A comparative study on dispersion of carbon nanotubes in (styrene-butadiene rubber)-based nanocomposites

Effective dispersion of multi-walled carbon nanotubes in aqueous solution using an ionic-gemini dispersant

In recent years, due to their high specific mechanical properties, polymer matrix composites have been widely used. In particular, carbon nanotubes have been used as reinforcement because of their exceptional properties. In this work, the degree of dispersion and alignment of multiwalled carbon nanotubes into polyvinyl alcohol was quantified, which is a key information to optimize the mechanical properties of composites. For the dispersion of the multiwalled carbon nanotubes into the solution, a magnetic stirring and ultrasonic agitation were used. Finally, the mixture was dried to obtain a multiwalled carbon nanotubes reinforced polymer. The composites were mechanically stretched to obtain sheets with multiwalled carbon nanotubes aligned in the stretching direction. The layers obtained were prepared for transmission electron microscopy analysis. A dispersion quantification method based on the statistical distribution of horizontal and vertical separation distance between carbon nanotubes was used; a lognormal distribution was obtained. The angle of carbon nanotubes with respect to the stretching direction was used to quantify the alignment degree of carbon nanotubes. The bulk mechanical properties of the composites were measured by nanoindentation test; tensile test allowed to measure the mechanical properties of the composites in both the stretching and perpendicular directions to the stretching direction. Multiwalled carbon nanotubes showed a good dispersion and alignment degree and this, in conjunction with stretching, produced a high increase of both the stiffness and strength in the stretching direction, which allowed an increment of the mechanical properties measured by nanoindentation test; the best properties of the composites were reached with 0.5 wt% of MWCNTs.

Sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (NaDDBS) are used as surfactants to improve the dispersion of multi-walled carbon nanotubes (MWNTs) in cement mortar and fabricate piezoresistive carbon-nanotube/cement mortar composite. The piezoresistivity of carbon-nanotube/cement mortar composite with different content levels of MWNTs and different surfactants were explored under repeated loading and impulsive loading. Experimental results indicate that NaDDBS has higher efficiency than SDS for the dispersion of MWNTs in cement mortar. The response of the electrical resistance of carbon-nanotube/cement mortar composite with NaDDBS to external force is more stable and sensitive than that of carbon-nanotube/cement mortar composite with SDS. These findings indicate that the use of NaDDBS is an effective way for improving the dispersion of MWNTs in cement-based composite and fabricating MWNTs filled cement-based composite with stable and strong piezoresistive response.

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

We studied the dispersity of multi-walled carbon nanotubes (MWNTs) combined with different metal- lic particles (Ni and Fe). An ultrasonic-assisted water-bath dispersion process was used to dis- perse the metal-coated MWNTs in different solutions and the dispersity was measured using an ultraviolet-visible spectrophotometer. The dispersity and morphology of the MWNTs were characterized using field-emission scanning electron microscopy (FE-SEM) together with digital image processing technology. Effects of dispersant type (sodium dodecyl benzene sulfonate (SDBS), oleic acid, and polymer (TNEDIS)) and surfactant dosage on the dispersity of the metal-coated MWNTs were investigated under controlled and uncontrolled temperatures and results were compared with those from the untreated MWNTs. The results showed that the negative effects of temperature on the ultrasonic dispersion process could be eliminated through a temperature-controlled system. Moreover, the TNEDIS, SDBS, and oleic acid were arranged in the descending order of the dispersion effect degree. The untreated MWNTs, Ni-coated MWNTs, and Fe-coated MWNTs were arranged in the descending degree of dispersity order. Since the metal coating makes the MWNTs harder and more fragile, the metal-coated MWNTs are more likely to fracture during the ultrasonic dispersion process.

