Removal of natural organic matter in water using functionalised carbon nanotube buckypaper

A simple, surfactant-free assembly process was used to prepare multi-wall carbon nanotube (CNT) buckypapers using a highly efficient purification, sonication, and filtration process. To achieve effective dispersion of CNT into ethanol, a minimum 5-min sonication time was required. Here, we fabricated a buckypaper with pore size of 41 ± 10 nm and porosity of 72.9% with a 10-min sonication. The as-prepared buckypaper was used as a membrane for humic acid (HA) removal from water. During purification process, carboxylic and hydroxylic functional groups were introduced onto the CNT surface. The functional groups increased the hydrophilicity of the CNTs and improved the removal efficiency of HA by the buckypaper. The buckypaper prepared from purified CNTs exhibited excellent removal of HA (>93%) and a long lifetime for filtration.     

Mechanical and electrical properties of carbon nanotube buckypaper reinforced silicon carbide nanocomposites

The nanocomposite was produced via phenolic resin infiltrating into a carbon nanotube (CNT) buckypaper preform containing B₄C fillers and amorphous Si particles followed by an in-situ reaction between resin-derived carbon and Si to form SiC matrix. The buckypaper preform combined with the in-situ reaction avoided the phase segregation and increased significantly the volume fraction of CNTs. The nanocomposites prepared by this new process were dense with the open porosities less than 6%. A suitable CNT–SiC bonding was achieved by creating a B₄C modified interphase layer between CNTs and SiC. The hardness increased from 2.83 to 8.58 GPa, and the indentation fracture toughness was estimated to increase from 2.80 to 9.96 MPa m^1/2, respectively, by the reinforcing effect of B₄C. These nanocomposites became much more electrically conductive with high loading level of CNTs. The in-plane electrical resistivity decreased from 124 to 74.4 μΩ m by introducing B₄C fillers.     

Hierarchical carbon nanotube membrane with high packing density and tunable porous structure for high voltage supercapacitors

We reported the fabrication of a hierarchical carbon nanotube (CNT) membrane by using the 90% granulated double- or triple-walled CNTs and 10% 100 μm long multiwalled CNTs as the linker. The membrane with packing density of 420 kg/m³, excellent electrical conductance and good mechanical strength, functioned as both the electrode and current collector and allowed the weight ratio of CNTs increased up to 45–50% based on the weight of CNT, electrolyte and separator. The granulated double or triple walled CNTs, by the aggregation at high temperature etching using CO₂, simultaneously exhibited high surface area and tunable pore structure and high pore volume, and were favorable for the ion transport of organic electrolyte, due to the effect of opening cap or side wall by the CO₂. The CNT membrane electrode, exhibited the capacitance of 57.9 F/g and the energy density of 35 W h/kg, as operated at 4 V.     

Electromagnetic interference shielding properties of polymer-grafted carbon nanotube composites with high electrical resistance

Poly(methyl methacrylate) (PMMA)-grafted multiwalled CNTs were prepared, and then dispersed into additional PMMA matrix, yielding highly insulated PMMA–CNT composites. The volume resistivity of PMMA–CNT was as high as 1.3 × 10¹⁵ Ω cm even at 7.3 wt% of the CNT. The individual CNTs electrically-isolated by the grafted PMMA chains in PMMA–CNT transmitted electromagnetic (EM) waves in the frequency range of 0.001–1 GHz, whereas the percolated CNTs in a conventional composite prepared by blending PMMA with the pristine CNTs strongly shielded the EM waves. This result suggests that the intrinsic conductivity of the CNT itself in PMMA–CNT does not contribute to the EM interference (EMI) shielding in the frequency range of 0.001–1 GHz. On the other hand, PMMA–CNT exhibited EMI shielding at the higher frequency range than 1 GHz because the dielectric loss of the CNT itself was rapidly increased over 1 GHz. At 110 GHz, PMMA–CNT with 7.3 wt% of the CNT had EMI SE of as high as 29 dB (0.57 mm thickness), though is slightly lower than that of the percolated conventional composite (35 dB). Thus, it is demonstrated that the highly insulated PMMA–CNT has the good EMI shielding at extremely high frequency range (30–300 GHz).     

