Doped polyaniline/multiwalled carbon nanotube composites: Preparation and characterization

Polyaniline (PANI)/multiwalled carbon nanotube (MWNT) composites with a uniform tubular structure were prepared from in situ polymerization by dissolving amino‐functionalized MWNT (a‐MWNT) in aniline monomer. For this the oxidized multiwalled nanotube was functionalized with ethylenediamine, which provided ethylenediamine functional group on the MWNT surface confirmed by Fourier‐transform infrared spectra (FT‐IR). The a‐MWNT was dissolved in aniline monomer, and the in situ polymerization of aniline in the presence of these well dispersed nanotubes yielded a novel tubular composite of carbon nanotube having an ordered uniform encapsulation of doped polyaniline. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. The thermal stability and electrical conductivity of the PANI /MWNTs composites were characterized by thermogravimetric analysis (TGA) and conventional four‐probe method respectively. Compared with pure PANI, the electrical conductivity and the decomposition temperature of the MWNTs/PANI composites increased with the enhancement of MWNT content in PANI matrix. POLYM. COMPOS., 34:1119–1125, 2013. © 2013 Society of Plastics Engineers     

Fabrication of conducting polyaniline–multiwalled carbon nanotube nanocomposites and their use as templates for loading gold nanoparticles

A new and effective route to synthesize conducting polyaniline‐multiwalled carbon nanotube (PANI ‐f‐MWNT) nanocomposites (where ‘f’ denotes that the MWNTs have been functionalized) starting with amine‐protected 4‐aminophenol is reported. Aminophenol‐functionalized MWNTs were initially synthesized by functionalizing acyl chloride‐terminated nanotubes with N‐(tert‐butoxycarbonyl)‐4‐aminophenol followed by the in situ chemical oxidative grafting of aniline in the presence of ammonium persulfate as an oxidizing agent. Control of the morphology and thickness of the polymer–MWNT nanocomposites was achieved by varying the weight ratios of aniline monomers and MWNTs in the polymerization process. Fourier transform infrared spectroscopy was employed to characterize the initial changes in surface functionalities which also confirmed that PANI was covalently grafted to the MWNTs. Electron microscopy and UV‐visible absorption spectroscopy were employed to characterize the morphology and chemical structure of the resulting hybrids. The results obtained indicate that the structure of the MWNTs was not perturbed by the incorporation of PANI. The content of the polymer in the nanocomposites was determined thermogravimetrically, while the electrical conductivity was obtained using four‐probe measurements. The PANI ‐f‐MWNT nanocomposites were adopted as templates for further decoration with gold nanoparticles in solution, thus opening new possibilities for their prospective technological applications. Copyright © 2010 Society of Chemical Industry     

Preparation and characterization of composites of polyaniline nanorods and multiwalled carbon nanotubes coated with polyaniline

Composites of polyaniline (PANI) nanorods and multiwalled carbon nanotubes (MWNTs) coated with PANI were prepared by in situ polymerization with perchloric acid as a dopant. Transmission electron microscopy images showed that the coexisting composites of PANI nanorods and MWNTs coated with PANI were formed at low MWNT contents. The interaction between MWNTs and PANI was proved by Fourier transform infrared and ultraviolet–visible spectra. The electrical conductivity of a dedoped PANI/MWNT composite with a 16.3 wt % concentration of MWNTs reached 3.0 × 10^?3 S/cm, which was 6 orders of magnitude higher than that of dedoped PANInanorods. The results also showed that coexisting composites of PANI nanorods and MWNTs coated with PANI had high electrochemical activity and good cyclic stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of hybrid polyaniline/carbon nanotube nanocomposites by dynamic interfacial inverse emulsion polymerization under sonication

This article describes an ultrasonically assisted in situ interfacial dynamic inverse emulsion polymerization process of aniline in the presence of multiwalled carbon nanotubes (MWNT) in chloroform. During polymerization, MWNT are coated with polyaniline (PANI) forming a core‐shell structure of nanowires, as evidenced by cryogenic transmission electron microscopy. Thermogravimetric analysis curves and conversion measurements provided important knowledge regarding the unique polymerization method. Scanning electron microscopy images and surface resistivity imply that PANI/MWNTs are characterized by a structural synergistic effect. The PANI coating of MWNT leads to a remarkable improvement in separation and dispersion of MWNT in chloroform, which otherwise would rapidly coagulate and settle. The presented interfacial dynamic polymerization process is very fast, reaching 82% conversion within 5 min of sonication and produces stable clear dispersions of doped PANI in chloroform. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of thermal imidization on mechanical properties of poly(amide‐co‐imide)/multiwalled carbon nanotube composite films

