Comparison of the stability of multiwalled carbon nanotube dispersions in water

Continuous real-time monitoring of the nanotube concentration in aqueous solution using UV-Vis spectroscopy allows quantitative comparison of the stability of different types of nanotube dispersions. Systematic investigation of the effects of nanotube length and functionalisation for thin multiwalled carbon nanotubes (MWNT) has revealed that shorter MWNT form more stable dispersions than longer nanotubes of the same diameter. MWNT shortened to an average length of approximately 1 microm form stable dispersions in water with concentrations up to 0.013 mg ml(-1) in the absence of surfactants or solubilising functional groups. The introduction of carboxylic or thiol groups on the surface of shortened nanotubes further increases the stability of MWNT dispersions (up to 0.24 mg ml(-1)). The introduction of surfactant or surface charge on MWNT has contrasting effects on functionalised and non-functionalised nanotubes, destabilising and stabilising their dispersions, respectively.     

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     

Voltammetric determination of disinfectants at multiwalled carbon nanotube modified glassy carbon electrode

The voltammetric method for simultaneous determination of some disinfectants at glassy carbon electrode modified with multiwalled carbon nanotubes is presented. The examined compounds are: 2-phenylphenol, 4-chloro-3-methylphenol, triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol and 2-mercaptobenzothiazole. The measurements has been performed using cyclic voltammetry and differential pulse voltammetry in Britton-Robinson buffers as supporting electrolytes. The modification of electrode surface with multiwalled carbon nanotubes enhances the peak current. It is possible to measure mixtures of two compounds (2-phenylphenol and 2-mercaptobenzothiazole, 4-chloro-3-methylphenol and 2-mercaptobenzothiazole, triclosan and 2-mercaptobenzothiazole) in the solution of pH 9.9, which provides the best separation of oxidation peaks.     

Flow cytometry-based evaluation and enrichment of multiwalled carbon nanotube dispersions

The uniform aqueous dispersion of carbon nanotubes (CNTs) is a vital but challenging task required for their utilization in most technologies. We propose and demonstrate a technique based on forward- and side-scatter analysis on a flow cytometer to characterize the components in a dispersion of multiwalled CNTs (MWCNTs). The method simultaneously distinguishes various MWCNT components such as short and long CNTs, nanotube bundles, and particulates. It also detects the emergence of new CNT populations as a result of centrifugation. We use this method, together with classical methods such as UV and Raman spectroscopy, to observe and study the multistep MWCNT dispersion process in various surfactants (Pluronic, Triton X-100, sodium dodecyl sulfate, and cetyl trimethylammonium bromide). On the basis of the distinct scatter patterns obtained, we confirm and elaborate the surfactant-assisted unzipping mechanism of MWCNT dispersion. We also show that the ultrasonic energy spent after MWCNT unbundling and unwinding can be minimized and the process optimized for each surfactant by correct end point detection through scatter analysis. The ability to enrich nanotube population in dispersion by using the sorting mode of a flow cytometer is confirmed by electron microscopy and Raman spectroscopy. This method can thus be used for observing and enriching MWCNT components and as a complementary technique to UV spectroscopy for studying and optimizing MWCNT dispersion in surfactants.     

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.     

Solid-phase extraction using multiwalled carbon nanotubes and quinalizarin for preconcentration and determination of trace amounts of some heavy metals in food,water and environmental samples

A solid phase extraction procedure has been developed using multiwalled carbon nanotubes (MWCNTs) as a solid sorbent and quinalizarin [1,2,5,8-tetrahydroxyanthracene-9,10-dione] as a chelating agent for separation and preconcentration of trace amounts of some heavy metal ions, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) before their determination by flame atomic absorption spectroscopy (FAAS). The influences of the analytical parameters, including pH, amounts of quinalizarin and adsorbent, sample volume, elution conditions such as volume and concentration of eluent, flow rates of solution and matrix ions, were investigated for the optimum recoveries of the analyte ions. No interference effects were observed from the foreign metal ions. The preconcentration factor was 100. The detection limit (LOD) for the investigated metals at the optimal conditions were observed in the range of 0.30–0.65 μg L^?1. The relative standard deviation (RSDs), and the recoveries of standard addition for this method were lower than 5.0% and 96–102%, respectively. The new procedure was successfully applied to the determination of analytes in food, water and environmental samples with satisfactory results.     

