Modification of multiwall carbon nanotubes via soap‐free emulsion polymerization of acrylonitrile

A novel method for the synthesis of polyacrylonitrile (PAN)‐coated multiwall carbon nanotubes (MWCNTs) via a simple soap‐free emulsion polymerization is presented for the first time. The polymerization was initiated with conventional anionic ammonium persulfate (APS) at 65 °C. The modification of PAN on MWCNT surfaces was confirmed by Fourier‐transform infrared (FT‐IR) spectroscopy, X‐ray photoelectron spectra (XPS), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), and Raman spectroscopy. It is found that all the surfaces of the MWCNTs were coated by PAN chains, and the PAN coating thickness could be controlled by simply adjusting the polymerization time. The obtained PAN‐coated MWCNTs could be well dispersed in water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2057–2062, 2010     

掺杂羧基化碳纳米管的纳米碳纤维前驱体的制备及表征

为获得结构完整、 性能优良的纳米碳纤维前驱体, 采用静电纺丝法制备了掺杂羧基化多壁碳纳米管(MWCNTs)的聚丙烯腈(PAN)纳米纤维. 用扫描电子显微镜、 偏振红外光谱、 透射电子显微镜、 拉曼光谱及拉伸性能测试等对杂化纳米纤维的微观结构和力学性能进行了研究, 分析了MWCNTs含量的影响. 实验结果表明, 5%(质量分数)的MWCNTs掺杂量为杂化纳米纤维直径的突变点, 且MWCNTs的加入有利于PAN分子链的取向, MWCNTs在PAN纤维中大体上沿纤维轴向取向分布. 3%MWCNTs/PAN杂化纳米纤维的拉伸强度和拉伸模量分别达到88.6 MPa和3.21 GPa.     

Functionalized carbon nanotube/polyacrylonitrile composite nanofibers: fabrication and properties

The functionalized multi‐walled carbon nanotubes (f‐MWCNTs) were obtained by Friedel–Crafts acylation, which introduced aromatic amine groups onto the sidewall. And the grafted yield was adjusted by controlling the concentration of the catalyst. The composite solutions containing f‐MWCNTs and polyacrylonitrile (PAN) were then prepared by in‐situ or ex‐situ solution polymerization. The resulting solutions were electrospun into composite nanofibers. In the in‐situ polymerization, morphological observation revealed that f‐MWCNTs was uniformly dispersed along the axes of the nanofibers and increased interfacial adhesion between f‐MWCNTs and PAN. Furthermore, two kinds of f‐MWCNTs/PAN composite nanofibers had a higher degree of crystallization and a larger crystal size than PAN nanofibers had, so the specific tensile strengths and modulus of the composite nanofibers were enhanced. And the thermal stability of f‐MWCNTs/PAN from in‐situ method was higher than that of ex‐situ system. When the f‐MWCNTs content was less than 1 wt%, the specific tensile strengths and modulus of nanofibers were enhanced with increase in the amounts of f‐MWCNTs, and f‐MWCNTs/PAN of in‐situ system provided better mechanical properties than that of ex‐situ system. Copyright © 2010 John Wiley & Sons, Ltd.     

2D SAXS/WAXD analysis of pan carbon fiber microstructure in organic/inorganic transformation

Structure of PAN fibers during pre-oxidation and carbonization was studied using two dimensional small angle X-ray scattering/wide angle X-ray diffraction(2D SAXS/WAXD).The SAXS results show that during pre-oxidation between 180 ℃ and 275 ℃,the volume content of microvoids increases with the temperature increasing,which may be one of reasons for the decrease of tensile strength of pre-oxidized fibers.253 ℃ was the critical transition temperature,the length,diameter,aspect ratio and orientation distribution of microvoids increased with temperature before this temperature and decreased after this temperature.After the high temperature carbonization,lots of spindly microvoids formed.WAXD patterns demonstrate that the crystallite size of PAN fibers first increased before 230 ℃ and then decreased with the increase of temperature during the pre-oxidation.The diffraction peak of PAN fibers at 2θ≈ 17° almost disappeared at the end of preoxidation while the diffraction peak of aromatic structure at 2θ≈ 25° appeared at 253 ℃.During carbonization,the peak intensity at 2θ≈ 25° increased apparently due to the formation of graphite structure.The results obtained give a deep understanding of the microstructure development in the PAN fibers during pre-oxidation and carbonization,which is important for the preparation of high performance carbon fibers.     

