The influence of cobaltous chloride modification on physical properties and microstructure of modified PAN fiber during carbonization

Modification of polyacrylonitrile (PAN) fibers with cobaltous chloride has increased crystal size, crystallinity, and density, and also improved tensile strength and modulus of the resulting carbon fibers. In this study, the effect of cobaltous chloride modification on the physical properties, microstructure, and elemental composition of PAN fibers during the carbonization process was examined. The resultant carbon fibers developed from modified PAN fibers had a lower formation temperature of carbon basal planes than those fibers that developed from the original one. The modification process not only improved the tensile strength but also increased the tensile modulus by about 15% of the resulting carbon fibers at carbonization temperature of 1300°C. A higher stacking size (L_c), or a greater carbon basal plane in crystalline, is one of the reasons to improve the modulus and conductivity of the final carbon fibers. The modification process also increased the electrical conductivity by about 15% at 1300°C and by about 150% at 2500°C. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2409–2415, 1998     

Raman spectroscopic study of the microstructure of carbon films developed from cobalt chloride‐modified polyacrylonitrile

Polyacrylonitrile (PAN) was modified with cobalt chloride at 90°C for 5 min. The carbon films prepared from original and modified PAN films were carbonized up to 1300°C. The structure of the resulting carbon film was studied using X‐ray diffraction and Raman spectroscopy. The stacking size obtained from X‐ray diffraction approaches the L_c value of the resulting carbon films as the heat treatment temperature increased. The mean average carbon basal planes in crystalline (Lc/d) also increased with increasing pyrolysis temperature. Raman spectra confirmed the progressive structural ordering as treatment temperature increased. During pyrolysis, a substantial decrease in the intensity of the band near the 1350 cm⁻¹ region was observed, indicating a decrease in the disordered structure. The crystal size (L_a) of the resulting carbon films also showed a remarkable increase with increased heat treatment temperature. The resulting carbon films developed from the modified PAN films had higher L_c and L_a than those developed from the original PAN film. It was established that cobalt catalyzes graphitization of amorphous carbon during pyrolysis. This modification not only promoted the growth of crystal size but also increased the close packing of the carbon basal planes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2219–2225, 1999     

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     

The influence of continuous stabilization on the properties of stabilized fibers and the final activated carbon fibers. Part I

This study found that, during continuous stabilization and carbonization, the shrinkage behavior of polyacrylonitrile (PAN) fibers affects the morphology and properties of the stabilized fibers, the carbon fibers, and the final activated carbon fibers. In the stabilized fibers, a higher shrinkage of the PAN fibers during the stabilization process increased the oxygen content and the core proportion and decreased the formation of ladder polymers. The effect of the shrinkage behavior of the PAN fibers on the fracture surfaces of the stabilized fibers is discussed. A microstructure model of stabilized fibers is presented, depicting fine radial structure at the fiber center. When stabilized fibers were carbonized during a continuous carbonization process, a hole structure was found in the fiber center at the temperature of 800°C, and a hollow core was found at the temperature of 1300°C. The shrinkage behaviors during the stabilization stage and the formation of the hole and the hollow core in the fiber's center during the carbonization stage are discussed. The carbon fibers developed from shrunk stabilized fibers have a lower density and lower preferred orientation than fibers developed from unshrunk stabilized fibers. But the fibers developed in this new process have greater nitrogen and oxygen content, and have a greater porosity than the traditionally-produced fibers. The mechanical properties df the new and the traditional fibers are comparable. These characteristics are very valuable in the production of activated carbon fibers, which will be described in our next paper.     