Effects of multiwalled carbon nanotube on holographic polymer dispersed liquid crystal

The morphology and electro‐optical performance of holographic polymer dispersed liquid crystal (HPDLC) were investigated with the addition of multiwalled carbon nanotube (CNT), both pristine and chemically modified one (CNT‐C?C). With the addition of CNT, the diffraction efficiency increased and showed a maximum at 0.6% while nucleation was delayed due to the increased mixture viscosity. Film was driven only with CNT due to the induced local electric field of polymer to overcome the threshold resistance. Among the two types of CNT, chemically modified one gave finer CNT dispersion, lower mixture viscosity, larger liquid crystal (LC) droplet, higher diffraction efficiency, and shorter response time while the pristine CNT decreased the driving voltage. Copyright © 2010 John Wiley & Sons, Ltd.     

Multi-walled carbon nanotube bound nickel Schiff-base complexes as reusable catalysts for oxidation of alcohols

Nickel salen and salophen complexes have been covalently anchored on multi-walled carbon nanotubes (MWNTs). The MWNT-supported nickel complexes have been characterized by inductive coupled plasma spectroscopy, FT-IR spectroscopy, UV-Vis spectrophotometry, transmission electron microscopy, and X-ray diffraction. The catalytic performance for the oxidation of primary and secondary alcohols was evaluated using periodic acid as oxidant. Reaction conditions have been optimized for MWNT-supported salen and salophen complexes by considering the effect of parameters such as solvent, reaction time, concentration of catalyst, amount of oxidant, etc. The catalytic activity was higher for supported catalysts than similar homogeneous ones. These supported catalysts were highly stable and reused several times without the loss of catalytic activity.     

n-Type field-effect transistors made of an individual nitrogen-doped multiwalled carbon nanotube

We report on the fabrication and characterization of field-effect transistor based on an individual multiwalled nitrogen-doped carbon nanotube. Our measurements show that the N-doped carbon nanotubes have n-type properties. The contact properties of the tube and Pt electrodes are also studied in detail. Temperature dependence of two-terminal transport experiments suggests that transport is dominated by thermionic emission and tunneling through a 0.2 eV Schottky contact barrier.     

A binder-free Ge-nanoparticle anode assembled on multiwalled carbon nanotube networks for Li-ion batteries

Germanium (Ge) nanoparticle-multiwalled carbon nanotube (MWCNT) anodes are fabricated through the anchoring of Ge on the surface of electrophoretically pre-deposited MWCNT networks via a thermal evaporation process. This Ge-MWCNT nanocomposite displays a large reversible capacity of over 800 mA h g(-1) at 1 C even after 200 cycles.     

Rheological signatures of ethylene methyl acrylate‐multiwalled carbon nanotube nanocomposites

The rheological behavior of nanocomposites based on multiwalled carbon nanotube (MWNT) with three commercial grades of ethylene methyl acrylate (EMA) copolymers containing 9, 24, and 30 wt% methyl acrylate (MA) was investigated under dynamic and steady shear flow (in a capillary) conditions. Storage modulus (in dynamic shear) value increases especially at higher frequency levels due to increased polymer‐filler interactions. Both the unfilled and filled composites exhibit rheological behavior of non‐Newtonian fluids. In both steady shear and capillary flow, the nanocomposites register a slightly higher viscosity than neat EMAs, with dependence on the MWNTs content. All systems with various loading of MWNTs represent an increase in elastic response with increasing frequency. The die swell decreases with the MWNTs loading. Dynamic and steady shear rheological properties register a good correlation in regard to the viscous versus elastic response of such systems inline with the Cox–Merz concept. Increased MA content leads to inferior dispersion of MWNTs in EMA matrix. Morphological studies exhibit that MWNTs become more aligned along longitudinal direction after extrusion leading to improved dispersion. Copyright © 2010 John Wiley & Sons, Ltd.     

