Photoactive multi-walled carbon nanotubes: synthesis and utilization of benzoin functional MWCNTs

This study describes a facile method for the synthesis of functionalized multi-walled carbon nanotubes (MWCNTs) carrying photoactive group. The synthesis of MWCNTs-based macro-photoinitiator was achieved by the esterification reaction between benzoin moiety and acyl chloride functional MWCNTs. Synthesized MWCNT-based photoinitiator (MWCNTs–benzoin) was used in the photopolymerization of styrene to yield polystyrene (PS)-grafted MWCNTs (MWCNTs–PS) by “grafting from” method. The efficiency of MWCNTs–benzoin photoinitiator was determined by evaluating the effect of initiator to monomer ratio and reaction period on photopolymerization of styrene. Fourier transform infrared spectroscopy, Raman and X-ray photoelectron spectroscopy analyses confirmed the covalent bonding for functionalization of MWCNTs and determined the final structures. Thermogravimetric analysis, gel permeation chromatography and UV spectroscopy were performed to evaluate the grafting efficiency of PS that covalently grafted to MWCNTs, and high efficiency of MWCNTs–benzoin as a macro-photoinitiator was also confirmed. Scanning electron microscopy was used to determine the surface morphology of functionalized MWCNTs and MWCNTs–PS.     

Synthesis and characterization of polyurethane-grafted single-walled carbon nanotubes via click chemistry

Polyurethane (PU)-grafted carbon nanotubes were synthesized by the coupling of alkyne moiety decorated single walled carbon nanotube (SWCNT) with azide moiety containing PU using Cu(I) catalyzed Huisgen [3 + 2] cycloaddition click chemistry. The azide moiety containing poly(s-caprolactone)diol was synthesized by ring-opening polymerization and further used for PU synthesis. Alkyne-functionalizion of SWCNT was completed by the reaction of p-aminophenyl propargyl ether with SWCNT using a solvent free diazotization procedure. Nuclear magnetic resonance, Fourier transform infrared, and Raman spectroscopic measurements confirmed the functionalization of SWCNT. Scanning electron microscopy and transmission electron microscopy images showed an excellent dispersion of SWCNTs, and specially debundling of SWCNTs could be observed due to polymer assisted dispersion. A quantitative grafting was successfully achieved even at high content of functional groups.     

Controlled fabrication of theophylline imprinted polymers on multiwalled carbon nanotubes via atom transfer radical polymerization

Theophylline imprinted polymers were synthesized on the surface of multiwalled carbon nanotubes via atom transfer radical polymerization using brominated multiwalled carbon nanotubes as an initiator. The nanotube-based initiator was prepared by directly reacting acyl chloride-modified multiwalled carbon nanotubes with 2-hydroxylethyl-2'-bromoisobutyrate. The grafting copolymerization of 2-hydroxyethyl-2-methyl-2-propenoate and ethylene glycol dimethacrylate in the presence of template theophylline led to thin molecularly imprinted polymer films coating multiwalled carbon nanotubes. The thickness of molecularly imprinted polymer films prepared in this study was about 5 nm as determined by transmission electron microscopy. Fourier-transform infrared spectroscopy was utilized to follow the introduction of initiator groups as well as polymers on the carbon nanotube surfaces. Thermogravimetric analysis indicated that the molecularly imprinted polymers were successfully grown from the carbon nanotube surfaces, with the final products having a polymer weight percentage of ca. 50 wt%. The adsorption properties, such as adsorption dynamics, special binding and selective recognition capacity, of the as-prepared molecularly imprinted polymer films were evaluated. The results demonstrated that the composite of molecularly imprinted polymers and multiwalled carbon nanotubes not only possessed a rapid dynamics but also exhibited a good selectivity toward theophylline, compared to caffeine.     

