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.     

Development of a disposable electrode modified with carbonized,graphene‐loaded nanofiber for the detection of dopamine in human serum

A one‐step electrode surface modification is proposed in which a disposable, screen‐printed carbon electrode is functionalized with carbonized, electrospun polyacrylonitrile (PAN)‐loaded graphene (G) nanoparticles to form a composite, CPAN5G‐4x. The electrochemical behavior of the CPAN5G‐4x electrode was examined by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy and X‐ray diffraction were used to characterize the surface morphology and physical properties of the carbonized composite nanofibers before and after modification. The modified electrode was found to be effective for the detection of dopamine (DA) using square‐wave voltammetry (SWV) in the presence of interfering substances such as ascorbic acid and uric acid. With the addition of sodium dodecyl sulfate (SDS) to an optimized solution of phosphate‐buffered saline (PBS) at a pH of 2, the fabricated electrode exhibited enhanced electrocatalytic activity toward the oxidation of DA relative to PBS without SDS at a pH of 7.4. The SWV current displayed a linear response to DA concentrations ranging from 0.5 to 100 μM, with a limit of detection of 70 nM (S/N = 3) and a sensitivity of 1.4258 μA μM^?1 cm^?2. Finally, the CPAN5G‐4x electrode was used to determine DA levels in human serum. The modified electrode can potentially be harnessed for further electrochemical biosensor applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40858.     

Mass production of carbon nanotube‐reinforced polyacrylonitrile fine composite fibers

A facile and large‐scale production method of polyacrylonitrile (PAN) fibers and carboxyl functionalized carbon nanotube reinforced PAN composite fibers was demonstrated by the use of Forcespinning® technology. The developed polymeric fibers and carbon nanotube‐reinforced composite fibers were subsequently carbonized to obtain carbon fiber systems. Analysis of the fiber diameter, homogeneity, alignment of carbon nanotube and bead formation was conducted with scanning electron microscopy. Thermogravimetric analysis, electrical, and mechanical characterization were also conducted. Raman and FTIR analyses of the developed fiber systems indicate interactions between carbon nanotubes and the carbonized PAN fibers through π–π stacking. The carbonized carbon nanotube‐reinforced PAN composite fibers possess promising applications in energy storage applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40302.     

Carbonized electrospun polyvinylpyrrolidone/metal hybrid nanofiber composites for electrochemical applications

Electrospinning is a very versatile and efficient method of fabricating nanofibers with the desired properties. Polyvinylpyrrolidone (PVP) in ethanol solution was electrospun into nanofibers and used as a precursor for the preparation of carbon nanofibers. Cobalt chloride was also incorporated with PVP nanofibers to produce carbon nanofiber composites with enhanced electrical conductivity and electrochemical properties. The surface morphology and physical properties of the electrospun nanofibers, carbonized nanofibers, and their composites were observed by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. The electrochemical behavior of the carbon nanofiber composites was studied by drop‐casting on a working surface of the screen‐printed carbon electrode and examined by cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that carbon nanofiber composites were decorated with cobalt nanoparticles and enhanced the charge‐transfer efficiency on the electrode surface. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45639.     

Electrospun polymer of intrinsic microporosity fibers and their use in the adsorption of contaminants from a nonaqueous system

The smooth and uniform polymer of intrinsic microporosity (PIM‐1) fibers, which have high adsorption capacities toward organic contaminants from nonaqueous systems, were successfully obtained by electrospinning. According to the N₂ adsorption–desorption analysis, the surface area of the PIM‐1 fibers was higher than that of the PIM‐1 powder. The higher surface area of the fibers did not come from the interfiber pores but from intrafiber pores formed by the fast evaporation of the solvent in the electrospinning process. The PIM‐1 fibers had more mesopores than the PIM‐1 films. As a result, the adsorption rates of the dyes on the fibers were much higher than those on the dense films. We found that the adsorption data fitted perfectly with the pseudo‐second‐order model and intraparticle diffusion model. The adsorption mechanism between the dyes and PIM‐1 was π–π interaction. Therefore, the dye could be desorbed from PIM‐1 with toluene; this was a better π‐electron‐rich donor than the dye. In summary, we believe that the use of PIM‐1 fibers for organic solvent recovery is a green, sustainable, and efficient method, and they have a great potential for industrial applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43475.     

