Thermal stability and electrical properties of dodecyl-benzene-sulfonic-acid doped nanocomposites of polyaniline and multi-walled carbon nanotubes

Electrically conductive dodecyl-benzene-sulfonic-acid (DBSA) doped polyaniline (Pani) nanocomposites were prepared with multi-walled carbon nanotubes (MWCNTs) by in situ oxidative polymerization of aniline in the presence of different amounts of MWCNTs. The stability of the nanocomposites in terms of DC electrical conductivity retention was studied in ambient atmosphere by isothermal accelerated aging and cyclic accelerated aging techniques. The MWCNT/Pani nanocomposites were observed to be thermally more stable under ambient environmental conditions than Pani. Such nanocomposites with high thermal stability may find a place as future materials for the replacement for Pani.     

Synthesis and characterization of HCl doped polyaniline grafted multi-walled carbon nanotubes core-shell nano-composite

Multi-walled carbon nanotubes (MWNTs) was modified with p-phenylenediamine (p-PDA) and hydrochloric acid (HCl) doped polyaniline (PANI) grafted MWNTs nano-composite was synthesized by in situ oxidation polymerization. Raman spectra, XPS, TEM and XRD reveal that modification does not decrease the integrity of outer graphite sheets in p-PDA modified MWNTs (p-MWNTs) excessively and results in phenylamine groups with concentration of 3.7% covalently grafted on the surface of p-MWNTs via amide bond. Oxidized phenylamine groups initiate polymerization and contribute to the formation of inner layer of PANI coatings. As self-assembly templates, p-MWNTs are encapsulated by PANI forming a homogeneous core (p-MWNTs)-shell (HCl doped PANI) nano-structure with controlled organization. In earlier reaction period, polymer chains are highly ordered and microcrystalline domains are enriched in the inner PANI layers. When deposition of PANI chains under less restriction, more amorphous parts are distributed in the outer layers of PANI coatings. TGA and conductivity data reveal that although chemical modification affects the performance of p-MWNTs, thermal stability and electronic conductivity at room temperature of HCl doped PANI grafted MWNTs nano-composite are highly improved owing to incorporation of p-MWNTs and covalent bindings between PANI and carbon nanotubes.     

Dispersion of functionalized multi-walled carbon nanotubes in multi-walled carbon nanotubes/liquid crystal nanocomposites and their thermal properties

A novel liquid crystal functionalized multi-walled carbon nanotubes (LC-MWNTs)/2-methyl-N,N′-bis(4′-methoxy benzoyloxy)-terephthalamide liquid crystal (LC) nanocomposite (LC-MWNTs/LC) was prepared via solution blend. The dispersion and thermal property of the nanocomposites with different loadings of LC-MWNTs (0.1-1 wt.%) were investigated using SEM, TGA and DSC. The results show that the dispersion of LC-MWNTs in LC matrix is more homogeneous than purified MWNTs. The decomposition temperature of nanocomposites exhibits obvious decrease at first and then increase with increasing concentration of LC-MWNTs, which is lower than that of LC for 0.1-0.4 wt.% LC-MWNT loadings and higher than that of LC for 0.5-1 wt.% LC-MWNT loadings. The addition of LC-MWNTs has little effects on the texture of smectic mesophase. These results illustrate the LC-MWNTs/LC nanocomposites, which have lower melting point and higher decomposition temperature than those of LC by adding adequate amount of LC-MWNTs, show a wide temperature range of mesophase and high thermostability. The increased mesophase temperature region of LC materials will be beneficial to their practical applications.     

Preparation and characterization of soluble and DBSA doped polyaniline grafted multi-walled carbon nanotubes nano-composite

