Effects of surface modification with 3‐aminopropyltriethoxysilane on structure and mechanical property of multiwalled carbon nanotube/polycarbonate composites

Hydroxyl functionalized multiwalled carbon nanotubes (H‐MWNTs) were silanized using 3‐aminopropyltriethoxysilane (APTES) in order to improve the dispersion and interfacial interaction in composites. MWNT/polycarbonate (PC) composites filled with H‐MWNTs and silanized MWNTs (S‐MWNTs) were fabricated by melt mixing and injection molding. Fourier transform infrared spectrometry (FTIR) and energy dispersion X‐ray spectroscopy (EDS) were employed to prove the presence of APTES on the surface of S‐MWNTs. In addition, thermogravimetric analysis (TGA) was used to evaluate the relative amount of introduced APTES. The microstructure and mechanical property of both composites were investigated by scanning electron microscopy (SEM), transmission electron microscope (TEM), tensile test and dynamic mechanical analysis (DMA). The SEM and TEM images showed that S‐MWNT/PC composites had better dispersion and interfacial adhesion than H‐MWNT/PC composites. A reinforcing and toughening effect on tensile behavior of composites was obtained after silane functionalization. The storage modulus of composites increased markedly as a function of MWNTs content, especially for the composites with S‐MWNTs. In summary, the silanization can improve the dispersion of MWNTs and the interfacial adhesion between MWNTs and PC so as to enhance the mechanical properties of composites. POLYM. COMPOS., 37:1914–1923, 2016. © 2015 Society of Plastics Engineers     

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

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

Flammability and thermal properties of epoxy/glass/MWNT Composites

The aim f this work is to study the effect of nanotubes on flammability properties of epoxy/glass composites. Multiwalled carbon nanotubes (MWNT) and its functionalized derivative (amino functionalized nanotubes) were incorporated into epoxy resin. To disperse MWNTs in the epoxy resin, different ways were employed. Microscopic observations showed that, the best dispersion state was gained by using ultrasonication method and high shear flow simultaneously. Thermal resistance of cured epoxy resins containing various amounts of nanotubes (0.25–0.7 wt %), was investigated by thermo gravimetric analysis (TGA). Introducing MWNTs and amino‐MWNTs to samples increased the initial thermal decomposition temperature for about 32 and 37°C, respectively. LOI measurements of composite samples showed an increase up to 32. Cone calorimetry test was carried out on epoxy/glass and epoxy/glass containing 0.5% MWNT. The results showed that, introducing 0.5% MWNTs decreases maximum average rate of heat emission for about 26%. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39849.     

A Study on Dispersion and Antibacterial Activity of Functionalizing Multi‐walled Carbon Nanotubes with Mixed Surfactant

The dispersibility in aqueous phase and antibacterial activity of multi‐walled carbon nanotubes (MWNT) with mixed surfactant functionalization has been studied. The ratio of 3:7 between hexadecyltrimethylammonium bromide and octylphenol ethoxylate (TX100) showed the highest dispersing power for MWNT. The use of mixed surfactants formed stable MWNT dispersions at lower total surfactant concentration compared to their concentrations when used alone. UV–Vis spectroscopy, transmission electron microscopy and Fourier transform infrared spectroscopy were employed to characterize the dispersion of MWNT in the aqueous phase. The result indicated that the surfactant molecules had been successfully adsorbed onto the surface of the MWNT. Bacterial toxicity assay showed that the mixed surfactant‐functionalized MWNT had a strong antibacterial activity and concentration dependence to Staphylococcus aureus. Based on the consideration of the cost and environmental impact, the use of mixed surfactant (CTAB‐TX100) should be more favorable for the stable dispersion of MWNT and the improvement of antibacterial activity than that of an individual surfactant. These observations suggested that the mixed surfactant‐functionalized MWNT might be a promising antibacterial agent for removal and inactivation of biological contaminants in water treatment applications.     

