Continuous carbonization of polyacrylonitrile-based oxidized fibers: Aspects on mechanical properties and morphological structure

By following the progression of continuous carbonization (300–1250°C) of polyacrylonitrile (PAN)-based oxidized fibers, variations in tensile mechanical properties and morphological structure are reported in detail along the carbonization line. The tensile strength and Young's modulus of the fibers generally increase throughout the carbonization stage. Meanwhile, the fiber diameter displays a significant decrease. The preferred orientation of carbon layer planes is observed to increase remarkably for temperatures over 400°C. In a similar manner, the stacking size increases significantly but reaches saturation around 600°C, a changing point corresponding to that observed for the variation of the Young's modulus. However, beyond about 1200°C, the stacking size again displays a marked increase. Results thus obtained are interpreted in relation to each other. Possible implications are also discussed. © 1994 John Wiley & Sons, Inc.     

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     

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 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.     

Effect of quasi‐carbonization processing parameters on the mechanical properties of quasi‐carbon/phenolic composites

In this work, quasi‐carbon fabrics were produced by quasi‐carbonization processes conducted at and below 1200°C. Stabilized polyacrylonitrile (PAN) fabrics and quasi‐carbon fabrics were used as reinforcements of phenolic composites with a 50 wt %/50 wt % ratio of the fabric to the phenolic resin. The effect of the quasi‐carbonization process on the flexural properties, interfacial strength, and dynamic mechanical properties of quasi‐carbon/phenolic composites was investigated in terms of the flexural strength and modulus, interlaminar shear strength, and storage modulus. The results were also compared with those of a stabilized PAN fabric/phenolic composite. The flexural, interlaminar, and dynamic mechanical results were quite consistent with one another. On the basis of all the results, the quasi‐static and dynamic mechanical properties of quasi‐carbon/phenolic composites increased with the applied external tension and heat‐treatment temperature increasing and with the heating rate decreasing for the quasi‐carbonization process. This study shows that control of the processing parameters strongly influences not only the mechanical properties of quasi‐carbon/phenolic composites but also the interlaminar shear strength between the fibers and the matrix resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Microwave pre‐oxidation for polyacrylonitrile precursor coated with nano‐carbon black

A surface coating was successfully applied through dipping the polyacrylonitrile (PAN) precursor fibers in a carbon black (CB) bath containing a hydrolyzed binder. The coated fibers were pre‐oxidized over the microwave furnace at temperatures ranging from 100°C to 170°C for different heating times. The changes in chemical structure were studied by Fourier transfer infrared spectroscopy combined with elemental analyzer. X‐ray diffraction was employed to study the crystalline structure and its related parameters. Differential scanning calorimeter and thermogravimetry were used for thermal analysis. In addition, the fiber morphology and the mechanical properties were also evaluated. Scanning electron microscopy results confirmed the presence of CB on the surface of PAN precursor. The analysis in the chemical structure showed an apparent response of coated PAN fibers to the microwave heating, since the microwave field induced the cyclization and crosslinking reactions. The crystallinity and the crystallite height decreased. Furthermore, the tensile strength and elongation of pre‐oxidized fibers decreased with the increase of heating time. The measured oxygen content revealed that the pre‐oxidized fibers can withstand the high temperatures on the following stage (carbonization). POLYM. ENG. SCI., 59:457–464, 2019. © 2018 Society of Plastics Engineers     

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.     

Improvement in the properties of PAN‐based carbon films by modification with cobaltous chloride

Carbon films were developed from polyacrylonitrile (PAN) modified with cobalt chloride. The modification was carried out by immersing PAN in a 5% cobaltous chloride (CoCl₂) solution at 90°C for 5 min, oven‐dried, and then manufactured into films. The original and modified PAN films were oxidized at 220°C for 2 and 6 h in air, respectively, and finally carbonized at 1300°C. The density, microstructure, elemental analyzer, electrical conductivity, and morphology were all studied. According to the results, it was found that films modified with cobalt chloride have a greater stacking height of carbon‐layer planes (L_c), density, electrical conductivity, and nitrogen content after carbonization. Moreover, during the carbonization stage, the cobalt ions promote a catalytic action. The carbon films developed from the modified film not only improved electrical conductivity by 12–38%, but also increased tensile strength by 29–36% and the tensile modulus by 69–110%. Therefore, carbon films having better mechanical properties can be obtained after such modification. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1745–1751, 1999     

Desirable electrical and mechanical properties of continuous hybrid nano-scale carbon fibers containing highly aligned multi-walled carbon nanotubes

The continuous highly aligned hybrid carbon nanofibers (CNFs) with different content of acid-oxidized multi-walled carbon nanotubes (MWCNTs) were fabricated through electrospinning of polyacrylonitrile (PAN) followed by a series of heat treatments under tensile force. The effects of MWCNTs on the micro-morphology, the degree of orientation and ordered crystalline structure of the resulting nanofibers were analyzed quantitatively by diversified structural characterization techniques. The orientation of PAN molecule chains and the graphitization degree in carbonized nanofibers were distinctly improved through the addition of MWCNTs. The electrical conductivity of the hybrid CNFs with 3 wt% MWCNTs reached 26 S/cm along the fiber direction due to the ordered alignment of MWCNTs and nanofibers. The reinforcing effect of hybrid CNFs in epoxy composites was also revealed. An enhancement of 46.3% in Young’s modulus of epoxy composites was manifested by adding 5 wt% hybrid CNFs mentioned above. At the same time, the storage modulus of hybrid CNF/epoxy composites was significantly higher than that of pristine epoxy and CNF/epoxy composites not containing MWCNTs, and the performance gap became greater under the high temperature regions. It is believed that such a continuous hybrid CNF can be used as effective multifunctional reinforcement in polymer matrix composites.     

