Retention Of Multi-walled Carbon Nanotubes Research Articles

A study on retention of MWCNT in robocasted MWCNT-HAP scaffold structures using vacuum sintering technique and their characteristics

Bioceramic scaffolds are being widely employed in bone tissue engineering applications for their ability to interact with host tissues without inducing any toxicity. Additionally, bioceramics possess good biocompatibility, osteointegration, osteoinduction, and biodegradation characteristics. Hydroxyapatite (HAP) is one such bioceramic known to exhibit closeness to natural bone in terms of chemical composition. The present reports additive manufacturing of HAP and Multiwalled carbon nanotubes (MWCNTs) reinforced HAP scaffold structures for bone tissue engineering applications using the Robocasting technique. Carboxymethyl Cellulose (CMC) was employed as the polymeric binder in this study to prepare the highly viscous HAP and CNT-HAP slurry ideal for robocasting of the scaffold structures. Different percentages of MWCNT (0.5, 1 and 2 wt%) incorporated into the developed CNT-HAP scaffold structures and were vacuum sintered at 1000 °C for 15 min. Vacuum sintering was found to effectively prevent oxidation of MWCNT which is subjected to decomposition at temperatures above 400 or 500 °C in Oxygen atmosphere as per literature. Further, the retention of MWCNTs in the developed CNT-HAP structures post sintering was confirmed using FESEM imaging. The mechanical characterizations revealed that 0.5CNT-HAP structures exhibited highest compression strength (3.36 ± 0.67 MPa) in comparison to 1CNT-HAP and 2CNT-HAP structures. Also, the in vitro biological characterizations demonstrated that the developed CNT-HAP scaffold structures were cytocompatible and remained stable for about 35 days at 37 °C.

Non-monotonic contribution of nonionic surfactant on the retention of functionalized multi-walled carbon nanotubes in porous media

The concentration of nonionic surfactants like Triton X-100 (TX100) can influence the transport and fate of emerging contaminants (e.g., carbon nanotubes) in porous media, but limited research has previously addressed this issue. This study investigates the co-transport of functionalized multi-walled carbon nanotubes (MWCNTs) and various concentrations of TX100 in saturated quartz sand (QS). Batch experiments and molecular dynamics simulations were conducted to investigate the interactions between TX100 and MWCNTs. Results indicated that the concentration ratio of MWCNTs and TX100 strongly influences the dispersion of MWCNTs and interaction forces between MWCNTs and QS during the transport. Breakthrough curves of MWCNTs and TX100 and retention profiles of MWCNTs were determined and simulated in column studies. MWCNTs strongly enhanced the retention of TX100 in QS due to the high affinity of TX100 for MWCNTs. Conversely, the concentration of TX100 had a non-monotonic impact on MWCNT retention. The maximum transport of MWCNTs in the QS occurred at an input concentration of TX100 that was lower than the critical micelle concentration. This suggests that the relative importance of factors influencing MWCNTs changed with TX100 sorption. Results from interaction energy calculations and modeling of competitive blocking indicate that the predictive ability of interaction energy calculations and colloid filtration theory may be lost because TX100 mainly altered intermolecular forces between the MWCNT and porous media. This study provides new insights into the co-transport of surfactants and MWCNTs in porous media, which can be useful for environmental applications and risk management.

28-Day inhalation toxicity study with evaluation of lung deposition and retention of tangled multi-walled carbon nanotubes

Lung deposition and retention measurements are now required by the newly revised OECD inhalation toxicity testing guidelines 412 and 413 when evaluating the clearance and biopersistence of poorly soluble nanomaterials, such as multi-walled carbon nanotubes (MWCNTs). However, evaluating the lung deposition concentration is challenging with certain nanomaterials, such as carbon-based and iron-based nanomaterials, as it is difficult to differentiate them from endogenous elements. Therefore, the current 28-day inhalation toxicity study investigated the lung retention kinetics of tangled MWCNTs. Male Sprague Dawley rats were exposed to MWCNTs at 0, 0.257, 1.439, and 4.253 mg/m3 for 28 days (6 h/day, 5 days/week, 4 weeks). Thereafter, the rats were sacrificed at day 1, 7, and 28 post-exposure and the pulmonary inflammatory response evaluated by analyzing the bronchoalveolar lavage fluid. Plus, the blood biochemistry, hematology, and histopathology of the lungs were also examined. The lung deposition and retention of MWCNTs were determined based on the elemental carbon content in the lungs after tissue digestion. The number of polymorphonuclear cells and LDH concentration were both found to be significantly higher with the medium and high concentrations (1.439 and 4.253 mg/m3) and dose dependent. The estimated retention half-life for the high concentration (4.253 mg/m3) was about 35 days. The results of this study indicate that tangled MWCNTs seem to have a relatively shorter retention half-life when compared to previous reports on rigid MWCNTs, and the no-observed adverse effect level (NOAEL) for the tested tangled MWCNTs was 0.257 mg/m3 in a previous rat 28-day subacute inhalation toxicity study.

