了熔融纺丝路线制备聚丙烯腈原丝的方法。利用共聚改性、增塑改性、纺丝后处理等方法,可以制备聚丙烯腈基碳纤维,并提出了由熔融纺丝制备聚丙烯腈基碳纤维的可行路线。     

The effect of molecular weight on the cross section and properties of polyacrylonitrile precursor and resulting carbon fiber

In this study, we investigated the effect of molecular weight in the range 1.65?4.29 × 10⁵ (M _w) on the cross section, surface, thermal, and mechanical properties of polyacrylonitrile (PAN) precursor and its resulting carbon fiber. From the results, it can be seen that the molecular weight, with the same solid content of polymer, changes from 1.65 × 10⁵ to 4.29 × 10⁵ and the cross section of PAN precursor changes from a circular shape with no notable grooves surface to a been shape with a surface containing deep and straight grooves. PAN precursor with higher molecular weight has a higher onset of exothermic temperature and a higher peak temperature, but has a higher aromatization index (AI value) due to its thin and flat cross section, which causes rapid cyclization during oxidation. An increase in molecular weight results in an increase in crystal size and preferred orientation and a decrease in average pore diameter. This decrease can improve the mechanical properties of PAN precursor and its resulting carbon fiber.     

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     

Fabrication and Characterization of Highly Oriented Composite Nanofibers with Excellent Mechanical Strength and Thermal Stability

Here, highly‐oriented poly(m‐phenylene isophthalamide)/polyacrylonitrile multi‐walled carbon nanotube (PMIA/PAN‐MWCNT) composite nanofiber membranes with excellent mechanical strength and thermal stability are successfully produced using electrospinning. It is demonstrated that the cooperation of multi‐walled carbon nanotubes (MWCNT) and high‐speed rotating collection is beneficial to the acquisition of highly oriented fibers and effectively improves the mechanical strength of the membrane along the orientation direction. Specifically, the tensile stress of poly(m‐phenylene isophthalamide)/polyacrylonitrile (PMIA/PAN) membrane is enhanced significantly from 10.6 to 20.7 MPa, benefiting from the highly oriented alignment of the fibers as well as the reinforcing effect of MWCNTs on the fibers. Furthermore, the stressing process of single fiber and fiber aggregates is carefully simulated, and the influence of MWCNTs on the mechanical properties of PMIA/PAN‐MWCNT membranes is analyzed comprehensively, providing a meaningful auxiliary means for the study of mechanical properties. In addition, the composite nanofiber membrane has the advantages of both PMIA and PAN, possessing high temperature resistance, flame‐retardancy, and chemical stability, for an ideal high‐temperature material. In short, the as‐prepared PMIA/PAN‐MWCNT composite membrane with excellent comprehensive property emerges a promising application in many fields, especially in high‐tech.