In this study, experimental and numerical studies were performed to investigate the relationship among the functionalization method, weight fraction of MWCNTs, thermal imidization cycle, and mechanical properties of various PAI/MWCNT composite films. Poly(amide‐co‐imide)/multiwalled carbon nanotube composite films were prepared by solution mixing and film casting. The effects of chemical functionalization and weight fraction of multiwalled carbon nanotubes on thermal imidization and mechanical properties were investigated through experimental and numerical studies. The time needed to achieve sufficient thermal imidization was reduced with increasing multiwalled carbon nanotube content when compared with that of a pure poly(amide‐co‐imide) film because multiwalled carbon nanotubes have a higher thermal conductivity than pure poly(amide‐co‐imide) resin. Mechanical properties of pure poly(amide‐co‐imide) and poly(amide‐co‐imide)/multiwalled carbon nanotube composite films were increased with increasing imidization time and were improved significantly in the case of the composite film filled with hydrogen peroxide treated multiwalled carbon nanotubes. Both the tensile strength and strain to failure of the multiwalled carbon nanotube filled poly(amide‐co‐imide) film were increased substantially because multiwalled carbon nanotube dispersion was improved and covalent bonding was formed between multiwalled carbon nanotubes and poly(amide‐co‐imide) molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of homogeneously dispersed polyamide 6/MWNTs nanocomposites via simultaneous in situ anionic ring‐opening polymerization and compatibilization

Toluene 2, 4‐diisocyanate (TDI) functionalized multiwalled carbon nanotubes (MWNTs‐NCO) were used to prepare monomer casting polyamide 6 (MCPA6)/MWNTs nanocomposites via in situ anionic ring‐opening polymerization (AROP). Isocyanate groups of MWNTs‐NCO could serve as AROP activators of ?‐caprolactam (CL) in the in situ polymerization. Fourier transform infrared (FTIR) showed that a graft copolymer of PA6 and MWNTs was formed in the in situ polymerization. MWNTs‐PA6 covalent bonds of the graft copolymer constituted a strong type of interfacial interaction in the nanocomposites and increased the compatibility of MWNTs and MCPA6 matrix. The nanocomposites were characterized for the morphology, mechanical, crystallization, and thermal properties through field emission transmission electron microscopy (FETEM), tensile testing, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). FETEM analysis showed that MWNTs were homogeneously dispersed in MCPA6 matrix. The initial tensile strengths and tensile modulus of the nanocomposite with 1.5 wt % loading of MWNTs were enhanced by about 16 and 13%, respectively, compared with the corresponding values for neat MCPA6. DSC analysis indicated that the crystallization temperature of the nanocomposites was increased by 8°C by adding 1.5 wt % MWNTs compared with pure MCPA6. Besides, it was found that the thermal stability of MCPA6 was improved by the addition of the MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of P(AN‐co‐VA‐co‐DEMA) fibers coated with multiwalled carbon nanotubes by electrostatic interactions

P(AN‐co‐VA‐co‐DEMA) terpolymers were synthesized by aqueous precipitation copolymerization of acrylonitrile (AN), vinyl acetate (VA), and 2‐dimethylamino ethyl methacrylate (DEMA) with an Na₂S₂O₅–NaClO₃ redox initiating system and fibers from these terpolymers were thus prepared by a wet spinning method. Functionalized multiwalled carbon nanotube (F‐MWNT) networks were created on the surface of P(AN‐co‐VA‐co‐DEMA) fibers by a simple dipping method. The morphology and interfacial interactions of the obtained F‐MWNTs‐coated fibers were characterized by scanning electron microscope, Raman spectroscopy, and Fourier transform infrared spectroscopy. The results showed that F‐MWNTs were assembled on the fibers and the density of F‐MWNTs can be controlled by adjusting the F‐MWNTs content in the dipping solution. The assembly process was driven by electrostatic interactions between the negative charges on the nanotube sidewalls and the positive charges of the fibers. The F‐MWNTs‐coated fibers had a good conductivity. The volume resistivity of the fibers coated with 1.18 wt % F‐MWNTs reached 0.27 Ω·cm, while the original mechanical properties were preserved. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42545.     