Two commonly used dispersants, octyl phenol ethoxylate (Triton X-100) and sodium dodecyl sulfate (SDS), were employed to explore the effects of single or mixed surfactants on the dispersion, sedimentation and aggregation of multi-walled carbon nanotubes (MWCNTs). Non-ionic surfactant TX100 showed much superior capability to anionic surfactant SDS in dispersing MWCNTs due to the benzene ring structure in its tail group. The addition of SDS reduced the adsorption of TX100 on the surface of MWCNTs and the consequent suspension of MWCNTs. The dispersing ability of TX100–SDS binary mixture was between those of individual SDS and TX100. The introduction of SDS greatly retarded the sedimentation and aggregation of suspended MWCNTs. The critical coagulation concentration (CCC) values of suspended MWCNTs dispersed by TX100 (2000 mg l−1), SDS (2000 mg l−1) and TX100–SDS (2000 mg l−1 of each component) were 48.6, 398 and 324 mM, respectively, for Na+ treatments. The CCC values were much lower for Ca2+ treatments, which were 30.4 and 32.1 mM, respectively, for MWCNTs dispersed by TX100 and TX100–SDS mixture. Overall, these results demonstrated that although the introduction of SDS did not improve the ability of TX100 in suspending MWCNTs, the suspensions exhibited more stable properties than those dispersed by TX100 alone. Our findings have important implications for the design of surfactant mixtures and the prediction of the behaviour and fate of MWCNTs in the water environment.

It is difficult to disperse multi-walled carbon nanotubes (MWCNTs) into Mg matrix composites homogeneously due to the high specific surface energy between MWCNTs. This would affect the mechanical properties of magnesium matrix composites reinforced by MWCNTs tremendously. The key is to overcome MWCNTs aggregate together, and gain the homogeneous dispersion of MWCNTs. Moreover, the density difference of Mg matrix and MWCNTs is another problem which prevents MWCNTs from dispersing homogeneously into Mg matrix composites. In order to solve these problems, a new practical method of homogeneous dispersion of carbon nanotubes into Mg matrix composites was presented basing on combination the tow step ball milling and ultrasonication dispersion methods. First, a certain amount of MWCNTs was ball-milled in ethanol solution contain 5 wt.% sodium stearate at various rotation speeds (100 rpm-300 rpm) and ball-milled times (0.5 H-2 H) to break MWCNTs hard aggregation. Second, MWCNTs which were subjected to the ball-milling were dispersed further in ethanol solution containing (SDS, DBS) using ultrasonication method. Third, the Mg powers were mixed with good dispersion of carbon nanotubes solution and ball-milled for 1 H to make MWCNTs coated uniformly on the surface of the magnesium substrate. The results were mainly examined by field emission scanning electron microscopy (SEM). It was found that MWCNTs were dispersed well and some of these MWCNTs had directional arrangement. Furthermore, MWCNTs were homogeneously dispersed into Mg matrix composites. These results suggest that this method has good application for magnesium matrix composites reinforced by carbon nanotubes.

Stable dispersion of multi-walled carbon nanotubes (MWNTs) has been prepared by using chitosan (CS) as dispersant, and it was quantitatively characterized by UV-Vis-NIR Spectrophotometer. When the sediment time reaches 375 hours, the supernatant concentration of MWNTs declines 18 % for the bare MWNTs suspension, compared with 6.5 % for the MWNTs dispersed by CS. Morphologies of MWNTs were observed by scanning electron micrograph (SEM) and atomic force microscope (AFM) in detail. The results of AFM clearly show the CS is wrapped on the wall of MWNTs. Finally, we study that the cytotoxicity of MWNTs dispersed by CS on cancer cells. Our results show that MWNTs dispersed by CS have no obvious cytotoxicity on Hela cells.