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

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

The unique morphology role of thorn surface in determining electrochemical performance of polyaniline nano‐fibers via one‐step method

Polyaniline nano‐fibers with thorn surface morphology (T‐PANI) were synthesized by one‐step polymerization with adding additional aniline at later stage of chemical oxidation synthesis. In order to investigate the morphology role in determining electrochemical performance, the nano‐fibers PANI without thorn (PANI) was synthesized by the same polymerization process but at different time to add additional aniline. Material structures were characterized by field emission scanning electron microscope and Brunauer‐Emmett‐Teller method, and electrochemical performance was tested through cyclic voltammograms, galvanostatic charge‐discharge and electrochemical impedance spectroscopy. The data showed that the specific capacitance of T‐PANI was 443 F g^?1 at 5 mA cm^?2, which was much more than that of PANI (338 F g^?1 at 5 mA cm^?2). The solution resistance, charge transfer resistance, and diffuse resistance of T‐PANI were also lower than these of PANI. The results indicate that the thorn surface structure plays an important role in determining the electrochemical performance of polyaniline, which attribute to the improvements in pore size, pore distribution, special surface area, and conductivity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42266.     

Microbial origin xanthan gum‐based solid polymer electrolytes

Natural polymers are widely used as matrices for solid polymer electrolytes (SPEs) in electrochemical devices due to their richness in nature, low cost, and biodegradation properties. Xanthan gum (XG) is a natural polymer obtained from microbial origin and when dissolved form transparent solution with high viscosity and stability even in different temperature conditions. This article describes the synthesis of XG‐based SPEs with proton conduction. These new materials were obtained by crosslinking XG with glutaraldehyde, plasticized with ethylene glycol, and doped with acetic acid as ions source. The ionic conducting membranes, casted from this polymer solution, showed a high ionic conductivity of 7.93 × 10^?5 S cm^?1 at room temperature, a microscopically homogeneous surface, thermal stability, and predominantly amorphous structure. These results prove that XG‐based SPEs are very promising new materials that could be applied in modern electrochemical devices. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46229.     

Surface modification of polyimide fibers by novel alkaline–solvent hydrolysis to form high‐performance fiber‐reinforced composites

We modified polyimide (PI) fibers by a novel hydrolysis approach and fabricated PI‐fiber‐reinforced novolac resin (NR) composites with enhanced mechanical properties. We first used an alkaline–solvent mixture containing potassium hydroxide liquor and dimethylacetamide (DMAc) for the surface modification of the PI fibers. The results indicate that the surface roughness and structure of the PI fibers were controlled by the hydrolysis time and the content of DMAc. With the optimized hydrolysis conditions, the tensile modulus of modified PI fibers improved 15% without compromises in the fracture stress, fracture strain, or thermal stability. The interfacial shear strength between the modified PI fibers and NR increased 57%; this indicated a highly enhanced interfacial adhesion. Finally, the tensile and flexural strengths of the composites increased 72 and 53%, respectively. This research provides an effective method for the surface modification of PI fibers and expands their applications for high‐performance composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46595.     

Self‐healing polyurethane nanocomposite films with recoverable surface hydrophobicity

It is a great challenge for self‐healing materials to recover their mechanical property and surface hydrophobicity simultaneously after being damaged severely, such as deep and wide surface scratches. In this work, a series of hydrophobic films were prepared by mixing perfluoroalkyl‐loaded SiO₂ nanoparticles with thermally self‐healing polyurethane. The Diels–Alder reaction of furan groups with bismaleimides endowed the polyurethane with self‐healing property, and the introduction of perfluoroalkyl chains gave surface hydrophobicity. When being heated, the low surface energy compounds could gradually move onto the surface to make the surface hydrophobicity recoverable. The self‐healing mechanical property and recoverable hydrophobicity would improve the durability and expand the application of polyurethane nanocomposites as self‐cleaning and self‐healing coatings/surfaces. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46421.     

