In situ Polymerization of Multi-Walled Carbon Nanotube/Nylon-6 Nanocomposites and Their Electrospun Nanofibers

Multiwalled carbon nanotube/nylon-6 nanocomposites (MWNT/nylon-6) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and pristine MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced aromatic amine (COC₆H₄-NH₂) groups onto the side wall. Scanning electron microscopy (SEM) images obtained from the fractured surfaces of the nanocomposites showed that the F-MWNTs in the nylon-6 matrix were well dispersed as compared to those of the P-MWNTs. Both nanocomposites could be electrospun into nanofibers in which the MWNTs were embedded and oriented along the nanofiber axis, as confirmed by transmission electron microscopy. The specific strength and modulus of the MWNTs-reinforced nanofibers increased as compared to those of the neat nylon-6 nanofibers. The crystal structure of the nylon-6 in the MWNT/nylon-6 nanofibers was mostly γ-phase, although that of the MWNT/nylon-6 films, which were prepared by hot-pressing the pellets between two aluminum plates and then quenching them in icy water, was mostly α-phase, indicating that the shear force during electrospinning might favor the γ-phase, similarly to the conventional fiber spinning.     

Preparation of electrospun nanofibers of carbon nanotube/polycaprolactone nanocomposite

Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and unfunctionalized MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced the aromatic amine (COC₆H₄-NH₂) groups on the side wall. The F-MWNTs were chemically bonded with the PCL chains in the F-MWNT/PCL, as indicated by the appearance of the amide II group in the FT-IR spectrum. The TGA thermograms showed that the F-MWNT/PCL had better thermal stability than PCL and P-MWNT/PCL. The PCL and the nanocomposite nanofibers were prepared by an electrospinning technique. The nanocomposites that contain more than 2 wt% of MWNTs were not able to be electrospun. The bead of the F-MWNT/PCL nanofiber was formed less than that of the P-MWNT/PCL. The nanocomposite nanofibers showed a relatively broader diameter than the pure PCL nanofibers. The MWNTs were embedded within the nanofibers and were well oriented along the axes of the electrospun nanofibers, as confirmed by transmission electron microscopy.     

Studies on the synthesis of electrospun PAN‐Ag composite nanofibers for antibacterial application

We have successfully synthesized polyacrylonitrile (PAN) nanofibers impregnated with Ag nanoparticles by electrospinning method at room temperature. Briefly, the PAN‐Ag composite nanofibers were prepared by electrospinning PAN (10% w/v) in dimethyl formamide (DMF) solvent containing silver nitrate (AgNO₃) in the amounts of 8% by weight of PAN. The silver ions were reduced into silver particles in three different methods i.e., by refluxing the solution before electrospinning, treating with sodium borohydride (NaBH₄), as reducing agent, and heating the prepared composite nanofibers at 160°C. The prepared PAN nanofibers functionalized with Ag nanoparticles were characterized by field emission scanning electron microscopy (FESEM), SEM elemental detection X‐ray analysis (SEM‐EDAX), transmission electron microscopy (TEM), and ultraviolet‐visible spectroscopy (UV‐VIS) analytical techniques. UV‐VIS spectra analysis showed distinct absorption band at 410 nm, suggesting the formation of Ag nanoparticles. TEM micrographs confirmed homogeneous dispersion of Ag nanoparticles on the surface of PAN nanofibers, and particle diameter was found to be 5–15 nm. It was found that all the three electrospun PAN‐Ag composite nanofibers showed strong antibacterial activity toward both gram positive and gram negative bacteria. However, the antibacterial activity of PAN‐Ag composite nanofibers membrane prepared by refluxed method was most prominent against S. aureus bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Co-axial electrospinning with sodium thiocyanate solution for preparing polyacrylonitrile nanofibers

A modified co-axial electrospinning process including electrolyte solution as sheath fluid for preparing high quality polymer nanofibers is investigated. A series of polyacrylonitrile (PAN) nanofibers were fabricated utilizing the modified process with sodium thiocyanate solutions in N, N-dimethylacetamide (DMAc) as sheath fluids. Field-emission scanning electron microscopy results demonstrated that the sheath sodium thiocyanate solutions had significant influence on the quality of PAN nanofibers. High quality PAN nanofibers in terms of fiber diameters and their distributions, surface morphology and structure have been successfully produced. The diameters of nanofibers (D, nm) could be manipulated simply by adjusting the concentrations of sodium thiocyanate (C, mg ml^-1) in the sheath fluids with a scaling law of D = 324 C ^-0.1806. The mechanism about the influence of sodium thiocyanate solutions on the formation of PAN fibers is discussed and it is felt that co-axial electrospinning with electrolyte solution is a facile process for achieving high quality polymer nanofibers.     