Development of novel synthetic method of carbon nanotubes from electrospun polystyrene fibers by using microwave heating

We have developed a novel synthetic method that enables us to easily synthesize metal‐capsulated carbon nanotubes (CNTs) in a laboratory by using a combined technology of electrospinning‐metallization and microwave heating. These techniques greatly shorten the time for the synthesis of the CNTs in comparison with the conventional methods. TEM analysis confirmed a successful formation of the CNTs, and the resulting CNTs were multi‐walled and found to be about 25–100 nm in diameters. The products prepared by heating at 600 and 900°C exhibited less‐developed and strongly curved CNTs, whereas the products prepared by heating at 700 and 800°C relatively well‐developed long CNTs. Copyright © 2010 John Wiley & Sons, Ltd.     

Uniaxially aligned carbon nanofibers derived from electrospun precursor yarns

Unlike conventional electrospun polymer fibers deposited on a target electrode as a randomly oriented mesh, poly(p‐xylenetetrahydrothiophenium chloride) was electrospun into centimeters‐long yarns vertically on the surface of the electrode but parallel to the electric field. The diameter of the yarn was strongly affected by the concentration, spinning rate, and viscosity of the polymer solution, but less dependent on the applied voltage. The subsequent carbonization of thus‐electrospun yarns at 600–1000 °C resulted in uniaxially aligned carbon nanofibers with average diameters of 127–184 nm. On the basis of Raman spectra, the graphitic crystallite size and the molar fraction of graphite were estimated to be 1.2–1.4 and 0.21–0.24 nm, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 305–310, 2008     

Characteristic assessment of stabilized polyacrylonitrile nanowebs for the production of activated carbon nano-sorbents

Polyacrylonitrile(PAN) nanofibers with average diameter of 300 nm were produced by electro-spinning. The nanofibers were stabilized at different temperatures in the range of 180-270 ℃ in several duration times and heating rates. Fourier transforms infrared(FTIR) spectroscopy, differential scanning calorimetry(DSC) and X-ray diffraction(XRD) analyzing techniques were employed to measure the extent of stabilization reaction. By all procedures, the ranges of temperature and duration time recommended were about 250-270 ℃ and 1-2 h, respectively. Increasing the activation temperature from 800 ℃ to 1200 ℃ caused porosity and pore volume development up to 60% and 0.532 cm3/g, respectively. Pore width of all samples was calculated to be about 0.7 nm confirming micro-pore structure of the produced PAN based activated carbon nanofibers. Comparing dye adsorption for different adsorbents including chitin and granular activated carbon(GAC) showed the highest efficiency for the produced activated carbon nanofibers(ACNFs).     

Fundamental study of crystallization,orientation, and electrical conductivity of electrospun PET/carbon nanotube nanofibers

The morphology, structure, and properties of polyethylene terephthalate (PET)/Carbon Nanotubes (CNT) conductive nanoweb were studied in this article. Nanocomposite nanofibers were obtained through electrospinning of PET solutions in trifluoroacetic acid (TFA)/dichloromethane (DCM) containing different concentrations and types of CNTs. Electrical conductivity measurements on nanofiber mats showed an electrical percolation threshold around 2 wt % multi‐wall carbon nanotubes (MWCNT). The morphological analysis results showed smoother nanofibers with less bead structures development when using a rotating drum collector especially at high concentrations of CNTs. From crystallographic measurements, a higher degree of crystallinity was observed with increasing CNT concentrations above electrical percolation. Spectroscopy results showed that both PET and CNT orientation increased with the level of alignment of the nanofibers when the nanotube concentration was below the electrical percolation threshold; while the orientation factor was reduced for aligned nanofibers with higher content in CNT. Considerable enhancement in mechanical properties, especially tensile modulus, was found in aligned nanofibers; at least six times higher than the modulus of random nanofibers at concentrations below percolation. The effect of alignment on the mechanical properties was less important at higher concentrations of CNTs, above the percolation threshold. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2052–2064, 2010     