The effect of pre-carbonization on the properties of PAN-based carbon fibers

A continuous stabilization and two-stage carbonization process was used to prepare polyacrylonitrile (PAN)-based carbon fibers, The effect of pre-carbonization (300 to 550°C) on the final properties and microstructure of carbon fibers was measured. Experimental results using an X-ray diffractometer indicated the presence of a less ordered structure at 2Θ from 5 to 18° in the pre-carbonized fibers and the final carbon fibers. This study found that the pre-carbonization process strongly affects the microstructure of the resulting carbon fibers. The results also showed that a suitable pre-carbonization was very conducive to improvement in tensile strength or in Young's modulus of the final carbon fibers. When the final carbon fiber was pre-carbonized at 300 and 550°C, respectively, these fibers had a higher tensile strength and higher Young's modulus than carbon fibers pre-carbonized at other conditions.     

Influence of continuous stabilization on the physical properties and microstructure of PAN-based carbon fibers

A continuous stabilization and carbonization process was used to prepare polyacrylonitrile (PAN)-based carbon fibers. The stepwise stabilization of PAN fibers was tried at various temperatures. The effect of stepwise stabilization on the physical properties and microstructure of the final carbon fibers is reported in this article. The fixed temperature in stepwise stabilization is kept below the fusion temperature of PAN precursors to avoid overstabilization of the fibers. The optimum stepwise stabilization process not only increases the amount of ladder polymer in stabilized fiber but also improves the physical and mechanical properties of the resultant carbon fibers. The formation of closed pores from open pores in carbon fiber occurs at 1100°C, but the formation of closed pores occurs at 200°C lower for carbon fiber developed from overstabilized fiber. The effect of continuous stepwise stabilization on the properties of resulting stabilized fibers and the variation in physical properties, element composition, and microstructure of carbon fibers during the carbonization process are also reported in this article.     

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     

Characterization of PAN-based nonburning (nonflammable) fibers

In this article, a continuous stabilization process is used to make nonburning (nonflammable) fibers from polyacrylonitrile (PAN) fibers. The effect of the shrinkage behavior and the stretching process of PAN fibers during the stabilization process on the physical properties, morphology, and flammability of the resultant nonourning fibers is studied for the first time. The higher shrinkage of PAN fibers during the continuous stabilization process is found to increase the diameter, the core proportion, and flammability and decrease the Al value, density, mechanical properties, and formation of oriented molecular chains in the resultant nonburning fibers. The effect of the shrinkage behavior of PAN fibers on the fracture surface of the nonburning fibers is also discussed. The nonburning fibers show a fracture structure radiating from the fiber center to the boundary. The structures are composed of small and fine radial strip-layer–like fibrils. Nonburning fibers developed using an optimum stretch process, not only had increased preferred orientation and density, but also had improved mechanical properties. Those fibers also have sufficient nonflammability. © 1993 John Wiley & Sons, Inc.     

Carbon fibers derived from UV‐assisted stabilization of wet‐spun polyacrylonitrile fibers

A rapid, dual‐stabilization route for the production of carbon fibers from polyacrylonitrile (PAN) precursor fibers is reported. A photoinitiator, 4,4′‐bis(diethylamino)benzophenone, was added to PAN solution before the fiber wet‐spinning step. After a short UV treatment that induced cyclization and crosslinking at a lower temperature, precursor fibers could be rapidly thermo‐oxidatively stabilized and successfully carbonized. Scanning electron microscopy micrographs show no deterioration of the microstructure or hollow‐core formation in the fibers due to UV treatment or presence of photoinitiator. Fast‐thermally stabilized pure PAN‐based carbon fibers show hollow‐core fiber defects due to inadequate thermal stabilization, but such defects were not observed in carbon fibers derived from fast‐thermally stabilized fibers that contained photoinitiator and were UV treated. Tensile testing results confirm that fibers containing 1 wt % photoinitiator and UV treated for 5 min display higher tensile modulus than all other sets of thermally stabilized and carbonized fibers. Wide‐angle X‐ray diffraction results show a higher development of the aromatic structure and molecular orientation in thermally stabilized fibers. No significant increase in interplanar spacing or decrease in crystals size were observed within the UV‐stabilized carbon fibers containing photoinitiator, but such fibers retain a higher extent of molecular orientation when compared with control fibers. These results establish for the first time, the positive effect of the external addition of photoinitiator and UV treatment on the properties of the PAN‐based fibers, and may be used to reduce the precursor stabilization time for faster carbon fiber production rate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40623.     

