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     

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     

Effects of activation temperature on the properties and structure of PAN‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of activation temperature of a precursor fiber on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the BET surface area of the PAN‐ACHF and surface area of mesopores in the PAN‐ACHF increased very remarkably and reached 1422 m² g^?1 and 1234 m² g^?1, respectively, when activation temperature is 1000°C. The adsorptions to creatinine and VB₁₂ of PAN‐ACHF were much high and reached 99 and 84% respectively. In PAN‐ACHF which went through the activation at 700°C and 800°C, the micropore filling mainly occurred at low relative pressures, multimolecular layer adsorption occurred with the increasing of relative pressure, and the filling and emptying of the mesopores by capillary condensation occurred at high relative pressures. But in PAN‐ACHF which went through the activation at 900°C, a mass of mesopores resulted in the large pore filling by capillary condensation. The dominant pore sizes of mesopores in PAN‐ACHF are from 2 nm to 5 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3778–3783, 2006     

Electrically conductive polymeric bi‐component fibers containing a high load of low‐structured carbon black

Melt spinning at semi‐industrial conditions of carbon black (CB) containing textiles fibers with enhanced electrical conductivity suitable for heating applications is described. A conductive compound of CB and high density polyethylene (HDPE) was incorporated into the core of bi‐component fibers which had a sheath of polyamide 6 (PA6). The rheological and fiber‐forming properties of a low‐structured and a high‐structured CB/HDPE composite were compared in terms of their conductivity. The low‐structured CB gave the best trade‐off between processability and final conductivity. This was discussed in terms of the strength of the resulting percolated network of carbon particles and its effect on the spin line stability during melt spinning. The conductivity was found to be further enhanced with maintained mechanical properties by an in line thermal annealing of the fibers at temperatures in the vicinity of the melting point of HDPE. By an adequate choice of CB and annealing conditions a conductivity of 1.5 S/cm of the core material was obtained. The usefulness of the fibers for heating applications was demonstrated by means of a woven fabric containing the conductive fibers in the warp direction. By applying a voltage of 48 V the surface temperature of the fabric rose from 20 to 30°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42255.     

Effects of oxidation and particle shape on critical volume fractions of silver‐coated copper powders in conductive adhesives for microelectronic applications

The effects of oxidation and particle shape on critical volume fractions of silver‐coated copper powders in conductive adhesives are investigated. Silver‐coated copper powders with spherical and flake‐shaped particles were oxidized at temperatures of 30°C, 175°C and 240°C for two hours and dispersed in an epoxy matrix. As silver‐coated copper powders are oxidized at 30°C and 175°C, the critical volume fractions of the conductive adhesives are slightly affected by oxidation and particle shape at these temperatures. As the oxidation temperature approaches 240°C, the critical volume fractions of the conductive adhesives are strongly affected by oxidation temperature and particle shape, owing to the formation of oxides such as Cu₂O on the surface of silver‐coated copper powder—Cu diffuses from the interior to the surface of silver‐coated copper powder and reacts with the oxygen in the air. Silver‐coated copper powder with flake‐shaped particles shows lower critical volume fractions in conductive adhesives than silver‐coated copper powder with spherically shaped particles. Polym. Eng. Sci. 44:2075–2082, 2004. © 2004 Society of Plastics Engineers.     

X‐band dielectric and microwave‐absorbing properties of the incompletely carbonized polyacrylonitrile cloth

Incompletely carbonized polyacrylonitrile (PAN) cloths were prepared by heating stabilized PAN cloth at 600–800°C in different atmosphere. Their X‐band dielectric and microwave‐absorbing properties were investigated. Results showed that the complex permittivity constantly increased with the increasing heating temperature due to the growth of carbon sheets. Conversely, the cloths carbonized in air exhibit lower complex permittivity than those carbonized in nitrogen because the reaction with oxygen restricts the progress of carbonization. The reflection loss below ?10 dB can be obtained in X band for the sample carbonized at 650°C for 2 h in air. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal and mechanical properties of hybrid carbon/oxidized polyacrylonitrile fibers‐epoxy composites