Soluble and highly doped polyaniline (PANI) grafted multi-walled carbon nanotubes (MWNTs) nano-composite was synthesized by in situ oxidation polymerization, de-doping with ammonium hydroxide and doping the PANI-Emeraldine base (PANI-EB) grafted MWNTs nano-composite in N-methyl-2-pyrrolidinone (NMP) with Dodecyl benzene sulfonic acid (DBSA). Transmission electron microscope (TEM), Raman spectra, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and standard four-probe methods were employed to characterize morphology, chemical structure and electronic conductivity of the nano-composite. The results show that oxidized phenylamine groups of phenylamine groups contained MWNTs (p-MWNTs) initiate PANI polymerization on the surface of p-MWNTs. PANI coatings graft on the surface of p-MWNTs via amide bond forming homogeneous core (p-MWNTs)–shell (PANI) nano-structures. After doping PANI-EB grafted MWNTs nano-composite with DBSA, the attachment of soluble DBSA doped PANI chains on the surface of p-MWNTs via covalent bonding renders p-MWNTs compatible with polymer matrix and lead to DBSA doped PANI grafted MWNTs nano-composite soluble and stable in NMP. Owing to incorporation of p-MWNTs and chemical bridges between p-MWNTs and PANI chains, conductivity of DBSA doped PANI grafted MWNTs nano-composite at room temperature is increased by about two orders of magnitude over neat DBSA doped PANI.     

Thermo-physical properties of epoxy nanocomposites reinforced with amino-functionalized multi-walled carbon nanotubes

The modification of multi-walled carbon nanotubes (MWNTs) with amine groups was investigated by FTIR, Raman spectroscopy and XPS after such steps as carboxylation, acylation and amidation. Nanotube-reinforced epoxy polymer composites were prepared by mixing amino-functionalized MWNTs with epoxy resin and curing agent. DSC, TGA, SEM and flexural test were used to investigate the thermal and mechanical properties of the composites. The results showed that amino-functionalized MWNTs could enhance the interfacial adhesion between the nanotubes and the matrix, thus greatly improve the thermal and mechanical properties of the resin epoxy bulk material.     

Study on dispersion and electrical property of multi-walled carbon nanotubes/low-density polyethylene nanocomposites

Sonication is one of the promising approaches to disperse nanoparticles into the base material thoroughly. Furthermore, coupling treatments for MWNTs and polymer matrix also contribute to homogenous dispersion of MWNTs among polymer matrix. In this paper, MWNTs and KH-550 were dispersed with acetone via sonication method, then, the MWNTs/low density polyethylene (LDPE) composites was prepared by using melt blending process. Effects of MWNTs and LDPE coupling treatment on dispersion and electrical property of the MWNTs/LDPE nanocomposites were investigated. SEM observation on fracture surfaces of the nanocomposites explained the functions of sonication and coupling treatment on the dispersion, and electrical conductivity of the nanocomposites was measured by four-contact scheme. The results displayed that the optimum sonication temperature was 70 °C and the optimum sonication amount of MWNTs particles in 200 ml KH-550 acetone solution was 20 g. Moreover, dispersion of the nanocomposites was improved with increasing sonication power amplitude. Furthermore, dispersion and electrical conductivity of the nanocomposites with coupling treatment LDPE were better than those of the nanocomposites with uncoupling treatment LDPE. The good dispersion and electrical conductivity enhancement are based on the strong bonding and coupling reaction of MWNTs and LDPE matrix, which associated greatly with sonication and coupling treatment.     

Thermoelectric properties of porous multi-walled carbon nanotube/polyaniline core/shell nanocomposites

Porous polyaniline (PANI)-coated multi-walled carbon nanotube (MWNT) core/shell nanohybrids were fabricated through in situ polymerization and subsequently assembled into macroscopic composites. N(2) adsorption/desorption analysis indicated that the volume of nanopores increased significantly, which could make a significant contribution to phonon scattering. Thermal annealing was also carried out to improve the Seebeck coefficient of the as-produced nanocomposites. The optimal sample showed electrical conductivity of 14.1?S?cm(-1), a Seebeck coefficient of 79.8?μV K(-1) and thermal conductivity of 0.27?W?mK(-1), resulting in a highest figure of merit (ZT) of 0.01 at a very low loading of MWNTs (<1?wt%). These results will provide a potential direction to enhance thermoelectric performance of organic materials and also facilitate the application of organic materials in thermal energy harvesting or cooling.     

