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The ever-increasing demand for materials to have superior properties and satisfy functions in the field of soft robotics and beyond has resulted in the advent of the new field of four-dimensional (4D) printing. The ability of these materials to respond to various stimuli inspires novel applications and opens several research possibilities. In this work, we report on the 4D printing of one such Shape Memory Polymer (SMP) tBA-co-DEGDA (tert-Butyl Acrylate with diethylene glycol diacrylate). The novelty lies in establishing the relationship between the various characteristic properties (tensile stress, surface roughness, recovery time, strain fixity, and glass transition temperature) concerning the fact that the print parameters of the laser pulse frequency and print speed are governed in the micro-stereolithography (Micro SLA) method. It is found that the sample printed with a speed of 90 mm/s and 110 pulses/s possessed the best batch of properties, with shape fixity percentages of about 86.3% and recovery times as low as 6.95 s. The samples built using the optimal parameters are further subjected to the addition of graphene nanoparticles, which further enhances all the mechanical and surface properties. It has been observed that the addition of 0.3 wt.% of graphene nanoparticles provides the best results.

The human activity of heating homes contributes a significant amount of CO2 in the total of the UK Green House Gases and the process of retrofitting residential stock and equipping new dwellings with lower and carbon neutral technologies could be complex, costly and physically challenging. This paper investigates the feasibility of a composite mixture of carbon nanotubes (CNT) and graphene material applied as a printed layer to the underside of a cementitious flooring substrate, acting as a radiant underfloor heater. Screening sample tests confirm instant radiant heating at low DC voltages with remarkably low conduction heat losses through the substrate.

We report on the development of a method of formation of free-standing gold-carbon nanotube (CNT) composites. It is based on a quick and simple decoration of CNT films with the application of chloroauric aqueous solution. Flexible and conductive macroassemblies of any size and shape can be created with ease. Addition of as little as 1% of Au by weight allowed for reduction of resistance by more than a quarter. Higher Au doping resulted in further decrease of resistance, but not so significant. From the practical point of view, these composites are a new type of materials with high electrical conductivity, but also offer resistance to corrosion.

Carbon nanotubes (CNT) fibres were printed from liquid suspension. The resulting fibres are highly conductive, with conductivity close to the one of standard CNT fibres, flexible and very versatile. The printed fibres are comparable to fibres that can be gained from direct spinning, carpet spinning and spinning from superacids, but offer broader range of composition and are simpler and safer to produce as no high-temperature equipment and dangerous chemicals need to be used. Any CNT material can be implemented, allowing the use of a variety of CNT structures, different densities of the fibres and various shapes for the final product. Keywords: Carbon nanotubes, Electrical conductivity, Macroassemblies, Fibre, Tape

In this study we examine multiwall carbon nanotube (MWCNT) based nanosystems i.e. aligned MWCNT matrices, as potential scaffolds for cell growth and tissue engineering. We present the effect of samples purification and surface modification on the viability, adhesiveness and morphology of human normal gingival fibroblasts (HGF-1) and human osteosarcoma (U2OS) cell lines. We employ spectroscopic and analytical techniques (Scanning Electron Microscopy, Thermal Gravimetric Analysis, Atomic Force Microscopy, Raman and Fourier Transform Infrared Absorption Spectroscopy and Confocal Microscopy) in order to characterize the obtained structures. Furthermore, we analyze the expression level of selected cell adhesion-related genes by the quantitative real-time (qRT-PCR) method and the cell viability for MWCNT powders. We show that the surface structure of MWCNTs carpets contributes to the adhesion of cells. Additionally, we report the increased expression level of integrin, talin and fibronectin, proteins which are involved in cell attachment. We speculate that carbon nanotube based materials can be consider as potential candidates for biomedical purposes and as a biocompatible scaffold for cell growth.