Fabrication and mechanical properties of carbon nanotube yarns spun from ultra-long multi-walled carbon nanotube arrays

Carbon nanotube (CNT) yarns have been fabricated by dry spinning from vertically aligned millimeter-long multi-walled carbon nanotube (MWCNT) arrays and their mechanical properties have been studied. By using 2-mm long CNTs and densely packing of CNT yarns we achieved a tensile strength of 1068 MPa and Young’s modulus of 55 GPa. Our CNT yarns have diameters of tens of micrometers being easy to handle and possessing high effective load capacity up to 0.81 N. We discuss mechanical properties of CNT yarns spun from relatively thick MWCNT along with a detailed analysis of various post-spin processes and their effect on CNT yarns characteristics. Also, we point out the difference between mechanical properties of dry spun CNT yarns and conventional spun textile yarns.     

Preparation-microstructure-property relationships in double-walled carbon nanotubes/alumina composites

Double-walled carbon nanotube/alumina composite powders with low carbon contents (2–3 wt.%) are prepared using three different methods and densified by spark plasma sintering. The mechanical properties and electrical conductivity are investigated and correlated with the microstructure of the dense materials. Samples prepared by in situ synthesis of carbon nanotubes (CNTs) in impregnated submicronic alumina are highly homogeneous and present the higher electrical conductivity (2.2–3.5 S cm⁻¹) but carbon films at grain boundaries induce a poor cohesion of the materials. Composites prepared by mixing using moderate sonication of as-prepared double-walled CNTs and lyophilisation, with little damage to the CNTs, have a fracture strength higher (+30%) and a fracture toughness similar (5.6 vs 5.4   MPa m^1/2) to alumina with a similar submicronic grain size. This is correlated with crack-bridging by CNTs on a large scale, despite a lack of homogeneity of the CNT distribution.     

On the manufacturing and electrical and mechanical properties of ultra-high wt.% fraction aligned MWCNT and randomly oriented CNT epoxy composites

The effect of CNT orientation on electrical and mechanical properties is presented on the example of an ultra-high filler loaded multi-walled carbon nanotube (68 wt.% MWCNTs) epoxy-based nanocomposite. A novel manufacturing method based on hot-press infiltration through a semi-permeable membrane allows to obtain both, nanocomposites with aligned and randomly oriented CNTs (APNCs and RPNCs) over a broad filler loading range of ≈10–68 wt.%. APNCs are based on low-defected, mm-long aligned MWCNT arrays grown in chemical vapour deposition (CVD) process. Electrical conductivity and mechanical properties were measured parallel and perpendicular to the direction of CNTs. RPNCs are based on both, aligned mm-long MWCNTs and randomly oriented commercial μm-long and entangled MWCNTs (Baytube C150P, and exemplarily Arkema Graphistrength C100). The piezoresistive strain sensing capability of these high-wt.% APNCs and RPNCs had been investigated towards the influence of CNT orientations. For the highest CNT fraction of 68 wt.% of unidirectional aligned CNTs a Young’s modulus of E_|| ≈ 36 GPa and maximum electrical conductivity of σ_|| ≈ 37·10⁴ S/m were achieved.     

Improved mechanical performance of solution-processed MWCNT/Ag nanoparticle composite films with oxygen-pressure-controlled annealing

A method for the synthesis of solution process-based MWCNT/Ag nanoparticle composite thin films as electrode or interconnect materials for flexible electronic devices is presented. The method produces homogeneously-dispersed CNT networks and increases the density of the Ag matrix, which are major factors in determining the mechanical performance of CNT/Ag films. By introducing nanometer-sized Ag particles as a matrix material, the agglomeration of CNTs is suppressed. In addition, the generation of pores during the synthesis procedure is effectively restrained by oxygen-pressure-controlled annealing. The elastic modulus of the pristine Ag films was observed to increase by 34% by adding 5 wt% CNTs. An improvement in the fatigue resistance of the CNTs under cyclic tensile deformation was confirmed. The normalized resistance change ((R ? R_o)/R_o) of the Ag films containing 5 wt% CNTs after fatigue testing was reduced by about 27% compared to that of the pristine Ag films. For industrial application the process has the advantage of relatively low-temperature processing without any high pressure compaction compared to the conventional powder metallurgy techniques normally used.     