Surfactants for CNTs dispersion in zirconia-based ceramic matrix by sol–gel method

Zirconium oxide is a ceramic material widely studied due to its mechanical and electrical properties that can be improved with the use of carbon nanotubes (CNTs) as reinforcement. The synthesis of CNT/zirconia composites by sol–gel method is still very scarce, due to the hydrophobic nature of the CNTs, being their dispersion in aqueous medium an intrinsic difficulty to the synthesis. In this work, we present a sol–gel synthesis for MWCNTs/zirconia composites, where two kinds of surfactants, sodium and ammonium stearates dissolved in water (1 g/100 mL), were used as dispersant agents for multiwall carbon nanotubes (MWCNTs). They are cheap and easy to prepare, and were very effective in dispersing the MWCNTs. Different quantities of MWCNTs (up to 5 wt%) were added in the solution of stearate/water and this solution with the highly dispersed MWCNTs was added to the zirconia sol–gel, producing composites of MWCNTs/zirconia with different concentrations of MWCNTs. All the powders were heat treated at 300 and 500 °C and the powder characterization was performed by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and infrared spectroscopy (FTIR). The composite MWCNTs/zirconia remained amorphous at 300 °C and presented a tetragonal phase at 500 °C with an average grain size of about 20 ± 3 nm, determined by the Scherrer equation from the XRD patterns. For these crystalline samples, TEM images suggest a more effective interaction between MWCNTs with ZrO₂ matrix, where it can be observed that the carbon nanotubes are fully coated by the matrix.     

丙烯腈-衣康酸基纳米纤维纱线的热稳定及碳化研究

碳纳米纤维主要以聚丙烯腈(PAN)作为前驱体,通过纺丝、热稳定、碳化等后处理工艺制备而得.但是,PAN基纳米纤维取向度低、致密性差,热稳定后环化度低,碳化后导电性差等缺点阻碍其在高性能碳纳米纤维领域的发展.因此,在PAN分子链中引入衣康酸(IA),通过溶液聚合法合成了P(AN-co-IA)共聚物并通过静电纺丝法制备了P...     

Vanadium/cobalt oxides–anchored flexible carbon nanofibers with tunable magnetism as recoverable peroxidase-like catalysts

High-efficiency peroxidase-like catalysts that can be easily recycled are desperately needed for the rapid and accurate detection of H₂O₂. Herein, a novel flexible membrane composed of vanadium/cobalt oxides–anchored carbon (VCoO/C) nanofibers has been purposely designed and fabricated by electrospinning and subsequent carbonization, where there are processing temperature-dependent morphology, composition, and versatile properties. As the carbonization temperature increases from 600°C to 900°C, the saturation magnetization of the as-prepared VCoO/C nanofibers rises gradually. When treated at 750°C under Ar protection, the resultant VCoO/C-750 nanofibers yield superior peroxidase-like catalytic activity toward H₂O₂ with a low limit of detection of 0.44 μM (signal-to-noise ratio = 3). The combination of magnetic behavior and flexibility enables the effective recovery of catalysts. It is believed that our results will open a new avenue for the controlled preparation of flexible nanofiber materials, which are endowed with multiple functions.     

