Commercial Multi-walled Carbon Nanotubes Research Articles

Physiological aspects of the interaction of multi-walled carbon nanotubes with Beauveria bassiana (Balsamo) Vuillem in entomopathogenic spores

The objective of the study was to evaluate the in vitro effect of aqueous suspensions of commercial multi-walled carbon nanotubes (MWCNTs) on spores of three entomopathogenic fungus species of Beauveria bassiana. Spores were placed in contact with MWCNTs for 1, 24, 72 and 216 h and then an in vitro evaluation in the subculture was performed on the linear growth of the vegetative mycelium of the spores after the contact with nanomaterial, as well as its sporulation after completion of the culture. No fungistatic effect of MWCNTs against B. bassiana spores was identified. Modification of vegetative mycelium surface growth in the culture of spores after contact with MWCNTs was mainly due to less effective inoculation, especially when shorter contact times with nanomaterial were applied. For one of the investigated strains, growth stimulation was observed in the culture of spores in contact with nanotubes for 72 and 216 h. Based on the significant intensification of sporulation observed in combination with the longest (216 h) contact with the investigated spore strains before culture with MWCNTs, it can be concluded that the tested nanomaterial constitutes a stress factor and may modify the metabolism of B. bassiana cells. Detailed evaluation of B. bassiana metabolic changes induced by MWCNTs should be conducted.

ANALYSIS OF MICROWAVE ABSORBING PROPERTIES OF EPOXY MWCNT COMPOSITES

In the ongoing search for new materials for microwave absorption applications, Carbon Nanotubes deserve a special consideration due to their outstanding properties. In this paper, microwave absorbing properties of epoxy resin based composites containing commercial Multi Walled Carbon Nanotubes used as flllers have been analyzed. The complex permittivity of the composites was measured in a wide frequency band (3{18GHz). The absorbing properties of a single-layer absorber backed by a metallic plate considering several concentration of CNTs was simulated taking into account the measured permittivity.

One-pot synthesis of carbon nanotube–graphene hybrids via syngas production

Multi-walled carbon nanotubes (MWCNTs) are limited by entanglement, and it is rather difficult to prevent graphene stacking in a polymer composite. These two challenges can be addressed by developing a MWCNT–graphene hybrid where MWCNTs and graphene are born as twins. We in this study employed a syngas production method using microwave irradiation for a one-pot synthesis of porous, crumpled and loose MWCNT–graphene hybrids, investigated the substrate compositions, measured their performance as electrodes for energy storage devices, and proposed the synthesis mechanisms. A number of hybrids, including MWCNT–graphene, MWCNT–cup-stacked CNT and MWCNT–graphitic nanofiber, were synthesized on Cr–Ni, Fe–Ni and Ni–CeO2 substrates, respectively. TEM analysis shows that the two challenges have been markedly addressed in the hybrids. They performed better in terms of capacitive properties than commercial MWCNTs.

Monodisperse SnO2 nanocrystals functionalized multiwalled carbon nanotubes for large rate and long lifespan anode materials in lithium ion batteries

A facile way towards high rate and long lifespan anode materials based on SnO2 and commercial multiwalled carbon nanotubes (MWCNTs) is readily achieved through a combination of activation and hydrothermal treatment. The former endows the MWCNTs with abundant hydrophilic radicals, while the latter guarantees intimate connection between SnO2 and MWCNTs; eventually, monodisperse SnO2 nanocrystals ca. 3nm are firmly anchored on the MWCNTs without agglomeration. When used for lithium ion batteries (LIBs) anodes, the hybrid composite exhibits excellent cycling capability with high reversible capacity about 700 mAh g−1 (based on total weight of the composite) for 150 cycles at 0.1 A g−1 superior to both components involved. Besides large rates of 5 A g−1 with recoverable initial reversible capacity, it also last for more than 1000 cycles with little capacity decay, outperforming most SnO2 based carbon nanotubes composites (SnO2/CNTs) so far. Insights into the electrochemical processes reveal the hybrid composite exhibits enhanced redox capacitance and interfacial capacitance in comparison with SnO2 nanocrystals which indicate the perfect interfaces and robust structure of the hybrid composite.