Fabrication of MWNTs/nylon conductive composite nanofibers by electrospinning

MWNT/nylon 6, 6 composite nanofibers were fabricated using an electrospinning method, and the electrical properties were examined as a function of the filler concentration. Initially, the pristine, purified MWNTs were treated with a 3:1 mixture of concentrated H₂SO₄/HNO₃ to introduce carboxyl groups onto the MWNT surface. The carboxylated MWNTs were then treated with thionyl chloride and an ethylenediamine solution for amide functionalization. FT-IR spectroscopy was used to examine the functionalization of the MWNTs. Nylon 6, 6 is readily soluble in formic acid. Therefore, the amide functionalized MWNTs were dispersed in formic acid. The solution remained stable and uniform for more than 40 h. –NH₂ termination of the MWNTs improved the dispersion stability of the MWNTs in formic acid. The MWNTs-suspended in a solution of nylon 6, 6 in formic acid was electrospun to obtain the nanofibers. The electrical properties of the nanofibers were examined as a function of the filler concentration. The results showed that the I–V properties of the nanofiber sheet improved with increasing filler concentration.     

Electrospun polyacrylonitrile/zinc chloride composite nanofibers and their response to hydrogen sulfide

In this work, we explore the electrospinning of polyacrylonitrile (PAN)/zinc(II) chloride (ZnCl₂) composite nanofibers and the response of these nanofibers to hydrogen sulfide (H₂S). Solution properties, including surface tension, viscosity, and conductivity, have been measured and integrated with the results of a variety of other analytical techniques to investigate the effects of ZnCl₂ salt on the structure and thermal properties of electrospun nanofibers. It is found that the addition of ZnCl₂ reduces the diameter and inhibits the instantaneous cyclization reaction of these nanofibers. Additionally, exposing PAN/ZnCl₂ fibers to H₂S leads to the formation of PAN/zinc sulfide (ZnS) composite nanofibers that contain ZnS crystals on the surface. These results indicate that PAN/ZnCl₂ composite nanofibers could find applications in H₂S sensing and removal, or as precursors for semiconductor ZnS-coated polymer nanofibers.     

Preparation of TiO<Subscript>2</Subscript> incorporated polyacrylonitrile electrospun nanofibers for adsorption of heavy metal ions

This paper describes the adsorption of lead and cadmium ions from an aqueous solution using a composite of titanium dioxide (TiO₂)-incorporated polyacrylonitrile (PAN) electrospun nanofibers. Adsorption capacities and the mechanical response of the PAN/TiO₂ composite electrospun nanofibers are investigated at different weight percentages of TiO₂ (0.5, 1.0, 2.0, and 5.0 wt.%). The adsorption capacities of the composite PAN/TiO₂ (2.0 and 5.0 wt.%) for Pb(II) and Cd(II) are remarkably increased by approximately 114 and 47%, respectively, compared to those of pure PAN electrospun nanofibers. Moreover, the adsorption of Pb(II) and Cd(II) by PAN/TiO₂ nanofibers reaches an equilibrium within 60 min, and the process can be described using the nonlinear pseudo-second-order kinetic model. The adsorption isotherm study can be represented by the Langmuir model, which suggests the homogeneous distribution of monolayer adsorptive sites on the composite nanofiber surface. Furthermore, the ultimate tensile strength and ductility of all nanofiber membranes are measured through a uniaxial tension test. Mechanical tests reveal a reduction in the tensile strength of the PAN/TiO₂ composite nanofibers with increase in TiO₂ amount due to the possible formation of agglomerates and voids in the nanofiber structure.     

Preparation and characterization of electrospun Ag/polyacrylonitrile composite nanofibers

Novel composite nanofibers consisting of Ag nanoparticles and polyacrylonitrile (PAN) were fabricated successfully. The Raman properties of these Ag/PAN nanofibers were studied at low temperatures, which showed good Raman characteristics. In the process, a PAN solution containing Ag ions was directly electrospun to obtain nanofiber films containing Ag ions, and the Ag ions of resulting composite nanofibers were reduced to Ag nanoparticles in N₂H₅OH aqueous solution. Then, we treated Ag/PAN composite nanofibers at 100 °C, 200 °C, 400 and 600 °C, respectively. The Ag/PAN nanocomposite film was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) patterns and surface-enhanced Raman scattering (SERS) spectroscopy.     