Nowadays, hybrid composites are one of the important materials in industry due to their special properties. In this research, hybrid oxidized polyacrylonitrile (PAN) and carbon fibers reinforcement were used in epoxy matrix. The hybrid composites were fabricated using the hand lay‐up technique by placing the reinforcements in different layering sequences. Thermal and mechanical properties of these hybrid composites were investigated by thermal analysis, horizontal burning, tensile and bending tests. The tensile test results indicated that increasing oxidized polyacrylonitrile fibers (OPFs) to carbon fibers ratio decreased tensile strength and elastic modulus but increased failure strain. Hybrid oxidized PAN and carbon fibers reinforcement in composites led to decreasing flexural stress and modulus, and increasing flame retardancy. Thermal analysis results also showed that the maximum rate of mass loss in all composites was 370.6°C. It was also found that the maximum and minimum amounts of char residue at 900°C were related to the composites with four layers of carbon and OPFs, respectively. POLYM. COMPOS., 38:1412–1417, 2017. © 2015 Society of Plastics Engineers     

Effects of activation time on the properties and structure of polyacrylonitrile‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of activation time of a precursor fiber on the microstructure, specific surface area, pore‐size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. The BET surface area of PAN‐ACHF and surface area of mesopores gradually increase with activation time extending, and reach the maximum values, 780 and 180 m² g^?1, respectively, when fibers are activated at 800°C for 100 min. The adsorption ratio to creatinine changes little with activation time extending and all values over all activation time are above 90%. The adsorption ratio to VB₁₂ gradually increases with activation time extending before 60 min, and then becomes relatively constant from 60 to 100 min. The number of pores on the surface of PAN‐ACHF increases with activation time extending. The amount of mesopores in PAN‐ACHF made of fibers activated for different time increases with activation time extending and the dominant pore sizes of mesopores in PAN‐ACHF range from 2 to 5 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2565–2569, 2006     

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     

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

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

Guanine oxidation signal enhancement in single strand DNA with polyacrylonitrile/polyaniline (PAN/PAni) hybrid nanofibers

Pure polyacrylonitrile (PAN) and polyacrylonitrile/polyaniline (PAN/PAni) hybrid nanofibers (NFs) were produced via electrospinning and used to monitor guanine oxidation in single strand DNA (ssDNA) by electrochemical methods. Two different methodologies were conducted. First, pre‐synthesized PAni was added into electrospinning PAN solution and electrospun into composite PAN/PAni nanofibrous structure on cylindrical pencil graphite (PGE) surface. In the second route, PAN NFs were electrospun on a PGE surfaces and polymerization of PAni was conducted on the surfaces of the as‐spun PAN NFs. NFs were kept at ?18 °C in a refrigerator for several days. ssDNA was immobilized on the prepared NFs and guanine oxidation signals were observed for each system. The results revealed that use of PAN NFs enhanced signal intensity from 0.92 µA (PGE) to 1.04 µA (PAN NFs). Addition of PAni to PAN increased signal intensity to 1.23 µA. When the PAN NF surfaces were coated with PAni, signal enhancement continued to increase up to 4.19 µA for fourth day and decreased again when PAni‐coated NFs were kept at ?18 °C in the refrigerator. Since the prepared system is fast and cheap, it is promising for application in DNA biosensor devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45567.     

Studies on fibers spun from poly(vinyl alcohol‐b‐acrylonitrile) emulsions prepared by ultrasonic technique. II. Properties of the fibers

The moisture content of poly(vinyl alcohol‐b‐acrylonitrile) fibers decreases with an increasing hydrophobic AN content and crystallinity of the fibers; however, the copolymer fiber with 26.94% AN, drawn × 5, and heat‐treated at 200°C has a moisture content value slightly lower than that of commercial PVA fiber, but much higher than that of commercial PAN fiber. The block copolymer fibers have a water‐retention value higher than that of commercial PVA fiber, owing to the presence of voids in these fibers, and have a stronger wicking ability than that of commercial PVA, PAN fibers, and wool and cotton mainly due to the grooved surface and bulk porous morphology of the fibers. The tensile strength of the copolymer fibers with an appropriate AN content are lower than that of commercial PVA fiber, but higher than that of commercial PAN fiber and much higher than that of wool and cotton. The melting temperatures of the copolymer fibers increase with increasing heat‐treatment temperature. The copolymer fibers possess a lower peak cyclizing temperature than that of the PAN fiber and have a higher thermal stability than that of both PVA and PAN fibers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 989–994, 2001     