Fumed silica/polymer hybrid nanoparticles prepared by redox-initiated graft polymerization in emulsions

Hybrid particles comprising aggregated fumed silica nanoparticles as the core and hydrophobic polymers existing around the nanoparticles were prepared by ‘grafting from’ polymerization in emulsions. The emulsion polymerization employed cetyltrimethylammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant, respectively, to stabilize the emulsion polymerization. The polymerization was initiated by the redox reaction between ceric ion Ce(IV) and the amine groups on the surfaces of aminated fumed silica nanoparticles that were modified by 3-aminopropyltriethoxysilane. Infrared spectroscopy and thermogravimetric analysis demonstrated that both poly(methyl methacrylate) (PMMA) and polystyrene (PS) were successfully grafted onto the fumed silica surface. The type of surfactant greatly affected the grafting ratio, monomer-to-polymer conversion, and morphology of the product. When CTAB was used as the surfactant, both the grafting ratio and monomer-to-polymer conversion were lower than when SDS was used, but transmission electron microscopy and light scattering analysis indicated that most of the resultant particles were sub-100 nm hybrid nanoparticles with a non-spherical shape and particles sizes of 75–90 and 57–85 nm for PMMA and PS-grafted fumed silica, respectively. Whereas, when SDS was used as the surfactant, the particles agglomerated to form large irregular clusters or even networks, possibly due to the electrostatic attractions between SDS and Ce(IV) and/or the aminated fumed silica nanoparticles in aqueous solution.     

PP/碳纳米管复合材料的制备及电性能

采用原子转移自由基(ATRP)活性聚合方法在多壁碳纳米管(MWNT)表面接枝丙烯酸丁酯聚合物(PBA),并以此对聚丙烯(PP)进行改性。红外光谱(FT-IR)及透射电子显微镜(TEM)测试结果表明,采用ATRP法成功地将PBA接枝到多壁碳纳米管(MWNT)表面。对PP/MWNT复合材料电性能研究表明,MWNT-PBA的添加比MWNT-COOH更能降低复合材料的电阻率。MWNT-PBA的加入可使PP从绝缘材料转变为抗静电材料。MWNT-PBA和MWNT-COOH加入PP都能提高材料的电性能,而MWNT-PBA比MWNT-COOH的作用更加明显。     

Preparation and decoloration property of polystyrene-grafted palygorskite nanoparticles

The polymerization of styrene on inorganic palygorskite nanorods was carried out by reverse atom transfer radical polymerization (RATRP) in a completely controlled manner to form structurally well-defined PS-grafted hybrid nanocomposite. Well-defined PS chains were grown from the nanoparticle surfaces to yield individual particles composed of a palygorskite core and a well-defined outer PS layer. It has been found that the dispersibility of palygorskite particles in organic solvents is significantly improved by grafting polymers onto the surface of palygorskite particles. So the holding time of PS-palygorskite is prolonged in organic solvents. Active point of adsorption in palygorskite surface is adequately utilized. The polymer-grafted palygorskite nanoparticles possess excellent decoloration capacity in organic solvents.     

Evaluating industrial grade functionalized multiwalled carbon nanotubes by X-ray photoelectron spectroscopy

Utilization of carbon nanotubes in various applications is a function of their dispersion in respective matrix which effectively depends on the functionalization employed. Functional group distribution on Carbon Nanotube surface is usually a complex mixture of groups depending on the oxidizing agent employed. In this regard, nine varieties of Industrial grade multiwalled carbon nanotubes belonging to 10–30, 20–40 and 50–80?nm outer diameter ranges but differing in functionality (carboxyl and hydroxyl) were analyzed. X-ray photoelectron spectroscopy was employed to quantify the different functionalities on pristine, hydroxyl and carboxyl functionalized multiwalled carbon nanotubes and high-resolution transmission electron microscopy was used to image the internal structure including the side wall damage in functionalized varieties. X-ray photoelectron spectroscopy measurements on nine batches have suggested the presence of carbonyl, carboxyl and hydroxyl functional groups on all multiwalled carbon nanotubes in different proportions. This implies that it is not possible to have exclusive hydroxyl or carboxyl functionalization on a CNT surface Additionally, comparison is drawn between already existing deconvolution procedures from literature.     

