The effects of triethylenetetramine grafting of multi‐walled carbon nanotubes on its dispersion,filler‐matrix interfacial interaction and the thermal properties of epoxy nanocomposites

This study describes the influence of triethylenetetramine (TETA) grafting of multi‐walled carbon nanotubes (MWCNTs) on the dispersion state, interfacial interaction, and thermal properties of epoxy nanocomposites. MWCNTs were first treated by a 3:1 (v/v) mixture of concentrated H₂SO₄/HNO₃, and then TETA grafting was performed. Chemically grafted MWCNT/bisphenol‐A glycidol ether epoxy resin/2‐ethyl‐4‐methylimidazole nanocomposites were prepared. TETA grafting could establish the connection of MWCNTs to the epoxy matrix and transform the smooth and nonreactive MWCNT surface into a hybrid material that possesses the characteristics of both MWCNTs and TETA, which facilitates homogeneous dispersion of MWCNTs and improves nanotube‐epoxy interfacial interaction. Therefore, the impact property, glass transition temperature, thermal stability, and thermal conductivity of epoxy nanocomposites are enhanced. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

A strategy for enhancement of mechanical and electrical properties of polycarbonate/multi-walled carbon nanotube composites

Two poly(3-hexylthiophene)-g-polycaprolactones (P3HT-g-PCLs) with different degrees of polymerization (DP) of P3HT backbone were synthesized and used as a compatibilizer for bisphenol A polycarbonate (PC)/multi-walled carbon nanotube (MWCNT) composites. Both field emission-scanning electron microscopy and melt-state rheology show that MWCNTs are homogeneously dispersed in PC matrix when P3HT-g-PCL is added to PC/MWCNT composites. As a consequence, the mechanical and electrical properties of PC/MWCNT composites are dramatically improved when a small amount of P3HT-g-PCL is added to PC/MWCNT composites. It is also found that P3HT-g-PCL with lower DP of P3HT backbone is more effective to homogeneously disperse MWCNTs in PC matrix than that with higher DP of P3HT. This is because the π-π interaction between MWCNTs and P3HT-g-PCL with lower DP of P3HT is stronger than the case of P3HT with higher DP of P3HT, as evidenced by fluorescence emission spectra.     

Characterizations on the amidized multiwalled carbon nanotubes grafted with polyaniline via in situ polymerization

A multiwalled carbon nanotubes (MWCNTs) were carboxylated after refluxing with sulfuric and nitric acids. These attached carboxylic acid groups were further condensated with o‐phenylene diamine into amide catalyzed by dicyclohexyl carbodiimide (DCC). The obtained amidized MWCNTs were in situ‐polymerized with aniline monomers to graft a conducting polyaniline (PANI) onto MWCNT (ES‐g‐MWCNTs) through the polymerization occurring in the ortho‐ and meta‐positions. The reduced conductivity of the MWCNT after carboxylation can be recovered after grafting with PANI, which owns a strong λ_max at the near infrared region due to the extended conjugation from MWCNTs to PANI. Transmission electronic microscopic pictures show a gradual broadening of the MWCNT diameter after carboxylation, amidization, and polymerization. The weight loss from the thermogravimetric thermograms due to the carboxylations of MWCNTs, amidized MWCNTs, and the PANI grafted MWCNTs into CO₂ can be used to estimate the degree of carboxylation, amidization, and grafting of PANI. The degree of carboxylation of MWCNT calculated from ESCA spectrum is around 23% close to that estimated from TGA thermogram. The doping level of redoped PANI‐grafted MWCNT is found to be 27.78% much less than the maximum 50% of neat PANI. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of multi‐walled carbon nanotube/poly(ethylene terephthalate) nanoweb

Multi‐walled carbon nanotube (MWCNT)/Poly(ethylene terephthalate) (PET) nanowebs were obtained by electrospinning. For uniform dispersion of MWCNTs in PET solution, MWCNTs were functionalized by acid treatment. Introduction of carboxyl groups onto the surface of MWCNTs was examined by Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) analysis. MWCNTs were added into 22 wt % PET solution in the ratio of 1, 2, 3 wt % to PET. The morphology of MWCNT/PET nanoweb was observed using field emission‐scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM). The nanofiber diameter decreased with increasing MWCNT concentration. The distribution of the nanofiber diameters showed a bi‐modal shape when MWCNTs were added. Thermal and tensile properties of electrospun MWCNT/PET nanowebs were examined using a differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA) and etc. Tensile strength, tensile modulus, thermal stability, and the degree of crystallinity increased with increasing MWCNT concentration. In contrast, elongation at break and cold crystallization temperature showed a contrary tendency. Electric conductivities of the MWCNT/PET nanowebs were in the electrostatic dissipation range. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Stabilization and dispersion of PtRu and Pt nanoparticles on multiwalled carbon nanotubes using phosphomolybdic acid,and the use of the resulting materials in a direct methanol fuel cell