Conductive chitosan/multi walled carbon nanotubes electrospun nanofiber feasibility

The current study focuses on the electrospinning of chitosan (CHT)/multi walled carbon nanotubes (MWNTs) composite nanofiber using a highly stable dispersion. The acetic acid (1–100%) and trifluoroacetic acid/dichloromethane (TFA/DCM 70: 30) was tested as solvent, and the TFA/DCM (70 : 30) is most preferred for fiber formation process with acceptable electrospinnability. Moreover, a new protocol was used to establish proper technique for preparation of electrospinning solution. FT-IR spectroscopy utilized to infer the extent of interaction between CHT polymer chain and MWNT filaments. A quite simple technique was employed to show the stability of electrospinning solution before nanofiber formation process. Scanning electronic microscope (SEM) was employed to show the influence of spinning parameters on surface morphology of electrospun fiber. Under optimized condition, homogeneous and beadfree CHT/MWNTs nanofibers and known physical characteristics were prepared. The formation of conducting nanofibers based on CHT nanocomposites can be considered as a significant improvement in electrospinning of CHT/CNT dispersion. The direct outcome of the current study includes the homogeneous CHT/MWNTs nanofibers with an average diameter of 275 nm and a conductivity of 9×10⁻⁵ S/cm. These results are extremely important for further investigation regarding biomedical applications.     

Improving Mechanical Properties of Carbon/Epoxy Composite by Incorporating Functionalized Electrospun Polyacrylonitrile Nanofibers

Electrospun functionalized polyacrylonitrile grafted glycidyl methacrylate (PAN‐g‐GMA) nanofibers are incorporated between the plies of a conventional carbon fiber/epoxy composite to improve the composite's mechanical performance. Glycidyl methacrylate (GMA) is successfully grafted onto polyacrylonitrile (PAN) polymer powder via a free radical mechanism. Characterization of the electrospun PAN and PAN‐g‐GMA nanofibers indicates that the grafting of GMA does not significantly alter the tensile properties of the PAN nanofibers but results in an increase in the diameter of nanofibers. Statistical analysis of the mechanical characterization studies on PAN‐carbon/epoxy hybrid composites conclusively shows that the composite reinforced with functionalized PAN nanofibers has greater mechanical properties than that of both the neat PAN nanofiber enriched hybrid composite and control composite (without nanofibers). The improved performance is attributed to the grafted glycidyl groups on PAN, leading to stronger interactions between the nanofibers and the epoxy matrix. PAN‐g‐GMA nanofiber reinforced composite outperforms their neat PAN counterparts in tensile strength, short beam shear strength, flexural strength, and Izod impact energy absorption by 8%, 9%, 6%, and 8%, respectively. Compared to the control composite, the improvements resulting from the PAN‐g‐GMA nanofiber incorporation are even more pronounced at 28%, 41%, 32%, and 21% in the corresponding tests, respectively.

     

Multi-walled carbon nanotubes reinforced nylon 6 composites

Multiwalled carbon nanotubes (MWNT) were functionalized with amine groups using a ‘grafting to’ technique. The oxidized MWNT (MWNT-COOH) were converted to the acyl chloride functionalized MWNT (MWNT-COCl) by treating them with thionyl chloride (SOCl₂), and then MWNT-COCl was reacted with hexamethylenediamine to prepare MWNT-NH₂. The formation of MWNT-NH₂ was confirmed through the FTIR observation. MWNT-NH₂/nylon 6 composites with different MWNT loadings were prepared by the simple melt compounding approach. A fine dispersion of MWNTs throughout nylon 6 matrix was observed by SEM and TEM. The fractured surface of the composites showed not only a uniform dispersion of MWNTs but also a strong interfacial adhesion with the matrix, as evidenced by the presence of many broken but strongly embedded MWNTs in the matrix in the absence of debonding of MWNTs from the matrix. Incorporation of MWNTs improved the mechanical properties significantly. Higher thermal stability was obtained for the composites with better dispersed MWNTs.     

Photocatalytic Deposition of Silver Nanoparticles onto Organic/Inorganic Composite Nanofibers

Summary: In this work, silver nanoparticles were embedded in electrospun organic/inorganic composite nanofibers consisting of PAN and TiO₂ through photocatalytic reduction of the silver ions in silver nitrate solutions under UV irradiation. The morphology and diameter of PAN/TiO₂ composite nanofibers could be controlled by varying the initial contents of TiO₂ in the spinning solution. From TEM images and UV‐Vis spectra, it has been confirmed that monodisperse silver nanoparticles with a diameter of ≈2 nm were deposited selectively upon the titania of the as prepared composite nanofibers. The amount of Ag nanoparticles embedded on composite nanofibers was greatly influenced by the amount of TiO₂ in composite nanofibers, reflecting the role of titania as the inorganic stabilizer and photocatalyst.