Fabrication of speedy and super‐water‐absorbing non‐woven cloth with hierarchical three‐dimensional network structure

A novel speedy and super‐water‐absorbing non‐woven cloth with hierarchical three‐dimensional network (3D‐SS‐PET) was fabricated through the induction of UV copolymerization on polyethylene terephthalate (PET) fibers followed by a volume phase transition. The macroscopic three‐dimensional network implied that the PET non‐woven substrates are complicated three‐dimensional fibrous materials including oriented fibers in preferential or random directions. The microscopic three‐dimensional network is poly(acrylic acid‐co‐acrylamide) (poly(AA‐co‐AM)) crosslinked copolymer layers on the fiber surface. The rapid volume phase transition was achieved by immersing the swelled non‐woven poly(AA‐co‐AM) modified PET (PET‐g‐AA‐co‐AM) in ethanol. The above process was an essential step to prepare the copolymer chain; after that the fiber surface was extended to form abundant capillary channels and plenty of space between fibers. The water contact angle decreased remarkably from 130° to 0°, while the absorbing capacity of the saturated water and the average water‐absorbing rate experienced an increasing trend, rising from 300 to 324.6 g g^?1 in 24 h and 18.6 and 222 g (g min)^?1 in 40 s, respectively. It was concluded that surface hydrophilicity and capillaries of the hydrophilic modified macroscopic fibrous structure enhanced the water‐absorbing rate and the swelling process contributed to the higher water absorption capacity. This speedy and super‐water‐absorbing material exhibits great potentiality in diapers, sanitary napkins, wound dressings, surgical pads, and hygroscopic and sweat‐free underwear in extremely cold areas. © 2018 Society of Chemical Industry     

Ethane‐selective carbon composites CPDA@A‐ACs with high uptake and its enhanced ethane/ethylene adsorption selectivity

Novel composites (CPDA@A‐ACs) of carbonized polydopamine (CPDA) and asphalt‐based activated carbons (A‐ACs) were successfully synthesized, and characterized for adsorption separation of ethane/ethylene. The resulting CPDA@A‐ACs exhibited high Brunauer–Emmett–Teller surface area of 1971 m²/g. The O and N contents on CPDA@A‐ACs are higher than those on A‐ACs due to the introduction of CPDA. Interestingly, CPDA@A‐ACs exhibited great preferential adsorption of ethane over ethylene. Its ethane capacity reached as high as 7.12 mmol/g at 100 kPa and 25°C, and its ethane/ethylene adsorption selectivity became higher compared to A‐ACs, reaching as high as 3.0～20.6 below 100 kPa, significantly superior to the reported ethane‐selective adsorbents. Simulation results revealed the mechanism of enhanced selectivity toward C₂H₆/C₂H₄, and suggested that the surface oxygen functionalities of the composites play predominant role in enhancing ethane/ethylene adsorption selectivity. Fixed‐bed experiments showed that C₂H₆/C₂H₄ mixtures can be well separated at room temperature, suggesting great potential for industrial C₂H₆/C₂H₄ separation. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3390–3399, 2018     

Improvement of carbon materials performance by nitrogen functional groups in electrochemical capacitors in organic electrolyte at severe conditions

N-doped activated carbon fibers have been synthesized by using chemically polymerized aniline as source of nitrogen. Commercial activated carbon fibers (A20) were chemically modified with a thin film of polyaniline (PANI) inside the microporosity of the carbon fibers. The modified activated carbon fibers were carbonized at 600 and 800 °C, respectively. In this way, activated carbon fibers modified with surface nitrogen species were prepared in order to analyze their influence in the performance of electrochemical capacitors in organic electrolyte. Symmetric capacitors were made of activated carbon fibers and N-doped activated carbon fibers and tested in a two-electrode cell configuration, using triethylmethylammonium tetrafluoroborate/propylene carbonate (TEMA-BF₄/PC) as electrolyte. The effect of nitrogen species in the degradation or stabilization of the capacitor has been analyzed through floating durability tests using a high voltage charging (3.2 V). The results show higher stabilizing effect in carbonized samples (N-ACF) than in non-carbonized samples and pristine activated carbon fibers, which is attributed to the presence of aromatic nitrogen group, especially positively charged N-functional groups.     