Preparation and characterization of carbon fibers from polyacrylonitrile precursors

The present work deals with the preparation of carbon fibers from polyacrylonitrile (PAN) fibers. The chemical composition and physical properties of the starting fibers were determined. The PAN fibers were stabilized in air at the temperatures (230, 270, and 300°C) with the heating time from 40 to 420 min. The effects of both final stabilization temperature and heating rate on the chemical and physical properties of the prepared stabilized fibers were studied. The chosen stabilized fibers samples were carbonized in argon atmosphere at the temperatures (1000, 1200, and 1400°C) with different heating rates 5, 10, 15, and 20°C min^?1. The effects of both carbonizing temperature and heating rate on the weight loss, density, elemental composition, and IR absorption spectra of carbonized fibers were also studied. The fiber sample, which was carbonized at 1400°C, contains 97.55% carbon, 1.75% nitrogen, and 1.4% hydrogen. This means that carbonizing the stabilized fibers at 1400°C in argon atmosphere is suitable to get oxygen‐free carbon fibers. Therefore, the used carbonizing temperature in the present work (1400°C) is suitable to produce moderate heat‐treated carbon fibers with the heating rate of 15°C min^?1. The modulus of the prepared carbon fibers was compared to that of industrially produced fibers using the results of X‐ray analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of carbon fibers from linear low density polyethylene

Carbon fibers were produced from linear low density polyethylene (LLDPE) instead of commonly used precursors, such as viscose rayon, mesophase pitch and polyacrylonitrile (PAN). Cross-linked fibers were produced at various temperatures, times and stress conditions during a sulfuric acid treatment using LLDPE fibers obtained from dry-wet spinning. The effects of cross-linking were analyzed using a range of characterization techniques, such as differential scanning calorimetry, color change, fourier transform infrared spectroscopy, elemental analysis, density, scanning electron microscopy, and single filament mechanical properties. The carbonization process of cross-linked fibers was carried out at 950 °C for 5 min in a nitrogen atmosphere. The carbon fibers with the best mechanical properties were obtained from the cross-linked fiber with the highest tensile modulus. In particular, the carbon fibers with the best mechanical properties (tensile strength and tensile modulus of 1.65 GPa and 110 GPa, respectively), similar to commercial-grade carbon fiber, were obtained from the cross-linked fiber that had undergone a carbonization process with a stress of 0.25 MPa after an acid treatment for 150 min at 140 °C and a stress of 0.26 MPa.     

Mechanical properties of natural fiber hybrid composites based on renewable thermoset resins derived from soybean oil,for use in technical applications

Natural fiber composites are known to have lower mechanical properties than glass or carbon fiber reinforced composites. The hybrid natural fiber composites prepared in this study have relatively good mechanical properties. Different combinations of woven and non‐woven flax fibers were used. The stacking sequence of the fibers was in different orientations, such as 0°, +45°, and 90°. The composites manufactured had good mechanical properties. A tensile strength of about 119 MPa and Young's modulus of about 14 GPa was achieved, with flexural strength and modulus of about 201 MPa and 24 GPa, respectively. For the purposes of comparison, composites were made with a combination of woven fabrics and glass fibers. One ply of a glass fiber mat was sandwiched in the mid‐plane and this increased the tensile strength considerably to 168 MPa. Dynamic mechanical analysis was performed in order to determine the storage and loss modulus and the glass transition temperature of the composites. Microstructural analysis was done with scanning electron microscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of the oxidation temperature on the structure and properties of polyacrylonitrile‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of the oxidation temperature of the PAN hollow fiber precursor on the microstructure, specific surface, pore size distribution, and adsorption properties of PAN‐based activated carbon hollow fiber (PAN‐ACHF) were studied. When PAN hollow fibers were oxidized at 270°C, because of drastic oxidation, chain scission occurred, and the number of pores within and on the surface of the resultant PAN‐ACHF increased, but the pores were just in the thinner region of the skin of PAN‐ACHF. The surface area of PAN‐ACHF reached a maximum when the oxidation temperature was 270°C. The adsorption ratios to creatinine were all higher than 90% at all oxidation temperatures, and the adsorption ratio to VB₁₂ reached a maximum (97%) at 230°C. The dominant pore sizes of the mesopores in PAN‐ACHF ranged from 2 to 5 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 203–207, 2005     

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     

A study of the thermomechanical properties of carbon fiber-polypropylene composites

Short fiber composites were produced using polypropylene as matrix and polyacrylonitrile (PAN)-based fibers or vapor grown carbon fibers (VGCF) as reinforcement. The strength, stiffness, and coefficient of thermal expansion (CTE) of the composites were measured. The VGCF-composites showed strength and CTE that are competitive with those of “conventional” PAN-fiber composites, but the stiffness was marginally lower. Micromechanical modeling of the PAN composite properties gives results consistent with the measurements. The models can be used to infer the apparent VGCF-properties from their composites.     

