Multi-walled carbon nanotubes covalently attached with poly(3-hexylthiophene) for enhancement of field-effect mobility of poly(3-hexylthiophene)/multi-walled carbon nanotube composites

For the purpose of enhancing the field-effect mobility of poly(3-hexylthiophene) (P3HT), multi-walled carbon nanotubes (MWCNTs) were functionalized by attaching covalently P3HT onto the MWCNT surface to yield P3HT-grafted MWCNTs (g-MWCNTs). When a small amount of g-MWCNTs was added to P3HT, the field-effect mobility of the composite was considerably increased as compared to either P3HT or the composites of P3HT and carboxylated MWCNTs (c-MWCNTs). This is because g-MWCNTs are better dispersed than c-MWCNTs in P3HT matrix and consequently g-MWCNTs act more effectively as conducting bridges connecting the crystallites of P3HT.     

Fabrication and characterization of homogeneous composites of polypropylene and multiwalled carbon nanotubes

The polypropylene‐grafted multiwalled carbon nanotubes (PP‐MWCNTs) were produced from the reaction of PP containing the hydroxyl groups and MWCNTs having 2‐bromoisobutyryl groups. The PP‐MWCNTs had a significantly rougher surface than the original MWCNTs. PP‐MWCNTs had PP layers of thickness 10–15 nm on the outer walls of the MWCNTs. PP/PP‐MWCNT composites and PP/MWCNT composites were prepared by solution mixing in o‐xylene. Unlike PP/MWCNT composites, PP‐MWCNTs were homogeneously dispersed in the PP matrix. As a consequence, the thermal stability and conductivity of PP/PP‐MWCNT composites were dramatically improved even if only 1 wt % of PP‐MWNTs was added to the PP matrix. The good miscibility of PP and PP‐MWCNTs plays a critical role in the formation of the homogeneous composites and leads the high thermal stability and conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High dispersion ability of fluorene‐based polyester as a polymer matrix for carbon nanotubes

The high compatibility of fluorene‐based polyester (FBP‐HX) as a polymer matrix for multiwalled carbon nanotubes (MWCNTs) is discussed. A low surface resistivity due to the fine dispersion of MWCNTs in FBP‐HX and polycarbonate (PC) is reported. With a solution‐casting method, a percolation threshold with the addition of between 0.5 and 1.0 wt % MWCNTs was observed in the MWCNT/PC and MWCNT/FBP‐HX composites. Because of the coverage of FBP‐HX on the MWCNTs, a higher surface resistivity and a higher percolation ratio of the MWCNT/FBP‐HX composites were achieved compared with the values for the MWCNT/PC composites. In the MWCNT/FBP‐HX composites, MWCNTs covered with FBP‐HX were observed by scanning electronic microscopy. Because of the coverage of FBP‐HX on the MWCNTs, FBP‐HX interfered with the electrical pathway between the MWCNTs. The MWCNTs in FBP‐HX were covered with a 5‐nm layer of FBP‐HX, but the MWCNTs in the MWCNT/PC composites were in their naked state. MWCNT/PC sheets demonstrated the specific Raman absorption of the MWCNTs only with the addition of MWCNTs of 1 wt % or above because of the coverage of the surface of the composite sheet by naked MWCNTs. In contrast, MWCNT/FBP‐HX retained the behavior of the matrix resin until a 3 wt % addition of MWCNTs was reached because of the coverage of MWCNTs by the FBP‐HX resin, induced by its high wettability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Low percolation threshold in polycarbonate/multiwalled carbon nanotubes nanocomposites through melt blending with poly(butylene terephthalate)