A facile gemini surfactant-improved dispersion of carbon nanotubes in polystyrene

Debundling and dispersion of carbon nanotubes (CNTs) are very important for preparation of polymer/CNT nanocomposites. In the present study, a self-prepared gemini surfactant, 6,6′-(butane-1,4-diylbis(oxy))bis(3-nonylbenzenesulfonic acid), is employed to achieve homogeneous and stable dispersion of multi-walled carbon nanotubes (MWNTs) in organic solvent and subsequent polystyrene (PS)/MWNT nanocomposite. Sedimentation, optical microscopy and transmission electron microscopy studies demonstrate that the gemini surfactant can greatly improve the dispersion and stabilization of MWNTs in toluene. Scanning electron microscopic images clearly confirm the homogenous dispersion of individual MWNTs in PS. In addition, desired enhanced electrical conductivity and thermal stability of the nanocomposite relative to those of the neat PS are obtained.     

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

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

Preparation and characterization of alkylated carbon nanotube/polyimide nanocomposites

BACKGROUND: The development of carbon nanotube‐reinforced composites has been impeded by the difficult dispersion of the nanotubes in polymers and the weak interaction between the nanofiller and matrices. Efficient dispersion of carbon nanotubes is essential for the formation of a functional nanotube network in a composite matrix. RESULTS: Multiwalled carbon nanotubes (MWNTs) were incorporated into a polyimide matrix to produce MWNT/polyimide nanocomposites. To disperse well the MWNTs in the matrix and thus improve the interfacial adhesion between the nanotubes and the polymer, ‘branches’ were grafted onto the surface of the nanotubes by reacting octadecyl isocyanate with carboxylated MWNTs. The functionalized MWNTs were suspended in a precursor solution, and the dispersion was cast, followed by drying and imidization to obtain MWNT/polyimide nanocomposites. CONCLUSION: The functionalized MWNTs appear as a homogeneous dispersion in the polymer matrix. The thermal stability and the mechanical properties are greatly improved, which is attributed to the strong interactions between the functionalized MWNTs and the polyimide matrix. Copyright © 2009 Society of Chemical Industry     

Preparation and dielectric properties of poly(ε‐caprolactone) compounded with “bucky gels”‐like mixture

Poly(ε‐caprolactone) (PCL) was melt compounded with “Bucky gels”‐like mixture that prepared by grinding multiwalled carbon nanotubes (MWNTs) and ionic liquids (ILs). Raman spectrum showed the significant interaction between ILs and MWNTs. The dielectric behavior of PCL nanocomposites based on unmodified and IL‐modified MWNTs was studied from 40 Hz to 30 MHz. The addition of ILs significantly enhanced the dielectric property of PCL/IL/MWNT ternary nanocomposites, which was much higher than that of the sum of PCL/IL with PCL/MWNT binary nanocomposites. The dielectric properties of PCL/IL/MWNT nanocomposites were mainly influenced by ILs in low frequency and were dominated by MWNTs in high frequency. SEM results revealed that a more uniform and fine dispersion of MWNTs were achieved throughout the PCL matrix because of ILs. The addition of ILs in nanocomposites changed the crystallinity of PCL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40231.     

Poly(ethylene terephthalate) nanocomposite fibers with functionalized multiwalled carbon nanotubes via in-situ polymerization

Poly(ethylene terephthalate) (PET) hybrids with newly synthesized functionalized multiwalled carbon nanotubes (MWNTs) were obtained by carrying out the in situ polycondensation of ethylene glycol with dimethyl terephthalic acid. The PET hybrids were melt-spun to produce monofilaments with various functionalized MWNT contents and draw ratios (DRs). The thermomechanical properties and morphologies of the PET hybrid fibers were determined using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (XRD), electron microscopy (SEM and TEM), and a universal tensile machine (UTM). The XRD analysis and TEM micrographs show that the levels of nanosize dispersion can be controlled by varying the MWNT content. It was found that the addition of only a small amount of functionalized MWNTs was sufficient to improve the properties of the PET hybrid fibers. The maximum enhancement in the ultimate tensile strength was found to arise at a functionalized MWNT content of 0.5 wt %. However, the initial modulus was found to increase linearly with increases in the functionalized MWNT loading from 0 to 1.5 wt %. The thermal properties and conductivities of the PET hybrid fibers were found to be better than those of pure PET fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication of hybrid ladderlike polysilsesquioxane‐grafted multiwalled carbon nanotubes