Synthesis and properties of amphiphilic block polymer functionalized multi-walled carbon nanotubes and nanocomposites

The grafting of poly(ethylene glycol)-block-polyacrylonitrile (PEG-b-PAN) amphiphilic block polymer onto multi-walled carbon nanotubes (MWCNTs) was achieved by combination of coupling reaction and redox radical polymerization. The chemical structure and yield of the resulting grafted polymer were characterized and confirmed by FT-IR and TGA. Transmission electron microscopy (TEM) images clearly indicated that the nanotubes were coated with a polymer layer. The concentrated DMF dispersions of MWCNT-g-(PEG-b-PAN) nanocomposite were stable for months, the viscoelasticity being monitored by rheometer. MWCNT-g-(PEG-b-PAN) hybrid nanocomposite membranes were fabricated by phase inversion in a wet process. The results showed that high concentration of MWCNTs could be dispersed in the polymer matrix. The morphology and surface hydrophilicity characteristics of the membrane could be controlled by the composition of MWCNT-g-(PEG-b-PAN) nanocomposite membrane.     

Mechanical and thermal properties of epoxy nanocomposites reinforced with amino-functionalized multi-walled carbon nanotubes

The functionalized multi-walled carbon nanotubes (MWNTs) with amino groups were prepared after such steps as oxidation, the addition of carboxyalkyl radicals, acylation and amidation. Besides oxidated-MWNTs/epoxy nanocomposites, amino-functionalized MWNTs/epoxy nanocomposites, in which MWNTs with amino groups acted as a curing agent and covalently attached into the epoxy matrix, were fabricated. Subsequently, the effects of MWNT content on the mechanical and thermal properties for the two systems were investigated. It is found that both the tensile strength and impact strength enhance with the increase of MWNT addition, and the most significant improvement of the tensile strength (+51%) and especially impact strength (+93%) is obtained with amine-treated MWNTs at an 1.5 wt.% content. Moreover, the thermal stability of the nanocomposites also distinctly improves. The improvement of the properties of the amine-treated MWNTs system is more remarkable than those of o-MWNTs system. The reasons for these changes were discussed.     

Dispersion characteristics and properties of poly(methyl methacrylate)/multi-walled carbon nanotubes nanocomposites

The preparation, characterization, and properties of poly(methyl methacrylate) (PMMA)/multi-walled carbon nanotubes (MWCNTs) nanocomposites are described. Nanocomposites have been prepared by melt-blending in a batch mixer. Both unmodified and surface modified MWCNTs have been used for the nanocomposites preparation. Using both unmodified and modified MWCNTs, the effect of surface modification in nanocomposites is investigated by focusing on three major aspects: dispersion characteristics, mechanical properties, and electrical conductivity measurements. Dispersion of the MWCNTs in the PMMA matrix is examined by scanning and transmission electron microscopy that revealed a homogeneous distribution-dispersion of MWCNTs in the PMMA matrix for both unmodified and modified MWCNTs. Thermomechanical behavior is studied by dynamic mechanical analyzer and results showed a substantial improvement in the mechanical properties of PMMA in conjunction to an increase in the elastic behavior. The tensile properties of neat PMMA moderately improved after nanocomposites preparation with both modified and unmodified MWCNTs, however, electrical conductivity of neat PMMA significantly improved after nanocomposites preparation with 2 wt% unmodified MWCNTs. For example, the through plane conductivity increased from 3.6 x 10(-12) S x cm(-1) for neat PMMA to 3.6 x 10(-9) S x cm(-1) for nanocomposite. The various property measurements have been conducted and results have shown that, in overall, surface modifications have very little or no effect on final properties of neat PMMA.     

Preparation and properties of the polyimide/multi-walled carbon nanotubes (MWNTs) nanocomposites

The polyimide/multi-walled carbon nanotubes (MWNTs) nanocomposite films were prepared by mixing of poly(amic acid) (PAA) solution and MWNTs/DMAc suspension follow by mixture casting, evaporation and thermal imidization. To increase the chemical compatibility between polyimide matrix and MWNTs, MWNTs were modified with mixed strong acid. The results show that the dispersion of the MWNTs is improved greatly in the polyimide matrix after acid modification. The modified MWNTs are dispersed homogeneously in the polyimide matrix while the structure of the polyimide and MWNTs structures is stable in the preparation process. With the incorporation of MWNTs, the mechanical properties of the resultant nanocomposite films were greatly improved due to the strong interfacial interaction between the modified MWNTs and the polyimide matrix. The thermal stability of the nanocomposites was lower a little than pure polyimide because of the drop of thermostability of MWNTs through acid-treatment. The electrical conductivity and the dielectric constant of the nanocomposites were also having sharp increase, which is favorable for practical use in anti-static materials and embedded capacitors.     

