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     

Conducting polymer composites of multiwalled carbon nanotube filled doped polyaniline

A multiwalled carbon nanotube (c‐MWNT)/polyaniline (PANI) composite was synthesized by an in situ chemical oxidative polymerization process. With the carbon nanotube loading increased from 0 to 30 wt %, the conductivity also increased and became weakly temperature‐dependent. Fourier transform infrared spectroscopy studies showed that the synthesis by an in situ process led to effective site‐selective interactions between the quinoid ring of the PANI and the multiwalled nanotubes, facilitating charge‐transfer processes between the two components. The morphological analysis indicated that the c‐MWNTs were well dispersed and isolated, and the tubes became crowded proportionally to the weight percentage of c‐MWNTs used in the composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Polyaniline / carbon nanotube composites: starting with phenylamino functionalized carbon nanotubes

Summary Composites of carbon a nanotube with polymers are a developing and interesting area of research. The dispersion of the nanotube in polymer matrices is an important factor while making its nanocomposites. Even though in-situ polymerization approach offers a better approach for synthesizing homogeneous polymer nanotube composites, the dispersion of the nanotubes in the monomer solution is a problem. In this article we report a new chemical method for dispersing nanotubes in monomer and the preparation of uniform tubular composite of polyaniline (PANI) and multiwalled carbon nanotube (MWNT). For this the oxidized multiwalled nanotube (o-MWNT) was functionalized with p-phenylenediamine, which gave phenylamine functional groups on the surface. This functionalization helped to disperse the nanotubes in acidic solution. The in-situ polymerization of aniline in the presence of these well dispersed nanotubes gave a new tubular composite of carbon nanotube having an ordered uniform encapsulation of doped polyaniline. The phenylamine functional groups on the surface were grown into polyaniline chain so that the composite contains polyaniline functionalized CNT and they were no more an impurity in the final nanocomposite. The microscopic and structural properties of this composite were compared with that of a composite prepared under identical condition using o-MWNT.     

Incorporation of 4‐aminobenzene functionalized multi‐walled carbon nanotubes in polyaniline for application in formic acid electrooxidation

Incorporation of carbon nanotubes (CNTs) in conducting polymer can lead to new composites with enhanced electrical and mechanical properties. However, the development of such composites has been hampered by the inability to disperse CNTs in polymer matrix due to the lack of chemical compatibility between polymers and CNTs. Covalent sidewall functionalization of carbon nanotube provides a feasible route to incorporate carbon nanotube in polymer. In this work, 4‐aminobenzene groups were grafted onto the surface of multi‐walled carbon nanotube (MWNT) via C? C covalent bond. Polyaniline (PANI)/MWNT composites were fabricated by electrochemical polymerization of aniline containing well‐dissolved functionalized MWNTs. The obtained composites can be used as catalyst supports for electrooxidation of formic acid. Cyclic voltammogram results show that platinum particles deposited in PANI/MWNT composite films exhibit higher electrocatalytic activity and better long‐term stability towards formic acid oxidation than that deposited in pure PANI films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Doped polyaniline/multi-walled carbon nanotube composites: Preparation, characterization and properties

This study reports the synthesis of doped polyaniline in its emeraldine salt form (PANI-ES) with carboxylic acid and acylchloride groups contained multi-walled carbon nanotubes (designated as c-MWNTs and a-MWNTs) by in situ polymerization. Both Raman spectra and HRTEM images indicate that carboxylic acid and acylchloride groups formed at both ends and on the sidewalls of the MWNTs. Based on the π-π* electron interaction between aniline monomers and functionalized MWNT and hydrogen bonding interaction between the amino groups of aniline monomers and the carboxylic acid/acylchloride groups of functionalized MWNT, aniline molecules were adsorbed and polymerized on the surface of MWNTs. Structural analysis by FESEM and HRTEM showed that PANI-ES/c-MWNT and PANI-ES/a-MWNT composites are core (c-MWNT or a-MWNT)- shell (doped-PANI-ES) tubular structures with diameters of several tens to hundreds of nanometers, depending on the PANI content. The conductivities of 0.5 wt% functionalized MWNT containing PANI-ES/c-MWNT and PANI-ES/a-MWNT composites are 60-70% higher than that of PANI without MWNT.     

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     

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.     

Preparation and characterization of polyaniline/multi-walled carbon nanotube composites

This study describes the synthesis of doped polyaniline in its emeraldine salt form (PANI-ES) with carboxylic groups containing multi-walled carbon nanotubes (c-MWNTs) via in situ polymerization. Both Raman and FTIR spectra indicate that carboxylic acid groups formed at both ends and on the sidewalls of the MWNTs. Based on the π-π* electron interaction between aniline monomers and MWNT and hydrogen bonding interaction between the amino groups of aniline monomers and the carboxylic acid group of c-MWNT, aniline molecules were adsorbed and polymerized on the surface of MWNTs. Structural analysis using FESEM and HRTEM showed that PANI-ES/c-MWNT composites are core (c-MWNT)-shell (doped-PANI-ES) tubular structures with diameters of several tens to hundreds of nanometers, depending on the PANI content. The conductivities of these PANI-ES/c-MWNT composites are 50-70% higher than those of PANI without MWNT.     