Small‐angle X‐ray scattering investigation of carbon nanotube‐reinforced polyacrylonitrile fibers during deformation

Structural changes during deformation in solution‐ and gel‐spun polyacrylonitrile (PAN) fibers with multi‐ and single‐wall carbon nanotubes (CNTs), and vapor‐grown carbon nanofibers were investigated using synchrotron X‐ray scattering. Previously published wide‐angle X‐ray scattering (WAXS) results showed that CNTs deform under load, alter the response of the PAN matrix to stress, and thus enhance the performance of the composite. In this article, we find that the elongated scattering entities that give rise to the small‐angle X‐ray scattering (SAXS) in solution‐spun fibers are the diffuse matrix‐void interfaces that follow the Porod's law, and in gel‐spun fibers these are similar to fractals. The observed smaller fraction of voids in the gel‐spun fibers accounts for the significant increase in the strength of this fiber. The degree of orientation of the surfaces of the voids is in complete agreement with those of the crystalline domains observed in WAXS, and increases reversibly upon stretching in the same way as those of the crystalline domains indicating that the voids are integral parts of the polymer matrix and are surrounded by the crystalline domains in the fibrils. The solution‐spun composite fibers have a larger fraction of the smaller (<10 nm) voids than the corresponding control PAN fibers. Furthermore, the size distribution of the voids during elongation changes greatly in the solution spun PAN fiber, but not so in its composites. The scattered intensity, and therefore the volume fraction of the voids, decreases considerably above the glass transition temperature (T_g) of polymer. Implications of these observations on the interactions between the nanotubes and the polymer are discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2394–2409, 2009     

Novel mechanism for spinning continuous twisted composite nanofiber yarns

Highly aligned and twisted composite Nylon 6 nanofibers incorporating multiwall carbon nanotubes (MWCNTs) were successfully electrospun, using a novel mechanism. It has been found that; ultrasound combined with high speed shearing is the simplest and most convenient method to improve the dispersion of MWCNTs into a polymer matrix with a certain loading. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were conducted to characterize the morphology of nanofibers, the dispersion of MWCNTs and their alignment inside the fiber body. By manipulating the electrical forces during electrospinning and applying mechanical stretching to the electrospun nanofibers, high polymer chain orientation and better alignment of the MWCNTs particles along the fiber axis was achieved. Twist was applied to the nanofibers for providing the required inter fiber lateral cohesion interaction and friction thus, spinning a continuous twisted composite yarn. SEM images show twisted yarns with diameters ranging between 5 and 10 μm. The twist effect of the parallel bundle was investigated by controlling the twist per unit length using a motor speed controller at values of 100, 250, 500, 750 and 1000 rpm. The paper also provides a comprehensive review of various yarn spinning mechanisms of electrospun nanofibers.     

Polyelectrolyte‐grafted carbon nanotubes: Synthesis,reversible phase‐transition behavior,and tribological properties as lubricant additives

A novel polyelectrolyte‐grafted multiwalled carbon nanotubes (MWCNTs‐g‐PILs) which possesses a hard backbone of MWCNTs and a soft shell of brush‐like poly (ionic liquids) (PILs) has been synthesized via the surface atom transfer radical polymerization (ATRP). Chemical structure and the grafted PILs quantities of MWCNTs‐g‐PILs were determined by FTIR, TGA, and XPS. TEM and FE‐SEM observations indicate that the nanotubes were coated with a PILs layer, exhibiting core‐shell nanostructures with the PILs chains as the brush‐like or hairy shell and the MWCNTs as the hard backbone. Furthermore, the effect of counter‐anions on the solubility of MWCNTs‐g‐PILs was investigated. The results indicate that relative solubility of MWCNTs‐g‐PILs in various solvents could be switched by anion exchange. This tunable solubility results in the formation of the cycle of reversible phase‐transition. Tribological property of MWCNTs‐g‐PILs as additives in base lubricant 1‐methyl‐3‐butylimidaaolium hexafluorophosphate (LP104) was evaluated using an Optimol SRV oscillating friction and wear tester, confirming that MWCNTs‐g‐PILs are the excellent antiwear and friction‐reducing additives, which can amend the tribological properties of base lubricant significantly. This is attributed to the good dispersibility and core‐shell structure of MWCNTs‐g‐PILs. These results reported in this work may open primarily toward constructing a bridge among carbon nanotues (CNTs), ILs, and lubricant additives and secondarily to prove that CNTs (modified CNTs) as lubricant additives are promising candidates. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7225–7237, 2008     