Co-transport of multi-walled carbon nanotubes and sodium dodecylbenzenesulfonate in chemically heterogeneous porous media

Multi-walled carbon nanotubes (MWCNTs) are increasing used in commercial applications and may be released into the environment with anionic surfactants, such as sodium dodecylbenzenesulfonate (SDBS), in sewer discharge. Little research has examined the transport, retention, and remobilization of MWCNTs in the presence or absence of SDBS in porous media with controlled chemical heterogeneity, and batch and column scale studies were therefore undertaken to address this gap in knowledge. The adsorption isotherms of SDBS on quartz sand (QS), goethite coated quartz sand (GQS), and MWCNTs were determined. Adsorption of SDBS (MWCNTs » GQS > QS) decreased zeta potentials for these materials, and produced a charge reversal for goethite. Transport of MWCNTs (5 mg L−1) dramatically decreased with an increase in the fraction of GQS from 0 to 0.1 in the absence of SDBS. Conversely, co-injection of SDBS (10 and 50 mg L−1) and MWCNTs radically increased the transport of MWCNTs when the GQS fraction was 0, 0.1, and 0.3, especially at a higher SDBS concentration, and altered the shape of retention profile. Mathematical modeling revealed that competitive blocking was not the dominant mechanism for the SDBS enhancement of MWCNT transport. Rather, SDBS sorption increased MWCNT transport by increasing electrostatic and/or steric interactions, or creating reversible interactions on rough surfaces. Sequential injection of pulses of MWCNTs and SDBS in sand (0.1 GQS fraction) indicated that SDBS could mobilize some of retained MWCNTs from the top to deeper sand layers, but only a small amount of released MWCNTs were recovered in the effluent. SDBS therefore had a much smaller influence on MWCNT transport in sequential injection than in co-injection, presumably because of a greater energy barrier to MWCNT release than retention. This research sheds novel insight on the roles of competitive blocking, chemical heterogeneity and nanoscale roughness, and injection sequence on MWCNT retention and release.

Do Goethite Surfaces Really Control the Transport and Retention of Multi-Walled Carbon Nanotubes in Chemically Heterogeneous Porous Media?

Transport and retention behavior of multi-walled carbon nanotubes (MWCNTs) was studied in mixtures of negatively charged quartz sand (QS) and positively charged goethite-coated sand (GQS) to assess the role of chemical heterogeneity. The linear equilibrium sorption model provided a good description of batch results, and the distribution coefficients (KD) drastically increased with the GQS fraction that was electrostatically favorable for retention. Similarly, retention of MWCNTs increased with the GQS fraction in packed column experiments. However, calculated values of KD on GQS were around 2 orders of magnitude smaller in batch than packed column experiments due to differences in lever arms associated with hydrodynamic and adhesive torques at microscopic roughness locations. Furthermore, the fraction of the sand surface area that was favorable for retention (Sf) was much smaller than the GQS fraction because nanoscale roughness produced shallow interactions that were susceptible to removal. These observations indicate that only a minor fraction of the GQS was favorable for MWCNT retention. These same observations held for several different sand sizes. Column breakthrough curves were always well described using an advective-dispersive transport model that included retention and blocking. However, depth-dependent retention also needed to be included to accurately describe the retention profile when the GQS fraction was small. Results from this research indicate that roughness primarily controlled the retention of MWCNTs, although goethite surfaces played an important secondary role.