Modification of pristine multiwalled carbon nanotube by grafting with poly(methyl methacrylate) using benzoyl peroxide initiator

Multiwalled carbon nanotube was successfully grafted with poly(methyl methacrylate) by free radical mechanism using benzoyl peroxide initiator. The reaction was carried out in situ, where the initiator and methyl methacrylate monomer generated the polymer‐free radical that was subsequently grafted to the surface of the pristine multiwalled carbon nanotube. The multiwalled carbon nanotube grafted poly(methyl methacrylate) (MWCNT‐g‐PMMA) were characterized using Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, ¹³ C‐solid NMR spectroscopy, X‐ray photoelectron spectroscopy, and scan electron microscopy. From the result of the characterizations, the grafting of poly(methyl methacrylate) on to multiwalled carbon nanotube was confirmed, and a percentage grafting of 41.51% weight was achieved under optimized conditions with respect to the temperature and the amount of the initiator. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43270.     

A highly selective electrochemical sensor for nifedipine based on layer‐by‐layer assembly films from polyaniline and multiwalled carbon nanotube

An uniformly distributed film consisting of polyaniline (PANI) nanoparticles and carboxylic acid functionalized multiwalled carbon nanotubes (MWNTs‐COOH) was successfully assembled on ITO plates from a layer‐by‐layer (LBL) method by using electrostatic interactions as the main driving force. The good conjugation between PANI nanoparticles and MWNTs‐COOH resulted in significant electrochemical performance variation of the obtained films. In addition, the assembled MWNT‐COOH/PANI/ITO showed synergistic effect to the electrochemical oxidation of nifedipine (NIF) when used as a sensor. Compared with bare ITO, the oxidation potential of NIF can be decreased about 170 mV on MWNT‐COOH/PANI/ITO, and the lower detection limit of NIF was as low as 1.0 × 10^?6 mol/L. In addition, the assembled electrode gave no responses to interferences such as glucose, urea, ascorbic acid, and trisodium citrate, which showed high selectivity for recognition and quantification of NIF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43452.     

Efficient dispersion of multi‐walled carbon nanotubes by in situ polymerization

Multi‐walled carbon nanotube (MWNT)‐reinforced polyimide nanocomposites were synthesized by in situ polymerization of monomers in the presence of acylated MWNTs. The acyl groups associated with the MWNTs participated in the reaction through the formation of amide bonds. This process enabled uniform dispersion of MWNT bundles in the polymer matrix. The resultant MWNT–polyimide nanocomposite films were optically transparent with significant mechanical enhancement at a very low loading (0.5 wt%). Evidence has been obtained for improved interactions between the nanotubes and the matrix polymer. Copyright © 2006 Society of Chemical Industry     

Thermal stability and molecular interaction of polyurethane nanocomposites prepared by in situ polymerization with functionalized multiwalled carbon nanotubes

Polyurethane (PU) nanocomposites were prepared through conventional and in situ methods with multiwalled carbon nanotubes (MWNTs) functionalized with poly(ϵ-caprolactone). The thermal degradation and stability of PU–MWNT nanocomposites were investigated with nonisothermal thermogravimetry and were explained in terms of the interaction between MWNTs and PU molecules with Fourier transform infrared spectroscopy. The difference in thermal stability between the conventional and in situ nanocomposites was also compared. The thermal degradation of all the nanocomposite samples took place in two stages and followed a first-order reaction. The degradation temperature of the in situ nanocomposites was higher than that of the conventional nanocomposites with the same loading of MWNTs. The activation energy at 10% degradation and the half-life period were also higher in the in situ nanocomposites compared to the conventional nanocomposites. Such higher thermal stability of the in situ nanocomposites was ascribed to covalent bond formation between MWNTs and PU chains, which could result in better dispersion of MWNTs in the PU matrix for the in situ nanocomposites than for the conventional nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of polyimide/multi‐walled carbon nanotube nanocomposites

Polyimide/multi‐walled carbon nanotube (PI‐MWNT) nanocomposites were fabricated by an in situ polymerization process. Chemical compatibility between the PI matrix and MWNTs is achieved by pretreatment of the carbon nanotubes in a mixture of sulfuric acid and nitric acid. The dispersion of MWNTs in the PI matrix was found to be enhanced significantly after acid modification. The glass transition (T_g) and decomposition (T_d) temperature of PI‐MWNT nanocomposites were improved as the MWNT content increased from 0.5 to 15 wt%. The storage modulus of the PI/MWNT nanocomposites is nine times higher than that of pristine PI at room temperature. The tensile strength of PI doubles when 7 wt% MWNTs is added. The dielectric constant of the PI‐MWNT nanocomposites increased from 3.5 to 80 (1 kHz) as the MWNT content increased to 15 wt%. The present study demonstrates that enhanced mechanical properties can be obtained through a simple in‐situ polymerization process. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

