Interfacial modification of single‐walled carbon nanotubes for high‐loading‐reinforced polypropylene composites

In this article, we present a strategy for fabricating polypropylene (PP)/polypropylene‐regrafted single‐walled carbon nanotube (PP‐re‐g‐SWNT) composites with a high loading of single‐walled carbon nanotubes (SWNTs; 20 wt %). The PP‐re‐g‐SWNTs were characterized by X‐ray photoelectron, Fourier transform infrared spectroscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The PP‐re‐g‐SWNTs showed excellent interfacial adhesion and dispersion. Furthermore, PP molecules, about 72 wt % by mass, were homogeneously bonded onto the surface of the SWNTs according to TGA. In this hybrid nanocomposite system, the PP‐re‐g‐SWNTs were covalently integrated into the PP matrix and became part of the conjugated network structure (as evidenced by differential scanning calorimetry and dynamic mechanical analysis) rather than just a separate component. Accordingly, the PP/PP‐re‐g‐SWNT composites presented obvious improvements in mechanical properties and conductivity (from 10^?10 to 10^?2). Most importantly, the tensile and flexural strength of the PP/PP‐re‐g‐SWNT composites did not exhibit an obvious downturn with the addition of 20 wt % SWNTs; this was contrary to documented results. We believe that these new observations were due to the novel structure of the PP‐re‐g‐SWNTs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39817.     

Single‐walled carbon nanotube/poly(methyl methacrylate) composites for electromagnetic interference shielding

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) composites were prepared using coagulation method. The electrical conductivity and the electromagnetic interference (EMI) shielding of SWNT/PMMA composites over the X‐band (8–12 GHz) and the microwave (200–2000 MHz) frequency range have been investigated. The electrical conductivity of composites increases with SWNT loading by 13 orders of magnitude, from 10^?15 to 10^?2 Ω^?1 cm^?1 with a percolation threshold of about 3 wt% SWNTs. The effect of the sample thickness on the shielding effectiveness has been studied, and correlated to the electrical conductivity of composites. The data suggest that SWNT/PMMA composites containing higher SWNT loading (above 10 wt%) be useful for EMI shielding and those with lower SWNT loading be useful for electrostatic charge dissipation. The dominant shielding mechanism of SWNT/PMMA composites was also discussed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Single wall carbon nanotube dispersion and exfoliation in polymers

Dispersion and exfoliation of single wall carbon nanotubes (SWNTs) have been studied in poly(acrylonitrile) (PAN), poly(p‐phenylene benzobisoxazole) (PBO) solutions, and composite fibers using transmission electron microscopy. As a result of polymer assisted dispersion and exfoliation, the average SWNT bundle diameter in SWNT/PAN (5/95) was 11 nm, while the average diameter for the pristine SWNT bundles was about 30 nm. High resolution TEM of SWNT/PBO (10/90) composite fibers did not reveal the presence of SWNT aggregates or bundles, suggesting SWNT exfoliation as individuals. On the other hand, both oriented and unoriented nanotube bundles have been observed in SWNT/PBO samples containing 15 wt % nanotubes. Carbon nanotubes are 10⁵ times more radiation resistant than flexible polymers such as polyethylene, and 10³ times more resistant than highly radiation resistant polymers such as PBO. Therefore in the high resolution TEM study of nanotube/polymer composites, nanotubes can be observed long after the polymer has been damaged by electron radiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 985–989, 2005     

Synthesis of water-soluble single-walled carbon nanotubes by RAFT polymerization

Water-soluble single-walled carbon nanotubes (SWNTs) were synthesized by grafting poly(acrylamide) (PAM) from the surface of SWNT via reversible addition-fragmentation chain transfer (RAFT) polymerization. The RAFT agents were covalently attached to the SWNTs by functionalizing SWNTs with in situ generated diazonium compounds. The product was characterized by means of FT-IR, Raman, ¹H NMR, TGA and TEM. The results showed that PAM chains had successfully grafted from SWNT by RAFT polymerization. The amount of PAM grown from SWNT increased with the polymerization time. The acrylamide conversion increased linearly with the polymerization time, indicating the “living” characteristics of the RAFT polymerization. TEM was utilized to image PAM-g-SWNT, showing relatively uniform polymer coatings present on the surface of individual, debundled nanotubes.     