Here, we demonstrate an easy method for the preparation of highly electrically conductive polycarbonate (PC)/multiwalled carbon nanotubes (MWCNTs) nanocomposites in the presence of poly(butylene terephthalate) (PBT). In the presence of MWCNTs, PC and PBT formed a miscible blend, and the MWCNTs in the PC matrix were uniformly and homogeneously dispersed after the melt mixing of the PC and PBT–MWCNT mixture. Finally, when the proportion of the PC and PBT–MWCNT mixture in the blend/MWCNT nanocomposites was changed, an electrical conductivity of 6.87 × 10^?7 S/cm was obtained in the PC/PBT–MWCNT nanocomposites at an MWCNT loading as low as about 0.35 wt %. Transmission electron microscopy revealed a regular and homogeneous dispersion and distribution of the MWCNTs and formed a continuous conductive network pathway of MWCNTs throughout the matrix phase. The storage modulus and thermal stability of the PC were also enhanced by the presence of a small amount of MWCNTs in the nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal and mechanical stabilities of composite films from thiadiazol bearing poly(amide-thioester-imide) and multiwall carbon nanotubes by solution compounding

An amino acid containing poly(amide-thioester-imide) (PATEI) possessing a conjugated thiadiazol ring was shown to be effective for dispersing multiwall carbon nanotubes (MWCNTs) in N,N′-dimethylacetamide. Through casting of these dispersions, MWCNT/PATEI composite films were successfully fabricated on substrates and showed no signs of macroscopic aggregation. To increase the compatibility between PATEI matrix and MWCNTs, carboxyl-functionalized MWCNTs (f-MWCNTs) were used in this study. The f-MWCNTs were dispersed homogeneously in the PATEI matrix while the structure of the polymer and the MWCNTs structure were stable in the preparation process as revealed by transmission electron microscopy. Tensile tests and thermal analysis were carried out on free-standing composite films for different MWCNT loading levels. Results showed that overall mechanical and thermal properties of the composites were greatly improved as compared with the neat PATEI film. Fourier transform infrared spectroscopy, powder X-ray diffraction, and field emission electron microscopy were also used to evaluate the MWCNT/PATEI composite system.     

Characterization of conductive multiwall carbon nanotube/polystyrene composites prepared by latex technology

Conductive multiwall carbon nanotube/polystyrene (MWCNT/PS) composites are prepared based on latex technology. MWCNTs are first dispersed in aqueous solution of sodium dodecyl sulfate (SDS) driven by sonication and then mixed with different amounts of PS latex. From these mixtures MWCNT/PS composites were prepared by freeze-drying and compression molding. The dispersion of MWCNTs in aqueous SDS solution and in the PS matrix is monitored by UV–vis, transmission electron microscopy, electron tomography and scanning electron microscopy. When applying adequate preparation conditions, MWCNTs are well dispersed and homogeneously incorporated in the PS matrix. The percolation threshold for conduction is about 1.5 wt% of MWCNTs in the composites, and a maximum conductivity of about 1 S m⁻¹ can be achieved. The approach presented can be adapted to other MWCNT/polymer latex systems.     

Low percolation threshold and high electrical conductivity in melt‐blended polycarbonate/multiwall carbon nanotube nanocomposites in the presence of poly(ε‐caprolactone)

This study focuses on the electrical properties of polycarbonate (PC)/poly(ε‐caprolactone) (PCL)‐multiwall carbon nanotube (MWCNT) nanocomposites. MWCNTs were incorporated into thermoplastic PC matrix by simple melt blending using biodegradable PCL based concentrates with MWCNT loadings (3.5 wt%). Because of the lower interfacial energy between MWCNT and PCL, the nanotubes remain in their excellent dispersion state into matrix polymer. Thus, electrical percolation in PC/PCL‐MWCNT nanocomposites was obtained at lower MWCNT loading rather than direct incorporation of MWCNT into PC matrix. AC and DC electrical conductivity of miscible PC/PCL‐MWCNT nanocomposites were studied in a broad frequency range, 10¹?10⁶ Hz and resulted in low percolation threshold (p_c) of 0.14 wt%, and the critical exponent (t) of 2.09 from the scaling law equation. The plot of logσ_DC versus p^?1/3 showed linear variation and indicated the existence of tunneling conduction among MWCNTs. At low MWCNT loading, the influence of large polymeric gaps between conducting clusters is the reason for the frequency dependent electrical conductivity. Transmission electron microscopy and field emission scanning electron microscopy showed that MWCNTs were homogeneously dispersed and developed a continuous interconnected network path throughout the matrix phase and miscibility behavior of the polymer blend. POLYM. ENG. SCI., 54:646–659, 2014. © 2013 Society of Plastics Engineers     