Morphology and structure changes of aromatic copolysulfonamide fibers heat‐drawn at various temperatures

Pre‐drawn aromatic copolysulfonamide (co‐PSA) fibers were prepared by wet spinning and then heat drawing at temperatures varying from 350 to 390 °C, which are below the decomposition temperature. The fibers were then characterized using tensile testing, dynamic mechanical analysis, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The relationship between structure and properties of the co‐PSA fibers drawn at different temperatures was investigated. The heat‐drawn co‐PSA fibers displayed similar glass transition temperature of about 355 °C, which was higher than that of pre‐drawn co‐PSA fibers of 345 °C. The crystal orientation was high as a crystalline structure formed during heat drawing and the crystallinity increased with the heat‐drawing temperature. However, the tenacity of the co‐PSA fibers did not increase linearly with the draw temperature. When the drawing temperature was higher than the glass transition temperature, a decrease in tenacity was observed, which could be attributed to an increase of crystallite size of the (100) plane and a decrease of the long period of the lamellar structure. © 2014 Society of Chemical Industry     

Polysilazane‐based heat‐ and oxidation‐resistant coatings on carbon fibers

Carbon fibers must be protected from a high‐temperature oxidizing environment because, at approximately 500°C and above, the fibers exhibit reduced mass and strength stability. The fibers can be protected by the application of thermal coatings, which simultaneously improve the adhesive properties of the carbon fibers in the composite materials. Polysilazanes are a new family of heat‐resistant polymer coatings that are converted into silicone carbide or silicone nitride ceramic structures at high temperatures. The converted ceramics are resistant to the effects of high temperatures. In this research work, polysilazane‐based coatings were applied to carbon filament (CF) rovings with the dip‐coating method. Tensile testing at room temperature and under thermal stress was carried out to assess the mechanical and thermomechanical properties of both coated and uncoated rovings. Scanning electron microscopy and energy‐dispersive X‐ray analysis were performed to evaluate the surface topographical properties of the coated and uncoated rovings. Thermogravimetric analysis was executed to determine the thermal stability of the polymer coatings. The coating performance on the CF rovings was determined by assessment of the test results obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Distribution of monomeric,dimeric and polymeric products of stigmasterol during thermo‐oxidation

When plant sterols are oxidized at moderate temperatures (≤100 °C), products mainly derive from hydroperoxides, but at temperatures close to 200 °C, thermal reactions such as dehydration and condensation become important. Although sterols are often subjected to frying conditions, very little is known of their thermal reactions. In this study, stigmasterol was thermo‐oxidized at 180 °C, and the formation of dimers and polymers and the amounts of monomers were measured by high‐performance size‐exclusion chromatography. The products were further characterized by polarity using solid‐phase extraction fractionation. During heating, the amounts of monomers decreased at a steady rate, and those of dimers and polymers increased. After 3 h of heating, 21% of the material existed in higher‐molecular‐weight products. The amount of polar monomers increased especially during the first hour, demonstrating the formation of oxides and their further reactions, while that of mid‐polar monomers decreased constantly, indicating losses of stigmasterol. Polar dimers contributed to approximately 60% of the dimers, and polar polymers to approximately 78% of the polymers, which suggests that in most higher‐molecular‐weight products at least one of the sterol moieties was oxidized. This study showed that a significant proportion of thermo‐oxidation products are not polar monomeric oxides which are commonly analyzed as oxidation products.     

Effect of Microwave Processing on the Crystallization and Energy Density of BaO‐Na2O‐Nb2O5‐SiO2‐B2O3 Glass‐Ceramics

Barium sodium niobate (BNN) glass‐ceramics were successfully synthesized through a controlled crystallization method, using both a conventional and a microwave hybrid heating process. The dielectric properties of glass‐ceramics devitrified at different temperatures and conditions were measured. It was found that the dielectric constant increased with higher crystallization temperature, from 750°C to 1000°C, and that growth of the crystalline phase above 900°C was essential to enhancing the relative permittivity and overall energy storage properties of the material. The highest energy storage was found for materials crystallized conventionally at 1000°C with a discharge energy density of 0.13 J/cm³ at a maximum field of 100 kV/cm. Rapid microwave heating was found to not give significant enhancement in dielectric properties, and coarsening of the ferroelectric crystals was found to be critical for higher energy storage.     

