Nylon 610/functionalized multiwalled carbon nanotube composite prepared from in‐situ interfacial polymerization

Pristine multiwalled carbon nanotubes (P‐MWNTs) were functionalized with 4‐chlorobenzoic acid via “direct” Friedel‐Crafts acylation in polyphosphoric acid (PPA)/phosphorous pentoxide (P₂O₅) medium. The resultant 4‐chlorobenzoyl‐functionalized MWNTs (F‐MWNTs) were soluble in chlorinated solvents such as dichloromethane, chloroform, and carbon tetrachloride. A large scale of nylon 610/F‐MWNT composite could be conveniently prepared by in situ interfacial polymerization of 1, 6‐hexamethylenediamine (HMDA) in an aqueous phase, and sebacoyl chloride with F‐MWNTs in an organic phase. Similarly, nylon 610/P‐MWNT composite was also prepared for comparison. The state of F‐MWNTs dispersion in nylon 610 matrix was distinctively better than that of P‐MWNTs, which could be clearly discerned by both naked eye and scanning electron microcopy (SEM). As a result, the tensile strength of nylon 610/F‐MWNT composite was 4.9‐fold higher than that of nylon 610/P‐MWNT composite. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6041–6050, 2008     

Comparison of the properties of waterborne polyurethane/multiwalled carbon nanotube and acid‐treated multiwalled carbon nanotube composites prepared by in situ polymerization

A series of waterborne polyurethane (WBPU)/multiwalled carbon nanotube (CNT) and WBPU/nitric acid treated multiwalled carbon nanotube (A‐CNT) composites were prepared by in situ polymerization in an aqueous medium. The optimum nitric acid treatment time was about 0.5 h. The effects of the CNT and A‐CNT contents on the dynamic mechanical thermal properties, mechanical properties, hardness, electrical conductivity, and antistatic properties of the two kinds of composites were compared. The tensile strength and modulus, the glass‐transition temperatures of the soft and hard segments (T_gs and T_gh, respectively), and ΔT_g (T_gh − T_gs) of WBPU for both composites increased with increasing CNT and A‐CNT contents. However, these properties of the WBPU/A‐CNT composites were higher than those of the WBPU/CNT composites with the same CNT content. The electrical conductivities of the WBPU/CNT1.5 and WBPU/A‐CNT1.5 composites containing 1.5 wt % CNTs (8.0 × 10⁻⁴ and 1.1 × 10⁻³ S/cm) were nearly 8 and 9 orders of magnitude higher than that of WBPU (2.5 × 10⁻¹² S/cm), respectively. The half‐life of the electrostatic charge (τ_1/2) values of the WBPU/CNT0.1 and WBPU/A‐CNT0.1 composites containing 0.1 wt % CNTs were below 10 s, and the composites had good antistatic properties. From these results, A‐CNT was found to be a better reinforcer than CNT. These results suggest that WBPU/A‐CNT composites prepared by in situ polymerization have high potential as new materials for waterborne coatings with good physical, antistatic, and conductive properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3973–3985, 2005     

Electrochemical application of titanium dioxide nanoparticle/gold nanoparticle/multiwalled carbon nanotube nanocomposites for nonenzymatic detection of ascorbic acid

Titanium dioxide nanoparticle/gold nanoparticle/carbon nanotube (TiO₂/Au/CNT) nanocomposites were synthesized, and then characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDX). A TiO₂/Au/CNT nanocomposite-modified glassy carbon (GC) electrode was prepared using the drop coating method and was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric current–time response (I-T). The modified material is redox-active. The nonenzymatically detected amount of ascorbic acid (AA) on the TiO₂/Au/CNT electrode showed a linear relationship with the AA concentration, for concentrations from 0.01 to 0.08 μM; the sensitivity was 117,776.36 μA?·?cm^?2?·?(mM)^?1, and the detection limit was 0.01 μM (S/N?=?3). The results indicated that the TiO₂/Au/CNT nanocomposite-modified GC electrode exhibited high electrocatalytic activity toward AA. This paper describes materials consisting of a network of TiO₂, Au, and MWCNTs, and the investigation of their synergistic effects in the detection of AA.     