Study of efficiency of different commercial carbon nanotubes on manufacturing of epoxy matrix composites

The influence of geometry and structure of different commercial multi-walled carbon nanotubes (MWCNTs) have been analysed. MWCNTs have been characterized by transmission and high-resolution scanning electron microscopy, measurement of specific surface area by nitrogen isotherm and X-ray diffraction. The behaviour of carbon nanotube/epoxy composites has been studied by dynamic mechanical thermal analysis, differential scanning calorimetry, measurements of density and electrical conductivity. Composites manufactured at the same experimental conditions and with the same nanofiller content presented different thermal, mechanical and electrical properties. Despite using MWCNTs with similar aspect ratio, the presence of surface defects on the nanotube structure induces an important decrease in storage modulus and electrical conductivity of composites. The functionalization of MWCNTs leads to composites with lower electrical conductivity due to the breaking of sp2 carbon delocalization and also due to the insulating polymer film wrapping the nanotube. In contrast, resin reinforced with long MWCNTs present higher modulus and electrical conductivity than those filled with shorter nanotubes.

Inhibition of catecholamine secretion by iron-rich and iron-deprived multiwalled carbon nanotubes in chromaffin cells

The assay of the toxic effects of carbon nanotubes (CNTs) on human health is a stringent need in view of their expected increasing exploitation in industrial and biomedical applications. Most studies so far have been focused on lung toxicity, as the respiratory tract is the main entry of airborne particulate, but there is also recent evidence on the existence of toxic effects of multiwalled carbon nanotubes (MWCNTs) on neuronal and neuroendocrine cells (Belyanskaya et al., 2009; Xu et al., 2009; Gavello et al., 2012). Commercial MWCNTs often contain large amounts of metals deriving from the catalyst used during their synthesis. Since metals, particularly iron, may contribute to the toxicity of MWCNTs, we compared here the effects of two short MWCNTs samples (<5μm length), differing only in their iron content (0.5 versus 0.05% w/w) on the secretory responses of neurotransmitters in mouse chromaffin cells.We found that both iron-rich (MWCNT+Fe) and iron-deprived (MWCNT−Fe) samples enter chromaffin cells after 24h exposure, even though incorporation was attenuated in the latter case (40% versus 78% of cells). As a consequence of MWCNT+Fe or MWCNT−Fe exposure (50–263μg/ml, 24h), catecholamine secretion of chromaffin cells is drastically impaired because of the decreased Ca2+-dependence of exocytosis, reduced size of ready-releasable pool and lowered rate of vesicle release. On the contrary, both MWCNTs were ineffective in changing the kinetics of neurotransmitter release of single chromaffin granules and their quantal content. Overall, our data indicate that both MWCNT samples dramatically impair secretion in chromaffin cells, thus uncovering a true depressive action of CNTs mainly associated to their structure and degree of aggregation. This cellular “loss-of-function” is only partially attenuated in iron-deprived samples, suggesting a minor role of iron impurities on MWCNTs toxicity in chromaffin cells exocytosis.

Multiwall carbon nanotubes filled polypropylene nanocomposites: Rheological and electrical properties

Two types of commercial multiwall carbon nanotubes (MWCNTs), Baytubes® C70P and C150P were incorporated into polypropylene (PP) using melt blending technique that employs a twin screw extruder (TSE) to prepare the nanocomposites of two different concentrations (1 and 3 wt%). Subsequently, American Society for Testing and Materials (ASTM) standard samples were prepared with an injection molding machine. The prepared nanocomposites were characterized by their rheological and electrical properties using a rheometer and a picoammeter/voltage source, respectively. The effect of different types of MWCNTs and loading percentage in rheological and electrical properties was investigated in detail. The rheological analysis demonstrated a considerable dependence of the melt rheological properties of the PP/MWCNTs nanocomposites on the MWCNTs loading. The storage modulus (G′), loss modulus (G″) and complex viscosity increased with increasing MWCNTs loading. In addition, type C70P exhibited superior rheological properties compared to C150P. In terms of electrical properties, the addition of MWCNTs in the PP matrix decreased the volume resistivity of the matrix in a manner, proportional to the MWCNTs loading. No significant difference in volume resistivity was observed between the MWCNTs types. POLYM. ENG. SCI., 54:1134–1143, 2014. © 2013 Society of Plastics Engineers

Functionalization by Acidic Treatment in the Purification of Multiwalled Carbon Nanotubes (MWCNTs)

Comparative studies of two multi-walled carbon nanotubes (MWCNT) from different manufacturers were reported. The purification and functionalization of commercial multiwall carbon nanotubes were investigated. MWCNTs were treated with boiling concentrated HNO3 under a reflux condenser for 2 hours at 100 °C in order to purify and oxidize the raw material. The oxidized MWCNTs were rinsed with deionized water until stabilization of the filtrate pH. The measurement technique was by thermogravimetric analysis (TGA) for thermal analysis decomposition products. Meanwhile, the chemical shifted in MWCNTs can be determined by using Raman Spectroscopy.

