High Concentration Of Multi-walled Carbon Nanotubes Research Articles

Toxic effects of multi-walled carbon nanotubes and ZnO nanoparticle exposure on pathology and apoptosis on the liver of Cyprinus carpio

ZnO nanoparticles (ZnONPs) and carbon nanotubes (CNTs) are frequently used nanoparticles with unique features. Aquatic organisms are exposed to a combination of contaminants in natural water systems, so the combination effect of two or more nanomaterials has caused much concern. In this study, the toxicity to the liver of common carp was explored under four weeks of exposure to single ZnONPs or in combination with multi-walled CNTs (MWCNTs). The results demonstrated that ZnONPs induced pathological changes and apoptosis in the liver. In combination, decreased pathological changes were observed in the LSC-ZnONPs group (50 mg L-1 ZnONPs and 0.25 mg L-1 MWCNTs) at the microscopic level and ultrastructural level, and increased pathological changes in the HSC-ZnONPs group (50 mg L-1 ZnONPs and 2.5 mg L-1 MWCNTs). A 52% reduction in the percentage of TUNEL-positive nuclei in the LSC-ZnONPs group and a 33% increase in the HSC-ZnONPs group were observed compared to the ZnONPs group. The mRNA expression of apoptosis-related genes, including caspase3, BAX, and XBP1, were significantly up-regulated in the exposure groups, confirming the occurrence of apoptosis. Significantly decreased caspase 3 and BAX mRNA levels in the co-exposure groups were detected compared to the ZnONPs group. Nevertheless, the XBP1 mRNA level was significantly upregulated in the LSC-ZnONPs group, but downregulated in the HSC-ZnONPs group, indicating multiple signal pathways involved in the apoptosis. In conclusion, a low concentration of MWCNTs (0.25 mg L-1) decreased the toxic effect of ZnONPs on common carp, but a high concentration of MWCNTs (2.5 mg L-1) enhanced it. This study will contribute to developing future risk assessment and management strategies for nanomaterials.

The combined toxicity and mechanism of multi-walled carbon nanotubes and nano copper oxide toward freshwater algae: Tetradesmus obliquus

Nanoparticles (NPs) are widely used for their special physical properties and released into the natural environment. When two types of NPs exist in the same environment, the presence of one type of NP may affect the properties of the other type of NP. This study investigated the toxic effects of multi-walled carbon nanotubes (MWCNTs) and copper oxide nanoparticles (CuO NPs) on Tetradesmus obliquus. Both NPs had toxic effects on algae, and the toxic effects of MWCNTs were significantly stronger than CuO NPs which the 96-hr median effective concentration to algae were 33.8 and 169.2 mg/L, respectively. Oxidative stress and cell membrane damage were the main reasons for the toxicity of NPs to algae, and they were concentration-dependent, and the existence of CuO NPs in some groups reduced cell membrane damage caused by MWCNTs which may because that CuO NPs formed heteroaggregation with MWCNTs, reducing the contact of nanoparticles with cell membranes, then reducing physical damage. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) results indicated cell damage, the heteroaggregation of MWCNTs-CuO NPs and obvious nanoparticles internalization. In some groups, the presence of CuO NPs significantly reduced reactive oxygen species (ROS) level induced by MWCNTs. However, for the highest concentration group, the ROS level was much higher than that of the two NPs alone treatment groups, which might be related to the high concentration of MWCNTs promoting the internalization of CuO NPs. MWCNTs and CuO NPs affected and interacted with each other, causing more complex toxic effects on aquatic organisms.

In vivo study of conductive 3D printed PCL/MWCNTs scaffolds with electrical stimulation for bone tissue engineering

Critical bone defects are considered one of the major clinical challenges in reconstructive bone surgery. The combination of 3D printed conductive scaffolds and exogenous electrical stimulation (ES) is a potential favorable approach for bone tissue repair. In this study, 3D conductive scaffolds made with biocompatible and biodegradable polycaprolactone (PCL) and multi-walled carbon nanotubes (MWCNTs) were produced using the extrusion-based additive manufacturing to treat large calvary bone defects in rats. Histology results show that the use of PCL/MWCNTs scaffolds and ES contributes to thicker and increased bone tissue formation within the bone defect. Angiogenesis and mineralization are also significantly promoted using high concentration of MWCNTs (3 wt%) and ES. Moreover, scaffolds favor the tartrate-resistant acid phosphatase (TRAP) positive cell formation, while the addition of MWCNTs seems to inhibit the osteoclastogenesis but present limited effects on the osteoclast functionalities (receptor activator of nuclear factor κβ ligand (RANKL) and osteoprotegerin (OPG) expressions). The use of ES promotes the osteoclastogenesis and RANKL expressions, showing a dominant effect in the bone remodeling process. These results indicate that the combination of 3D printed conductive PCL/MWCNTs scaffold and ES is a promising strategy to treat critical bone defects and provide a cue to establish an optimal protocol to use conductive scaffolds and ES for bone tissue engineering.