Transport of Surface-modified Carbon Nanotubes through a Soil Column

Carbon nanotubes (CNTs) are widely manufactured nanoparticles, which are being utilized in a number of consumer products, such as sporting goods, electronics and biomedical applications. Due to their accelerating production and use, CNTs constitute a potential environmental risk if they are released to soil and groundwater systems. It is therefore essential to improve the current understanding of environmental fate and transport of CNTs. The transport and retention of CNTs in both natural and artificial media have been reported in literature, but the findings widely vary and are thus not conclusive. There are a number of physical and chemical parameters responsible for variation in retention and transport. In this study, a complete procedure of selected multiwalled carbon nanotubes (MWCNTs) is presented starting from their surface modification to a complete set of laboratory column experiments at critical physical and chemical scenarios. Results indicate that the stability of the commercially available MWCNTs are critical with their attached surface functional group which can also influence the transport and retention of MWCNT through the surrounding medium.

Transport of surface-modified carbon nanotubes through a soil column.

Carbon nanotubes (CNTs) are widely manufactured nanoparticles, which are being utilized in a number of consumer products, such as sporting goods, electronics and biomedical applications. Due to their accelerating production and use, CNTs constitute a potential environmental risk if they are released to soil and groundwater systems. It is therefore essential to improve the current understanding of environmental fate and transport of CNTs. The transport and retention of CNTs in both natural and artificial media have been reported in literature, but the findings widely vary and are thus not conclusive. There are a number of physical and chemical parameters responsible for variation in retention and transport. In this study, a complete procedure of selected multiwalled carbon nanotubes (MWCNTs) is presented starting from their surface modification to a complete set of laboratory column experiments at critical physical and chemical scenarios. Results indicate that the stability of the commercially available MWCNTs are critical with their attached surface functional group which can also influence the transport and retention of MWCNT through the surrounding medium.

Instillation versus inhalation of multiwalled carbon nanotubes: exposure-related health effects, clearance, and the role of particle characteristics.

Inhaled multiwalled carbon nanotubes (MWCNTs) may cause adverse pulmonary responses due to their nanoscale, fibrous morphology and/or biopersistance. This study tested multiple factors (dose, time, physicochemical characteristics, and administration method) shown to affect MWCNT toxicity with the hypothesis that these factors will influence significantly different responses upon MWCNT exposure. The study is unique in that (1) multiple administration methods were tested using particles from the same stock; (2) bulk MWCNT formulations had few differences (metal content, surface area/functionalization); and (3) MWCNT retention was quantified using a specialized approach for measuring unlabeled MWCNTs in rodent lungs. Male Sprague–Dawley rats were exposed to original (O), purified (P), and carboxylic acid functionalized (F) MWCNTs via intratracheal instillation and inhalation. Blood, bronchoalveolar lavage fluid (BALF), and lung tissues were collected at postexposure days 1 and 21 for quantifying biological responses and MWCNTs in lung tissues by programmed thermal analysis. At day 1, MWCNT instillation produced significant BALF neutrophilia and MWCNT-positive macrophages. Instilled O- and P-MWCNTs produced significant inflammation in lung tissues, which resolved by day 21 despite MWCNT retention. MWCNT inhalation produced no BALF neutrophilia and no significant histopathology past day 1. However, on days 1 and 21 postinhalation of nebulized MWCNTs, significantly increased numbers of MWCNT-positive macrophages were observed in BALF. Results suggest (1) MWCNTs produce transient inflammation if any despite persistence in the lungs; (2) instilled O-MWCNTs cause more inflammation than P- or F-MWCNTs; and (3) MWCNT suspension media produce strikingly different effects on physicochemical particle characteristics and pulmonary responses.

The effects of surfactants and solution chemistry on the transport of multiwalled carbon nanotubes in quartz sand-packed columns

The effect of different surfactants on the transport of multiwalled carbon nanotubes (MWCNTs) in quartz sand-packed columns was firstly investigated under various conditions. The stable plateau values (Cmax) of the breakthrough curves (BTCs), critical PVs (the number of pore volumes of infusions needed to reach the Cmax), maximum transport distances (Lmax), deposition rate coefficients (kd) and retention rates were calculated to compare the transport and retention of MWCNTs under various conditions. Stability of the MWCNT suspensions as a function of the influencing factors was examined to reveal the underlying mechanism of the MWCNT retention. Results showed that MWCNTs suspended by different surfactants presented different BTCs; the MWCNT transport increased with increasing sand size and MWCNT concentration; high flow velocity was favorable for the MWCNT transport, while high Ca2+ concentration and low pH were unfavorable for the transport; hetero-aggregation, straining and site blocking occurred during the transport.