Dispersion of multi‐walled carbon nanotubes in poly(aryl ether ketone) obtained by in situ polymerization

BACKGROUND: Recently, much work has focused on the efficient dispersion of carbon nanotubes (CNTs) throughout a polymer matrix for mechanical and/or electrical matrices. However, CNTs used as enhancement inclusions in a high‐performance polymer matrix, especially in poly(aryl ether ketone) (PAEK), have rarely been reported. Therefore, multi‐walled carbon nanotube (MWNT)‐modified PAEK nanocomposites were synthesized by in situ polymerization of monomers of interest in the presence of pre‐treated MWNTs. RESULTS: This process enabled a uniform dispersion of MWNT bundles in the polymer matrix. The resultant MWNT/PAEK nanocomposite films were optically transparent with significant mechanical enhancement at a very low MWNT loading (0.5 wt%). CONCLUSION: These MWNT/polymer nanocomposites are potentially useful in a variety of aerospace and terrestrial applications, due to the combination of excellent properties of MWNTs with PAEK. Copyright © 2009 Society of Chemical Industry     

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     

Preparation and characterization of polydiphenylamine/multi‐walled carbon nanotube composites

We describe the synthesis of methane sulfonic acid (MeSA)‐doped poly(diphenylamine) (PDPA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Diphenylamine monomers were adsorbed on to the surface of c‐MWNTs and polymerized to form PDPA/c‐MWNT composites. SEM and TEM images indicated two different types of materials: the thinner fibrous phase and the larger globular phase. The individual fibrous phase had a diameter around 100–130 nm, which should be the carbon nanotubes (diameter 20–30 nm) coated with a PDPA layer. The structure of PDPA/c‐MWNT composites was characterized by FTIR, UV‐visible spectroscopy and X‐ray diffraction patterns. The electrical conductivities of PDPA/c‐MWNT composites were much higher than that of PDPA without c‐MWNTs. Copyright © 2006 Society of Chemical Industry     

Poly (N‐methylaniline)/multi‐walled carbon nanotube composites—Synthesis,characterization, and electrical properties

This study described the synthesis of hydrochloric acid (HCl)‐doped poly (N‐methylaniline) (PNMA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Based on the π–π electron interaction between c‐MWNTs and the N‐methylaniline monomer and the hydrogen bond interaction between the carboxyl groups of c‐MWNTs and imine groups of N‐methylaniline monomers, N‐methylaniline molecules were adsorbed on the surface of c‐MWNTs and polymerized to form PNMA/c‐MWNT composites. Scanning electron microscopy images showed that both the thinner fibrous phase and the larger block phase could be observed. The individual fibrous phases had diameters from several tens to hundreds of nanometers, depending on the PNMA content. Transmission electron microscopy proved that PNMA/c‐MWNTs composite fibrous phases were core (c‐MWNT)‐shell (PNMA) tubular structures. The structure of PNMA/c‐MWNT composites was characterized by FTIR, UV–vis spectra, and X‐ray diffraction patterns. The electrical conductivities of PNMA/c‐MWNT composites were much higher than that of PNMA without c‐MWNTs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2356–2361, 2006     

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     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

Multiwalled carbon nanotube polymer composites: Synthesis and characterization of thin films

The aim of this article was to elucidate the basic relationships between processing conditions and the mechanical and electrical properties of multiwalled carbon nanotube reinforced polymer composites. In conventional chopped fiber reinforced polymer composites, uniform distributions of fibers throughout the matrix are critical to producing materials with superior physical properties. Previous methods have dispersed carbon nanotubes by aggressive chemical modification of the nanotubes or by the use of a surfactant prior to dispersion. 1 , 2 Here, ultrasonic energy was used to uniformly disperse multiwalled nanotubes (MWNTs) in solutions and to incorporate them into composites without chemical pretreatment. Polystyrene (PS) solutions containing MWNTs were cast and spun to yield thin film MWNT composites. The rheology of PS/MWNT suspensions was modeled using the Carreau equation. MWNTs were found to align at the shear rates generated by the spin casting process. The tensile modulus and strain to failure of samples compared well to classical micromechanical models, increasing with MWNT loading. The composite films showed lower strains at the yield stress than neat PS films. The presence of MWNTs at 2.5 vol % fraction approximately doubles the tensile modulus, and transforms the film from insulating to conductive (surface resistivity, ρ, approaching 10³ Ω/□). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2660–2669, 2002     

Synergistic effect of polyaniline and multiwalled carbon nanotube on the microstructure and the electric property in PP/PANI/MWNT composites