Damage sensing and mechanical properties of a laminate composite material containing MWCNTs during low-velocity impact

In this work, we present a new criterion, unlike other attempts, to evaluate and quantify the degree of damage of composite material when it subjected to a sudden impact load. Our criterion exploits the high intrinsic electrical conductivity property of the Multi-walled carbon nanotubes (MWCNTs) after dispersing different concentrations of them (0, 0.5, 1.0, 1.5 and 2.0 %) in the epoxy matrix of a glass fibre composite. Following this goal, the low-velocity impact and flexural after impact (FAI) tests on the MWCNTs-glass epoxy (i.e. MWCNTs-GF) nanocomposite were evaluated. At the same time, the changes in its electrical resistance were measured. The results showed that the properties of the self-sensing composites were significantly affected by impact energy. The damage after impact causes an increase in the electrical resistance of the MWCNTs-GF nanocomposite and increases with increased impact energy. In addition, the samples containing a high concentration of MWCNTs showed lower damage sensitivity under all impact energies levels as compared with the samples contain a lower MWCNTs concentration. Therefore, the results presented in this work have shown that it is possible to associate the change in electrical resistance of the MWCNTs-GF nanocomposite with the degree of damages caused by impact load.

Using a Novel Approach to Estimate Packing Density and Related Electrical Resistance in Multiwall Carbon Nanotube Networks.

In this work, we use contrast image processing to estimate the concentration of multi-wall carbon nanotubes (MWCNT) in a given network. The fractal dimension factor (D) of the CNT network that provides an estimate of its geometrical complexity, is determined and correlated to network resistance. Six fabricated devices with different CNT concentrations exhibit D factors ranging from 1.82 to 1.98. The lower D-factor was associated with the highly complex network with a large number of CNTs in it. The less complex network, having the lower density of CNTs had the highest D factor of approximately 2, which is the characteristic value for a two-dimensional network. The electrical resistance of the thin MWCNT network was found to scale with the areal mass density of MWCNTs by a power law, with a percolation exponent of 1.42 and a percolation threshold of 0.12 g/cm. The sheet resistance of the films with a high concentration of MWCNTs was about six orders of magnitude lower than that of less dense networks; an effect attributed to an increase in the number of CNT–CNT contacts, enabling more efficient electron transfer. The dependence of the resistance on the areal density of CNTs in the network and on CNT network complexity was analyzed to validate a two-dimension percolation behavior.

Tuning rigidity and negative electrostriction of multi-walled carbon nanotube filled poly(lactic acid)

Multi-walled carbon nanotubes (MWCNTs) were utilized as an effective filler and dibutyl phthalate (DBP) as a plasticizer in the electro-responsive poly (lactic acid) matrix. Under on and off electric field, the MWCNT/PLA/DBP composites showed electromechanical recoverability with typical fast response times less than 1 min. The 0.1%v/v MWCNT-1200/PLA/DBP possessed the highest positive storage modulus sensitivity value of 1.95 at the electric field strength of 1.5 kV/mm. The storage modulus response with a value close to zero was observed at a MWCNT content between 0.8 and 0.9 %v/v. At high MWCNT concentrations, the storage modulus response became negative definite at high electric field strengths. This negative electrostriction behavior was in contrast to the positive definite electrostrictive responses of other materials. In the bending experiments, the 0.1%v/v MWCNT-2100/PLA/DBP produced relatively higher bending responses and dielectrophoresis forces at electric field strengths below 300 V/mm. At higher electric field strengths and higher MWCNTs contents, the dipole moment interaction was screened resulting in the decreases in the electrostriction, bending response and dielectrophoresis force. Thus, it has been demonstrated here that the MWCNTs induced the negative electrostriction in the plasticized PLA, possibly through the physical screening and free volume.