In situ synthesis of polyamide 6/MWNTs nanocomposites by anionic ring opening polymerization

In situ anionic ring opening polymerization is used to prepare monomer casting polyamide 6 (MCPA6)/carbon nanotubes (CNTs) nanocomposites, whereby water is used as auxiliary dispersing agent of hydroxyl functionalized multiwalled carbon nanotubes (MWNTs‐OH) and ε‐caprolactam (CL) monomer. The MWNTs‐OH were dispersed homogenously in MCPA6 matrix when being observed through transmission electron microcopy. The well dispersed MWNTs‐OH existed at the center of many radial texture phases in MCPA6 matrix. Polarizing microscope analysis showed that these radial texture phases were MCPA6 spherulitic crystallities. Differential scanning calorimetry analysis revealed that the crystallization temperature of the MCPA6/MWNTs‐OH nanocomposites had been improved by adding only 0.2 wt % MWNTs‐OH when compared with pure MCPA6. The influence of MWNTs‐OH on the thermal stability of MCPA6 under nitrogen and air environments was also investigated by thermal gravimetric analysis (TGA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fabrication of multiwalled carbon nanotubes with polymer shells through surface RAFT polymerization

A core–shell hybrid nanostructure, possessing a hard backbone of multiwalled carbon nanotubes (MWNTs) and a soft shell of brush‐like poly(methyl methacrylate), has been successfully prepared via a reversible addition–fragmentation chain transfer (RAFT) process using a RAFT agent immobilized on MWNTs. Polymer‐modified MWNTs are easily dispersed in good solvents for the grafted polymer, such as toluene, tetrahydrofuran and CHCl₃. This observation has been confirmed by transmission electron microscopy analysis. The content of polymer in the functionalized MWNTs can be well controlled by the feed ratio. It is believed that realizing these hybrid structures, on the basis of such simple grafting, will pave the way for the design, fabrication, optimization and eventual application of more functional carbon nanotube‐related nanomaterials. Copyright © 2007 Society of Chemical Industry     

Synthesis and properties of poly(butylene terephthalate)/multiwalled carbon nanotube nanocomposites prepared by in situ polymerization and in situ compatibilization

A novel cyclic initiator was synthesized from dibutyl tin(IV) oxide and hydroxyl‐functionalized multiwalled carbon nanotubes (MWNTs) and was used to initiate the ring‐opening polymerization of cyclic butylene terephthalate oligomers to prepare poly(butylene terephthalate) (PBT)/MWNT nanocomposites. The results of Fourier transform infrared and NMR spectroscopy confirmed that a graft structure of PBT on the MWNTs was formed during the in situ polymerization; this structure acted as an in situ compatibilizer in the nanocomposites. The PBT covalently attached to the MWNT surface enhanced the interface adhesion between the MWNTs and PBT matrix and, thus, improved the compatibility. The morphologies of the nanocomposites were observed by field emission scanning electron microscopy and transmission electron microscopy, which showed that the nanotubes were homogeneously dispersed in the PBT matrix when the MWNT content was lower than 0.75 wt %. Differential scanning calorimetry and thermogravimetric analysis were used to investigate the thermal properties of the nanocomposites. The results indicate that the MWNTs acted as nucleation sites in the matrix, and the efficiency of nucleation was closely related to the dispersion of the MWNTs in the matrix. Additionally, the thermal stability of PBT was improved by the addition of the MWNTs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Functionalized carbon nanotubes with oligomeric intumescent flame retardant for reducing the agglomeration and flammability of poly(ethylene vinyl acetate) nanocomposites

A novel oligomeric phosphorous–nitrogen‐containing intumescent flame retardant poly (2,6‐diaminopyridine spirocyclic pentaerythritol bisphosphonate) (PDSPB) is synthesized, and subsequently multiwalled carbon nanotube (MWNT)‐grafted oligomeric intumescent flame retardant, MWNT‐g‐PDSPB, is fabricated via chemical grafting reaction and characterized. The grafting reaction was characterized by FTIR, NMR, and XPS. After high‐density PDSPB (88 wt%) were attached to the MWNTs, core‐shell nanostructures with MWNTs as the hard core and PDSPB as the soft shell were formed. The resultant MWNT‐g‐PDSPB was soluble and stable in polar solvents, such as DMF and DMSO. MWNT‐g‐PDSPB has excellent thermal stability and charring ability. The TEM results showed that the functionalized MWNTs could achieve better dispersion in poly(ethylene vinyl acetate) (EVA) matrix. The residue char of MWNT‐g‐PDSPB is as high as 70 wt%, and the grafting of intumescent flame retardant of PDSPB can improve both the dispersion of MWNTs in polymer matrix and flame retardancy of the nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Mechanical reinforcement of poly(1‐butene) using polypropylene‐grafted multiwalled carbon nanotubes