Morphology of silver nanoparticles embedded on PAN/TiO₂ composite nanofibers.     

Influence of iron (III) acetylacetonate on structure and electrical conductivity of Fe3O4/carbon composite nanofibers

Fe₃O₄/carbon composite nanofibers were prepared by electrospinning polyacrylonitrile (PAN), iron (III) acetylacetonate (AAI) and dimethyl formamide (DMF) compound solutions, followed by stabilization and carbonization processes. Emphasis was put on the influence of AAI on reactions during stabilization and carbonization. The effect of Fe₃O₄ on catalytic graphitization and electrical conductivity was also studied. Experimental results show that AAI has participated in the reactions and structural changes of PAN during stabilization and carbonization, and is evidenced to promote the processes. Fe₃O₄ nanoparticles exhibit catalytic effect on carbonization process that promote graphitization by a catalytic effect at low AAI content and inhibit the formation of graphitized layers when AAI content is excessive. Therefore, there exists an optimum AAI content (C_o) where composite nanofibers show the maximum graphitization degree and electrical conductivity. With proper amount of AAI addition, Fe₃O₄/carbon composite nanofibers showing high graphite degree and electrical conductivity could be achieved.     

Metallophthalocyanine/polyacrylonitrile nanofibers by solution blow spinning technique for enhanced photocatalytic activity by visible light

A novel photocatalyst, nano-sized zinc and cobalt phthalocyanines (MPc), are anchored on polyacrylonitrile (PAN) nanofibers in the presence or absence of TiO₂ and the process was realized with an innovative solution blow spinning (SBS) method for the first time. Novel nanofiber composites were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy techniques. According to the SEM micrographs, the immobilization of nano-Pcs on the surface of PAN nanofibers was uniform and does not involve agglomeration. The MPc/PAN composite yielded nearly complete degradation of methylene blue (MB) of a highly photocatalytic nature. It was also found that the presence of TiO₂ on MPc/PAN composite have no effect on photodegradation of MB. Also, the recycling of new photocatalysts required as little change as possible owing to their macroscopic structure and their flexible nature.     

Fabrication and characterization of magnetic cobalt ferrite/polyacrylonitrile and cobalt ferrite/carbon nanofibers by electrospinning

An electrospinning process was used to fabricate cobalt ferrite (CoFe₂O₄)-embedded polyacrylonitrile (PAN) nanofibers. Oleic acid-modified CoFe₂O₄ nanoparticles were dispersed in the PAN before spinning. The surface morphologies and structures of the nanofibers were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM observation showed that the average diameter of the CoFe₂O₄/PAN nanofibers was 110 nm, and the magnetic CoFe₂O₄ nanoparticles were embedded in the PAN nanofibers. X-ray photoelectron spectroscopy was used to characterize the CoFe₂O₄/PAN and CoFe₂O₄/carbon nanofibers. Fiber magnetic properties were measured by vibrating sample magnetometry, showing that the saturation magnetization of the CoFe₂O₄/PAN nanofibers was 45 emu/g and that the fibers demonstrated superparamagnetic behavior.     

Osteocompatibility characterization of polyacrylonitrile carbon nanofibers containing bioactive glass nanoparticles

A kind of composite carbon nanofibers (CNF) containing bioactive glass (BG) nanoparticles was produced for bone regeneration by a combination of electrospinning and sol–gel techniques. To produce the BG, compounds such as calcium nitrate, triethyl phosphate and tetraethyl orthosilicate were used as precursors and hydrolyzed to form a sol–gel solution, which was then added to a polyacrylonitrile (PAN) solution in N,N-dimethylformamide. The resulting mixture was electrospun to form PAN nanofibers containing the BG precursors. Upon oxidation and carbonization, the PAN nanofibers and BG precursors transformed into continuous CNF embedded with BG nanoparticles (CNF/BG). Through this fabrication technique, several CNF/BG composites were obtained by controlling the feeding ratios of the different precursors giving rise to BG nanoparticles with various compositions (i.e. containing 70–90 mol% of SiO₂ component). In vitro biomineralization in a simulated body fluid and co-culture with MC3T3-E1 osteoblasts studies were performed to evaluate the osteocompatibility of the CNF/BG nanoparticle composites. When compared to pure CNF, the CNF/BG composites showed an improved ability to promote the in vitro formation of apatite and MC3T3-E1 proliferation, which was found to be dependent upon the composition of BG nanoparticles.     