Ladderlike polysilsesquioxanes (LPSs) containing chloromethylphenyl groups were synthesized from (p‐chloromethyl)phenyltrimethoxysilane under basic conditions. Functionalized multiwalled carbon nanotubes (MWNT–COOH) were prepared by the acid treatment of pristine multiwalled carbon nanotubes (MWNTs). MWNT–COOH was reacted with LPS to prepare LPS‐grafted MWNTs via ester linkages. The functionalization of MWNTs with LPS significantly altered the surface roughness of the MWNTs; there was a significant increase in the diameter of the MWNTs. The LPS‐grafted MWNTs had a 10–20 nm thickness along the outer walls according to the functionalization of the MWNTs with LPS. An advantage of the hybrid LPS‐grafted MWNTs was shown as improved thermal behavior. The composition, thermal properties, and surface morphology of the LPS‐grafted MWNTs were studied by Fourier transform infrared spectroscopy, thermogravimetric analysis, energy‐dispersive spectroscopy, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Extension‐induced mechanical reinforcement in melt‐spun fibers of polyamide 66/multiwalled carbon nanotube composites

In this work, polyamide 66 (PA66) and its composites with multiwalled carbon nanotubes (MWNTs) were melt spun into fibers at different draw ratios. PA66 fibers at high draw ratio demonstrate a 40% increase in tensile strength, 66% increase in modulus and a considerable increase in toughness. It is demonstrated that this reinforcement can be mainly attributed to high‐draw‐ratio‐induced good dispersion and orientation of MWNTs, particularly the enhanced interfacial adhesion between MWNT and matrix thanks to interfacial crystallization. Our work provides a simple but efficient method to achieve good dispersion and strong interfacial interaction through melt spinning. Copyright © 2011 Society of Chemical Industry     

Preparation of antibacterial PDMAEMA‐functionalized multiwalled carbon nanotube via atom transfer radical polymerization

Poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) was grafted onto the bromine‐functionalized multiwalled carbon nanotubes (MWNTs) by applying an atom transfer radical polymerization (ATRP). The PDMAEMA‐functionalized MWNT was characterized by Fourier transform infrared, transmission electron microscopy, Raman spectroscopy, thermal gravimetric analysis, and four‐probe resistivity meter. The wt % of PDMAEMA present in the PDMAEMA‐functionalized MWNT was estimated by applying the thermogram results for thermal gravimetric analysis. Variations of PDMAEMA content in the PDMAEMA‐functionalized MWNT were tried by changing the ATRP process conditions such as the type of ligand and copper complex, the amount of DMAEMA based on the weight of bromine‐functionalized MWNT, and the polymerization temperature. The phase behavior of PDMAEMA‐functionalized MWNT in water depending on temperature and pH value was analyzed, and the PDMAEMA‐functionalized MWNT showed the amphipathic nature. The PDMAEMA‐functionalized MWNT clearly showed an antibacterial effect against E. coli as well as S. aureus. The highest viability loss of E. coli achieved in this study was ～ 42% with the PDMAEMA‐functionalized MWNT containing 53.9 wt % of PDMAEMA. The PDMAEMA‐functionalized MWNT showed sheet resistance less than ～ 9.68 × 10³ Ω/sq. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013     

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

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

Protein adsorption on functionalized multiwalled carbon nanotubes with amino‐cyclodextrin