Preparation polystyrene/multiwalled carbon nanotubes nanocomposites by copolymerization of styrene and styryl-functionalized multiwalled carbon nanotubes

Styryl-functionalized multiwalled carbon nanotubes (p-MWNTs) were prepared by esterification based on the carboxylate salt of carbon nanotubes and p-chloromethylstyrene in toluene. Then in situ radical copolymerization of p-MWNTs and styrene initiated by 2,2′-azobis(isobutyronitrile) (AIBN) was applied to synthesize composites of styryl-functionalized multiwalled carbon nanotubes and polystyrene (PS) (p-MWNTs/PS). Characterizations carried out by FT-IR, ¹H NMR, UV–vis show that styryl group covalently bond to the surface of MWNTs. The results of UV showed that the solutions of p-MWNTs/PS in chloroform have the hyperchromic effect. Transmission electron microscopy (TEM) images of p-MWNTs/PS composites and scanning electron microscopy (SEM) images of fracture surface of p-MWNTs/PS composites showed the functionalized nanotubes had a better dispersion than that of the unfunctionalized MWNTs in the matrix. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) suggested that the thermal stability of p-MWNTs/PS composites improved in the presence of MWNTs.     

Preparation of covalently functionalized graphene using residual oxygen-containing functional groups

When fabricated by thermal exfoliation, graphene can be covalently functionalized more easily by applying a direct ring-opening reaction between the residual epoxide functional groups on the graphene and the amine-bearing molecules. Investigation by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) all confirm that these molecules were covalently grafted to the surface of graphene. The resulting dispersion in an organic solvent demonstrated a long-term homogeneous stability of the products. Furthermore, comparison with traditional free radical functionalization shows the extent of the defects characterized by TEM and Raman spectroscopy and reveals that direct functionalization enables graphene to be covalently functionalized on the surface without causing any further damage to the surface structure. Thermogravmetric analysis (TGA) shows that the nondestroyed graphene structure provides greater thermal stability not only for the grafted molecules but also, more importantly, for the graphene itself, compared to the free-radical grafting method.     

Adsorption behavior of carbon nanotubes on polystyrene surfaces

Polystyrene (PS) was prepared using two different polymerization methods (dispersion polymerization and seed polymerization) to investigate the steric stabilizer effect during the adsorption process of carbon nanotubes (CNTs) on the surface of PS microspheres. Experiments with different microsphere diameters and difference types of CNTs were conducted to analyze the curvature effect of the spheres on the adsorption mechanism. The results showed that PS microspheres prepared through dispersion polymerization exhibited preferable adsorption behavior compared to PS spheres prepared through seed polymerization, suggesting that poly(N-vinylpyrrolidone) led to improved adsorption interactions between the CNTs and the PS microspheres in the CNTs dispersion. Additionally, the PS diameter and CNT curvature were examined with respect to the adsorption behavior between the PS microspheres and the CNTs. Multiwalled carbon nanotubes (MWCNTs) were found to be well adsorbed on the surface of PS microspheres measuring 2 microm. However, the MWCNTs were adsorbed much less on the surface of submicron-sized PS microspheres, compared with thinwalled carbon nanotubes (TWCNTs). On the other hand, TWCNTs were found to be suitable for adsorption on submicron-sized PS microspheres. These results also indicate that the curvature of the CNTs and the polymer microspheres are important to the CNT adsorption process.     

Soft purification of N-doped and undoped multi-wall carbon nanotubes

A soft method for purifying multi-wall carbon nanotubes (N-doped and undoped) is presented. The technique includes a hydrothermal/ultrasonic treatment of the material in conjunction with other subsequent treatments, including the extraction of polyaromatic compounds, dissolution of metal particles, bundle exfoliation, and uniform dispersion. This method avoids harsh oxidation protocols that burn (via thermal treatments) or functionalize (by introducing chemical groups) the nanotubes. We show a careful analysis of each purification step and demonstrate that the technique is extremely efficient when characterizing the materials using scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDAX), scanning tuneling electron microscopy (STEM), x-ray powder diffraction (XRD), diffuse reflectance Fourier transform infrared (DRFTIR) spectroscopy and thermogravimetric analysis (TGA).     