Synthesis and properties of poly(methyl methacrylate)/carbon nanotube composites covalently integrated through in situ radical polymerization

Poly(methyl methacrylate) (PMMA)/single‐walled carbon nanotube (SWNT) composites were synthesized by the grafting of PMMA onto the sidewalls of SWNTs via in situ radical polymerization. The free‐radical initiators were covalently attached to the SWNTs by a well‐known esterification method and confirmed by means of thermogravimetric analysis and Fourier transform infrared spectroscopy. Scanning electron microscopy and transmission electron microscopy were used to image the PMMA–SWNT composites; these images showed the presence of polymer layers on the surfaces of debundled, individual nanotubes. The PMMA–SWNT composites exhibited better solubility in chloroform than the solution‐blended composite materials. On the other hand, compared to the neat PMMA, the PMMA–SWNT nanocomposites displayed a glass‐transition temperature up to 6.0°C higher and a maximum thermal decomposition temperature up to 56.6°C higher. The unique properties of the nanocomposites resulted from the strong interactions between the SWNTs and the PMMA chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PEDOT‐PSS/singlewall carbon nanotubes composites

Poly(3,4‐ethylenedioxythiophene)‐single wall carbon nanotube (SWNT) composites were prepared via coating methods for improving electrical conductivity and flexibility, minimizing loss of transparency. Three types of surface modified SWNTs were prepared through different modification methods: carboxylated SWNT treated with nitric acid to form carboxylic acid group on their surfaces, 1‐pyrenebutyric acid wrapped SWNT, and 1‐pyrenebutyric acid, lithium salt wrapped SWNT. The surface modifiers had influence on the dispersion states of the SWNTs in 2‐propanol. The dispersion states had influence of aggregate concentrations of surface modified SWNTs in polymer matrix, showing lower aggregate concentration for the carboxylated SWNT than those of the other surface modified SWNTs. The dispersion behaviors of SWNTs were also related with transparency and electrical resistance, and flexibility of composite films. Based on the layer‐by‐layer coating method, SWNT composite film properties such as thickness, transparency, and electrical conductivity could be controlled and would be a good example for improving contradictory properties. POLYM. ENG. SCI., 48:1–10, 2008. © 2007 Society of Plastics Engineers     

Preparation and properties of the single‐walled carbon nanotube/cellulose nanocomposites using N‐methylmorpholine‐N‐oxide monohydrate

Single‐walled carbon nanotube (SWNT)/cellulose nanocomposite films were prepared using N‐methylmorpholine‐N‐oxide (NMMO) monohydrate as a dispersing agent for the acid‐treated SWNTs (A‐SWNTs) as well as a cellulose solvent. The A‐SWNTs were dispersed in both NMMO monohydrate and the nanocomposite film (as confirmed by scanning electron microscopy) because of the strong hydrogen bonds of the A‐SWNTs with NMMO and cellulose. The mechanical properties, thermal properties, and electric conductivity of the nanocomposite films were improved by adding a small amount of the A‐SWNTs to the cellulose. For example, by adding 1 wt % of the A‐SWNTs to the cellulose, tensile strain at break point, Young's modulus, and toughness increased ～ 5.4, ～ 2.2, and ～ 6 times, respectively, the degradation temperature increased to 9°C as compared with those of the pure cellulose film, and the electric conductivities at ? (the wt % of A‐SWNTs in the composite) = 1 and 9 were 4.97 × 10^?4 and 3.74 × 10^?2 S/cm, respectively. Thus, the A‐SWNT/cellulose nanocomposites are a promising material and can be used for many applications, such as toughened Lyocell fibers, transparent electrodes, and soforth. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New carbon nanotube–conducting polymer composite electrodes for drug delivery applications

A novel drug delivery system (DDS) based on a carbon nanotube (CNT)–poly(3,4‐ethylenedioxythiophene) (PEDOT) composite was constructed via a layering method. Single‐walled CNTs (SWNTs) were immobilized on a gold electrode using a layer‐by‐layer technique. In particular, cysteamine (Cys) was firstly bonded to the gold surface through the strong S? Au association and SWNTs were subsequently linked onto the Cys layer through condensation reaction of ? NH₂ and carboxyl groups by 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide/N‐hydroxysuccinimide coupling. X‐ray photoelectron spectroscopy and Raman spectroscopy demonstrate that this is a facile route for immobilizing CNTs on gold electrodes. Finally PEDOT was electropolymerized on the SWNT‐functionalized electrode to make a SWNT–PEDOT composite, and the modified electrode was applied as a DDS. Dexamethasone, as a model drug, was incorporated into PEDOT in the electropolymerization. Investigations of the electrochemical properties of SWNT–PEDOT demonstrate that SWNTs greatly improve the conductivity and increase the charge capacity of PEDOT. The composite exhibits a petal‐like surface structure, 20–30 nm thick and 100–200 nm wide. Compared to a DDS based on pure PEDOT synthesized under the same conditions, SWNT–PEDOT has the merits of higher drug release rate and larger release amount. The average mass release for every five voltammetry cycles increases from 1.4126 to 1.8864 mg cm^?2. Copyright © 2011 Society of Chemical Industry     