One-step synthesis of a graphene-carbon nanotube hybrid decorated by magnetic nanoparticles

Graphene-carbon nanotube (G-CNT) hybrids were synthesized by a one-step chemical vapor deposition process using a mixed catalyst of MgO and Fe/MgO. MgO layers acted as templates for the growth of graphene, and Fe particles on the MgO layers catalyzed the growth of single or double-walled CNTs. The G-CNT hybrids had porous structures with hierarchical pore distributions due to the composition of graphene with CNT network. Superparamagnetism with a saturation magnetization of 2.7 emu/g was found in the G-CNT hybrids due to the existence of Fe₃C nanoparticles of size ～3 nm. The graphene to CNT ratio was conveniently changed by varying the MgO to Fe/MgO ratio, as characterized by Raman analysis and specific surface area measurements. Furthermore, a simplified synthesis of G-CNT hybrids was demonstrated by using MgO supported Fe or Ni catalysts with a low metal concentration.     

Multifunctional bioceramic-based composites reinforced with silica-coated carbon nanotube core-shell structures

Carbon nanotube (CNT) possesses eminent mechanical properties and has been widely utilized to toughen bioceramics. Major challenges associated with CNT-reinforced bioceramics include the inhomogeneous dispersion of CNTs and the insufficient interfacial strength between the two phases. To address such issues, this research describes the first use of silica-coated CNT (S-CNT) core-shell structures to reinforce bioceramics using hydroxyapatite (HA) as a representative matrix. HA-based composites with 0.1–2 wt% S-CNT are sintered by spark plasma sintering to investigate their mechanical and biological properties. It is found that when 1 wt% raw CNT (R-CNT) is added, very limited increases in fracture toughness (K_IC) is observed. By contrast, the incorporation of 1 wt% S-CNT increased the K_IC of HA by 101.7%. This is attributed to more homogeneously dispersed fillers and stronger interfacial strengths. MG63 cells cultured on the 1 wt% S-CNT/HA pellets are found to proliferate faster and possess significantly higher alkaline phosphatase activities than those grown on the HA compacts reinforced with 1 wt% R-CNT, probably by virtue of the released Si ions from the SiO2 shell. Therefore, the S-CNT core-shell structures can improve both mechanical and biological properties of HA more effectively than the conventionally used R-CNTs. The current study also presents a novel and effective approach to the enhancement of many other biomedical and structural materials through S-CNT incorporation.     

Growth of carbon nanotube forests between a bi-metallic catalyst layer and a SiO2 substrate to form a self-assembled carbon–metal heterostructure

A special nanostructure was formed by the growth of carbon nanotubes (CNTs) between a substrate and a thin bi-metallic catalyst layer using a thermal chemical vapor deposition process. The catalyst layer is composed of adjacently disposed Cr and Ni phases formed prior to CNT growth. The Cr/Ni layer serves as a bi-metallic catalyst layer, which is pushed away from the substrate as a thin and continuous nanomembrane with the growth of CNTs. The self-assembled CNT–catalyst heterostructure possesses a smooth surface (RMS = 2.9 nm) with a metallic shine. Directly interlinked to the Cr/Ni layer, dense and vertically aligned multi-walled CNTs are found. Compared to conventional CNT films, the structure has significant advantages for CNT integration. From technology point of view, the structure allows further processing without impact on the CNTs as well as transfer of pristine vertically aligned CNTs to arbitrary substrates. Moreover, the as-grown CNT films provide an interface ideal for further electrical, thermal and mechanical contacting of CNT films. We present structural investigations of this special CNT–metal heterostructure. Furthermore, we discuss possible interface mechanisms during catalyst layer formation and CNT growth.     

Effect of particle size,heating rate and CNT addition on densification,microstructure and mechanical properties of B4C ceramics

Monolithic B₄C ceramics and B₄C–CNT composites were prepared by spark plasma sintering (SPS). The influence of particle size, heating rate, and CNT addition on sintering behavior, microstructure and mechanical properties were studied. Two different B₄C powders were used to examine the effect of particle size. The effect of heating rate on monolithic B₄C was investigated by applying three different heating rates (75, 150 and 225 °C/min). Moreover, in order to evaluate the effect of CNT addition, B₄C–CNT (0.5–3 mass%) composites were also produced. Fully dense monolithic B₄C ceramics were obtained by using heating rate of 75 °C/min. Vickers hardness value increased with increasing CNT content, and B₄C–CNT composite with 3 mass% CNTs had the highest hardness value of 32.8 GPa. Addition of CNTs and increase in heating rate had a positive effect on the fracture toughness and the highest fracture toughness value, 5.9 MPa m^1/2, was achieved in composite with 3 mass% CNTs.     