A comparison of reinforcement efficiency of various types of carbon nanotubes in polyacrylonitrile fiber

Polyacrylonitrile (PAN)/carbon nanotubes (CNTs) composite fibers were spun from solutions in dimethyl acetamide (DMAc), using single wall (SWNTs), double wall (DWNTs), multi wall (MWNTs) carbon nanotubes, and vapor grown carbon nanofibers (VGCNFs). In each case, CNT content was 5 wt% with respect to the polymer. Structure, morphology, and properties of the composite fibers have been characterized using X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, tensile tests, dynamic mechanical tests, as well as thermal shrinkage. While all nanotubes contributed to property improvements, maximum increase in modulus (75%) and reduction in thermal shrinkage (up to 50%) was observed in the SWNT containing composites, and the maximum improvement in tensile strength (70%), strain to failure (110%), and work of rupture (230%) was observed in the MWNTs containing composites. PAN orientation is higher in the composite fiber (orientation factor up to 0.62) than in the control PAN fiber (orientation factor 0.52), and the PAN crystallite size in the composite fiber is up to 35% larger than in the control PAN (3.7 nm), while the overall PAN crystallinity diminished slightly. Nanotube orientation in the composite fibers is significantly higher (0.98 for SWNTs, 0.88 for DWNTs, and 0.91 for MWNTs and VGCNFs) than the PAN orientation (0.52-0.62). Improvement in low strain properties (modulus and shrinkage) was attributed to PAN interaction with the nanotube, while the improvement in high strain properties (tensile strength, elongation to break, and work of rupture) at least in part is attributed to the nanotube length. Property improvements have been analyzed in terms of nanotube surface area and orientation.     

Preparation and properties of electrospun PAN/Fe3O4 magnetic nanofibers

Polyacrylonitrile (PAN)/Fe₃O₄ composite nanofibers were prepared via the electrospinning of the PAN spinning solutions with magnetite Fe₃O₄ nanoparticles. The experimental results showed that the morphology and diameter of the nanofibers strongly depended upon concentrations of PAN and salt additives in the spinning solutions. A suitable PAN concentration and LiCl additives could effectively prevent the occurrence of beads in the electrospinning process and affected the diameters of the electrospun nanofibers. The breaking strength and breaking strain decreased when the magnetite Fe₃O₄ nanoparticles were incorporated. The prepared PAN/Fe₃O₄ nanofibers were superparamagnetic at room temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A kinetic study of in situ polyaniline–gold composite film formation

Chloroaurate acid (HAuCl₄) was used as an oxidant and aniline (ANI) was used as a reducing agent to prepare a polyaniline–gold (PANI-Au) composite film by in situ polymerization. The formation of the composite film was monitored using a quartz crystal microbalance (QCM). The effects of the concentrations of HAuCl₄ and ANI as well as the reaction temperature on the formation of the PANI-Au composite film are discussed. The kinetics of the reaction were investigated by the QCM technique. The results indicate that the kinetics of the reaction are of order 0.5 with respect to HAuCl₄ and 1.5 with respect to aniline. The film growth rate increased with increasing ANI, HAuCl₄ concentration and reaction temperature. The activation energy calculated from the temperature dependence of the growth rate was 40.32 ± 0.15 kJ/mol. In situ UV-visible spectra of the reaction process were obtained and compared to the reaction process using the QCM technique.     

Effects of poly (vinyl alcohol) (PVA) content on preparation of novel thiol-functionalized mesoporous PVA/SiO2 composite nanofiber membranes and their application for adsorption of heavy metal ions from aqueous solution

Thiol-functionalized mesoporous poly (vinyl alcohol)/SiO₂ composite nanofiber membranes and pure PVA nanofiber membranes were synthesized by electrospinning. The results of Fourier transform infrared (FTIR) indicated that the PVA/SiO₂ composite nanofibers were functionalized by mercapto groups via the hydrolysis polycondensation. The surface areas of the PVA/SiO₂ composite nanofiber membranes were >290 m²/g. The surface areas, pore diameters and pore volumes of PVA/SiO₂ composite nanofibers decreased as the PVA content increased. The adsorption capacities of the thiol-functionalized mesoporous PVA/SiO₂ composite nanofiber membranes were greater than the pure PVA nanofiber membranes. The largest adsorption capacity was 489.12 mg/g at 303 K. The mesoporous PVA/SiO₂ composite nanofiber membranes exhibited higher Cu²⁺ ion adsorption capacity than other reported nanofiber membranes. Furthermore, the adsorption capacity of the PVA/SiO₂ composite nanofiber membranes was maintained through six recycling processes. Consequently, these membranes can be promising materials for removing, and recovering, heavy metal ions in water.