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     

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.     

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.     

Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part I: Effect of carbon nanotubes on stabilization

Addition of carbon nanotubes (CNTs) in polyacrylonitrile (PAN) fibers significantly improves the mechanical properties of the resulting carbon fibers. This study focuses on the effect of different types of CNTs on chemical, mechanical and structural changes during the stabilization of gel-spun CNT/PAN composite fibers. Among the different types of CNTs, it was observed that CNTs containing more walls had lower reinforcement efficiency than CNTs containing fewer walls. Similarly CNTs containing fewer walls exhibited higher orientation of the ladder polymer and greater effect on the formation of β-amino nitrile in the stabilized fibers. Wide angle X-ray diffraction, infrared spectroscopy, and scanning electron microscopy were used to determine the optimum stabilization time. Additionally, it was found that the higher tension applied during stabilization improved the properties of the stabilized fibers, and the addition of CNTs increased the maximum tension that the fiber can bear.     

The role of structural evolution of polyacrylonitrile fibers during thermal oxidative stabilization on mechanical properties

The effects of chemical and physical structural evolution of polyacrylonitrile (PAN)-based carbon fibers precursor during thermal oxidative stabilization (TOS) on the mechanical properties of stabilized fibers were systematically studied. The results of Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, and density gradient column showed that the PAN fibers treated with high temperature and for long time have higher extent of cyclization, oxygen content, and crosslinking content. The crystallinity and crystallite size decreased with the increase of TOS time and temperature, whereas the bulk density of the stabilized fibers increased. The mechanical property results indicated that the decrease in tensile strength was inseparable from the formation of the cyclic structure and the amorphization transition of the crystal structure. The fibers have better structural stability when the extent of cyclization was 80–83%, the crystallinity was 34–45%, and the bulk density of stabilized fibers was 1.33–1.35 g/cm³, but exceeding these ranges, a serious skin-core structure appeared.     

Study of flame‐resistant acrylic fibers reinforced by poly(vinyl alcohol)

Acrylic fibers [polyacrylonitrile (PAN) fibers] have excellent flame‐retardant properties after they are modified by hydrazine hydrate and metal ions; however, their widespread applications are restricted because of poor mechanical properties. To improve the mechanical properties of these modified PAN fibers, poly(vinyl alcohol) (PVA) was added to the spinning solution of PAN as an effective reinforcing agent. The structure of the fibers before and after modification was studied by Fourier transform infrared spectroscopy, scanning electron microscopy, energy‐dispersive spectroscopy, and wide‐angle X‐ray diffraction. The mechanical properties and flame resistance of the fibers after treatment were also tested by a single‐fiber tensile tester and a limiting oxygen index (LOI) analyzer, respectively. We found that the LOI of the modified fibers was reduced from 54.7 to 29.1 after the introduction of 50 wt % PVA; however, the tensile strength was dramatically improved from about 1.50 cN/dtex to more than 4.00 cN/dtex. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43006.     

Polyacrylonitrile/acrylamide‐based carbon fibers prepared using a solvent‐free coagulation process: Fiber properties and its structure evolution during stabilization and carbonization