A simple criterion to evaluate the degree of damage in composite materials after sudden impact loads by exploiting the MWCNTs piezoresistive property

Composite materials are widely used in various important applications due to their good engineering properties. However, these properties can be reduced by sudden impact loading effects. In this work, a new approach for condition monitoring was proposed, which unlike other efforts, does not require additional sensors, but instead is carried out directly by exploiting of the multi-wall carbon nanotubes (MWCNTs) piezoresistive property. An epoxy resin was modified with different concentrations of MWCNTs in order to fabricate a nanocomposite material with high electrical conductivity. These nanocomposites were used as a matrix for a glass fibre composite to fabricate MWCNTs/glass/epoxy (MWCNTs-GE) nanocomposites. Scanning electron microscopy (SEM) and Raman spectroscopy were used to investigate the presence of the MWCNTs and their interaction with the matrix. Mechanical, electrical, damage factor and damage sensitivity properties were examined experimentally and statistically as the specimens were subjected to different levels of impact energies. The results showed that the changes in electrical resistance of specimens increased with increasing the impact of energy. Moreover, the MWCNTs-GE nanocomposite specimens containing a high concentration of MWCNTs showed a lower damage factor and a lower damage sensitivity under all impact energies levels. Therefore, the results given in this study have shown that it is possible to correlate between the degree of damages incurred by the impact load with the changes in electrical resistance of the MWCNTs-GE nanocomposites both during, and after, impact.

Hybrid nanoarchitecturing of hierarchical zinc oxide wool-ball-like nanostructures with multi-walled carbon nanotubes for achieving sensitive and selective detection of sulfur dioxide

This work reports a facile glycerol-assisted solvothermal method for synthesizing hierarchical three-dimensional (3D) wool-ball-like zinc oxide (ZnO) nanostructures and their subsequent modifications with multi-walled carbon nanotubes (MWCNTs) as modifiers for achieving sensitive and selective detection of toxic sulfur dioxide (SO2) gas. Structurally, the as-synthesized 3D wool-ball-like ZnO is assembled of two-dimensional (2D) plate-like structures, which themselves are arranged by numerous small nanoparticles. Furthermore, in this work we observed an interesting new phenomenon in which when a high concentration of MWCNTs is introduced, many small nanorods grew on the surface of the plate-like structures which assemble the 3D wool-ball-like ZnO nanostructures. When evaluated for SO2 detection, the ZnO/MWCNTs (10:1) composite (ZnO:MWCNTs = 10:1) shows a high response of 220.8 to 70 ppm of SO2 gas (approximately three times higher than the response of pure wool-ball-like ZnO) at an optimum operating temperature of 300 °C. Additionally, the composite also displays good stability and selectivity to SO2 with the response to 50 ppm of SO2 being 7–14 times higher than the responses to other tested gases at a similar concentration. The excellent sensing performance of the wool-ball-like ZnO/MWCNTs (10:1) composite is mainly attributed to: (i) the formation of p-n heterojunctions at the ZnO/MWCNTs interfaces, which greatly enhance the resistance changes upon exposure to SO2 gas and (ii) the increased amount of adsorption sites for O2 and SO2 gas molecules owing to the larger surface area of the composite and defects sites generated by the functionalization process of MWCNTs.

Influence of adding multiwalled carbon nanotubes on the adhesive strength of composite epoxy/sol–gel materials

The tensile shear strength of a composite epoxy/sol–gel system modified with different ratios of multiwall carbon nanotubes (MWCNTs) was evaluated using a mechanical testing machine. The experimental results showed that the shear strength increased when lower than ~0.07 wt% of MWCNTs were added in the composite solution. The increase of the shear strength was attributed to both the mechanical load transfer from the matrix to the MWCNTs and the high specific surface area of this material that increased the degree of crosslinking with other inorganic fillers in the formulation. However, a decrease in the adhesive shear strength was observed after more than ~0.07 wt% MWCNTs were added to the composite. The reason for this may be related to the high concentration of MWCNTs within the matrix leading to excessively high viscosity, dewetting of the substrate surfaces, and reduced bonding of MWCNTs with the matrix, thereby limiting the strength. SEM observation of the fracture surfaces for composite epoxy/sol–gel adhesive materials with 0.01 wt% MWCNTs showed a mixed interfacial/cohesive fracture mode. This fracture mode indicated strong links at the adhesive/substrate interface, and interaction between CNTs and the matrix was achieved; therefore, adhesion performance of the composite epoxy/sol–gel material to the substrate was improved. An increase of a strong peak related to the C–O bond at ~1733 cm−1 in the FTIR spectra was observed. This peak represented crosslinking between the CNT surface and the organosilica nanoparticles in the MWCNTs-doped composite adhesive. Raman spectroscopy was also used to identify MWCNTs within the adhesive material. The Raman spectra exhibit peaks at ~1275 cm−1 and in the range of ~1549–1590 cm−1. The former is the graphite G-band, while the latter is the diamond D-band. The D-band and G-band represent the C–C single bond and C=C double bond in carbon nanotubes, respectively.