PtRu and Pt nanoparticles were deposited on the surface of multiwalled carbon nanotubes (MWCNTs) with the assistance of phosphomolybdic acid (PMo) by a one-pot hydrothermal reduction strategy. Transmission electron microscopy shows a high-density PtRu (or Pt) nanoparticles uniformly dispersed on the surface of the MWCNTs with an average diameter of 1.8 nm for PtRu nanoparticles and 2.4 nm for Pt nanoparticles. Moreover, the as-prepared PMo/PtRu/MWCNT and PMo/Pt/MWCNT electrocatalysts are highly electroactive for the electrochemical oxidation of methanol. Cyclic voltammograms show a high electrochemical surface area (ESA) and a large current density for methanol oxidation at the modified electrode by PMo/PtRu/MWCNT and PMo/Pt/MWCNT electrocatalysts. Electrochemical impedance spectroscopy reveals a high CO tolerance for PMo/PtRu/MWCNT and PMo/Pt/MWCNT electrocatalysts in the electrochemical catalysis of methanol oxidation. For comparison, PtRu/MWCNT and Pt/MWCNT electrocatalysts were prepared in control experiments without PMo. The results demonstrate that PtRu and Pt nanoparticles deposited on MWCNTs in the presence of PMo were superior to those on MWCNTs without PMo in several respects including: (1) a smaller size and a higher dispersion; (2) a higher ESA; (3) a larger current density for methanol oxidation; (4) a higher tolerance for CO poisoning.     

Increasing the thermal conductivity of palmitic acid by the addition of carbon nanotubes

Four different methods, acid oxidation, mechanochemical reaction, ball milling, and grafting following acid oxidation, were used to treat multi-walled carbon nanotubes (MWCNTs). During treatment, hydroxyl groups, carboxylic groups, and amidocyanogen were introduced onto the surfaces of the MWCNTs. The MWCNTs were dispersed into palmitic acid (PA) to prepare phase change composites with high thermal conductivity. Both chemical treatment and ball milling help to break the MWCNT aggregates and to enhance their dispersibility. Measurements show that the thermal conductivity increase of the composites is highly dependent on the MWCNT pretreatment process. We propose that the difference in the interfacial thermal resistance between the MWCNTs and the matrix is due to the difference of the MWCNT surface state caused by different treatment processes. In all the MWCNT/PA composites, the one containing MWCNTs with hydroxyl groups, treated by a mechanochemical reaction, has the highest thermal conductivity increase, which, at room temperature, is up to 51.6% for a MWCNT addition of 1.0%.     

Increasing the interfacial strength in carbon fiber/epoxy composites by controlling the orientation and length of carbon nanotubes grown on the fibers

Multi-walled carbon nanotubes (MWCNTs) were grafted onto carbon fibers (CFs) using an injection chemical vapor deposition method. The orientation and length (16.6–108.6 μm) of the MWCNTs were controlled by the surface treatment of the CFs and the growth time, respectively. The interface between the MWCNTs and the CFs indicated the grafted CNTs were immobilized by embedding catalyst on CFs. Two orders of magnitude increase in the specific surface areas of CFs was obtained by grafting the MWCNT. MWCNT–CF hybrids exhibited good wettability with the epoxy resin due to the surface roughness and capillary action. Single-fiber composite fragmentation tests revealed an remarkable improvement of interfacial shear strength (IFSS) controlled by the orientation and length of MWCNTs. MWCNTs with an perpendicular alignment and long length showed a high IFSS in epoxy composites due to better wettability and a large contact interface between the hybrids and the resin. Hybrids with an optimum length (47.2 μm) of aligned MWCNTs showed a dramatic improvement of IFSS up to 175% compared to that of pristine CFs.     