Iron/multiwalled carbon nanotube (Fe/MWCNT) hybrid materials characterization: thermogravimetric analysis as a powerful characterization technique

Journal of Thermal Analysis and Calorimetry - Nanomaterials and nanocomposites have gained relevance in science and technology due to their excellent properties. Therefore, the characterization of...     

Solution-chemical synthesis of carbon nanotube/ZnS nanoparticle core/shell heterostructures

A facile solution-chemical method has been developed to be capable of encapsulating a multiwalled carbon nanotube (MWCNT) with ZnS nanocrystals without using any bridging species. The thickness of the ZnS shell can be tuned easily by controlling the experimental conditions. The optical properties of the MWCNT/ZnS heterostructures were investigated using UV-vis absorption and photoluminescence spectroscopy. The optical absorption spectrum indicates that the band gap of ZnS nanocrystallites is 4.2 eV. On the basis of the photoluminescence spectrum, charge transfer is thought to proceed from ZnS nanocrystals to the nanotube in the ZnS-carbon nanotube system. These special heterostructures are very easily encapsulated within a uniform silica layer by a modified-St?ber process and still show better stability even after heat treatment at 400 degrees C, which makes them appealing for practical applications in biochemistry and biodiagnostics.     

Amperometric determination of xanthine in fish meat by zinc oxide nanoparticle/chitosan/multiwalled carbon nanotube/polyaniline composite film bound xanthine oxidase

Xanthine oxidase (XOD) was immobilized on a composite film of zinc oxide nanoparticle/chitosan/carboxylated multiwalled carbon nanotube/polyaniline (ZnO-NP/CHIT/c-MWCNT/PANI) electrodeposited over the surface of a platinum (Pt) electrode. A xanthine biosensor was fabricated using XOD/ZnO-NP/CHIT/c-MWCNT/PANI/Pt as working electrode, Ag/AgCl as reference electrode and Pt wire as auxiliary electrode connected through a potentiostat. The ZnO-NPs were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and the enzyme electrode was characterized by cyclic voltammetry, scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and electrochemical impedance spectroscopy (EIS). The biosensor showed optimum response within 4 s at 0.5 V potential, pH 7.0, 35 °C and linear range 0.1-100 μM with a detection limit of 0.1 μM. The enzyme electrode was employed for determination of xanthine in fish meat during storage. The electrode lost 30% of its initial activity after 80 uses over one month, when stored at 4 °C.     

Synthesis,characterization, and electrical properties of polypyrrole/multiwalled carbon nanotube composites

Size‐controllable polypyrrole (PPy)/multiwalled carbon nanotube (MWCNT) composites have been synthesized by in situ chemical oxidation polymerization directed by various concentrations of cationic surfactant cetyltrimethylammonium bromide (CTAB). Raman spectra, FTIR, SEM, and TEM were used to characterize their structure and morphology. These results showed that the composites are core (MWCNT)–shell (PPy) tubular structures with the thickness of the PPy layer in the range of 20–40 nm, depending on the concentration of CTAB. Raman and FTIR spectra of the composites are almost identical to those of PPy alone. The electrical conductivities of these composites are 1–2 orders of magnitude higher than those of PPy without MWCNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6449–6457, 2006     

In situ quantum dot growth on multiwalled carbon nanotubes

The generation of nanoscale interconnects and supramolecular, hierarchical assemblies enables the development of a number of novel nanoscale applications. A rational approach toward engineering a robust system is through chemical recognition. Here, we show the in situ mineralization of crystalline CdTe quantum dots on the surfaces of oxidized multiwalled carbon nanotubes (MWNTs). We coordinate metallic precursors of quantum dots directly onto nanotubes and then proceed with in situ growth. The resulting network of molecular-scale "fused" nanotube-nanocrystal heterojunctions demonstrates a controlled synthetic route to the synthesis of complex nanoscale heterostructures. Extensive characterization of these heterostructures has been performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, UV-visible spectroscopy, and X-ray diffraction (XRD).     