Laser-Directed Assembly of Aligned Carbon Nanotubes in Three Dimensions for Multifunctional Device Fabrication.

Laser-directed assembly of multiwalled carbon nanotubes (MWNTs) in 3D space is investigated via a two-photon polymerization technique. MWNT-thiol-acrylate (MTA) composite resins are developed with high MWNT concentrations up to 0.2 wt%, over one order of magnitude higher than previously published work. Significantly enhanced electrical and mechanical properties of the 3D micro-/nanostructures are achieved. Microelectronic devices made of the MTA resins are demonstrated.

Properties characterisation of polycarbonate and multi‐walled carbon nanotubes composites prepared by solution technique

AbstractPolycarbonate (PC) and multi‐walled carbon nanotubes (MWNTs) composites were prepared by solution method where 0–20% w/w MWNTs were added into two types of PC solutions, i.e. a low and a high molecular weight solution. The composites were processed into plastic sheets using a compression moulding technique in order to study their mechanical, electrical, physical, and rheological properties. The results showed that addition of MWNTs at 1% w/w enhanced the tensile strength and modulus by up to 23 and 75%, respectively, and reduced their electrical resistivity significantly from being an insulator (1 × 1016 − 1 × 1017 Ω‐cm) to a semi‐conductor (8 × 108 Ω‐cm), indicating a percolation threshold. A slight improvement in the mechanical properties was observed at up to 4% w/w MWNTs; however, the volume resistivity remained unchanged. As the amount of MWNTs increased >4% w/w, the mechanical properties drastically deteriorated because of the MWNTs agglomerating and segregating onto the surfaces. The segregation of the agglomerates was also supported by the surface resistivity and shear viscosity results, which decreased as MWNTs increased. MWNTs were found to interact better with the low molecular weight PC matrix and produced more homogeneous composites. The studies of composite colour and MWNTs dispersion confirmed the findings of both mechanical and electrical properties. This research demonstrates the possibility of preparation of PC and MWNTs composites at high MWNTs concentrations, which can be very useful for a master batch process. © 2015 Curtin University of Technology and John Wiley & Sons, Ltd.

Investigation of cure kinetics in epoxy/multiwalled carbon nanotube nanocomposites

ABSTRACTWith the increased interest in thermoset resin nanocomposites, it is important to understand the effects of the material on nanoscale characteristics. In this study, a curing reaction of an epoxy resin, which contained 0.25, 0.50, or 1.00 wt % of multiwalled carbon nanotubes (MWCNTs), at different heating rates was monitored by differential scanning calorimetry; cure kinetics were also evaluated to establish a relationship between crosslinking (network formation) and mechanical properties. MWCNT concentrations above 0.25 wt % favored crosslinking formation and decreased the activation energy (Ea) in the curing reaction. Examination of the kinetic mechanism suggests that the MWCNT locally restricted the spatial volume and favored the formation of nodular morphology in the resin, especially for high MWCNT concentrations. The MWCNT exhibited some entanglement in the matrix, which hindered a more pronounced effect on the mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39857.

An evaluation of the impact of multiwalled carbon nanotubes on soil microbial community structure and functioning

This study evaluated the impacts of multiwalled carbon nanotubes (MWNTs) on microbial community composition and functioning in a sandy loam soil over 90d. We used test concentrations in the range of lower MWNT concentrations (10mg/kg) to extremely high MWNT concentrations (10,000mg/kg) as a worst case scenario. We observed no effects of MWNTs on soil respiration, enzymatic activities, and microbial community composition at 10, 100 and 1000mg/kg. However, increases in fungal fatty acid methyl ester markers were observed at the highest treatment. In addition, pyrosequencing demonstrated a decreased abundance of some bacterial genera like Derxia, Holophaga, Opitutus and Waddlia at the highest treatment while bacterial genera that are considered potential degraders of recalcitrant contaminants (such as polycyclic aromatic hydrocarbons) like Rhodococcus, Cellulomonas, Nocardioides and Pseudomonas increased. These results suggest a shift in soil microbial community composition to more tolerant microbial populations in the presence of extremely high MWNT concentrations. It is unlikely that the change observed at 10,000mg/kg is due to metal or carbon impurities as the MWNTs used in this study were of high purity. Given the need for wide-ranging data for regulation and risk assessment of nanomaterials, this study provides valuable data.