Mechanical and surface properties of polyurethane/fluorinated multi‐walled carbon nanotubes composites

To improve the mechanical and surface properties of poly(etherurethane) (PEU), multi‐walled carbon nanotubes (MWCNTs) were surface grafted by 3,3,4,4, 5,5,6,6,7,7,8,8,8‐tridecafluoro‐1‐octanol (TDFOL) (MWCNT‐TDFOL) and used as reinforcing agent for PEU. Fourier‐transform infrared spectroscopy revealed the successful grafting of MWCNTs. PEU filled with MWCNT‐TDFOL could be well dispersed in tetrahydrofuran solution, and tensile stress–strain results and dynamic mechanical analysis showed a remarkable increase in mechanical properties of PEU by adding a small amount of MWCNT‐TDFOL. Contact angle testing displayed a limited improvement (just 9°) in the hydrophobicity of PEU surface by solution blending with MWCNT‐TDFOL. However, a large improvement of surface hydrophobicity was observed by directly depositing MWCNT‐TDFOL powder on PEU surface, and the water contact angle was increased from 80° to 138°. Our work demonstrated a new way for the modification of carbon nanotubes and for the property improvement of PEU. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of aminosilane‐functionalized carbon nanotubes on the rheometric,mechanical, electrical and thermal degradation properties of epoxidized natural rubber nanocomposites

We describe the preparation, characterization and physical properties of multiwalled carbon nanotube (MWCNT)‐filled epoxidized natural rubber (ENR) composites. To ensure better dispersion in the elastomer matrix, the MWCNTs were initially subjected to aminopropyltriethoxysilane (APS) treatment to bind amine functional groups (?NH₂) on the nanotube surface. Successful grafting of APS on the MWCNT surface through Si–O–C linkages was confirmed using Fourier transform infrared spectroscopy. Grafting of APS on the MWCNT surface was further corroborated using elemental analysis. ENR nanocomposites with various filler loadings were prepared by melt compounding to generate pristine and APS‐modified MWCNT‐filled elastomeric systems. Furthermore, we determined the effects of various filler loadings on the rheometric, mechanical, electrical and thermal degradation properties of the resultant composite materials. Rheometric cure characterization revealed that the torque difference increased with pristine MWCNT loading compared to the gum system, and this effect was more pronounced when silane‐functionalized MWCNTs were loaded, indicating that this effect was due to an increase in polymer–carbon nanotube interactions in the MWCNT‐loaded materials. Loading of silane‐functionalized MWCNTs in the ENR matrix resulted in a significant improvement in the mechanical, electrical and thermal degradation properties of the composite materials, when compared to gum or pristine MWCNT‐loaded materials.© 2013 Society of Chemical Industry     

Microwave-assisted poly(glycidyl methacrylate)-functionalized multiwall carbon nanotubes with a ‘tendrillar’ nanofibrous polyaniline wrapping and their interaction at bio-interface

Multiwall carbon nanotubes (MWCNTs) were activated by microwave irradiation and covalently functionalized with poly(glycidyl methacrylate) (PGMA) through free radical polymerization using ‘fishing process’ when the propagating polymer radicals were attached onto the graphitic surface of the nanotube. The PGMA-functionalized MWCNTs were then used as a precursor to non-covalently wrap polyaniline (PAni) nanofiber onto them. The functionalized nanotubes exhibited stable dispersion up to 180 days in tetrahydrofuran, dimethyl formamide and dimethyl sulfoxide. Fourier transform infrared analyses indicated the attachment of the epoxide and benzenoid–quinoid functional moieties onto the nanotube surface. The PGMA coating on the nanotube and surrounding PAni nanofiber on the MWCNT scaffold were confirmed by transmission electron microscopy. The Raman spectroscopy confirmed the phonon-assisted modification of the nanotube. The differential action of the pristine and functionalized MWCNTs against an opportunistic bacterium (Escherichia coli ) and its plasmid deoxyribonucleic acid was also investigated. Pristine nanotubes exhibited bacterial inhibitory action and no condensation with the pET-32α(+) plasmid. On the other hand, the anti-bacterial PAni nanofiber and functionalized nanotubes showed complex formation with the bacterial plasmid.     

Effect of the nanostructure and surface chemistry on the gas adsorption properties of macroscopic multiwalled carbon nanotube ropes

The NO₂ adsorption properties of macroscopic multiwalled carbon nanotube (MWCNT) ropes and acid treated MWCNT ropes, obtained by the floating catalyst chemical vapour deposition process, have been examined. The structural characterisation shows that these ropes constitute bundles of MWCNTs. This bundled structure is found to control the electrical and gas adsorption properties of the material. The electrical resistance of these ropes decreases upon exposure to NO₂ with a high sensitivity even at room temperature. The adsorption of the NO₂ onto MWCNT bundles is found to be more stable with temperature in comparison to isolated MWCNTs revealing the complex nature of the adsorption process. These adsorption sites, which are created within the bundles of carbon nanotubes, are more stable requiring higher desorption energy. The surface of the MWCNT ropes is also modified with acid treatment, which increases the response to NO₂ by a factor 100% due to increased polar interactions between the gas molecules and the existing functionalised surface. These results suggest the possibility of using these macroscopic MWCNT ropes as low cost gas sensing materials.     