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     

Studies on fibers spun from poly(vinyl alcohol‐b‐acrylonitrile) emulsions prepared by ultrasonic technique. I. Characterization of fiber structure

The structural characteristics of poly(vinyl alcohol‐b‐acrylonitrile) fibers with different AN contents were studied by comparison with that of PVA and PAN fibers. X‐ray diffraction analysis showed that both PVA and PAN blocks in the copolymer fibers formed crystals. Two glass transition temperatures corresponding to PVA and PAN components appeared on the dynamic mechanical spectrum of the copolymer fiber, indicative of their incompatibility in the fiber. SEM intuitively exhibited a longitudinal cracked and grooved surface morphology similar to that of PAN fiber and revealed an internal microdomain separation morphology for the block copolymer fibers. TEM showed a morphological structure intermediate between those of PVA and PAN fibers for the block copolymer fibers. It was also found that the copolymer fiber with the lower AN content has a sheath–core structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 979–988, 2001     

Effect of thermal aging on electrical conductivity of the 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid‐doped polyaniline fiber

The thermal characteristics of inherently conductive polyaniline (PANi) fiber have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Fibers show five major weight losses at ∼100°C, 165°C, 215°C, 315°C, and 465°C, which are associated with the removal of moisture, residual solvent, decompositions of the sulfonic acid and degradation of PANi fiber, respectively. The 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPSA) that dopes the PANi (in fiber form) performs two‐stage decompositions. The conductivity of the drawn fibers aged at 50°C, 100°C, 150°C, and 190°C under vacuum for various periods of time decreases, particularly at temperatures higher than 100°C. The reduction in conductivity of the fiber aged at temperatures lower than 100°C is mainly due to the evaporation of the residual solvent (15–20% in the as‐spun fiber). Further decrease in conductivity of the fiber aged at temperatures higher than 100°C is caused by the decomposition of the dopant AMPSA. The temperature‐dependent conductivity of the fiber was measured at 15 K (−258.5°C) to 295 K (21.5°C). The conductivity of both aged and un‐aged fibers is all temperature activated, however, the conductivity of the un‐aged fibers is higher than that of the aged fibers. Although a negative temperature coefficient was observed in the temperature range from 240 K (–24.5°C) to 270 K (–3.5°C) for the un‐aged fibers, it was disappeared when the fibers were thermal aged at 100°C for 24 h in vacuum oven. These results indicate that the residual solvent trapped inside the fiber enhanced the electrical conductivity of the fibers and its “metallic” electrical conductivity at temperatures ∼263 K (–10°C). © 2001 John Wiley & Sons, Inc. † J Appl Polym Sci 79: 2503–2508, 2001     

Characterization of polyacrylonitrile,poly(acrylonitrile‐co‐vinyl acetate), and poly(acrylonitrile‐co‐itaconic acid) based activated carbon nanofibers

In this study, three different acrylonitrile (AN)‐based polymers, including polyacrylonitrile (PAN), poly(acrylonitrile‐co‐vinyl acetate) [P(AN‐co‐VAc)], and poly(acrylonitrile‐co‐itaconic acid) [P(AN‐co‐IA)], were used as precursors to synthesize activated carbon nanofibers (ACNFs). An electrospinning method was used to produce nanofibers. Oxidative stabilization, carbonization, and finally, activation through a specific heating regimen were applied to the electrospun fibers to produce ACNFs. Stabilization, carbonization, and activation were carried out at 230, 600, and 750 °C, respectively. Scanning electron microscopy, thermogravimetric analysis (TGA), and porosimetry were used to characterize the fibers in each step. According to the fiber diameter variation measurements, the pore extension procedure overcame the shrinkage of the fibers with copolymer precursors. However, the shrinkage process dominated the scene for the PAN homopolymer, and this led to an increase in the fiber diameter. The 328 m²/g Brunauer–Emmett–Teller surface area for ACNFs with PAN precursor were augmented to 614 and 564 m²/g for P(AN‐co‐VAc) and P(AN‐co‐IA), respectively. The TGA results show that the P(AN‐co‐IA)‐based ACNFs exhibited a higher thermal durability in comparison to the fibers of PAN and P(AN‐co‐VAc). The application of these copolymers instead of AN homopolymer enhanced the thermal stability and increased the surface area of the ACNFs even in low‐temperature carbonization and activation processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44381.