Improvement of Vickers hardness measurement on SWNT/Al2O3 composites consolidated by spark plasma sintering

Dense alumina composites with different carbon nanotube content were prepared by colloidal processing and consolidated by Spark Plasma Sintering (SPS). Single-wall carbon nanotubes (SWNTs) were distributed at grain boundaries and also into agglomerates homogeneously dispersed. Carrying out Vickers hardness tests on the cross-section surfaces instead of top (or bottom) surfaces has shown a noticeable increase in the reliability of the hardness measurements. This improvement has been mainly attributed to the different morphology of carbon nanotube agglomerates, which however does not seem to affect the Vickers hardness value. Composites with lower SWNT content maintain the Vickers hardness of monolithic alumina, whereas it significantly decreases for the rest of compositions. The decreasing trend with increasing SWNT content has been explained by the presence of higher SWNT quantities at grain boundaries. Based on the results obtained, a method for optimizing Vickers hardness tests performance on SWNT/Al₂O₃ composites sintered by SPS is proposed.     

Synthesis of pyrene‐capped polystyrene for dispersion of pristine single‐walled carbon nanotubes

Pyrene‐capped polystyrene (PyPS) with various molecular weights (M?_n) was synthesized through the anionic polymerization method and characterized using UV, Fourier transform infrared and NMR spectroscopy and gel permeation chromatography. The polymers were then used for non‐covalent functionalization of pristine single‐walled carbon nanotubes (SWNTs). The functionalization efficiency was assessed by measuring the SWNT dispersibility in chloroform. In the presence of PyPS, the dispersibility can be as high as 372.5 mg L^?1, and the dispersions containing more than 1.25 mg mL^?1 of PyPS are very stable with no solid deposits observed after being centrifuged at 5000 rpm for 15 min. Once the PyPS concentration is converted to the molar concentration of the pyrene unit and the dispersibility redefined as nanotube content per molar pyrene unit, the renewed dispersibility is found to be independent of M?_n of PyPS within the detected M?_n range. For a certain PyPS polymer, however, both nanotube dispersibility and dispersion stability are strongly dependent on the PyPS concentration. These results suggest that PyPS may be used as an excellent dispersant for subsequent preparation of polystyrene/SWNT composites. Copyright © 2011 Society of Chemical Industry     

Effect of polymer chain length on the solubility of polystyrene grafted single‐walled carbon nanotubes in tetrahydrofuran

BACKGROUND: While carbon nanotubes are highly interesting materials for a variety of applications, their inherent insolubility limits widespread applications and solution‐phase processing. It is known that chemical functionalization can overcome this insolubility problem, and covalent grafting of polymers to the nanotube surface has been shown to be effective. In this study, the effect of polymer molecular weight on the solubility of polymer–nanotube conjugates was investigated. RESULTS: A series of nitroxide‐capped polystyrene polymers ranging in molecular weight from 2900 to 105 000 g mol^?1 were grafted to single‐walled carbon nanotubes (SWNTs). The resulting polystyrene–SWNT conjugates exhibited different degrees of solubility in tetrahydrofuran. Subsequent thermogravimetric and UV‐visible spectroscopy analyses indicated that carbon nanotube solubility reached a maximum when a polymer sample with a weight‐average molecular weight of 10 000 g mol^?1 was used. Higher and lower molecular weights resulted in reduced solubilities. CONCLUSION: Polymer chains of intermediate length maximize SWNT solubility, while lengths that are too low or too high seem to diminish the ability of the polymer–SWNT conjugates to remain in solution. Copyright © 2008 Society of Chemical Industry     

Fluorescence turn‐on chemical sensor based on water‐soluble conjugated polymer/single‐walled carbon nanotube composite

A chemical sensor for methyl viologen (MV²⁺), based on a water‐soluble conjugated polymer/single‐walled carbon‐nanotube (SWNT) composite, was fabricated. Water‐soluble poly(m‐phenylene ethynylene) with sulfonic acid side‐chain groups (mPPE‐SO₃) was synthesized via a Pd‐catalyzed Sonogashira coupling reaction and used to prepare a highly stable mPPE‐SO₃/SWNT composite with strong π–π interactions in water. The relationship between the optical properties and sensing capability of the mPPE‐SO₃/SWNT composite in aqueous solution was investigated. The addition of MV²⁺ enhanced the fluorescence intensity of the mPPE‐SO₃/SWNT composite by inducing a conformational change of the polymer from a helical to a random‐coil structure. The water‐soluble mPPE‐SO₃/SWNT composite enabled highly sensitive fluorescence detection of MV²⁺ in aqueous solutions with no precipitation resulting from reaggregation of the SWNTs. This mPPE‐SO₃/SWNT composite sensor system is therefore an effective turn‐on chemical sensor for MV²⁺. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43301.     