Dispersion of multi-walled carbon nanotube using soluble polysilsesquioxane containing alkylammonium side chains and triiodide counterions

In this study, we found that 1-pentanol dispersion of multi-walled carbon nanotube (MWCNT) was obtained when ultrasonication of MWCNT was performed in 1-pentanol solution of ammonium group-containing polysilsesquioxane with triiodide anions (PSQ-I₃). Dispersibility of MWCNT in 1-pentanol was first investigated by the presence of absorption at 750 nm in UV–Vis measurements. In addition, the number-average particle size estimated by dynamic light scattering measurement of 1-pentanol dispersion of MWCNT/PSQ-I₃ was assessed to be 120.3 ± 34.8 nm. The dispersion passed through a membrane filter with ca. 7 μm pores, indicating that large MWCNT aggregates in micrometer scale did not exist in 1-pentanol. Furthermore, the transmission electron microscopy image of the sample obtained by drying 1-pentanol dispersion of MWCNT/PSQ-I₃ showed many lines with ca. 10 nm diameter derived from MWCNT, indicating that MWCNTs were individually dispersed in PSQ matrix.     

Carbon nanotubes coated with diamond nanocrystals and silicon carbide by hot-filament chemical vapor deposition below 200 °C substrate temperature

Multi-walled carbon nanotubes (MWCNTs) dispersed onto a silicon substrate have been coated with diamond nanocrystals (DNC) and silicon carbide (SiC) from solid carbon and silicon sources exposed to H₂ activated by hot filament chemical vapor deposition (HFCVD) at around 190 °C substrate temperature. MWCNT coating by DNC initiates during filament carburization process at 80 °C substrate temperature under conventional HFCVD conditions. The hybrid nanocarbon material was analyzed by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, electron energy loss spectroscopy, selected area electron diffraction, X-ray diffraction and Raman spectroscopy. The structure of the MWCNTs is preserved during coating and the smooth DNC/SiC coating is highly conformal. The average grain size is below 10 nm. The growth mechanism of DNC and SiC onto MWCNT surface is discussed.     

Amino functionalization of multiwalled carbon nanotubes by gamma ray irradiation and its epoxy composites

In this paper, γ‐ray radiation technique was utilized to simply functionalize multi‐walled carbon nanotube (MWCNT) with amino groups. The successful amino functionalization of MWCNTs (MWCNTs‐Am) was proven and the physicochemical properties of MWCNTs before and after radiation grafting modifications were characterized using FT‐IR, X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results indicated that the γ‐ray radiation had the visible effects on the surface properties of MWCNTs. The effects of various functionalized MWCNTs on morphological, thermal, and mechanical properties of an epoxy‐based nanocomposite system were investigated. Utilizing in situ polymerization, 1 wt% loading of MWCNT was used to prepare epoxy‐based nanocomposites. Compared to the neat epoxy system, nanocomposites prepared with MWCNT‐Am showed 13.0% increase in tensile strength, 20.0% increase in tensile modulus, and 24.1% increase in thermal decomposition temperature. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

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.     

Functionalization of multiwalled carbon nanotubes with uniform polyurea coatings by molecular layer deposition

In this study, we demonstrate a flexible method for functionalizing multiwalled carbon nanotubes (MWCNTs) with polyurea (PU) coatings using molecular layer deposition (MLD). Uniform and conformal PU films can be deposited on the surface of pristine MWCNTs without any surface treatment. The PU shell thickness and wrapping amount are precisely tunable by changing the number of MLD cycles. The present MLD functionalizing treatment provides better dispersion of the MWCNTs in highly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, and 1-methyl-2-pyrrolidinone. Furthermore, the PU layers improve the compatibility between MWCNTs and the polyurethane matrix. Significant increases in tensile strength and modulus are obtained, resulting in greatly enhanced mechanical properties of PU-functionalized MWCNT/polyurethane composites.     