Effect of compatibilizer on morphology,thermal, and rheological properties of polypropylene/functionalized multi‐walled carbon nanotubes composite

Multi‐walled carbon nanotubes (MWCNTs) filled polypropylene (PP) composites were prepared by a corotating intermeshing twin screw extruder. To improve the dispersion of MWCNTs, the surface of MWCNT was modified with 1,10‐diaminodecane, and maleic anhydride grafted polypropylene (MA‐g‐PP) was used as a compatibilizer. Micrographs of well dispersed functionalized MWCNTs (diamine‐MWCNT) were observed due to the reaction between MA‐g‐PP and diamine‐MWCNT in PP/MA‐g‐PP/diamine‐MWCNTs composites. The different behaviors in crystallization and melting temperatures of PP/MA‐g‐PP/diamine‐MWCNTs composite were observed compared to PP and PP/neat‐MWCNT. Especially, the decomposition temperature of the composite was increased by 50°C compared to PP. PP/MA‐g‐PP/diamine‐MWCNTs composite showed the highest complex viscosity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Graphene nanoplate and multiwall carbon nanotube–embedded polycarbonate hybrid composites: High electromagnetic interference shielding with low percolation threshold

This study has reported the preparation of polycarbonate (PC)/graphene nanoplate (GNP)/multiwall carbon nanotube (MWCNT) hybrid composite by simple melt mixing method of PC with GNP and MWCNT at 330°C above the processing temperature of the PC (processing temperature is 280°C) followed by compression molding. Through optimizing the ratio of (GNP/MWCNT) in the composites, high electromagnetic interference shielding effectiveness (EMI SE) value (∼21.6 dB) was achieved at low (4 wt%) loading of (GNP/MWCNT) and electrical conductivity of ≈6.84 × 10⁻⁵ S.cm⁻¹ was achieved at 0.3 wt% (GNP/MWCNT) loading with low percolation threshold (≈0.072 wt%). The high temperature melt mixing of PC with nanofillers lowers the melt viscosity of the PC that has helped for better dispersion of the GNPs and MWCNTs in the PC matrix and plays a key factor for achieving high EMI shielding value and high electrical conductivity with low percolation threshold than ever reported in PC/MWCNT or PC/graphene composites. With this method, the formation of continuous conducting interconnected GNP‐CNT‐GNP or CNT‐GNP‐CNT network structure in the matrix polymer and strong π–π interaction between the electron rich phenyl rings and oxygen atom of PC chain, GNP, and MWCNT could be possible throughout the composites. POLYM. COMPOS., 37:2058–2069, 2016. © 2015 Society of Plastics Engineers     

The role of non-covalent interactions and matrix viscosity on the dispersion and properties of LLDPE/MWCNT nanocomposites

Linear low density polyethylene (LLDPE)/multi-walled carbon nanotube (MWCNT) composites were prepared by melt compounding, following two different compatibilization strategies that involved non-covalent interactions between the matrix and the filler. The first approach involved grafting pyridine aromatic moieties on the maleated polyolefin backbone, which are able to interact by π–π stacking with the surface of the nanotubes. The second method implemented non-covalent/non-specific surface functionalization of the MWCNTs with a hyperbranched polyethylene (HBPE). The enhanced interfacial interactions established in the composites containing LLDPE functionalized with pyridine grafts improved the dispersion of the nanotubes within the polymer matrix. Dispersion was also favoured by higher matrix viscosity. Composites containing finely dispersed MWCNTs exhibited an increase in the rheological and electrical percolation thresholds, and a significant improvement in mechanical properties. On the contrary the composites based on the low viscosity matrix contained large amounts of aggregates, which promoted lower percolation thresholds. Manipulation of matrix viscosity and compatibilization resulted in composites with good mechanical properties, and low percolation thresholds.     