银/碳纳米管纳米复合物制备及性质研究

基于苯环与碳纳米管之间较强的π-π共轭效应和醛基对银氨溶液的还原作用,利用吸附在碳纳米管上的香草醛分子原位还原[Ag(NH3)2]+,成功获得了纳米银/碳纳米管(Ag-NPs/CNTs)复合纳米材料。紫外-可见吸收光谱和荧光光谱结果表明,碳纳米管对香草醛分子有较强的吸附作用及银纳米粒子的形成。透射电镜结果表明,碳纳米管表面形成了大小约5.0 nm银纳米颗粒。所制备的纳米复合材料表现出较明显的荧光特性,且对浓度为1.0×10-7～6.0×10-7 mol/L的H2O2表现出较好的电催化还原能力。     

A general route to prepare one- and three-dimensional carbon nanotube/metal nanoparticle composite nanostructures

Adsorption of polyethyleneimine (PEI)-metal ion complexes onto the surfaces of carbon nanotubes (CNTs) and subsequent reduction of the metal ion leads to the fabrication of one-dimensional CNT/metal nanoparticle (CNT/M NP) heterogeneous nanostructures. Alternating adsorption of PEI-metal ion complexes and CNTs on substrates results in the formation of multilayered CNT films. After exposing the films to NaBH4, three-dimensional CNT composite films embedded with metal nanoparticles (NPs) are obtained. UV-visible spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy are used to characterize the film assembly. The resulting (CNT/M NP)n films inherit the properties from both the metal NPs and CNTs that exhibit unique performance in surface-enhanced Raman scattering (SERS) and electrocatalytic activities to the reduction of O2; as a result, they are more attractive compared to (CNT/polyelectrolyte)n and (NP/polyelectrolyte)n films because of their multifunctionality.     

Layer-by-layer self-assembly of multiwalled carbon nanotube polyelectrolytes prepared by in situ radical polymerization

Anionic and cationic multiwalled carbon nanotube polyelectrolytes, prepared by covalent modification of multiwalled carbon nanotubes (MWCNTs) with poly(acrylic acid) and poly(acrylamide), were used for the layer-by-layer (LBL) self-assembly of MWCNTs on different substrates with polyelectrolytes, such as poly(diallyldimethylammonium chloride) and sodium poly(styrenesulfonate). Thermogravimetric analysis, Raman spectroscopy, and scanning electron microscopy (SEM) were used to demonstrate the modification of MWCNTs. Investigations using Fourier transform infrared spectroscopy, atomic force microscopy, SEM, and ultraviolet-visible spectroscopy proved this method to be practicable for preparing LBL films.     

Functionalized multiwall carbon nanotube/gold nanoparticle composites

Multiwall carbon nanotubes (MWCNTs) were chemically oxidized in a mixture of sulfuric acid and nitric acid (3:1) while being ultrasonicated. The effect of oxidative ultrasonication at room temperature on development of functional groups on the carbon nanotubes was investigated. The dispersability and the carboxylic acid group concentration of functionalized MWCNTs (fMWNTs) varied with reaction time. The concentration of carboxylic acid groups on fMWNTs increased from 4 x 10(-4) mol/g of fMWNTs to 1.1 x 10(-3) mol/g by doubling the treatment period from 4 to 8 h. The colloidal stability of aqueous fMWCNTs dispersions was enhanced through elongated oxidation. fMWCNTs that were reacted longer than 4 h did not precipitate in aqueous media for at least 24 h. The layer-by-layer self-assembly of polyelectrolytes on fMWCNTs was characterized by zeta potential measurements. The zeta potential of fMWCNTs changed from negative charge to positive charge when cationic polyelectrolytes were self-assembled on their surface. With addition of anionic polyelectrolytes, cationic polyelectrolyte coated fMWCNTs showed the expected charge reversal as expected for multilayer self-assembly. Complex formation of positively charged gold nanoparticles and negatively charged fMWCNTs was achieved with and without polyelectrolyte coatings by electrostatic interaction. The complex formation was characterized by high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. The here found complex formation of positively charged colloidal gold and defect sites on fMWNTs indicates the location of functional groups on carbon nanotubes. It is suggested that positively charged colloids such as gold nanoparticles could be used for detection of defect sites on carbon nanotubes.     