Processing and properties of sol gel derived alumina–carbon nano tube composites

High purity alumina–carbon nano tube (CNT) composites were prepared by an aqueous sol–gel processing route. CNTs were dispersed in alumina sol containing appropriate amount of MgO precursor. Aqueous slurry of alumina was seeded into the sol followed by gelation, drying and calcination at 1000 °C for 1 h. The calcined powder consisting of alumina-coated CNTs and alumina was milled, sieved, dried, pressed and pressureless sintered at 1400–1600 °C for 1 h in nitrogen atmosphere. Sintered samples were further isostatically hot pressed at 1300 °C and the properties were compared with the pressureless sintered samples. Phase formation was followed by XRD study, CNT retention was confirmed by Raman studies and the samples were further characterized for mechanical and microstructural properties.     

Overcoming the quality–quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion–extraction process

Dispersion-printing processes are essential for the fabrication of various devices using carbon nanotubes (CNTs). Insufficient dispersion results in CNT aggregates, while excessive dispersion results in the shortening of individual CNTs. To overcome this tradeoff, we propose here a repetitive dispersion–extraction process for CNTs. Long-duration ultrasonication (for 100 min) produced an aqueous dispersion of CNTs with sodium dodecylbenzene sulfonate with a high yield of 64%, but with short CNT lengths (a few μm), and poor conductivity in the printed films (∼450 S cm⁻¹). Short-duration ultrasonication (for 3 min) yielded a CNT dispersion with a very small yield of 2.4%, but with long CNTs (up to 20–40 μm), and improved conductivity in the printed films (2200 S cm⁻¹). The remaining sediment was used for the next cycle after the addition of the surfactant solution. 90% of the CNT aggregates were converted into conductive CNT films within 13 cycles (i.e., within 39 min), demonstrating the improved conductivity and reduced energy/time requirements for ultrasonication. CNT lines with conductivities of 1400–2300 S cm⁻¹ without doping and sub-100 μm width, and uniform CNT films with 80% optical transmittance and 50 Ω/sq sheet resistance with nitric acid doping were obtained on polyethylene terephthalate films.     

Influence of wall number and surface functionalization of carbon nanotubes on their antioxidant behavior in high density polyethylene

Carbon nanotubes (CNTs) are extensively incorporated as reinforcement into polymeric materials due to their extraordinary properties. The antioxidant ability of CNTs in high density polyethylene (HDPE) was studied. Single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), and hydroxylated multi-walled carbon nanotubes (MWCNTs-OH) were involved to investigate the influence of wall number and surface functionalization of CNTs on their antioxidant behavior in HDPE. Based on measurements of the oxidation induction temperature and oxidation induction time of CNT/HDPE composites, it is found that the antioxidant ability of the three kinds of CNTs is in the following order: MWCNTs-OH > MWCNTs > SWCNTs. The antioxidant ability and mechanism of CNTs are further examined by electron spin resonance spectra and Raman spectra. It is observed that the antioxidant behavior of CNTs obeys a free radical scavenging mechanism. The order of the radical scavenging efficiency and the defect concentration for CNTs are in good agreement with that of their antioxidant ability in HDPE. With more walls and surface hydroxyl groups, the CNTs have more structural defects and exhibit higher antioxidant ability. The study raises the possibility that CNTs can improve antioxidant properties as well as mechanical properties of polymer matrix.     

Fabrication and toughening behavior of carbon nanotube (CNT) scaffold reinforced SiBCN ceramic composites with high CNT loading

Uniform dispersion, high loading and three-dimensional (3D) continuous network of carbon nanotube (CNT) are desired for high-performance nanocomposites to fully utilize the superior strength and toughness of CNTs. In this work, monolithic CNTs/SiBCN composites with high CNT loading (10 wt% and 20 wt%) were prepared from 3D scaffold-like CNT cottons and a liquid polyborosilazane (PBSZ) precursor through precursor infiltration and pyrolysis process. The 3D CNT scaffold in the nanocomposite can function as passive filler and gas path to ensure formation of monolithic bulks. Moreover, direct infiltration of PBSZ into the pores among CNT cotton can hinder agglomeration of CNTs and localize CNTs at the original sites, guarantee good alignment and high CNT concentration in the final nanocomposite. This highly concentrated 3D CNT reinforcement in the nanocomposite shows unique resistance to cracking under external stress related to the complex fracture behavior of CNT bundles during the cracking formation and extension process (including CNT bridging, aligning, pulling out and then breaking), which more favors for absorbing energies and enhance toughness of the ceramic composites.     