Polyester and multiwalled carbon nanotube composites: characterization,electrical conductivity and antibacterial activity

Poly(butylene terephthalate) (PBT) composites containing multiwalled carbon nanotubes (MWCNTs) were prepared using a melt‐blending process and used to examine the effects on the composite structure and properties of replacing PBT with acrylic acid‐grafted PBT (PBT‐g‐AA). PBT‐g‐AA and multihydroxyl‐functionalized MWCNTs (MWCNTs‐OH) were used to improve the compatibility and dispersibility of the MWCNTs within the PBT matrix. The composites were characterized morphologically using transmission electron microscopy, and chemically using Fourier transform infrared, solid‐state ¹³C NMR and UV‐visible absorption spectroscopy. The antibacterial and electrical conductivity properties of the composites were also evaluated. MWCNTs or MWCNTs‐OH enhanced the antibacterial activity and electrical conductivity of the PBT/MWCNT or PBT‐g‐AA/MWCNTs‐OH composites. The functionalized PBT‐g‐AA/MWCNTs‐OH composites showed markedly enhanced antibacterial properties and electrical conductivity due to the formation of ester bonds from the condensation of the carboxylic acid groups of PBT‐g‐AA with the hydroxyl groups of MWCNTs‐OH. The optimal proportion of MWCNTs‐OH in the composites was 1 wt%; in excess of this amount, the compatibility between the organic and inorganic phases was compromised. Copyright © 2011 Society of Chemical Industry     

Noncovalent compatibilization of polypropylene/MWCNT composites using an amino‐pyridine grafted polypropylene matrix

Polypropylene (PP)/multiwalled carbon nanotube (MWCNT) composites are prepared by implementing noncovalent compatibilization. The compatibilization method involves PP matrix functionalization with pyridine (Py) aromatic moieties, which are capable of π–π interaction with MWCNT sidewalls. Imaging revealed that the addition of 25 wt% of PP‐g‐Py to neat PP is capable of drastically reducing nanotube aggregate size and amount, compared to a matrix containing the equivalent amount of a maleated PP (PP‐g‐MA). Raman spectroscopy confirms improved polymer/nanotube interaction with the PP‐g‐Py matrix. The electrical percolation threshold appears at a MWCNT loading of approximately 1.2 wt%, and the maximum value of the electrical conductivity achieved is 10⁻² S/m, irrespective of the functionalization procedure. The modulus of the composites is improved with the addition of MWCNTs. Furthermore, composites functionalized with Py display significant improvements in composite ductility compared with their maleated counterparts because of the improved filler dispersion. POLYM. COMPOS., 37:2794–2802, 2016. © 2015 Society of Plastics Engineers     

Non-destructive functionalization of multi-walled carbon nanotubes with naphthalene-containing polymer for high performance Nylon66/multi-walled carbon nanotube composites

A new compatibilizer, poly(vinyl benzyloxy methyl naphthalene)-g-poly(t-butyl methacrylate-co-methacrylic acid), was synthesized for Nylon 66 (N66)/multi-walled carbon nanotube (MWCNT) composites. It has been shown that the naphthalene unit in the main chain of the compatibilizer interacts with MWCNTs by π–π interaction and that the carboxylic acid unit in the graft chain of the compatibilizer interacts with the amide group of N66. The use of the compatibilizer produces well-dispersed MWCNTs in N66 matrix, which results in improved mechanical and electrical properties of the composites, while the simple mixture of N66/MWNCTs without the compatibilizer exhibits poor mechanical and electrical properties due to severe aggregation of MWCNTs. It is also found that the compatibilizer with a small amount of carboxylic acids is more effective for improving the mechanical and electrical properties of N66/MWCNT composites.     