A novel amino‐cyclodextrin was synthesized, and it was covalently attached to multiwalled carbon nanotubes (MWNTs). The functionalized MWNTs (f‐MWNTs) have very good aqueous dispersibility. Bovine serum albumin (BSA) was adsorbed onto f‐MWNTs through noncovalent interactions, including the hydrophobic interaction of the residues of BSA with the wall of MWNT and the guest–host interaction of the residues with the cyclodextrin (CD) moieties of f‐MWNTs. The ultraviolet–visible (UV–vis) absorption of the f‐MWNT‐BSA hybrid was measured with UV–vis spectrometer, and the absorbance can be described well with the Beer–Lambert law. The X‐ray diffraction patterns have indicated that the crystalline form of BSA has been changed after the adsorption of BSA on f‐MWNTs. The circular dichroism spectra have shown that a high percentage of α‐helical content can be retained for BSA adsorbed on f‐MWNTs. The results also indicate that the change of secondary structure of BSA is mainly due to the hydrophobic interaction of the residues of BSA with the wall of f‐MWNT, whereas the secondary structure is much less affected by the interaction of the CD moieties with BSA. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Improvement of dispersion of carbon nanotubes in epoxy resin through pyrogallol functionalization

Multiwalled carbon nanotubes (MWNTs) were functionalized with pyrogallol. The functionalized MWNTs were well‐dispersed in the epoxy/curing agent/ethanol solution, as demonstrated by UV‐vis spectra and optical micrographs. Epoxy resin/MWNTs composites were prepared via solution mixing method. The cure behavior was characterized using differential scanning calorimetry. Pyrogallol‐functionalized carbon nanotubes (CNTs) reacted with the epoxy through the mediation reaction of pyrogallol with the curing agent, leading to the interfacial bonding between the functionalized carbon nanotubes (CNTs) and the resin matrix. Due to the excellent dispersion and interfacial bonding, the mechanical strength and electrical conductivity of the epoxy resin/CNTs composites have been improved. POLYM. ENG. SCI. 56:1079–1085, 2016. © 2016 Society of Plastics Engineers     

Superior reinforcement in polyamide 1010/multiwalled carbon nanotube composites realized by high‐rate drawing and incorporation of compatibilizer

To realize the full potential of carbon nanotubes (CNTs) in polymer/CNT nanocomposites, many complicated chemical treatments have been developed to modify the CNTs. Nevertheless, the reinforcing efficiency is still not satisfactory in most cases. In this study, a dramatically improved mechanical enhancement is obtained for polyamide 1010/multiwalled carbon nanotube (MWNT) composites simply by exerting high‐rate drawing and incorporating a commercially available compatibilizer. For the fibers prepared at high draw ratio, their tensile strength and modulus are improved by 137 and 132%, respectively, through adding only 0.5 wt% MWNTs. In particular, the increase in strength is at a very high level for the case of non‐covalent interaction since CNTs could be stretched to failure according to theoretical calculation. It is demonstrated that this reinforcement is mainly attributed to the compatibilizer inducing good dispersion, and the high‐rate drawing inducing strong interfacial interaction and orientation of MWNTs. Copyright © 2012 Society of Chemical Industry     

Ultrasound assisted twin screw extrusion of polymer-nanocomposites containing carbon nanotubes

The unique morphology and strong intertube attraction between carbon nanotubes (CNTs) make the dispersion of CNTs challenging and hence limit its effective use. A novel method for the continuous dispersion of multi-walled carbon nanotubes (MWNTs) in a polymer matrix for manufacturing high performance nanocomposites was developed using an ultrasonically assisted twin screw extrusion process. Reduction of the die pressure and variation of the ultrasonic power consumption as a function of amplitude were measured at various MWNT loadings. The effect of ultrasound on rheological, electrical, morphological and mechanical properties of polyetherimide (PEI) matrix and PEI-filled with 1-10 wt% MWNTs was studied. In the treated nanocomposites, the complex viscosity, storage and loss moduli were increased and damping characteristics were decreased as compared to untreated ones. Rheological and electrical percolations were found to be between 1 and 2 wt% MWNT loading. Ultrasonic treatment does not affect the electrical conductivity of nanocomposites. Mechanical properties such as Young's modulus and tensile strength were significantly increased with MWNT loading but moderately with ultrasonic treatment at high loadings and certain ultrasonic amplitudes. The morphology and state of dispersion of MWNTs were investigated by means of HRSEM. In the ultrasonically treated nanocomposites, the obtained micrographs showed excellent dispersion of MWNTs in PEI matrix.     