Functionalization of multiwalled carbon nanotube via surface reversible addition fragmentation chain transfer polymerization and as lubricant additives

Polymer‐grafted multiwalled carbon nanotube (MWCNT) hybrid composite which possess a hard backbone of MWCNT and a soft shell of brush‐like polystyrene (PSt) were synthesized. The reversible addition fragmentation chain transfer (RAFT) agents were successfully immobilized onto the surface of MWCNT first, and PSt chains were subsequently grafted from sidewall of MWCNT via RAFT polymerization. Chemical structure of resulting product and the quantities of grafted polymer were determined by Fourier transform infrared, thermal gravimetric analysis, nuclear magnetic resonance, and X‐ray photoelectron spectra. Transmission electron microscopy and field emission scanning electron microscopy images clearly indicate that the nanotubes were coated with a polymer layer. Furthermore, the functionalized MWCNT as additives was added to base lubricant and the tribological property of resultant MWCNT lubricant was investigated with four‐ball machines. The results indicate that the functionalization led to an improvement in the dispersion of MWCNT and as additives it amended the tribological property of base lubricant. The mechanism of the significant improvements on the tribological properties of the functionalized MWCNT as additives was discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3014–3023, 2008     

Sequential extraction for the speciation of some heavy metals in soils

The five step sequential extraction for speciation of copper and nickel originally designed for sediments has been applied to soil samples. The extractant solutions were: 1 mol/l ammonium acetate, 1 mol/l hydroxylammonium chloride in 25% acetic acid (1∶1), 0.1 mol/l hydrochlorid acid, 0.5 mol/l sodium hydroxide and 8 mol/l nitric acid. The residue was decomposed by HF and HNO₃. Using this procedure the metal fraction bound to the organic matter can be distinguished. The concentrations of analytes were determined in the soil extracts by FAAS and ETAAS. Accuracy was assessed by comparing the sum of the contents of copper and nickel in soil extracts with the total certified values of CRMs of soils. The overall recovery values for nickel was 84–105% and for copper 105–114%.     

Fast preparation of hydroxyapatite/superhydrophilic vertically aligned multiwalled carbon nanotube composites for bioactive application

A method for the electrodeposition of hydroxyapatite films on superhydrophilic vertically aligned multiwalled carbon nanotubes is presented. The formation of a thin homogeneous film with high crystallinity was observed without any thermal treatment and with bioactivity properties that accelerate the in vitro biomineralization process and osteoblast adhesion.     

Electric-field induced elastic stretching of multiwalled carbon nanotube clusters: a realistic model

The oscillating electric-field induced stretching phenomenon of multiwalled carbon nanotube (MWCNT) clusters in liquid crystal medium demonstrates distinct threshold behaviour under optical microscopic investigation. The optimum field required for the initiation of MWCNT cluster stretching is found to depend on their length in the field-off state. The phenomenon has been explained in light of a classical theoretical model assuming MWCNT agglomerates as a single electric dipole. The spring constant and induced charge obtained by fitting the formulated theoretical model show good agreement with previous reports, hence establish the proposed dipolar reorientation mechanism of MWCNT clusters induced by the electric field.     

Preparation of conductive PTFE nanocomposite containing multiwalled carbon nanotube via latex heterocoagulation approach

Conductive poly(tetrafluoroethylene) (PTFE) composites containing surface-modified multiwalled carbon nanotubes (MWCNTs) were prepared by a simple heterocoagulation process in water. Two different types of MWCNT were used and compared: carboxylated MWCNT and cetyltrimethyl ammonium bromide (CTAB)-stabilized MWCNT. Aqueous PTFE dispersion was mixed with the well-dispersed MWCNT dispersions and they were heterocoagulated with the aid of a flocculant, polyaluminum chloride at an elevated temperature. After particle growth and successive stabilization step, particulated PTFE/MWCNT composites were prepared in the size range of 10–100 μm. The MWCNT-containing PTFE composites have improved thermal stability and electrical conductivity. Importantly, the percolation threshold for the electrical conductivity was achieved at a low concentration of MWCNT using this heterocoagulation process.     