Polyacrylonitrile (PAN)/acrylamide (AM) fibers were fabricated via dry‐jet wet spinning process using a solvent‐free coagulation bath. The effects of AM loading as comonomer on the mechanical and thermal properties of PAN‐based carbon fiber have been studied. The thermal stability and mechanical stability of the fibers were characterized using differential scanning calorimetry (DSC) and tensile testing. Fibers fabricated from PAN with 5 wt% AM had the highest Young Modulus at 5.54 GPa. It also showed better exothermic trend process with broader exothermic peak and lower initiation stabilization temperature compared with homopolymer PAN. The elemental composition and chemical structure evolution of the fibers during the heat treatment processes were evaluated by elemental analyzer and Fourier Transform Infrared Spectroscopy. Crystal structure evolution of the fibers during the heat treatment process was elucidated by X‐ray diffraction (XRD) analysis. The elemental analyzer, XRD and FTIR results revealed that pyrolysis process used had successfully transformed PAN/AM fibers produced from solvent free coagulation bath into carbon fibers that were comparable with the conventional coagulation bath. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

浅谈提高聚丙烯腈基碳纤维性能的几种关键技术

从国外研究较多的共聚单体、聚丙烯腈原丝的改性、上油油剂等三个方面论述了提高聚丙烯腈基碳纤维性能的几种关键技术。聚丙烯腈原丝的热性能与共聚单体的种类和加入量有重要关系。共聚单体的加入促进纤维预氧化反应 ,使碳纤维性能和炭化收率都得到提高。各种各样的化学试剂用于改性聚丙烯腈原丝后 ,对改善最终碳纤维的结构和性能有重要的作用。油剂的使用对聚丙烯腈原丝的质量 ,如耐热性、亲水性、集束性、分纤性及加工毛丝率等有重要的影响     

The effect of modification on structure and dynamic mechanical behavior during the processing of acrylic fiber to stabilized fiber

Polyacrylonitrile (PAN) fibers pretreated with potassium permanganate have reduced the time required for stabilization, and also improved mechanical properties of the resultant carbon fibers. In this study, the effect of modification on the stabilization process and the dynamic mechanical properties of PAN fibers have been examined. The beta peak appeared at about 125°C on the loss tangent curves caused by molecular motion in the PAN fiber. Appearing at about 254°C, the alpha peak is attributed to chemical reactions and molecular motion in the formation of the crystalline phase of stabilized fibers. The alpha peak of the modified PAN fiber had lower absorption and had a smaller peak in the temperature range of 212–239°C. This indicated that potassium permanganate acts as a catalyst to lower the reaction temperature by about 20°C of the initial cyclization reaction. The dynamic storage modulus analysis indicated that modified PAN fibers have a lower initial transition temperature and that formation of the ladder polymer is gradual and steady.     

Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part III: Effect of stabilization conditions on carbon fiber properties

The oxidative stabilization process of gel-spun carbon nanotube (CNT)/polyacrylonitrile (PAN) composite fibers have been studied and optimized. Optimum stabilization time depends on both the applied tension and temperature. Various characterization methods including thermal shrinkage, dynamic mechanical analysis, infrared spectroscopy, and wide angle X-ray diffraction are used to monitor the chemical and structural evolution during stabilization and carbonization. The relationship between the stabilization conditions of CNT/PAN composite fiber and the tensile properties of the resulting carbon fibers were investigated. By optimizing stabilization conditions, CNT/PAN based carbon fibers with a tensile strength of 4 GPa and a tensile modulus of 286 GPa were obtained using batch carbonization processing at 1100 °C.     

Bimodification of polyacrylonitrile (PAN) fibers

A new technique for the modification of PAN fibers has evolved, in which the starting precursor material is impregnated with an aliphatic carboxylic acid, as well as KMnO₄. The bimodification of PAN, attempted by us for the first time, is aimed at achieving dual advantages in plasticization effect, as well as in a catalytic effect in a single treatment. The unmodified, unimodified, and bimodified precursors have been characterized for their mechanical, thermal, and physical behavior during various stages of processing to carbon fibers. These results are discussed in detail. The study further shows an 18% improvement in the mechanical properties of carbon fibers, prepared from bimodified precursor, as compared to that of unmodified precursor. One of the reasons for such improvement is the lowering in diameter of PAN fibers and in the resulting carbon fibers. © 1993 John Wiley & Sons, Inc.