Functionalizing carbon nanotubes by grafting cyclotriphosphazene derivative to improve both mechanical strength and flame retardancy

An intumescent flame‐retardant, hex(4‐carboxylphenoxy) cyclotriphosphazene (HCPCP) was synthesized and covalently grafted on to the surface of multiwalled carbon nanotubes (MWNTs) to obtain MWNT‐HCPCP. MWNT/epoxy resin (EP) and MWNT‐HCPCP/ EP nanocomposites were prepared via thermal curing. Transmission electron microscopy results showed that a core–shell structure with MWNTs as the hard core and HCPCP as the soft shell were formed after HCPCP (10 wt%) were attached to the MWNTs. The results of flammability tests showed an increased limited oxygen index value for MWNT‐HCPCP/EP nanocomposites. The mechanical properties including tensile strength and elongation were both dramatically improved due to the better dispersion of MWNT‐HCPCP in the EP matrix. The grafting of HCPCP can improve both the dispersion of nanotubes in polymer matrix and flame retardancy of the nanocomposites. POLYM. COMPOS., 35:2187–2193, 2014. © 2014 Society of Plastics Engineers     

Shape‐memory polyurethane/multiwalled carbon nanotube fibers

Shape‐memory polyurethane/multiwalled carbon nanotube (SMP–MWNT) composites with various multiwalled carbon nanotube (MWNT) contents were synthesized, and the corresponding SMP–MWNT fibers were prepared by melt spinning. The influence of the MWNT content on the spinnability, fracture morphology, thermal and mechanical properties, and shape‐memory behavior of the shape‐memory polymer was studied. The spinning ability of SMP–MWNTs decreased significantly with increasing MWNT content. When the MWNT content reached 8.0 wt %, the fibers could not be produced because of the poor rheological properties of the composites. The melt‐blending, extrusion, and melt‐spinning processes for the shape‐memory fiber (SMF), particularly at low MWNT contents, caused the nanotubes to distribute homogeneously and preferentially align along the drawing direction of the SMF. The crystallization in the SMF was promoted at low MWNT contents because it acted as a nucleation agent. At high MWNT contents, however, the crystallization was hindered because the movement of the polyurethane chains was restricted. The homogeneously distributed and aligned MWNTs preserved the SMF with high tenacity and initial modulus. The recovery ratio and recovery force were also improved because the MWNTs helped to store the internal elastic energy during stretching and fixing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Doped polyaniline/multiwalled carbon nanotube composites: Preparation and characterization

Polyaniline (PANI)/multiwalled carbon nanotube (MWNT) composites with a uniform tubular structure were prepared from in situ polymerization by dissolving amino‐functionalized MWNT (a‐MWNT) in aniline monomer. For this the oxidized multiwalled nanotube was functionalized with ethylenediamine, which provided ethylenediamine functional group on the MWNT surface confirmed by Fourier‐transform infrared spectra (FT‐IR). The a‐MWNT was dissolved in aniline monomer, and the in situ polymerization of aniline in the presence of these well dispersed nanotubes yielded a novel tubular composite of carbon nanotube having an ordered uniform encapsulation of doped polyaniline. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. The thermal stability and electrical conductivity of the PANI /MWNTs composites were characterized by thermogravimetric analysis (TGA) and conventional four‐probe method respectively. Compared with pure PANI, the electrical conductivity and the decomposition temperature of the MWNTs/PANI composites increased with the enhancement of MWNT content in PANI matrix. POLYM. COMPOS., 34:1119–1125, 2013. © 2013 Society of Plastics Engineers