A comparative study on characterizations of biomass derived activated carbons prepared by both normal and inert atmospheric heating conditions

In the present study, cost effective activated carbon from wasteland biomass of Calotropis gigantea stem was prepared at 400 °C, 600 °C, 750 °C and 900 °C carbonization temperatures in normal atmosphere (NA) and at 600 °C, 750 °C in inert atmosphere (IA) of nitrogen by using Potassium Carbonate (K₂CO₃) as chemical activating agent in the impregnation ratios of 0.5, 1 and 2. Activated carbons prepared under NA and IA were characterized and compared. Field Emission Scanning Electron Microscopy (FESEM) study confirmed presence of micropores and mesopores. While Xray Diffraction (XRD) analysis confirmed presence of both disordered amorphous carbon humps and graphitic crystallite peaks. Presences of functional groups were more prominent in NAC; found from Fourier Transform Infra-Red Spectroscopy (FTIR) analysis. BET surface area at 750 °C at chemical impregnation ratio 1 under NA was recorded highest containing both micropores and mesopores. Disordered carbon structure was confirmed from RAMAN spectroscopic analysis and nanoporous structure of activated carbon was confirmed from HRTEM analysis. NA activated carbons processed from wasteland weed can be preferred for different adsorption related applications as they are reasonable with improved properties.     

Oxidation, deformation, and destruction of carbon nanotubes in aqueous ceric sulfate

A simple wet chemical method involving only ultrasonic processing in dilute ceric sulfate (CS) was used to functionalize carbon nanotubes (CNTs). Unexpectedly, single-walled and multiwalled carbon nanotubes (SWCNTs and MWCNTs) were cut, oxidized, and disintegrated by sonication in 0.1 N CS for 2-5 h. Transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction spectroscopy (XRD), Raman scattering, and photoacoustic Fourier transform infrared spectroscopy (FTIR) were used to probe wall damage during the chemical processing. Cyclic voltammetry and impedance spectroscopy were used to evaluate the conductivity of the CS-treated CNTs. This one-step process resulted in the destruction of SWCNTs to produce nonconducting amorphous carbon. MWCNTs were oxidized and converted to graphitic materials and amorphous carbon with retained conductivity.     

Controlled Nanofiber Composed of Multi‐Wall Carbon Nanotube/Poly(Ethylene Oxide)

We have successfully fabricated poly(ethylene oxide) (PEO) nanofibers containing embedded multi‐wall carbon nanotubes (MWCNTs). An initial dispersion of the MWCNTs in distilled water was achieved using sodium dodecyl sulfate. Subsequently, the dispersion was decanted into a PEO solution, which enabled separation of the MWCNTs and their individual incorporation into the PEO nanofibers on subsequent electrospinning. Initially, the carbon nanotube (CNT) rods were randomly oriented, but owing to the sink‐like flow in the electrospinning wedge, they became gradually oriented along the streaming direction, in order that oriented CNTs were obtained on entering the electrospun jet. Individual MWCNTs became embedded in the nanofibers, and were mostly aligned along the fiber axis. Evidence of load transfer to the nanotubes in the composite nanofiber was observed from the field‐emission scanning electron microscopy, transmission electron microscopy and conductivity data.     