Preparation and properties of polyurethane/multiwalled carbon nanotube nanocomposites by a spray drying process

A spray drying approach has been used to prepare polyurethane/multiwalled carbon nanotube (PU/MWCNT) composites. By using this method, the MWCNTs can be dispersed homogeneously in the PU matrix in an attempt to improve the mechanical properties of the nanocomposites. The morphology of the resulting PU/MWCNT composites was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM observations illustrate that the MWCNTs are dispersed finely and uniformly in the PU matrix. X‐ray diffraction results indicate that the microphase separation structure of the PU is slightly affected by the presence of the MWCNTs. The mechanical properties such as tensile strength, tensile modulus, elongation at break, and hardness of the nanocomposites were studied. The electrical and the thermal conductivity of the nanocomposites were also evaluated. The results show that both the electrical and the thermal conductivity increase with the increase of MWCNT loading. In addition, the percolation threshold value of the PU composites is significantly reduced to about 5 wt % because of the high aspect ratio of carbon nanotubes and exclusive effect of latex particles of PU emulsion in dispersion. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dispersability of multiwalled carbon nanotubes in polycarbonate-chloroform solutions

The dispersion of commercial multiwalled carbon nanotubes (MWCNTs, Nanocyl™ NC7000) in chloroform and in polycarbonate (PC)-chloroform solutions was investigated by variation of the polymer concentration, MWCNT amount and sonication time and compared with PC/MWCNT composites, which were processed by melt mixing, subsequently dissolved in chloroform and dispersed via sonication under the same conditions. The sedimentation behaviour was characterised under centrifugal forces using a LUMiSizer^® separation analyser. The space and time resolved extinction profiles as a measure of the stability of the dispersion and the particle size distribution were evaluated. Sonication up to 5 min gradually increases the amount of dispersed particles in the solutions. A significant improvement of the MWCNT dispersion in chloroform was achieved by the addition of PC indicating the mechanism of polymer chain wrapping around the MWCNTs. In dispersions of melt mixed PC/MWCNT composites the dispersion of MWCNTs is significantly enhanced already at a low sonication time of only 0.5 min due to very efficient polymer wrapping during the melt mixing process. However, the best dispersion quality does not lead to the highest electrical conductivity of thin composite films made of these PC/MWCNT dispersions.     

Mechanical and electrical properties of multi walled carbon nanotube/ABC block terpolymer composites

Composites of multi-walled carbon nanotubes (MWCNTs) in ABC block terpolymer matrices of different compositions are studied. The composites were obtained by dispersion of MWCNTs in poly(styrene-block-butadiene-block-methyl methacrylate) (SBM) in a selective solvent for the M block, followed by solvent evaporation and compression molding. The structures of the MWCNT/SBM composites are investigated by transmission electron microscopy. The processing conditions, i.e. solvent cast or compression molding, induce different non-equilibrium microstructures and the MWCNTs modify the SBM organization only locally. We show that by fixing the processing procedure we are able to obtain samples with reproducible microstructure and properties. The electrical conductivity thresholds of these composites are lower than 1 wt.%. The reinforcing effect of the MWCNTs measured by dynamical mechanical analysis is mainly related to the SBM microstructures of the matrix and to the MWCNT dispersion quality.     

Properties of surface‐modified multiwalled carbon nanotube filled poly(ethylene terephthalate) composite films

Poly(ethylene terephthalate) (PET)/multiwalled carbon nanotube (MWCNT) composites were prepared by in situ polymerization. To improve the dispersion of MWCNTs in the PET matrix, functionalized MWCNTs having acid groups (acid‐MWCNTs) and acetic groups (acetic‐MWCNTs) on their surfaces were used. The functional groups were confirmed by infrared spectrometry. Scanning electron microscopy showed that acetic‐MWCNTs had a better dispersion in the PET matrix than pristine MWCNTs and acid‐MWCNTs. A reaction between PET and acetic‐MWCNTs was confirmed by a shift of the Raman G band to a higher frequency and an increase of the complex viscosity in the rheological properties. The composites containing functionalized MWCNTs showed a large increase in their tensile strengths and moduli. The values of the strengths and moduli of the PET/acetic‐MWCNT composites were higher than those of the PET/acid‐MWCNT composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Reduction of percolation threshold through double percolation in melt‐blended polycarbonate/acrylonitrile butadiene styrene/multiwall carbon nanotubes elastomer nanocomposites