Application of the dry‐spinning method to produce poly(ε‐caprolactone) fibers containing bovine serum albumin laden gelatin nanoparticles

We designed and manufactured a polymeric system with combined hydrophilic–hydrophobic properties by loading gelatin nanoparticles (GNPs) containing bovine serum albumin (BSA) into poly(ε‐caprolactone) (PCL) fibers. Our ultimate goal was to create a device capable of carrying and releasing protein drugs. Such a system could find several biomedical applications, such as those in controlled release systems, surgical sutures, and bioactive scaffolds for tissue engineering. A two‐step desolvation method was used to produce GNPs, whereas PCL fibers were produced by a dry‐spinning method. The morphological, mechanical, and thermal properties of the produced system were investigated, and the distribution of nanoparticles both inside and on the surface of the fibers was examined. The effect of the particles on the biodegradability of the fibers was also evaluated. In vitro preliminary tests were performed to study the release of BSA from nanoparticle‐laden fibers and to compare this with its release from free nanoparticles. Our results indicate that the distribution of particles inside the fibers was quite homogeneous and only a few of them were present on the surface. The presence of the particles in the fibers did not affect the thermal properties of the PCL polymer matrix, although it created voids that affected the degradation characteristics so the PCL fibers favored faster erosion compared to the plain fibers. Preliminary results indicate that the release from GNP‐laden fibers occurred much more slowly compared to that in the free GNPs. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44233.     

Accelerating the graphitization process of polyimide by addition of graphene

In this article, a composite film from polyimide and thermally exfoliated graphene was prepared through in situ polymerization, and the weight percent of thermally exfoliated graphene with respect to the polyimide monomers was 5 wt %. The film was carbonized at 1000°C for 1 h and then heat‐treated at various temperatures up to 2100°C. For comparison, the corresponding pure polyimide film was also prepared and heat‐treated at the same condition. It was found that the addition of graphene could effectively prevent the polyimide film from shrinking in the direction parallel to the film surface during the heat treatment. Furthermore, the results of density, X‐ray diffraction, shrinkage in the direction perpendicular to the film surface and scanning electron microscopy revealed that the graphitization process of the polyimide could be accelerated by addition of graphene obviously. In view of the above phenomena, a reasonable explanation was presented. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41274.     

Fabricating novel thermal crosslinked ultrafine fibers via electrospinning

In this article, we report the preparation of a kind of novel crosslinked ultrafine fiber by electrospinning of unsaturated polyester macromonomers (UPM) and subsequent thermal crosslinking. The UPM is prepared via a two‐step reaction with poly(2‐methyl‐1,3‐propyleneadipate) diol terminated (PMPA), isophorone‐diisocyanate (IPDI) and 2‐hydroxyethyl methacrylate (HEMA). Poly(3‐hydroxyl‐butyrate‐co‐3‐hydroxylvalerate) (PHBV) is chosen to improve the processability of the UPM. UPM/PHBV blend ultrafine fibers are successfully electrospun with a proper mass ratio of UPM to PHBV in dichloromethane solution. The fibers are thermally crosslinked after electrospinning. Measurement results indicate that the average diameter of the fibers is about 1 μm and the crosslinked fibers have good solvent‐stability and thermal‐stability. This novel fiber has potential applications in filtration and protective coating. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 107:2142–2149, 2008     