High temperature oxidative resistance of polyacrylonitrile-methylmethacrylate copolymer powder converting to a carbonized monolith

The doping of polyacrylonitrile (PAN) prior to carbonization can alter the physicochemical nature of the polymer under thermal treatment. The inclusion of a “lower” thermally stable monomer methyl methacrylate (MMA) enables fusion of PAN particles into monoliths and, depending on the heating rate, can control the expansion of the structure and establish pore formation through the volatilization and escape of its thermal degradation products. Moreover, geometry is maintained through the carbonization step, when heated up to 850 °C. The exothermic regime of PAN-co-MMA is much broader and the cyclization reaction starts at a lower temperature compared with that of the PAN homopolymer. TGA reveals that the thermal stability of the copolymer, compared with pure PAN at 800 °C, has increased by 30 wt.% in air, which is far higher than reported in previous studies of copolymers of PAN. The results show promise in providing a facile mechanism for the production of monolithic PAN-based carbons with the potential of controlled porosity.     

Finetuning hierarchical energy material microstructure via high temperature material synthesis route

Hierarchical energy materials such as graphite are a backbone of various scientifically and commercially important emerging technologies including high-energy density energy storage systems with fast charging capability, multifunctional catalyst systems, selective membrane separation systems, and next-generation nuclear material systems. Consequently, it is extremely crucial to develop an efficient and cost-effective route of bulk hierarchical material synthesis (e.g., carbonaceous materials with a well-controlled fraction of the graphitic content) to cater the extraordinary operational and energy material requirements in a very complex coupled thermophysicochemical environment. Here we present a fabrication of Polyacrylonitrile (PAN) derived carbon films and fibers (~with linear dimension ~100 nm) via electrospinning and spin coating methods ensued by a heat-treatment in the range of 1000–3000 °C under inert atmospheric conditions. Intriguingly, we observed at least a two orders of magnitude enhancement (~134%) in length of graphitic plane accompanied by 36% more graphitization when the carbonization temperature increased from 1000 °C to 3000 °C. Such significant enhancements were attributed to the differences in the fundamental nanomorphology of initial carbonaceous materials and their subsequent kinetic evolution as it was more favorable for underlying graphene layers in films to stack and bond to the adjacent ones without strong rotations as compared to fibers, which were further evident from fewer voids and cracks in the films. The covalent cross-links, substrate effect and physical entanglements of carbon domains in PAN-derived carbon films contributed to a higher graphitic length owing to more shear stress between the graphene layers, compared to fibers and undergoes an enormous transformation from turbostratic structures to ordered state along with nitrogen removing over high temperature heating. This morphology dependent graphitization was also investigated from computational approach and concluded in the similar thoughts. The outcomes from this systematic study can be beneficial to the carbon research community focusing in the morphology dependent applications, for instance catalysis, energy storage, sensors etc.     

A composite made from palladium nanoparticles and carbon nanofibers for superior electrocatalytic oxidation of formic acid

We report on a novel type of nanocomposite for use in the electrooxidation of formic acid in fuel cells. The material is composed of palladium nanoparticles (Pd-NPs) and carbon nanofibers (CNFs) and was prepared by electrospinning of the precursors Pd(acac)₂ and polyacrylonitrile, respectively, followed by thermal treatment to generate in-situ Pd-NPs that are well dispersed within the CNF framework. The nanocomposite was characterized by TEM, high-resolution TEM, SEM, XRD, Raman spectroscopy, and XPS. The size of the Pd-NPs ranges from 12 to 82 nm, depending on the temperature for carbonization (700–1,000 °C). The length and width of the CNF is in the order of tens of micrometers and 300 to 500 nm, respectively. TEM and XPS studies indicate that the Pd-NPs are firmly embedded in the CNF, resulting in a good electrochemical stability of the composite. The electrocatalytic properties of the composite with respect to the oxidation of formic acid were studied by cyclic voltammetry and chronoamperometry. They showed a distinctly improved electrocatalytic activity and stability compared to a commercial Pd-on-carbon catalyst. The Pd/CNF composite carbonized at 900 °C was found to display the best performance.