Influence of architecture on the Raman spectra of acid-treated carbon nanostructures

Raman spectroscopy was used to characterise 11 varieties of carbon nanostructures (CNSs) consisting on seven varieties of commercial multi-walled carbon nanotubes, two types of carbon nanofibres and two types of lab-synthesised single-walled carbon nanotubes. The Raman spectra of these CNSs provided information on the structural ordering of the as-received (or as-synthesised) material. Additionally, the CNSs were chemically treated by two mixtures of nitric and sulphuric acids at markedly different concentrations and then characterised by Raman spectroscopy. The features of the G and D Raman bands of the CNSs were used to assess structural modifications and generation of defects induced by the acid treatments. Changes in the Raman spectra before and after acidic treatment depend strongly on the initial intensity ratio of the G to D bands and the architecture (number of layers or diameter) of the CNSs.

A novel core–shell multi-walled carbon nanotube@graphene oxide nanoribbon heterostructure as a potential supercapacitor material

A novel core–shell heterostructure with multi-walled carbon nanotubes as the core and graphene oxide nanoribbons as the shell (MWCNT@GONR), fabricated by the facile unzipping of MWCNTs with the help of microwave energy, was used as a supercapacitor (SC) electrode material. Graphene nanopowder (GNP) and multi-walled carbon nanotubes (MWCNTs) have also been applied as SC materials for comparison. A smooth surface and a tube-like structure are found for the GNP and MWCNTs, respectively, while for the MWCNT@GONR material, graphene oxide sheet structures are observed on both sides of central nanotube cores that retain their tube-like structure. The specific capacitance is much better for the SC electrode with the MWCNT@GONR (252.4 F g−1) compared to the SC electrodes with commercial MWCNTs (39.7 F g−1) and GNP (19.8 F g−1), as determined using cyclic voltammetry (CV) at a scan rate of 50 mV s−1, which is due to the defective edges of the nanostructures in the former. The SC electrode with the MWCNT@GONR also exhibits good stability and capacitance retention even after 1000 cycles of galvanostatic charge–discharge testing, indicating its potential as a SC material. CV, galvanostatic charge–discharge (GC/D) and electrochemical impedance spectroscopy (EIS) were applied to analyze the SC performance.

Competitive adsorption of phenol and 3-chlorophenol on purified MWCNTs

A commercial multiwall carbon nanotube and its carboxylated derivate (CNTC and COOHC, respectively) was used after purification to study the competitive adsorption of phenol (P) and m-chlorophenol (CP) from 0.1M aqueous NaCl solutions without external pH control. The adsorption takes place practically exclusively on the external surface of the nanotubes. The uptake of P is suppressed in comparison to its single solute behaviour on both nanotubes, independently of the initial pollutant concentration. The uptake of CP however is more sensitive to the concentration and the surface chemistry of the nanotube. The measured co-adsorption isotherms were compared to the isotherms calculated from the competitive Langmuir model (CLM). Preferential adsorption of CP was observed in about 95% of the relative concentration range. The total adsorption may exceed the corresponding single component sorption capacity.

Surface-associated metal catalyst enhances the sorption of perfluorooctanoic acid to multi-walled carbon nanotubes

The perfluorooctanoic acid (PFOA) sorption behavior of two commercial multi-walled carbon nanotubes (MWCNTs) (C 150 P from Bayer MaterialScience: BA and C-MWNTs from NanoTechLabs Inc.: CP) was investigated from aqueous solution. The BA nanotubes contained Co/Mn/Mg/Al catalysts both on their outer surface and in the inner bore while CP contained Fe-based catalyst typically within the tubes. The adsorption isotherms of 14C-radiolabeled PFOA were measured by batch experiments and fitted to the Freundlich model (r2>0.92). The adsorption affinity and capacity on BA were significantly higher than on CP. Increasing the pH reduced the adsorption of PFOA due to the electrostatic interaction between the pH-sensitive surface and the adsorbate. Increasing the NaCl concentration led to the aggregation of the MWCNTs reducing the available surface and thus the adsorption capacity. Removal of the catalyst from the outer surface of BA changed the electrophoretic mobility from a positive to a negative value and also decreased the adsorbed amount of PFOA. The surface charge of the surface-associated metal catalyst favors the electrostatic sorption of PFOA. Such surface modifications may be a promising way to improve the sorption capacity of MWCNTs for pollutants such as PFOA and to broaden their potential application in water purification.