We demonstrate a method that involves melt blending of polycarbonate (PC) and melt‐blended acrylonitrile butadiene styrene (ABS) with multiwall carbon nanotubes (MWCNTs) to prepare electrically conducting PC/MWCNT nanocomposites at significantly low MWCNT loading. The partial solubility of ABS in PC led to a selective dispersion of the MWCNTs in the ABS phase after melt‐blending PC and ABS. Thus, a sudden rise in electrical conductivity (∼10⁸ orders of magnitude) of the nanocomposites was found at 0.328 vol% of MWCNT, which was explained in terms of double percolation phenomena. By optimizing the ratio of PC and the ABS–MWCNT mixture, an electrical conductivity of 5.58 × 10⁻⁵ and 7.23 × 10⁻³ S cm⁻¹ was achieved in the nanocomposites with MWCNT loading as low as 0.458 and 1.188 vol%, respectively. Transmission electron microscopy revealed a good dispersion and distribution of the MWCNTs in the ABS phase, leading to the formation of continuous MWCNT network structure throughout the matrix even at very low MWCNT loading. Storage modulus and thermal stability of the PC were also increased by the presence of a small amount of MWCNTs in the nanocomposites.POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Migration of MWCNTs during melt preparation of ABS/PC/MWCNT conductive composites via PC/MWCNT masterbatch approach

The migration of multi-walled carbon nanotubes (MWCNTs) from the thermodynamically favored polycarbonate (PC) phase to the acrylonitrile-butadiene-styrene (ABS) phase is observed when PC/MWCNT masterbatch is diluted with PC and ABS by melt mixing for 5 min with 70% of ABS having relatively high rubber content. The migration is explained by a combination of the morphology evolution, high rubber content and higher affinity of MWCNTs to polybutadiene (PB) than to PC. The high rubber content increases the probability of the contact between MWCNTs and elongated rubber particles during the morphology evolution, most MWCNTs are dragged out of the PC phase to the ABS phase by the surrounding rubber particles because of the better affinity of MWCNTs to PB than to PC. As a result of the selective localization of most MWCNTs in the continuous ABS phase, the resulting ABS/PC/MWCNT composites are conductive. However, with a long mixing time of 60 min, most MWCNTs come back to the PC phase due to the change in the structure of PB chains which decreases the interaction between MWCNTs and rubber particles, resulting in non-conductive materials.     

Thermal and mechanical properties of homogeneous ternary nanocomposites of regioregular poly(3‐hexylthiophene)‐wrapped multiwalled carbon nanotube dispersed in thermoplastic polyurethane: Dynamic‐ and thermomechanical analysis

An interesting correlation between initial loading and nature of wrapping of regioregular poly(3‐hexylthiophene) (rrP3HT) on multiwalled carbon nanotube and their combined effect on dynamic‐ and thermomechanical properties in ternary system (thermoplastic polyurethane as matrix) is highlighted. Wrapping of rrP3HT on carbon nanotube (CNT) makes the hexyl side chains thermally nonequivalent and composites more stable. Dynamic‐ and thermomechanical analysis ascertained the miscibility (single T_g = ?40°C), large mechanical reinforcement, and improved storage modulus of nanocomposites in the presence of CNT compared to its blends. Two breaks at ～ ?100 and ～ ?40°C for TPU‐P3HT composites (PHs) and TPU‐P3HT‐MWCNT composites (PHCs) in the loss modulus vs. temperature plot indicates two different types of transitions in P3HT chains. Dimensional stability by expansion probe technique measures low coefficient of thermal expansion of PHCs compared to its blends. Softening property by penetration probe technique suggests that 2.5 wt % loading of P3HT exhibits lowest degree of penetration compared to other nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013