Enhancing buckypaper conductivity through co-deposition with copper nanowires

Buckypapers, the thin sheets made from an aggregate of carbon nanotubes (CNTs), have demonstrated promising electrical and thermal conductivities. However, the high in-plane to perpendicular anisotropy makes its application as thermal interface materials difficult. In order to increase the perpendicular electrical and thermal conductivities, copper nanowires (Cu NWs) were introduced into buckypapers. The Cu NWs stuck into the empty spaces between CNTs, connected them perpendicularly, and even induced a certain perpendicular CNT alignment. The electrical conductivity increased continuously with increasing the Cu content, while the smallest anisotropy was observed at the 50 wt.% Cu filling because an in-plane Cu network formed and improved much more the in-plane conductivity above this filling. On the contrary, as CNTs are more thermally conducting than Cu, the loading of Cu NWs over 50 wt.% decreased the thermal conductivity. Our measurement showed a high perpendicular conductivity of 10.1 W/m K at the 50 wt.% loading, more than quadruple and double as compared with the ones for a pure buckypaper and the one filled with 67–75 wt.% Cu NWs.     

The hierarchical structure and properties of multifunctional carbon nanotube fibre composites

The axial mechanical, electrical and thermal properties of carbon nanotubes (CNTs) can be exploited macroscopically by assembling them parallel to each other into a fibre during their synthesis by chemical vapour deposition. Multifunctional composites with high volume fraction of CNT fibres are then made by direct polymer infiltration of an array of aligned fibres. The fibres have a very high surface area, causing the polymer to infiltrate them and resulting in a hierarchical composite structure. The electrical and thermal conductivities of CNT/epoxy composites are shown to be superior to those of equivalent specimens with T300 carbon fibre (CF) which is widely used in industry. From measurements of longitudinal coefficient of thermal expansion (CTE) of the composites we show that the CTE of CNT fibres is approximately ?1.6 × 10^?6 K^?1, similar to in-plane graphite. The combination of electrical, thermal and mechanical properties of CNT fibre composites demonstrates their potential for multifunctionality.     

Hydrogen-storage properties of MgH2–10Ni–2NaAlH4–2Ti–2CNT milled in a planetary ball mill under H2

A sample with a composition of 84 wt% MgH₂–10 wt% Ni–2 wt% NaAlH₄–2 wt% Ti–2 wt% CNT (named MgH₂–10Ni–2NaAlH₄–2Ti–2CNT) was prepared by milling in a planetary ball mill under H₂. Activation of the sample was not required. At the first cycle, the sample absorbed 3.75 wt% H for 10 min, and 4.17 wt% H for 60 min at 593 K under 12 bar H₂. Reactive mechanical grinding of Mg with Ni, NaAlH₄, Ti, and CNT is thought to create defects on the surface and in the interior of Mg, as well as to reduce Mg particle size.     

High performance carbon nanotube spun yarns from a crosslinked network

We report a new method to create covalent crosslinks between carbon nanotubes (CNTs) with reduced intertube and interbundle spaces, for improving the mechanical properties of CNT spun yarns. This is achieved through the pretreatment of a CNT yarn with 4-carboxybenzenediazonium tetrafluoroborate to form reactive carboxyphenyl groups on the CNT sidewalls. These carboxyphenyl groups are then reacted with a multifunctional crosslinker hexa(methoxymethyl) melamine, leading to a highly crosslinked network within the yarn. The CNT yarns were characterized by X-ray photoelectron spectroscopy, focused ion beam scanning electron microscope, and also assessed for their mechanical properties. The results showed that the method developed effectively improved mechanical properties of CNT yarns: we are able to produce CNT yarns with a tensile strength up to 2.5 GPa and Young’s modulus 121 GPa.