Biomembrane damage caused by exposure to multi-walled carbon nanotubes

Carbon nanotubes (CNTs) have potential as not only electrical materials but also biomedical devices. However, some findings have been reported indicating that the use of CNTs is accompanied by a risk of the development of certain diseases such as pulmonary fibrosis and pleura mesothelioma; and one of the reasons for this risk may be macrophage cell death. In the present study, to elucidate the mechanism of macrophage cell death by CNTs, we focused on biomembrane damage caused by multi-walled CNTs (MWCNTs). When the distribution of MWCNTs in RAW264 cells was observed under a light microscope, MWCNTs were located on the surface of the plasma membrane; and a portion of them seemed to stick into it. The acute cytotoxicity toward RAW264 cells was examined by performing the LDH cytotoxic test, and LDH release was detected after exposure to 100 µg/ml CNT. To examine the physical damage to biomembranes by CNT exposure, we conducted a calcein release assay using calcein-encapsulated liposomes. The results indicated that an increase in the permeability of the lipid bilayer was induced by MWCNTs. The present study thus demonstrated for the first time that a high concentration of MWCNTs was cytotoxic to macrophages and suggested that the direct physical perturbation of biomembranes by MWCNTs plays a role in this activity.

Synthesis and properties of amphiphilic block polymer functionalized multi-walled carbon nanotubes and nanocomposites

The grafting of poly(ethylene glycol)-block-polyacrylonitrile (PEG-b-PAN) amphiphilic block polymer onto multi-walled carbon nanotubes (MWCNTs) was achieved by combination of coupling reaction and redox radical polymerization. The chemical structure and yield of the resulting grafted polymer were characterized and confirmed by FT-IR and TGA. Transmission electron microscopy (TEM) images clearly indicated that the nanotubes were coated with a polymer layer. The concentrated DMF dispersions of MWCNT-g-(PEG-b-PAN) nanocomposite were stable for months, the viscoelasticity being monitored by rheometer. MWCNT-g-(PEG-b-PAN) hybrid nanocomposite membranes were fabricated by phase inversion in a wet process. The results showed that high concentration of MWCNTs could be dispersed in the polymer matrix. The morphology and surface hydrophilicity characteristics of the membrane could be controlled by the composition of MWCNT-g-(PEG-b-PAN) nanocomposite membrane.

Elucidation of the Reinforcing Mechanism in Carbon Nanotube/Rubber Nanocomposites

High-performance sealants using rubber composites containing multiwalled carbon nanotubes (MWNTs) were developed in order to probe and excavate oil in deeper wells. However, the stress-strain behavior and the reinforcing mechanism of highly concentrated MWNT/rubber composites subjected to large deformation remain largely unexplored. Here we report on the complete stress-strain relationships of MWNT/rubber composites under uniaxial tension before rupture, with a suggestion of a novel reinforcement effect of high concentration of MWNTs. A theoretical model is developed to understand the reinforcing mechanism and estimate the mechanical properties of MWNT/rubber composites under large deformation. We have demonstrated that persistence length and reorientation of MWNTs during stretch have a significant impact on mechanical properties, such as the modulus of the rubber composite. These results provide guidelines for developing MWNT-reinforced composites to achieve desired nonlinear and extreme mechanical performance for a wide range of applications.

Melt Dispersion and Electrospinning of Non‐Functionalized Multiwalled Carbon Nanotubes in Thermoplastic Polyurethane

Nanoscale fibers with embedded, aligned, and percolated non-functionalized multiwalled carbon nanotubes (MWCNTs) were fabricated through electrospinning dispersions based on melt-compounded thermoplastic polyurethane/MWCNT nanocomposite, with up to 10 wt.-% MWCNTs. Transmission electron microscopy indicated that the nanotubes were highly oriented and percolated throughout the fibers, even at high MWCNT concentrations. The coupling of efficient melt compounding with electrospinning eliminated the need for intensive surface functionalization or sonication of the MWCNTs, and the high aspect ratio as well as the electrical and mechanical properties of the nanotubes were retained. This method provides a more efficient technique to generate one-dimensional nanofibers with aligned MWCNTs.