Microstructure and properties of polyurethane nanocomposites reinforced with methylene-bis-ortho-chloroanilline-grafted multi-walled carbon nanotubes

Methylene-bis-ortho-chloroanilline (MOCA), an excellent cross-linker widely used to prepare cured polyurethane (PU) elastomers with high performance, was used to modify a multi-walled carbon nanotube. PU/carbon nanotube (CNT) nanocomposites were prepared by incorporation of the MOCA-grafted CNT into PU matrix. Fourier transform infrared spectra have shown that the modified CNTs have been linked with PU matrix. The microstructure of composites was investigated by Field-Emission Scanning Electron Microscopy. The results of Dynamic Mechanical Thermal Analysis and Differential Scanning Calorimetry have investigated the grafted CNTs as cross-linker in the cured composites. The studies on the thermal and mechanical properties of the composites have indicated that the storage modulus and tensile strength, as well as glass transition temperature and thermal stability are significantly increased with increasing CNT content.     

Studies on preparation and properties of the multi-walled carbon nanotubes (MWNTs)/epoxy nanocomposites

The MWNTs were coated with polyaniline (PANI) by in situ chemical oxidation polymerization method. FTIR spectroscopy, scanning electron microscope (SEM) and X-ray diffraction (XRD) indicated that the MWNTs were coated with PANI. The MWNTs/epoxy nanocomposites were fabricated by using the solution blending method. Differential scanning calorimetry (DSC), tensile testing, HP 4294A impedance analyzer and SEM were used to investigate the properties of the nanocomposites. The results showed that the modified carbon nanotubes were well dispersed in the polymer matrix. The nanocomposites have enhancements in mechanical, thermal and dielectric properties compare with the neat epoxy resin. The nanocomposites were proven to be a good polymer dielectric material.     

Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites

Electrically conducting nanocomposites of polyaniline (PANI) with carbon-based fillers have evinced considerable interest for various applications such as rechargeable batteries, microelectronics, sensors, electrochromic displays and light-emitting and photovoltaic devices. The nature of both the carbon filler and the dopant acid can significantly influence the conductivity of these nanocomposites. This paper describes the effects of carbon fillers like carbon black (CB), graphite (GR) and muti-walled carbon nanotubes (MWCNT) and of dopant acids like methane sulfonic acid (MSA), camphor sulfonic acid (CSA), hydrochloric acid (HCl) and sulfuric acid (H₂SO₄) on the electrical conductivity of PANI. The morphological, structural and electrical properties of neat PANI and carbon–PANI nanocomposites were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR), UV–Vis spectroscopy and the four-point probe technique, respectively. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies were also conducted for different PANI composites. The results show that PANI and carbon–PANI composites with organic acid dopants show good thermal stability and higher electrical conductivity than those with inorganic acid dopants. Also, carbon–PANI composites generally show higher electrical conductivity than neat PANI, with highest conductivities for PANI–CNT composites. Thus, in essence, PANI–CNT composites prepared using organic acid dopants are most suitable for conducting applications.     

Hydrogen sensing properties of multi-walled carbon nanotubes

The hydrogen sensing properties of multi-walled carbon nanotubes (MWNTs) synthesized by a hot filament CVD process are reported in this paper. The MWNTs were synthesized by a hot filament assisted chemical vapor deposition method using cobalt oxide nanoparticles as the catalyst on SiO₂ surfaces. The MWNTs were characterized with Raman spectroscopy and scanning electron microscopy. Two-terminal test devices were fabricated by depositing a layer of MWNTs between prefabricated gold electrodes on SiO₂ surfaces. The diameter of these MWNTs was in the 5–8 nm range. The sensitivity of carbon nanotubes was measured for different gas concentrations at different temperatures. It was found that the MWNTs were sensitive to H₂ in low temperature regions of 140–350 °C and had a maximum sensitivity (80%) at 230 °C. No sensitivity was observed at a temperature lower than 140 °C or higher than 400 °C. Though bare MWNTs are not sensitive to H₂ at room temperature, they exhibited very good sensing characteristics in the 140–300 °C range.     