An innovative multiscale (atomistic to mesoscale) model capable of predicting carbon nanotube (CNT) interactions and dispersion in water/surfactant/polymer systems was developed. The model was verified qualitatively with available experimental data in the literature. It can be used to computationally screen potential surfactants, solvents, polymers, and CNT with appropriate diameter and length to obtain improved CNT dispersion in aqueous medium. Thus the model would facilitate the reduction of time and cost required to produce CNT dispersed homogeneous solutions and CNT reinforced materials. CNT dispersion in any water/surfactant/polymer system depends on interactions between CNTs and surrounding molecules. Central to the study was the atomistic scale model which used the atomic structure of the surfactant, solvent, polymer, and CNT. The model was capable of predicting the CNT interactions in terms of potential of mean force (PMF) between CNTs under the influence of surrounding molecules in an aqueous solution. On the atomistic scale, molecular dynamics method was used to compute the PMF as a function of CNT separation and CNT alignment. An adaptive biasing force (ABF) method was used to speed up the calculations. Correlations were developed to determine the effective interactions between CNTs as a function of their any inter-atomic distance and orientation angle in water as well as in water/surfactant by fitting the calculated PMF data. On the mesoscale, the fitted PMF correlations were used as input An innovative multiscale (atomistic to mesoscale) model capable of predicting carbon nanotube (CNT) interactions and dispersion in water/surfactant/polymer systems was developed. The model was verified qualitatively with available experimental data in the literature. It can be used to computationally screen potential surfactants, solvents, polymers, and CNT with appropriate diameter and length to obtain improved CNT dispersion in aqueous medium. Thus the model would facilitate the reduction of time and cost required to produce CNT dispersed homogeneous solutions and CNT reinforced materials. CNT dispersion in any water/surfactant/polymer system depends on interactions between CNTs and surrounding molecules. Central to the study was the atomistic scale model which used the atomic structure of the surfactant, solvent, polymer, and CNT. The model was capable of predicting the CNT interactions in terms of potential of mean force (PMF) between CNTs under the influence of surrounding molecules in an aqueous solution. On the atomistic scale, molecular dynamics method was used to compute the PMF as a function of CNT separation and CNT alignment. An adaptive biasing force (ABF) method was used to speed up the calculations. Correlations were developed to determine the effective interactions between CNTs as a function of their any inter-atomic distance and orientation angle in water as well as in water/surfactant by fitting the calculated PMF data. On the mesoscale, the fitted PMF correlations were used as input in the Monte Carlo simulations to determine the degree of dispersion of CNTs in water and water/surfactant system. The distribution of CNT cluster size was determined for the CNTs dispersed in water with and without surfactant addition. The entropic and enthalpic contributions to the CNT interactions in water were determined to understand the dispersion mechanism of CNTs in water. The effects of CNT orientation, length, diameter, chirality and surfactant concentrations and structures on CNT interactions in water were investigated at room conditions. CNT interactions in polymer solution were also investigated with polyethylene oxide (PEO) polymer and water as a solvent. In all cases, the atomic arrangement of molecules was discussed in detailed. Simulations revealed that CNT orientation, length, diameter, and addition of surfactant and its structures can significantly affect CNT interactions (i.e., PMFs varied significantly) and in-turn the degree of CNT dispersion in aqueous solution. For all simulation cases, a uniform sampling was achieved by using the ABF method to calculate the governing PMF between CNTs indicating the effectiveness and convergence of the adaptive sampling scheme. The surfactant molecules were shown to adsorb at the CNT surface and contribute to weaker interactions between CNTs which resulted less CNT aggregate size at the mesoscale. Surfactant consisting with a benzene ring contributed much weaker interactions between CNTs as compared with that of without benzene ring. The increase in CNT length contributed the stronger CNT interactions where the increase in CNT diameter caused weaker CNT interactions in water. The interfacial characteristics between the CNT, surfactant and the polymer were also predicted and discussed. The model can be expanded for more solvents, surfactants, and polymers.

The potential properties of carbon nanotube-cement based materials strongly depend on the dispersion of carbon nanotubes (CNTs) within the cement matrix and the bonding between CNTs and the hydrated cement. The homogeneous dispersion of CNTs in the cement matrix yet is one of the main challenges due to strong van der Waals forces between nanotubes. In this study, a polycarboxylic ether based superplasticizer and ultra-sonication technique was used for dispersion of multi-walled carbon nanotubes (MWCNTs). Portland cement concrete specimens with different concentrations of MWCNTs (0.04 and 0.1 % by the weight of cement), with and without the presence of superplasticizer were investigated. Compressive strength test results revealed a significant improvement in mechanical properties of sample containing 0.1 % MWCNTs and 0.2 % superplasticizer. Moreover, field emission scanning electron microscopy (FESEM) images of fractured surfaces of hardened specimens showed a good dispersion of MWCNTs within the cement matrix. This method was developed to facilitate the uniform dispersion of MWCNTs in the cementitious concrete for better reinforcement in nanoscale and mechanical properties enhancement by transfer of load between the nanotubes and matrix.