Multi‐walled carbon nanotubes induce cytotoxicity and genotoxicity in human lung epithelial cells

The increasing use of nanomaterials in consumer products highlights the importance of understanding their potential toxic effects. We evaluated cytotoxic and genotoxic/oxidative effects induced by commercial multi-walled carbon nanotubes (MWCNTs) on human lung epithelial (A549) cells treated with 5, 10, 40 and 100 µg ml⁻¹ for different exposure times. Scanning electron microscopy (SEM) analysis, MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide] and lactate dehydrogenase (LDH) assays were performed to evaluate cytotoxicity. Fpg-modified comet assay was used to evaluate direct-oxidative DNA damage. LDH leakage was detected after 2, 4 and 24 h of exposure and viability reduction was revealed after 24 h. SEM analysis, performed after 4 and 24 h exposure, showed cell surface changes such as lower microvilli density, microvilli structure modifications and the presence of holes in plasma membrane. We found an induction of direct DNA damage after each exposure time and at all concentrations, statistically significant at 10 and 40 µg ml⁻¹ after 2 h, at 5, 10, 100 µg ml⁻¹ after 4 h and at 10 µg ml⁻¹ after 24 h exposure. However, oxidative DNA damage was not found. The results showed an induction of early cytotoxic effects such as loss of membrane integrity, surface morphological changes and MWCNT agglomerate entrance at all concentrations. We also demonstrated the ability of MWCNTs to induce early genotoxicity. This study emphasizes the suitability of our approach to evaluating simultaneously the early response of the cell membrane and DNA to different MWCNT concentrations and exposure times in cells of target organ. The findings contribute to elucidation of the mechanism by which MWCNTs cause toxic effects in an in vitro experimental model.

Carbon nanotube‐filled ethylene/vinylacetate copolymers: from in situ catalyzed polymerization to high‐performance electro‐conductive nanocomposites

Preparation and analysis of morphology, mechanical, and electrical properties of nanocomposites based on ethylene vinyl acetate (EVA) copolymer and commercial multiwalled carbon nanotubes (CNTs) was achieved. The used techniques for obtaining nanocomposites were the conventional melt‐mixing and the in situ ethylene polymerization/coating reaction, as catalyzed directly from CNT surface, with different polyethylene content (i.e. 55.0% and 66.6%). Nanocomposites were also prepared using crude CNTs. The incorporation in the molten state of such polyethylene surface‐coated CNTs, used as “masterbatch,” in EVA was demonstrated a good strategy for allowing the complete destructuring of the native bundle‐like aggregates, leading to the preparation of polymer nanocomposites with largely improved properties, even at very low nanofiller content. Copyright © 2011 John Wiley &amp; Sons, Ltd.

Interaction of phenol and dopamine with commercial MWCNTs

We report the adsorption of phenol and dopamine probe molecules, from aqueous solution with NaCl, on commercial multiwall carbon nanotubes (MWCNT) and on their carboxylated derivative. The nanotubes were fully characterized by high resolution transmission electron microscopy (HRTEM), small angle X-ray scattering (SAXS), potentiometric titration, electrophoretic mobility, and nitrogen adsorption (77K) measurements. The experimental pollutant isotherms, evaluated using the Langmuir model, showed that only 8–12% and 21–32% of the BET surface area was available for phenol and dopamine, respectively, which is far below the performance of activated carbons. Influence of the pH was more pronounced for the oxidized MWCNT, particularly with dopamine. The strongest interaction and the highest adsorption capacity occurred at pH 3 with both model pollutants on both types of nanotubes. Although the surface area available for adsorption is far lower in MWCNTs than in activated carbons, it is nonetheless substantial. In particular, delayed release of toxic molecules that are either adsorbed on the surface or trapped in the inner bore of such systems could constitute an environmental hazard. The need for further adsorption studies with regard to their environmental aspects is therefore pressing, particularly for MWCNTs in their functionalized state.

Adsorption of ciprofloxacin on surface-modified carbon materials

The adsorption capacity of ciprofloxacin (CPX) was determined on three types of carbon-based materials: activated carbon (commercial sample), carbon nanotubes (commercial multi-walled carbon nanotubes) and carbon xerogel (prepared by the resorcinol/formaldehyde approach at pH 6.0). These materials were used as received/prepared and functionalised through oxidation with nitric acid. The oxidised materials were then heat treated under inert atmosphere (N2) at different temperatures (between 350 and 900°C). The obtained samples were characterised by adsorption of N2 at −196°C, determination of the point of zero charge and by temperature programmed desorption. High adsorption capacities ranging from approximately 60 to 300mgCPxgC−1 were obtained (for oxidised carbon xerogel, and oxidised thermally treated activated carbon Norit ROX 8.0, respectively). In general, it was found that the nitric acid treatment of samples has a detrimental effect in adsorption capacity, whereas thermal treatments, especially at 900°C after oxidation, enhance adsorption performance. This is due to the positive effect of the surface basicity. The kinetic curves obtained were fitted using 1st or 2nd order models, and the Langmuir and Freundlich models were used to describe the equilibrium isotherms obtained. The 2nd order and the Langmuir models, respectively, were shown to present the best fittings.