Effective in situ synthesis and characteristics of polystyrene nanoparticle‐covered multiwall carbon nanotube composite

The higher surface area of selectively grown multiwall carbon nanotubes (MWCNTs) and the better proximity of the reactant species in in situ microemulsion polymerization were used to attach the polystyrene (PS) nanoparticles to the outer wall of MWCNTs. Attachment were achieved by replacing surfactant with PS nanoparticles. SEM showed that the MWCNTs and PS nanoparticles were distributed in the composite. High resolution transmission electron microscopy showed successful anchoring of PS nanoparticles to the outer wall of the MWCNTs. In addition, anchoring enhanced the Raman's G/D ratio of the MWCNT and degradation temperature in PS nanoparticles. A mechanism of attachment of PS nanoparticles on the outer wall of MWCNT was proposed. The modified MWCNTs exhibited good durability and dispersability in different organic solvents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1523–1529, 2009     

Characterization and electrical properties of polypyrrole/multiwalled carbon nanotube composites synthesized by in situ chemical oxidative polymerization

This study describes the preparation of polypyrrole (PPy)/multiwalled carbon nanotube (MWNT) composites by in situ chemical oxidative polymerization. Various ratios of MWNTs, which served as hard templates, were first dispersed in aqueous solutions with the surfactant cetyltrimethylammonium bromide to form micelle/MWNT templates and overcome the difficulty of MWNTs dispersing into insoluble solutions of pyrrole monomer, and PPy was then synthesized via in situ chemical oxidative polymerization on the surface of the templates. Raman spectroscopy, Fourier transform infrared (FTIR), field‐emission scanning electron microscopy (FESEM), and high‐resolution transmission electron microscopy (HRTEM) were used to characterize the structure and morphology of the fabricated composites. Structural analysis using FESEM and HRTEM showed that the PPy/MWNT composites were core (MWNT)–shell (PPy) tubular structures. Raman and FTIR spectra of the composites were almost identical to those of PPy, supporting the idea that MWNTs served as the core in the formation of a coaxial nanostructure for the composites. The conductivities of these PPy/MWNT composites were about 150% higher than those of PPy without MWNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1413–1418, 2006     

Poly(L-lactide) (PLLA)/multiwalled carbon nanotube (MWCNT) composite: characterization and biocompatibility evaluation

Much effort has been directed at the fabrication of carbon nanotubes (CNTs)/polymer composites and the characterization of their physical properties. Among them, composites comprising CNTs and the biocompatible polymers are of special interest due to their potential for specific biomedical applications. we report the preparation of the MWCNT/poly(L-lactide) composite and the corresponding spectroscopic (Raman) and the microscopic (SEM, TEM) characterization. The electronic transport, thermal properties, and biocompatibility of this composite have also been investigated. The Raman spectroscopic analysis suggests the interaction between PLLA and MWCNT occurs mainly through the hydrophobic C-CH3 functional groups. The DC conductivity of the composite increases as the MWCNT loading is increased. Such behavior can be described by a percolation mechanism in which a percolation threshold at about 14 wt % MWCNT loading is observed with the maximum end conductivity of 0.1 S x cm(-1). The DSC study of the PLLA/MWCNT composite reveals that the MWCNTs in the composite have the effect of inducing crystallization and plasticizing the polymer matrix. The results from the cell culture test suggest that the presence of MWCNT in the composite inhibits the growth of the fibroblast cells.     