Morphology and electrical properties of polyamide 6/polypropylene/multi-walled carbon nanotubes composites

Morphology, electrical properties and conductive mechanisms of polyamide 6/polypropylene/muti-walled carbon nanotubes (PA6/PP/MWNTs) composites with varied compositions and different blending sequences were investigated. The MWNTs were found to be located preferentially in the PA6 phase in the composites, whatever the PA6 was continuous or dispersed phase. While the incorporation of MWNTs changed the dispersed PA6 phase from spherical to elongated or irregular shape. The PA6/PP/MWNTs (20/80/4) composite with a dispersed PA6 phase exhibited a higher electrical conductivity in comparison with the PA6/PP/MWNTs (50/50/4) composite which has a co-continuous phase and exhibits double percolation. This was due to the formation of a conductive MWNTs networks in the PA6/PP/MWNTs (20/80/4) composite as proved by means of field emission scanning electron microscopy and rheological measurements. The morphology and electrical properties of the PA6/PP/MWNTs (20/80/4) composites were significantly influenced by blending sequences. When blending 3.9 phr MWNTs with a pre-mixed PA6/PP/MWNTs (20/80/0.1) composite, the dispersed PA6 phase formed an elongated structure, which was beneficial to the electrical properties.     

Electro-optical properties and frequency response of polymer-dispersed liquid crystal gratings doped with multi-walled carbon nanotubes

In this paper, a model developed for establishing the lowest possible driving voltage of Holographic polymer-dispersed liquid crystal (H-PDLC) based on the Maxwell–Wagner effect doped with specific nanotubes. The dependences of the turning point frequency on the doping concentration and the distribution of multi-walled carbon nanotubes (MWCNTs) are discussed. The MWCNTs can effectively adjust the relaxation frequency of grating, increase its LC droplet size, and decrease its dielectric permittivity. The diffraction efficiency and threshold voltage of the prepared switchable Bragg grating were found to reach 91% and 0.77 V μm^?1, respectively, at 5 kHz. By comparing the results of experiments and simulations, we obtained the mass distribution ratio of MWCNTs in the LC and polymer regions. It was found that the MWCNTs diffuse into the LC regions during the polymerization process, and the use of a suitable driving frequency and doping concentration can minimize the driving voltage. This work provides a reference for studying the dynamic range optical tuning and polymerization kinetics of nanoparticles in switchable gratings.

     

Influence of functionalization of multi-walled carbon nanotubes on the properties of ethylene vinyl acetate nanocomposites

Commercially available multiwalled carbon nanotubes (MWNT) were chemically modified by amine, acid and silane and their ethylene vinyl acetate (EVA) based nanocomposites were prepared. Unmodified and modified nanotubes were characterized by thermogravimetry, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy. Early degradation of modified nanotubes from the thermogravimetry study proved the presence of functional groups on nanotube surface. Increase in D-band to G-band ratio and a shift in radial breathing mode peaks from the Raman spectra indicated the generation of surface defects due to functionalization and variation in van der Waals force of attraction between nanotube aggregates on modification. The unmodified nanotubes improved the tensile strength by 30% with 4 weight% of filler. Amine modification imparted further increase in strength due to the presence of functional groups on the nanotube surface and the subsequent better dispersion of the nanotubes in the polymer matrix. The silane treatment imparted maximum improvement in various properties of the nanocomposites. The nanotubes provided better thermal degradation stability and also higher thermal conductivity to virgin EVA. The results were well supported by the morphological as well as swelling study of the various samples.     

纤维表面盐酸掺杂聚苯胺热稳定性能的研究

采用改进的原位化学聚合法制备了聚苯胺/涤纶导电复合织物。以盐酸作为掺杂剂,过硫酸铵为氧化剂,探讨了焙烘温度对纤维表面聚苯胺导电性能的影响,同时还利用FT-IR和XRD对不同焙烘条件下的聚苯胺的红外光谱和结构进行了表征和分析。