无电沉积法AuNPs-MWCNTs的制备及其对黄酮类化合物的电化学催化性能研究

利用多壁碳纳米管具有较低的还原电位,以多壁碳纳米管作为还原剂和负载基底,通过无电沉积法制备了负载纳米金粒子的碳纳米管催化剂。此种材料具有更多的活性位点,避免了纳米金粒子表面保护剂的存在造成其催化活性降低的缺陷,发现其对典型黄酮类化合物-芦丁和黄芩苷具有良好的电化学催化性能和较高的灵敏度,并将其应用于电化学分析检测黄酮类化合物。     

Synthesis and electrochemistry of multiwalled carbon nanotube films directly attached on silica substrate

Vertically aligned multiwalled carbon nanotubes (MWCNT) on silica substrate were selectively produced by the procedure of chemical vapor deposition (CVD). For the synthesis of the MWCNT films, either acetonitrile (ACN) or benzene (BZ) was used as carbon sources while ferrocene (FeCp₂) was adopted as catalyst. The packing organization of the aligned carbon nanotubes on the silica substrate, and thus the degree of disorder of the produced MWCNT films, was found to be different. Namely, the MWCNT₂ film, produced upon decay of BZ, seems to be more disordered compared to MWCNT₁, produced upon decomposition of ACN. In order to examine their prospective application as electrodes for the detection of electroactive compounds in organic solvent media, the techniques of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed. FeCp₂ was selected as the suitable standard electroactive substance for probing the fabricated MWCNT electrodes, in view of the fact that FeCp₂ undergoes a fast one-electron oxidation process forming the ferrocenium cation (FeCp₂⁺), which is rather stable during the time scale of the experiments. All electrochemical experiments were performed in ACN as solvent medium including n-tetrabutylammonium hexafluorophosphate as supporting electrolyte at room temperature. The extracted CV and EIS results were compared with those obtained using glassy carbon electrode. The findings demonstrate the successful detection of FeCp₂ in ACN at both MWCNT films. However, among the films investigated, the electrode produced upon decay of BZ seems to be better capacitor, most probably due to its higher surface area as well as to its small film thickness. Evidently, the high degree of disorder, which has been observed for MWCNT₂, plays an important role for the increase of its effective surface area and thus, its capacitance. It is, however, very interesting that the more disorder MWCNT₂ film provides, the greater charge transfer resistance.     

Thermal degradation and kinetic analysis of biodegradable PBS/multiwalled carbon nanotube nanocomposites

In this study, carbon nanotubes (CNTs) were first modified using N,N′‐ dicyclohexylcarbodiimide (DCC) dehydrating agents. Subsequently, the poly(butylene succinate)/multiwalled carbon nanotube (PBS/MWNTs) nanocomposites were prepared through facile melt blending. Thermal degradation of these PBS/MWNT nanocomposites was investigated; the kinetic parameters of degradation were calculated using the Coats and Redfern, Ozawa, and Horowitz and Metzger methods, respectively. It was found that the degradation reaction mechanism of PBS and the CNT‐C18 containing nanocomposites at lower temperature was likely to produce an F1 model through reaction of random chain cleavage (cis‐elimination). However, the reaction mechanism at higher temperature was likely to be a D1 model because of the dominant diffusion control effect. Moreover, it was found that the activation energies of CNT‐C18‐containing PBS nanocomposites were first increased with the content of CNT‐C18, but then decreased after the content was larger than 0.5 wt % for all models at differing heating rates. This may be due to the formation of a conductive network of CNTs in the polymer matrix at higher content of CNTs, which lead to better heat and electrical conductivity. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1231–1239, 2009