Comparison of flocculated and dispersed single‐wall carbon nanotube‐based coatings using nonionic surfactants

Single‐wall carbon nanotubes (SWNTs) are promising filler materials for advanced polymer composites, but the impressive properties that have been predicted theoretically have not been realized experimentally. This gap is generally attributed to aggregation and nonideal dispersion of the SWNTs. Here, nonionic surfactants based on poly(ethylene oxide) are used to disperse SWNTs in either water or ethanol using sonication. The dispersed aqueous SWNTs are stable, while the analogous ethanol system yields loosely flocculated SWNTs. After drying these dispersions, the electrical conductivity of the flocculated system is at least an order of magnitude greater than the dispersed system at the same SWNT loading with conductivity greater than 20 S/cm obtained for the flocculated systems containing unsorted, commercial SWNTs. These flocculated systems can be readily sprayed to create conductive coatings. Despite their high electrical conductivity, these coatings provide only modest electromagnetic interference shielding (<20 dB) when testing large areas (30.5 × 30.5 cm²), which suggests significant heterogeneity or defects in these coatings that are not readily visible by eye or scanning electron microscopy. This defect mechanism is consistent with a decrease in shield efficacy at high SWNT loadings, despite no statistical change in the electrical conductivity of the coating. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Properties of polyamide 6/multiwalled carbon nanotubes composites: The influence of processing methods

The objective of this work was to elucidate the influence of shear rates on the properties of polyamide 6/multiwalled carbon nanotube (PA6/CNT) composites which was realized by adopting different types of processing methods that feature different orders of magnitude in shear rates, such as compression molding (CM, ~0 s⁻¹), conventional injection molding (CIM, ~10² s⁻¹) and microinjection molding (μIM, ~10⁵ s⁻¹). Electrical conductivity (σ) results indicated that the prevailing high shearing conditions in injection molding was unfavorable for the formation of intact filler network, thereby resulting in a much lower σ than CM counterparts. Moreover, the σ of PA6/CNT microparts was higher than that of CIM macroparts when the filler content was less than 5 wt%, otherwise the σ of CIM macroparts prevailed over that of μIM counterparts. A better filler distribution was observed when PA6/CNT composites were processed under higher shearing conditions, as corroborated by SEM. In addition, CNTs were preferentially aligned along flow direction and a higher degree of CNT orientation was expected with increasing shear rates, as confirmed by Raman spectral analysis. The tensile strength of injection molded PA6/CNT samples increased with increasing filler concentrations, and the more preferential orientation and better distribution of CNT were considered to be the contributing factors. The comparative study of the properties of PA6/CNT composites that processed using different methods was important for their practical applications in industrial sectors.     

Carbon nanotube core–polymer shell nanofibers

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) and SWNT/polyacrylonitrile composite nanofibers were electrospun with SWNT bundles as the cores and the polymers as the shells. This was a novel approach for processing core (carbon nanotube)–shell (polymer) nanofibers. Raman spectroscopy results show strain‐induced intensity variations in the SWNT radial breathing mode and an upshift in the tangential (G) and overtone of the disorder (G′) bands, suggesting compressive forces on the SWNTs in the electrospun composite fibers. Such fibers may find applications as conducting nanowires and as atomic force microscopy tips. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1992–1995, 2005     

Investigation of molecular interaction between single‐walled carbon nanotubes and conjugated polymers

Single‐walled carbon nanotubes (SWNTs) have unique properties such as high electrical conductivity and high tensile strength. Their composites with polymers have a great role in new sciences such as organic solar cells and ultrastrong lightweight materials. In this article, molecular dynamic simulations with polymer consistent force field are performed to study the interaction between SWNTs and conjugated polymers including poly(2‐methoxy‐5‐(3‐7‐dimethyloctyloxy)‐1,4‐phenylenevinylene) (MDMO‐PPV), poly(3‐hexythiophene) (P3HT), and poly[(9,9′‐dioctylfluorenyl‐2,7‐diyl)‐co‐bis(N,N′‐(4,butylphenyl))bis(N,N′‐phenyl‐1,4‐phenylene)diamine] (PFB). We computed the interaction energy and morphology of polymers adsorbed to the surface of SWNTs was studied by the radius of gyration (Rg). The influence of important factors such as SWNT radius, chirality, and the temperature on the interfacial adhesion of SWNT–polymer and Rg of polymers were studied. We found that the strongest interaction between the SWNTs and these polymers was, first observed for P3HT, then MDMO‐PPV, and finally PFB. Our results showed that the interaction energy is influenced by SWNT radius and the specific monomer structure of the polymers, but the effects of chirality and temperature are very weak. In addition, we found that the temperature, chirality, and radius have not any important effect on the radius of gyration. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