The mechanical properties of poly(1‐butene) reinforced by pristine multiwalled carbon nanotubes (MWNTs) and polypropylene‐grafted MWNTs (PP‐g‐MWNTs) were evaluated. The incorporation of pristine MWNTs to PB led to an improvement in stiffness, but not in strength, ductility, and toughness. In comparison, PP‐g‐MWNTs were able to improve the stiffness, strength, and toughness of PB significantly, without compromising the ductility. The mechanical properties of PB improved with increasing amount of PP‐g‐MWNTs up to an effective MWNT content of 1.5 wt%. Further increase in the effective MWNT content led to a downturn in mechanical properties due to the existence of MWNTs bundles as observed by microscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical and thermal properties of functionalized multiwalled carbon nanotubes and multiwalled carbon nanotube–polyurethane composites

Multiwalled carbon nanotube (MWNT)–polyurethane (PU) composites were obtained by an in situ polycondensation approach. The effects of the number of functional groups on the dispersion and mechanical properties were investigated. The results showed that the functionalized MWNTs had more advantages for improving the dispersion and stability in water and N,N′‐dimethylformamide. The tensile strength and elongation at break of the composites exhibited obvious increases with the addition of MWNT contents below 1 wt % and then decreases with additions above 1 wt %. The maximum values of the tensile strength and elongation at break increased by 900 and 741%, respectively, at a 1 wt % loading of MWNTs. Differential scanning calorimetry measurements indicated that the addition of MWNTs resulted in an alteration of the glass‐transition temperature of the soft‐segment phase of MWNT–PU. Additionally, new peaks near 54°C were observed with differential scanning calorimetry because of the microphase‐separation structures and alteration of the segment molecular weights of the hard segment and soft segment of PU with the addition of MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of crosslink density on thermal conductivity of epoxy/carbon nanotube nanocomposites

The effect of the polymeric crosslink density on the thermal conductivity of an epoxy nanocomposite was investigated by adding two different diamine‐functionalized multiwalled carbon nanotubes (diamine‐MWNTs) to the epoxy resin as co‐curing agents and conducting fillers. Tetramethylenediamine (TMDA)‐MWNTs resulted in an epoxy nanocomposite with a higher crosslink density than octamethylenediamine (OMDA)‐MWNTs. Interestingly, epoxy/TMDA‐MWNT nanocomposites under 1.5 wt % nanotube concentration, showed a higher thermal conductivity than an epoxy/OMDA‐MWNT nanocomposite with the same concentration of nanotubes. In contrast, for higher diamine‐MWNT concentrations (over 2.0 wt %), the thermal conductivity of the epoxy/OMDA‐MWNT nanocomposite was higher than that with TMDA‐MWNTs. We observed that for low MWNT concentrations, where a percolating network was not formed, a high crosslink density enhanced the thermal conductivity via phonon transport. However, for high MWNT concentrations, a high crosslink density hinders the formation of a percolating network and lowers the thermal conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44253.     

Scrutinization of Polystyrene Microsphere-grafted Multiwalled Carbon Nanotube and Silver Nanoparticle-based Hybrids: Morphology,Thermal Properties,and Antibacterial Activity

Polystyrene microsphere (emulsion polymerization) was grafted on pure multiwalled carbon nanotube and amine-modified multiwalled carbon nanotube. Silver nanoparticle was also decorated on nanotube using chemical reduction (dimethylformamide). Amine-modified multiwalled carbon nanotube secures better silver attachment on nanotube wall. Polystyrene/Ag–amine-modified multiwalled carbon nanotube depicted fine dispersion in polymer latex due to modification. The 10% decomposition temperature and maximum degradation temperature of polystyrene/Ag–amine-modified multiwalled carbon nanotube was increased to 352 and 424°C. Antibacterial properties of nanocomposite were studied against respiratory track demolishing Gram-positive Staphylococcus aureus bacteria and two Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). Ag nanoparticle was found responsible to potential death rate of microbes.