Thermal decomposition kinetics of multiwalled carbon nanotube/polypropylene nanocomposites

In this study, non-isothermal crystallization of neat high density polyethylene (HDPE) and HDPE/titanium dioxide (TiO₂) composite was studied using differential scanning calorimetry. Non-isothermal kinetic parameters were determined by Jeziorny approach and Mo’s method. Polarized optical microscopy and wide angle X-ray diffraction were applied to observe the crystal morphology and investigate the crystal structure, respectively. It was found TiO₂ particles could act as nucleating agent during the crystallization process and accelerate the crystallization rate. The Avrami index indicated nucleating type and growth of spherulite of HDPE was relatively simple. The result of activation energy indicated it was more and more difficult for the polymer chains to crystallize into the crystal lattice as the crystallization progressed. HDPE/TiO₂ composites exhibited lower ΔE values, suggesting TiO₂ particle could make the crystallization of HDPE easier. HDPE/TiO₂ composites had much smaller spherulite size than that of neat HDPE. HDPE formed more perfect crystal when TiO₂ particles were added into its matrix without changing the original crystal structure of HDPE.     

A multiwalled carbon nanotube/dihydropyran composite film electrode for insulin detection in a microphysiometer chamber

We have developed a multiwalled carbon nanotube/dihydropyran (MWCNT/DHP) composite sensor for the electrochemical detection of insulin in a microfluidic device. This sensor has been employed for physiological measurements of secreted insulin from pancreatic islets in a Cytosensor^® previously modified to be a multianalyte microphysiometer (MAMP). When compared with other established electrochemical insulin sensors, the MWCNT/DHP composite film sensor presented improved resistance to fluidic shear forces, while achieving enhanced electrode kinetics. In addition, the preparation of the composite film is straightforward and facile with a self-polymerizing monomer, DHP, used to add mechanical stability to the film. The sensor film was able to detect insulin concentrations as low as 1 μM in the MAMP during calibration experiments. The MWCNT/DHP composite sensor has been successfully used for the direct detection of insulin secreted by islets in the microphysiometer.     

Templated synthesis of single-walled carbon nanotube and metal nanoparticle assemblies in solution

Carbon nanotube (CNT) and metal nanoparticle (NP) assemblies are conjugated nanosystems with potential applications in catalysis, sensing, and light harvesting. Due to poor solubility of CNTs, previously reported synthetic approaches are limited to large multi-walled CNTs, bundles of single-walled CNTs (SWNTs), or surface-bound CNTs. Here we report a solution-phase synthesis of SWNT-metal NP assemblies that is generally applicable to common metal elements. Key to the process is the poly(styrene-alt-maleic acid) surfactant which disperses SWNTs in aqueous solutions and acts as templates for the binding of metal ions and metal NPs.     

Semiconductor nanoparticle/polystyrene latex composite materials

Cadmium sulfide and cadmium selenide/cadmium sulfide core/shell nanoparticles stabilized with poly(cysteine acrylamide) have been bound to polystyrene (PS) latexes by three methods. First, anionic 5 nm diameter CdS particles were electrostatically attached to 130 nm surfactant-free cationic PS latexes to form stable dispersions when the amount of CdS particles was less than 10% of the amount required to form a monolayer on the surface of the PS particles or when the amount of CdS particles exceeded the amount required to form a monolayer on the PS particles. Transmission electron microscopy (TEM) showed nanoparticles on the surface of the latex particles. Fluorescence spectra showed unchanged emission from the nanoparticles. Second, anionic, surfactant-free PS latexes were synthesized in the presence of CdS and CdSe/CdS nanoparticles. TEM showed monodisperse latex particles with trapped nanoparticles. Third, surfactant-stabilized latexes were synthesized by copolymerization of styrene with vinylbenzyl(trimethyl)ammonium chloride electrostatically bound to the CdSe/CdS nanoparticle surface. Brownian motion of the submicroscopic composite particles in water was detected by fluorescence microscopy.