Mobility of TX100 suspended multiwalled carbon nanotubes (MWCNTs) and the facilitated transport of phenanthrene in real soil columns

The transport behavior of TX100 suspended multiwalled carbon nanotubes (MWCNTs) through different soil columns as well as their effects on the mobility of phenanthrene was systematically studied. Results showed that the mobility of MWCNTs varied with soils, which was found to be correlated positively to the average soil particle diameters and soil sand contents, while correlated negatively to soil clay contents. The retention of MWCNTs on soil columns is most likely due to surface deposition and physical straining. Co-transport of phenanthrene with MWCNTs was tested in three selected soils (soil HB, DX and BJ), where MWCNTs could act as carriers of phenanthrene and enhance the mobility of phenanthrene in soils. However, during passing through the soil columns phenanthrene initially adsorbed onto MWCNTs could be partially “stripped” off. In soil with the lowest phenanthrene sorption affinity and highest water velocity (soil HB), only 8.5% phenanthrene was desorbed during transport, suggesting that a strong MWCNT-associated phenanthrene mobile may occur in this soil. More than 80% of phenanthrene was stripped off in soils with higher sorption affinity (soil DX and BJ), indicating the limitation of the co-transport of phenanthrene and MWCNTs in such soils.

Transport and retention of multi-walled carbon nanotubes in saturated porous media: Effects of input concentration and grain size

Water-saturated column experiments were conducted to investigate the effect of input concentration (Co) and sand grain size on the transport and retention of low concentrations (1, 0.01, and 0.005 mg L−1) of functionalized 14C-labeled multi-walled carbon nanotubes (MWCNT) under repulsive electrostatic conditions that were unfavorable for attachment. The breakthrough curves (BTCs) for MWCNT typically did not reach a plateau, but had an asymmetric shape that slowly increased during breakthrough. The retention profiles (RPs) were not exponential with distance, but rather exhibited a hyper-exponential shape with greater retention near the column inlet. The collected BTCs and RPs were simulated using a numerical model that accounted for both time- and depth-dependent blocking functions on the retention coefficient. For a given Co, the depth-dependent retention coefficient and the maximum solid phase concentration of MWCNT were both found to increase with decreasing grain size. These trends reflect greater MWCNT retention rates and a greater number of retention locations in the finer textured sand. The fraction of the injected MWCNT mass that was recovered in the effluent increased and the RPs became less hyper-exponential in shape with higher Co due to enhanced blocking/filling of retention locations. This concentration dependency of MWCNT transport increased with smaller grain size because of the effect of pore structure and MWCNT shape on MWCNT retention. In particular, MWCNT have a high aspect ratio and we hypothesize that solid phase MWCNT may create a porous network with enhanced ability to retain particles in smaller grain sized sand, especially at higher Co. Results demonstrate that model simulations of MWCNT transport and fate need to accurately account for observed behavior of both BTCs and RPs.

Fate of nanoparticles during life cycle of polymer nanocomposites

Nanoparticles are increasingly used in consumer and structural polymeric products to enhance a variety of properties. Under the influence of environmental factors (e.g., ultraviolet, moisture, temperature) and mechanical actions (e.g., scratching, vibrations, abrasion), nanoparticles could potentially release from the products and thus have negative effects on the environment, health and safety. The fate of nanoparticles in polymer nanocomposites during their exposure to UV environment has been investigated. Epoxy polymer containing multi-walled carbon nanotubes (MWCNTs) and silica nanoparticles were studied. Specially-designed cells containing nanocomposite specimens were irradiated with UV radiation between 295 nm and 400 nm. Chemical degradation, mass loss and surface morphology of the epoxy nanocomposites, and release of nanoparticles were measured. Epoxy containing MWCNTs exposed to UV radiation degraded at a much slower rate than the unfilled epoxy or the epoxy/nanosilica composite. Photodegradation of the matrix resulted in substantial accumulation of nanoparticles on the composite surfaces. Silica nanoparticles were found to release into the environment, but MWCNTs formed a dense network on the composite surface, with no evidence of release even after prolonged exposure. Conceptual models for silica nanoparticle release and MWCNT retention on the surface during UV exposure of nanocomposites are presented.