A binder‐free Ir0.4Ru0.6‐oxide/functionalized multi‐walled carbon nanotube electrode for possible applications in supercapacitors

An initial study on a simple and inexpensive method to form an Ir_0.4Ru_0.6‐oxide (MMO) coating onto high‐area plasma functionalized multi‐walled carbon nanotubes (f‐MWCNTs) at the bench‐scale for possible supercapacitor (SC) applications is presented. f‐MWCNT electrodes are prepared in a two‐step process combining the growth of MWCNTs directly onto a 316 stainless steel mesh by thermal‐chemical vapour deposition (t‐CVD), followed by the addition of oxygen‐containing functionalities to their surface by plasma functionalization. The plasma functionalization step is done to: (i) improve electrode wettability and (ii) improve capacitive properties through the addition of pseudocapacitive oxygen functionalities. A simple dip‐dry method is then employed to coat the f‐MWCNTs with the desired MMO coating (Ir_0.4Ru_0.6‐oxide) prepared initially in a liquid precursor mixture. f‐MWCNT electrodes are suspended and dipped into the precursor then heated in air to evaporate the solvent while building the oxide layer. The resulting MMO/f‐MWCNT electrode exhibits excellent stability in 4 mol/L KOH electrolyte, yielding larger specific capacitance values than those obtained on bare f‐MWCNT electrodes; at a charging/discharging current density of 0.5 mA cm^?2, the MMO/f‐MWCNT and f‐MWCNT electrodes achieve specific capacitances of 664 ± 7 and 190 ± 30 F g^?1 in a 3‐electrode cell, respectively. The MMO/f‐MWCNT electrodes show good rate capability performance up to 10 mA · cm^?2 and excellent stability.

     

Functionalization of multi-walled carbon nanotubes with perfluoropolyether peroxide to produce superhydrophobic properties

Multi-walled carbon nanotubes (MWCNTs) have been functionalized through perfluoropolyether (PFPE) radicals obtained by thermal decomposition of linear PFPE peroxide. The reactivity of MWCNTs with PFPE peroxide has been compared with the direct fluorination of MWCNTs using elemental fluorine in mild conditions. The experimental results indicated that the functionalization with PFPE peroxide and the direct fluorination with elemental fluorine were suitable techniques to modify and control the physical-chemical properties of MWCNTs. After the introduction of PFPE chains on the MWCNT surface, the wettability of MWCNTs changed from hydrophilic to superhydrophobic, because the low surface energy properties of PFPE were transferred to the MWCNT surface. However, the linkage of PFPE chains weakly influenced the electrical properties of conductive MWCNTs. The amount of PFPE chains linked to the carbon nanotubes, the PFPE fluids obtained by homocoupling side-reactions and the decomposed portion of PFPE have been evaluated by mass balance. The modified MWCNTs have been characterized by X-ray photoelectron spectroscopy, thermal gravimetric analysis, X-ray diffraction, scanning electron microscopy, contact angle and surface area measurements. The effects of the chemical treatment on the conductive properties of MWCNTs have been studied by resistivity measurements at different applied pressures.     

Multiwalled carbon nanotubes functionalized with maleated poly(propylene) by a dry mechano-chemical process

Ball milling was used to graft maleated polypropylene (MAPP) on the surface of multiwalled carbon nanotubes (MWCNTs), with a view to preparing MWCNT/polypropylene composites with improved matrix/nanotube compatibility. The occurrence of the grafting reaction was evaluated by FTIR spectroscopy and the yield was quantified by thermogravimetric analysis, as a function of the milling time. Dispersion experiments confirmed the nanotube surface modification of the nanotubes since functionalized MWCNTs remained stably dispersed in an ethanol/xylene solution for more than 48 h after sonication. No evidences of significant structural damage after the mechano-chemical treatment were shown by Raman spectroscopy. Moreover, a layer attributable to the presence of grafted MAPP chains on MWCNT walls was clearly detected by transmission electron microscopy. The average thickness of this amorphous layer was evaluated and compared with quantitative TGA data.     

Poly(lauryl acrylate) and poly(stearyl acrylate) grafted multiwalled carbon nanotubes for polypropylene composites

Two new polymer grafts on an industrial grade multiwalled carbon nanotube (MWCNT) were prepared through a non-oxidative pathway employing controlled free radical polymerization for surface initiated polymer grafting. After photochemical introduction of an ATRP initiator onto the MWCNT, polymerizations of lauryl or stearyl acrylate were performed, resulting in two novel polymer modifications on the MWCNT (poly(lauryl acrylate) or poly(stearyl acrylate)). The method was found to give time dependent loading of polymers as a function of time (up to 38 wt% for both acrylates), and showed a plateau in loading after 12 h of polymerization. The modified nanomaterials were melt mixed into polypropylene composites with very low filler loading (0.3 wt%), whereafter both the thermal and electrical properties were investigated by DSC and dielectric resonance spectroscopy. The electrical properties were found to be substantially improved, where poly(lauryl acrylate) was found to be the superior surface modification, resulting in a conductive composite.