Spectroscopic and SEM studies of SWNTs: Polymer solutions and films

Raman spectra of SWNTs suspended in aqueous solutions containing fragmented single-stranded DNA (SWNT:DNA), and films obtained from this suspension have been obtained. SEM study of the dried films indicated that the nanotubes tend to aggregate into bundles which results in the enhancement of the Raman intensity of the G⁻ tangential band, and an upshift and broadening of the G⁺ band. The intensity of radial breathing modes of metallic SWNTs is higher in the SWNT:DNA films as compared to that of the SWNT:DNA solution. The Raman spectra of SWNT:PVP and SWNT:agaroza samples exhibit similar changes as the SWNT:DNA samples when films are cast from the corresponding solutions. Both films and the solution forms of SWNT:DNA yield luminescence spectra which indicates the presence of individual tubes or small bundles in the films. The luminescence bands of SWNT:DNA films are relatively wider and is attributed to the interaction of DNA with the nanotube surface in the solid state.     

Effect of high SWNT content on the room temperature mechanical properties of fully dense 3YTZP/SWNT composites

This paper is devoted to correlate the microstructure and room temperature mechanical properties of single-wall carbon nanotube (SWNT) reinforced 3 mol% yttria stabilized tetragonal zirconia with high SWNT content (2.5, 5 and 10 vol%). Fully dense composites were prepared by using a combination of aqueous colloidal powder processing and Spark Plasma Sintering. SWNTs were located at the ceramic grain boundaries and they were not damaged during the sintering process. The weak interfacial bonding between SWNTs and ceramic grains together with the detachment of SWNTs within thick bundles have been pointed out as responsible for the decrease of hardness and fracture toughness of the composites in comparison with the monolithic 3YTZP ceramic.     

Surface modification of single‐walled carbon nanotubes with polyethylene via in situ Ziegler–Natta polymerization

Single‐walled carbon nanotubes (SWNTs) were modified with polyethylene (PE) prepared by in situ Ziegler–Natta polymerization. Because of the catalyst pretreated on the surface of the SWNTs, the ethylene was expected to polymerize there. Scanning electron microscopy images and solubility measurements showed that the surface of the SWNTs was covered with a PE layer, and a crosslink may have formed between the SWNTs and PE. When the SWNTs covered with a PE layer were mixed with commercialized PE by melt blending, the resulting composite had better mechanical properties than the composite from the SWNTs without a PE layer. The yield strength, the tensile strength and modulus, the strain at break, and the fracture energy of the modified‐SWNT/PE composites were improved by 25, 15.2, 25.4, 21, and 38% in comparison with those of the raw‐SWNT/PE composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3697–3700, 2004     

Processing and properties of carbon nanotube/poly(methyl methacrylate) composite films

A systematic study of the reinforcement of single‐walled carbon nanotubes (SWNTs), multiwalled carbon nanotubes, and vapor‐grown carbon nanofibers (VGCNFs) in poly(methyl methacrylate) (PMMA) is reported. SWNT/PMMA composite films with various SWNT concentrations (from 0.5 to 50 wt % with respect to the weight of PMMA) were processed from nitromethane. Two types of SWNTs were used: SWNT‐A, which contained 35 wt % metal catalyst, and SWNT‐B, which contained about 2.4 wt % metal catalyst. Properties of different nanotubes containing composites were compared with 15 wt % carbon nanotubes (CNTs). Property enhancement included electrical conductivity, mechanical properties, and solvent resistance. The thermal degradation of PMMA in the presence of CNTs in air and nitrogen environments was studied. No variation in the thermal degradation behavior of PMMA/CNT was observed in nitrogen. The peak degradation temperature increased for the composites in air at low CNT loadings. Dynamic and thermomechanical properties were also studied. At a 35 wt % SWNT loading, a composite film exhibited good mechanical and electrical properties, good chemical resistance, and a very low coefficient of thermal expansion. Property improvements were rationalized in terms of the nanotube surface area. Composite films were also characterized with Raman spectroscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009