In this article, the volume conductivity of polypropylene (PP)/polyaniline (PANI)/multiwalled carbon nanotube (MWNT) composites was detected. When the ratio of PANI protonated with dodecylbenzene sulphonic acid (PANI‐DBSA) to MWNT is 2 to 3 and 3 to 17, the volume conductivity of the two composites is much higher than that of composites filled with solely PANI‐DBSA or MWNT. The synergistic effects of PANI‐DBSA and MWNT on the microstructure and the electric property of PP/PANI/MWNT composites were carefully analyzed by scanning electron microscope (SEM) and transmission electron microscopy. The SEM results illuminate that the dispersion and the continuity of the composites filled with PANI‐DBSA and MWNT are far better than that filled with only PANI‐DBSA or MWNT. Especially, the dispersion and continuity of PP/PANI/MWNT 5, in which the ratio of PANI‐DBSA to MWNT is 3 to 17, are the best among all the composites. When PANI‐DBSA is introduced in PP/PANI/MWNT composites, the size of agglomerated particles decreases, and the dispersion of conductive particles is improved evidently. Therefore, there is a synergistic action of PANI‐DBSA and MWNT, which is used to improve the dispersion of conductive particles and the volume conductivity of the PP/PANI/MWNT composites. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

A comparative study on dispersion of carbon nanotubes in (styrene‐butadiene rubber)‐based nanocomposites

The efficient dispersion of carbon nanotubes (CNTs) is a challenging task in reaching the usable nanocomposites. In this study, a comparative analysis on dispersion of multiwalled CNTs multiwalled carbon nanotubes (MWNTs) in styrene‐butadiene rubber (SBR) latex was carried out by using two anionic surfactants, sodium dodecyl benzene sulfonate and sodium lauryl sulfate. The MWNTs were first predispersed in distilled water using two surfactants individually followed by gentle mixing the MWNT predispersion into SBR latex. By using the technique of ultraviolet‐visible spectroscopy, the study on MWNT dispersion in aqueous media was focused on surfactant concentration, MWNT functionality, and ultrasonication time. The ultraviolet‐visible absorptions showed the positive effect of MWNT functionality in addition to surfactant concentration with no great effect of ultrasonication time over 15 min. In comparison with sodium lauryl sulfate, the existing benzene ring in the sodium dodecyl benzene sulfonate structure seems to result in higher adsorption of surfactant onto the MWNTs surface and, hence, better MWNT dispersion. The MWNT dispersion was further improved by using hydroxyl functionalized MWNTs mainly because of the formation of hydrogen bonding between the hydrophilic head of surfactant and the existing hydroxyl group of the functionalized MWNTs. After mixing the MWNT predispersion into SBR latex, the dispersion of MWNTs was further characterized by using electrical volume conductivity, microscopy technique, and rheological measurements. In rheometry tests of the lattices, the storage modulus at terminal zone was utilized for tracking the degree of MWNT dispersion in the nanocomposite. The pictures of scanning electron microscopy showed the efficiency of MWNT functionality in enhancing the degree of dispersion. In conductivity tests, the percolation threshold was obtained at about 1 part by weight per hundred parts of resin of the functionalized MWNT in dried film. J. VINYL ADDIT. TECHNOL., 23:28–34, 2017. © 2015 Society of Plastics Engineers     

Properties of ultrahigh‐molecular‐weight polyethylene nanocomposite films containing different functionalized multiwalled carbon nanotubes

We compared the thermomechanical properties, morphologies, gas permeabilities, and electrical conductivities of ultrahigh‐molecular‐weight polyethylene (UHMWPE) nanocomposite films containing two types of functionalized multiwalled carbon nanotubes (functionalized MWNTs). Both 2‐hydroxyethyl triphenyl phosphonium‐MWNT (Ph3P‐MWNT) and 1,1,1,3,3,3‐hexafluoro‐2‐phenyl‐2‐propanol‐MWNT (CF3‐MWNT) were used as reinforcing fillers in the fabrication of UHMWPE hybrid films. UHMWPE nanocomposites with various functionalized MWNT contents were solution‐cast to produce the films. The thermomechanical properties and morphologies of the UHMWPE hybrid films were then characterized using differential scanning calorimetry, thermogravimetric analysis, electron microscopy, and mechanical tensile analysis. Transmission electron microscopy studies showed that some of the MWNT particles were dispersed homogeneously within the polymer matrix (on the nanoscale), whereas others were agglomerated. We also found that the addition of only a small amount of functionalized MWNTs was sufficient to improve the thermomechanical properties and the gas barrier of the UHMWPE hybrid films. Even, those hybrid films with low functionalized MWNT contents (i.e., <1 wt%) were found to exhibit much better thermomechanical properties than the pure UHMWPE films. On the other hand, the values of the electrical conductivity remained constant, regardless of the amount of functionalized MWNTs. POLYM. ENG. SCI., 2009. © 2009 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