Concise route to styryl-modified multi-walled carbon nanotubes for polystyrene matrix and enhanced mechanical properties and thermal stability of composite

Effective functionalization of multi-walled carbon nanotubes (MWCNTs) with styryl group was carried out via the esterification reaction of the carboxylate salt of carbon nanotubes and 4-vinylbenzyl chlorides in toluene. The functionalized MWCNTs were characterized through FTIR and Raman spectra to confirm the styryl groups covalently connected to the surface of MWCNTs. The weight loss of functionalized moieties determined by thermogravimetry-differential scanning calorimertry analysis is around 36%. Nanotube-reinforced polystyrene were fabricated by mixing functionalized MWCNTs and polystyrene. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that the functionalized nanotubes had a better dispersion than the unfunctionalized MWCNTs in the matrix. Moreover, styryl-modified MWCNTs/PS nanocompsite presented obvious improvements in mechanical properties and thermal stability.     

The influence of carbon nanotube functionalization route on the efficiency of dispersion in polypropylene by twin-screw extrusion

The joint effect of chemical functionalization and polymer melt blending conditions on carbon nanotube dispersion in polypropylene, as well as its influence on the electrical and mechanical properties of the resulting composites were investigated. Melt blending was performed using a prototype twin screw extruder enabling sampling along the barrel. The carbon nanotube dispersion was assessed by optical and scanning electron microscopy. The functionalization reaction was tailored for compatibility with the polymer, and characterized by X-ray photoelectron spectroscopy. In particular, nanotubes covalently bonded to polypropylene showed distinctive dispersion ability, while the carbon nanotube dispersion remained stable even after re-melting. However, the polypropylene-functionalized nanotubes produced composites with higher electrical resistivity, possibly due to the insulating effect of the polymer bonded to the nanotubes surface.     

Effects of surface-functionalized multi-walled carbon nanotubes on the properties of poly(dimethyl siloxane) nanocomposites

The effects of surface-functionalized multi-walled carbon nanotubes (MWNTs) on the properties of poly(dimethyl siloxane) (PDMS) nanocomposites are investigated in the present study. The surface functionalization of MWNTs is carried out by diphenyl-carbinol functionalization followed by reaction with multifunctional silane, 3-aminopropyltriethoxisilane. Fourier transform infrared spectroscopy (FT-IR) and energy dispersion spectroscopy (EDS) analysis are used to confirm the presence of diphenyl-carbinol and silane on the surface of the MWNTs. The effects of the MWNTs’ surface treatment on the thermal and electrical properties of poly(dimethyl siloxane)-based (PDMS) nanocomposites are also studied. The results show that the grafting of silane molecules onto diphenyl-carbinol-functionalized MWNTs (SD-MWNTs) improves the dispersion of MWNTs in PDMS; this subsequently enhances the thermal conductivity and dynamic mechanical properties as compared to those containing unmodified (U-MWNTs) and diphenyl-carbinol-functionalized MWNTs (D-MWNTs). The electrical conductivity of the nanocomposites is shown to decrease due to the wrapping of MWNTs with non-electrical-conducting organic materials.     

Oxygen Barrier of Multiwalled Carbon Nanotube/Polymethyl Methacrylate Nanocomposites Prepared by in situ Method

Multiwalled carbon nanotubes (MWCNTs)/poly(methyl methacrylate) (PMMA) nanocomposites were prepared by ultrasonic assisted emulsifier free emulsion polymerization technique with variable concentration of functionalized carbon nanotubes. MWCNTs were functionalized with H 2 SO 4 and HNO 3 with continuing sonication and polished by H 2 O 2 . The appearance of Fourier transform infrared absorption bands in the PMMA/MWCNT nanocomposites showed that the functionalized MWCNT interacted chemically with PMMA macromolecules. The surface morphology of functionalized MWCNT and PMMA/MWCNT nanocomposites were studied by scanning electron microscopy. The dispersion of MWCNT in PMMA matrix was evidenced by high resolution transmission electron microscopy. The oxygen permeability of PMMA/MWCNT nanocomposites gradually decreased with increasing MWCNT concentrations.     