Surface modification of multi-wall carbon nanotubes by nitrogen attachment

Commercial multiwall carbon nanotubes (MWCNT-s) were treated by RF activated N 2 gas plasma at (nominally) room temperature. Treatment time of 5 to 10 min was applied at negative bias varying in the 0–300 V range. Surface chemical alterations were followed by X-ray photoelectron spectroscopy (XPS). All the applied treatments resulted in a significant build-up of nitrogen in the surface of MWCNT-s. The amount of nitrogen varied between 19 and 25 at.% depending on the treatment time and, in a lesser extent, also on biasing conditions. Interestingly, the nitrogen attachment was also significant (20 at.%) when the treatment commenced without bias. Evaluating the high-resolution N1s XP spectral region, typically three different chemical bonding states of the nitrogen was delineated. Peak component at 398.3 ± 0.3 eV is assigned to C N C type, at 399.7 ± 0.3 eV to sp 2 N in melamine-type ring structure and at 400.9 ± 0.3 eV to N substituting carbon in a graphite-like environment. Identical chemical bonding of the nitrogen was detected on the surface of highly oriented pyrolytic graphite (HOPG) and on microcrystalline graphite surfaces treated in the same way for comparison. Estimating the penetration depth of the nitrogen atoms by the SRIM program it was concluded that at the applied DC bias energy range the implanted nitrogen is incorporated in the top 2–4 monoatomic layers of the samples. A model for the distribution of the chemically bonded nitrogen on the outer walls of the MWCNT-s is proposed.

Impedance response of carbon nanotube–titania electrodes dried under modified gravity

The synthesis and impregnation of porous titania films by commercial multiwalled carbon nanotubes and nanotube rich carbon soot are reported. The samples were dried under terrestrial gravity g and in a centrifuge accelerated at 13g. X-Ray Diffraction data and Scanning Electron Microscopy images indicated differences in the crystal structure and tendency to agglomeration in both carbon types, providing different microstructures of functionally graded electrodes. Drying the samples in a centrifuge helps to the distribution of carbon nanoparticles and to the decrement of the impedance at the contact interfaces. The presence of titania weakens the differences observed in both drying protocols, but not the differences due to the carbon source. Superior capacitance and network conductivity were observed in electrodes based on commercial carbon nanotubes.

Functionalization of the surface of multiwalled carbon nanotubes

Features of functionalization of the surface of domestic commercial multiwalled carbon nanotubes by means of the thermal oxidation in air and treatment in nitric acid or a nitric-sulfuric acid mixture has been studied using the method of differential thermal analysis.

Preliminary Investigations into the Purification and Functionalization of Multiwall Carbon Nanotubes

about 50 h at 120 ‐ C in order to purify and oxidize the raw material. The oxidized multiwall carbon nanotubes were rinsed with deionized water until stabilization of the filtrate pH. Measurement techniques included elemental analysis (CHN), scanning electron microscopy with energy dispersive X-ray spectrometer, inductively coupled plasma mass spectrometry, Fourier transform infrared spectroscopy and thermal analysis. With the measurement techniques used the following information was obtained: CHN analysis provided information about the quantitative composition of the following elements carbon, hydrogen, nitrogen, scanning electron microscopy imaging provided information on shape, thickness and length of the nanotubes, energy dispersive X-ray spectrometry analysis of information about surface atomic composition of the quantitative analysis, inductively coupled plasma mass spectrometry quantitative analysis of the atomic composition (metals, especially Fe, Al), the Fourier transform infrared studies provided information about qualitative analysis of surface functional groups CxOyHz (COOH, OH, COO) and thermal gravimetric‐dier ential thermal analysis — quantitative analysis of thermal decomposition products. It was found that oxidation leads to the removal of amorphous carbon and forms mainly carboxylic functional groups linked to the nanotubes. The Fourier transform infrared spectra indicate the presence of some other structures, like ketone (quinone), acid anhydride, ether and epoxy groups. Nitric acid treatment also eectively removes aluminum oxide catalyst and iron catalyst from commercial multiwall carbon nanotubes.