A comparison of the effect of graphitization on microstructures and properties of polyacrylonitrile and mesophase pitch-based carbon fibers

Polyacrylonitrile (PAN) and mesophase pitch (MPP)-based carbon fibers were heat treated in the temperature range of 1300–2700 °C. After high-temperature heat treatment (HHT), the microstructures and mechanical properties of PAN and MPP-based carbon fibers were investigated. For both series of carbon fibers, the Young’s modulus increased with heat treatment temperature increasing. The tensile strength of PAN-based carbon fibers decreased, while that of MPP-based carbon fibers increased. After HHT at 2700 °C, the tensile strength of MPP-based carbon fibers exceeded that of PAN-based carbon fibers. The results could be ascribed to the variously original structures and the different routines of structural evolution. The physical entanglements and covalent cross-links of carbon ribbons in PAN-based carbon fibers contributed to a higher shear stress between the graphene layers, however, tended to generate voids and cracks during HHT due to an extensive transformation from turbostratic to ordered structure along with nitrogen removing. For MPP-based carbon fibers, they displayed a radial texture with ordered and parallel packing of layers in the transverse section. Thus, it was easier for the graphene layers to stack and bond to the adjacent ones without strong rotations, leading to fewer voids and cracks.     

Influence of activation time on the properties of polyacrylonitrile-based activated carbon hollow fiber

Activated carbon hollow fiber (ACHF) was prepared from polyacrylonitrile (PAN) hollow fiber through carbonization in nitrogen and activation with carbon dioxide. The effect of the activation time on the pore size distribution and the surface structure of the resulted ACHF was investigated. The results show that increasing the activation time at 800°C can increase the number of pores and reduce the crystal size, the tensile strength, the modulus, and the elongation. © 1995 John Wiley & Sons, Inc.     

Tension of carbonization for carbon fiber

The mechanical properties of carbon fiber, especially tensile modulus, are closely related to the orientation of crystals. Hence, the stretching of carbon fiber during carbonization is of importance. In this study, the tension arm between the carbonization furnaces was used to stretch carbon fiber. The relationships among the stretching tensions of the first stage carbonization (< 800°C) and the second stage carbonization (> 1200°C), the aromatization index for oxidized polyacrylonitrile fiber, and the properties of carbon fiber are discussed.     

Biopolyamide hybrid composites for high performance applications

This study focuses on the performance characteristics of wood/short carbon fiber hybrid biopolyamide11 (PA11) composites. The composites were produced by melt‐compounding of the fibers with the polyamide via extrusion and injection molding. The results showed that mechanical properties, such as tensile and flexural strength and modulus of the wood fiber composites were significantly higher than the PA11 and hybridization with carbon fiber further enhanced the performance properties, as well as the thermal resistance of the composites. Compared to wood fiber composites (30% wood fiber), hybridization with carbon fiber (10% wood fiber and 20% carbon fiber) increased the tensile and flexural modulus by 168% and 142%, respectively. Izod impact strength of the hybrid composites exhibited a good improvement compared to wood fiber composites. Thermal properties and resistance to water absorption of the composites were improved by hybridization with carbon fiber. In overall, the study indicated that the developed hybrid composites are promising candidates for high performance applications, where high stiffness and thermal resistance are required. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43595.     

Formation of a carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube hybrid reinforcement and its effect on the interfacial properties of carbon fiber/epoxy composites

A carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube (CF–POSS–CNT) hybrid reinforcement was prepared by grafting CNTs onto the carbon fiber surface using octaglycidyldimethylsilyl POSS as the linkage in an attempt to improve the interfacial properties between carbon fibers and an epoxy matrix. X-ray photoelectron spectroscopy, scanning electron microscopy, dynamic contact angle analysis and single fiber tensile testing were performed to characterize the hybrid reinforcements. Interlaminar shear strength (ILSS), impact toughness, dynamic mechanical analysis and force modulation atomic force microscopy were carried out to investigate the interfacial properties of the composites. Experimental results show that POSS and CNTs are grafted uniformly on the fiber surface and significantly increase the fiber surface roughness. The polar functional groups and surface energy of carbon fibers are obviously increased after the modification. Single fiber tensile testing results demonstrate that the functionalization does not lead to any discernable decrease in the fiber tensile strength. Mechanical property test results indicate the ILSS and impact toughness are enhanced. The storage modulus and service temperature increase by 11 GPa and 17 °C, respectively. POSS and CNTs effectively enhance the interfacial adhesion of the composites by improving resin wettability, increasing chemical bonding and mechanical interlocking.