An approach to enhance the dispersion of multi-walled carbon nanotubes (MWCNT) within a polymer matrix is reported. MWCNT surface was modified with a second type of particle, which constitutes a third phase. MWCNT were modified with polycarbosilane-derived silicon carbide (SiC) particles. X-ray diffraction confirmed the formation of β-SiC particles. At a loading level of 1.5 wt%, a fine dispersion of MWCNT throughout the polyethersulfone (PES) was observed by scanning electron microscopy (SEM), but at a higher loading (2.5 wt%), agglomerates of carbon nanotubes were observed. At 2.5 wt% loading, the incorporation of SiC-modified MWCNT in PES showed a homogeneous dispersion of carbon nanotubes throughout the matrix as confirmed by SEM and transmission electron microscopy (TEM). TEM analysis also confirmed the synergistic interactions and improved dispersion of MWCNT within the polymer matrix. Incorporation of SiC-modified MWCNT (SiC-MWCNT) significantly improved the mechanical and thermal properties of PES composites compared to pure PES and a composite containing an equal amount of unmodified MWCNT. The increased quality and improved state of dispersion in the case of a SiC-MWCNT-filled composite can be correlated to an increase of electrical resistivity.

ABSTRACTThis article presents the results of experiments performed to evaluate properties of dispersion of multiwalled carbon nanotubes (MWCNT) in water with sodium dodecyl sulfate (SDS) as a dispersant. Different samples of varying concentrations of MWCNTs were prepared for the analysis and properties including thermal conductivity, pH value, viscosity, wettability, etc., were evaluated. These properties were compared with the properties of conventional cutting fluid, which was taken as a mix of water and mineral oil. It was found that the thermal conductivity of the MWCNT dispersion was higher than the conventional cutting fluid by about 42%. There was a decrease in contact angle by about 70%. Thus, dispersing MWCNTs in water with SDS increases the thermal conductivity and wettability of fluid. The pH value of fluid with 0.2 vol% MWCNTs was found to be 8.4. It thus reduced the corrosive nature of water. Nanoparticles of MWCNTs did not have much influence on the viscosity of the base fluid. Thus, the use of MWCNTs in water with SDS appeared to result in a better cutting fluid for machining than conventional cutting fluid.

Stabilization of the aqueous dispersion of carbon nanotubes using different approaches

In vivo studies have demonstrated that the state of dispersion of carbon nanotubes (CNTs) plays an important role in generating adverse pulmonary effects. However, little has been done to develop reproducible and quantifiable dispersion techniques to conduct mechanistic studies in vitro. This study was to evaluate the dispersion of multiwalled carbon nanotubes (MWCNTs) in tissue culture media, with particular emphasis on understanding the forces that govern agglomeration and how to modify these forces. Quantitative techniques such as hydrophobicity index, suspension stability index, attachment efficiency, and dynamic light scattering were used to assess the effects of agglomeration and dispersion of as-prepared (AP), purified (PD), or carboxylated (COOH) MWCNTs on bronchial epithelial and fibroblast cell lines. We found that hydrophobicity is the major factor determining AP- and PD-MWCNT agglomeration in tissue culture media but that the ionic strength is the main factor determining COOH-MWCNT suspendability. Bovine serum albumin (BSA) was an effective dispersant for MWCNTs, providing steric and electrosteric hindrances that are capable of overcoming hydrophobic attachment and the electrostatic screening of double layer formation in ionic media. Thus, BSA was capable of stabilizing all tube versions. Dipalmitoylphosphatidylcholine (DPPC) provided additional stability for AP-MWCNTs in epithelial growth medium (BEGM). While the dispersion state did not affect cytotoxicity, improved dispersion of AP- and PD-MWCNTs increased TGF-β1 production in epithelial cells and fibroblast proliferation. In summary, we demonstrate how quantitative techniques can be used to assess the agglomeration state of MWCNTs when conducting mechanistic studies on the effects of dispersion on tissue culture cells.

Dispersion and stability of multi-walled carbon nanotubes in water as affected by humic acids