GMA‐based emulsion‐templated solid foams: Influence of co‐crosslinker on morphology and mechanical properties

Highly open porous polymer foams formed from high internal phase emulsions (polyHIPEs) are attracting significant interest because of their potential applications in many areas of advanced materials science. In this work, the influence of the crosslinker or co‐crosslinkers of different molecular weights on the morphology and mechanical properties of polyHIPEs containing glycidyl methacrylate (GMA) was studied. Several poly(ethylene glycol) dimethacrylate (PEGDMA) crosslinkers were considered. The results show that introducing higher molecular weight crosslinkers into polyHIPEs produces a more open structure, with significantly increased compression strength and deformation at breakage. This eliminated the undesirable brittleness and chalkiness commonly found in polyHIPE materials. The Young's modulus of GMA‐based polyHIPEs containing 40% poly(ethylene glycol) dimethacrylate increased by 50% and the crush strength by 400% when compared with traditional GMA/ethylene glycol dimethylacrylate polyHIPEs. This improvement in mechanical properties is expected to improve the suitability of polyHIPEs for use in a wide range of applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46295.     

Enhanced tribological performance of hybrid polytetrafluoroethylene/Kevlar fabric composite filled with milled pitch‐based carbon fibers

As self‐lubricating bearing liner materials, tribological properties of milled pitch‐based carbon fibers (CFs) modified polytetrafluoroethylene (PTFE)/Kevlar fabric composites were investigated, and the microscopic morphology of worn surface was studied. The results show that the appropriate incorporation of CFs can obviously reduce the wear rate of the fabric composite with almost unchanging friction coefficient. The wear rates of 5 wt % CF‐filled PTFE/Kevlar fabric composites are decreased by 30% and 48% for two kinds of composites made with fibers from different producers compared with unfilled fabric composites. Scanning electron microscopy observations show that the appropriate incorporation of CFs obviously improves the interfacial bonding and reduces pull‐out and fracture of Kevlar fiber. Meanwhile, the introduction of CFs at proper fraction is helpful to form smooth and continuous transfer film on the surface of metal counterpart. The improving mechanism of the CF is attributed to increasing mechanical strength, thermal conductivity and self‐lubricating effects. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46269.     

Recent advances in core/shell bicomponent fibers and nanofibers: A review

There has been a steady progress in developing synthetic fibers in the past few years. Bicomponent fibers and nanofibers in a core/shell (C/S) configuration, including two dissimilar materials have presented unusual potential for use in many novel applications. These fibers can be produced using a variety of materials via different techniques i.e., coaxial melt spinning and electrospinning. In this review, we discuss the recent advances in C/S fibers and nanofibers’ production. The first part has been assigned to the bicomponent fibers manufacturing technology, while production and applications of C/S nanofibers have been described in the second part. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46265.     

A novel carbonized polydopamine (C‐PDA) adsorbent with high CO2 adsorption capacity and water vapor resistance

Novel carbonized polydopamine adsorbents (C‐PDAs) with high surface area, high CO₂ adsorption capacity and superior moisture resistance performance were prepared by one‐step synthesis method using polydopamine as carbon precursor at different KOH/C ratios, and then characterized. CO₂ and water vapor adsorption performances of C‐PDAs were examined separately by static adsorption and fixed‐bed experiments. Results showed that BET area and pore volume of C‐PDA‐4 were up to 3342 m²/g and 2.01 cm³/g, respectively. Its CO₂ adsorption capacity reached up to 30.5 mmol/g at 25 bar, much higher than many other adsorbents including metal‐organic frameworks (MOFs). C‐PDAs prepared with high KOH/C ratios had low surface element concentrations of O and N resulting in low surface hydrophilic property. H₂O(g) isotherm of C‐PDA was much lower than those on Mg‐MOF‐74, Cu‐BTC, and MIL‐101(Cr). Fixed‐bed experiments showed that co‐presence of water vapor in feed stream with 30% RH had negligible impact on CO₂ working capacity of C‐PDA. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3730–3738, 2016