"Hairy" single-walled carbon nanotubes prepared by atom transfer radical polymerization

"Hairy nano-objects" are hybrid nanostructures comprising a core surrounded by a "hairlike" corona of flexible polymer chains, the role of which is typically to improve the solubility of the core material or to improve its dispersability and adhesion in other polymer matrices. Both aspects could be particularly useful with carbon nanotubes, especially in their applications as reinforcing agents. The controlled synthesis of hairy carbon nanotubes is accomplished by chemical modification with 2-bromopropionate followed by extension with poly(n-butyl acrylate) through atom transfer radical polymerization. The obtained hairy nanotubes are visualized at nearly molecular resolution with tapping-mode atomic force microscopy, providing insight into the uniformity of grafted chain lengths and grafting density. The grafting densities vary from approximately 1.0-10.0 chains nm(-1) along the nanotubes. Such a wide range of grafting density may indicate some chemical heterogeneity along and between the nanotubes; it may be also an indication of the challenges associated with carrying out chemical modification of nano-objects having high tendency to aggregate.     

Synthesis and characterization of Rosebengal/folicacid-functionalized multiwall carbon nanotubes

Multiwall carbon nanotubes (MWCNTs) were functionalized with a photosensitizer, rosebengal (RB), and folicacid (FA), an anti-cancer drug simultaneously and individually, which was characterized with various analytical instruments like Fourier Transform Iinfrared (FTIR) spectroscopy, UV–Vis spectroscopy, Thermogravimetric analysis (TGA), Photoluminescence (PL) spectroscopy, X-ray photoelectron spectroscopy (XPS), and Transmission electron microscopy (TEM). FTIR spectra confirmed the chemical modification of MWCNT. The chemical functionalization of MWCNT with RB was further supported by UV–Vis and PL spectra.     

Preparation and characterization of poly(N-isopropylacrylamide) films on a modified glass surface via surface initiated redox polymerization

A functionalization with 3-aminopropyltriethoxysilane (APTES) monolayer of a hydroxylated glass surface, followed by the surface initiated graft radical polymerization of N-isopropylacrylamide (NIPAm) using amino groups of APTES monolayer chemical bonded with glass surface and Ce⁴⁺ as a redox initiating system. The microstructure of poly(N-isopropylacrylamide) (PNIPAm) film obtained from the redox graft polymerization on the modified glass surfaces was examined by water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM), and the results showed that about 60 nm thickness of thermosensitive polymer (PNIPAm) film successfully formed.     

Functionalization of nitrogen-doped carbon nanotubes with gallium to form Ga-CN(x)-multi-wall carbon nanotube hybrid materials

In an effort to combine group III-V semiconductors with carbon nanotubes, a simple solution-based technique for gallium functionalization of nitrogen-doped multi-wall carbon nanotubes has been developed. With an aqueous solution of a gallium salt (GaI(3)), it was possible to form covalent bonds between the Ga(3+) ion and the nitrogen atoms of the doped carbon nanotubes to form a gallium nitride-carbon nanotube hybrid at room temperature. This functionalization was evaluated by x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy.     

Preparation,characterization, and properties of disulfide-containing polyethyleneimine grafted carbon nanotubes

Novel functionalized carbon nanotubes (CNTs) were prepared by grafting disulfide-containing polyethyleneimine (SSPEI) to CNTs. The SSPEI were synthesized by Michael addition between cystamine bisacrylamide and low molecular weight branched 1.8 kDa PEI. Three SSPEI grafted carbon nanotubes (CNTs-SSPEI) were successfully prepared through grafting SSPEI to CNTs. The grafted ratios were 32.26%, 43.11%, and 51.50%, respectively. Moreover, the grafted ratio could be tuned by adjusting the CNTs/SSPEI ratio during the process of preparation. The CNTs-SSPEI was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The CNTs-SSPEI showed better dispersability and stability in water than CNTs. In addition, the SSPEI on the surface of CNTs-SSPEI could be degraded in the presence of dithiothreitol.