Working towards improvement of the electrical performance of carbon fibre (CF) reinforced polymer composites used in aircrafts, we have developed new routes of production of hybrid carbon nanotube (CNT)/CF epoxy composites. It was shown that the use of CNT films produced via one-step chemical vapour deposition (CVD) based method and in-process control of films morphology combined with standard vacuum bagging based manufacture of the composites results in very good electrical performance of the final material, delivering high potential for lightning strike related applications including electromagnetic interference (EMI) shielding and static dissipation for the composite components used in aerospace and transport sector. Simultaneously, the process is much simpler, inexpensive and easy to upscale than previously proposed methods.

Copper–CNT (carbon nanotube) composite materials are promising alternatives to conventional conductors in applications ranging from interconnects in microelectronics to electrical cabling in aircraft and vehicles. Unfortunately, exploiting the full potential of these composites is difficult due to the poor Cu–CNT electro-mechanical interface. We demonstrate through large-scale ab initio calculations and sonication experiments that this problem can be addressed by CNT surface modification. Our calculations show that covalent functionalization of CNTs below 6.7 at% significantly improves Cu–CNT wetting and the mechanical properties of the composite. Oxidative pre-treatment of CNTs enhances the Young's modulus of the composite by nearly a factor 3 above that of pure Cu, whereas amination slightly improves the electrical current density with respect to the unmodified Cu–CNT system in the high bias regime. However, only nitrogen doping can effectively improve both the mechanical and electrical properties of the composite. As the experiments show, consistent with the calculations, substitutional doping with nitrogen effectively improves adhesion of the CNT to the Cu matrix. We also predict an improvement in the mechanical properties for the composite containing doped double-wall CNTs. Moreover, the calculations indicate that the presence of nitrogen dopants almost doubles locally the transmission through the nanotube and reduces the back scattering in the Cu matrix around the CNT. The computed electrical conductance of N-doped Cu–CNT “carpets” exceeds that of an undoped system by ∼160%.

Electrochemical deposition of copper on a carbon nanotube (CNT) fiber from a copper sulfate – sulfuric acid bath was studied in order to produce a carbon nanotube-copper composite wire. The high resistivity of the aerogel-spun fiber causes a non-uniform current distribution during deposition, which results in a drastic drop in the copper nuclei population density as sufficient overpotential is not available beyond a certain distance from the current feed point. Copper was found to fill the pores between CNT bundles from Focused Ion Beam (FIB) cut cross-sections confirming that aqueous based electrolytes can fill micropores between as-spun CNTs in a fiber network. The speed at which copper grows on the fiber surface was identified at ca. 0.08 mm/s with 1 mA applied current. The copper cladding showed columnar growth with a grain size an order of magnitude higher than the CNT-Cu region. The resulting composite was found to have specific conductivity similar to that of pure copper i.e. 98% of copper with 0.2 w-% of CNT, exhibiting a ninefold increase from the pure CNT fiber. Self-annealing was shown to decrease the resistance of the composite.

In this work, functionalized Multiwall Carbon Nanotubes of specified length and containing well-defined iron particles (O-MWCNT/Fe) were prepared. A significant enhancement in contrast in Magnetic Resonance Imaging was found for the investigated composites. The magnetic characterization revealed the ferromagnetic nature of iron particles embedded within O-MWCNTs. The enhancement of the 1 H spin–spin relaxation time of MRI scans using hydrophilic O-MWCNT/Fe as potential contrast agents was estimated for selected dispersive media. Moreover, the cytotoxicity of the hybrids was studied in two cell lines, i.e. cancer cells (HeLa) and fibroblasts (GM07492). The intracellular impact of O-MWCNT/Fes in HeLa cells was observed after staining of selected organelles (nuclei and mitochondria). Significant changes in cell morphology were found for water soluble MWCNT/Fes with diameters above 30 nm.

Carbon nanotube fibres are a new class of materials highly promising for many electrical/electronic applications. The range of applications could be extended through the modification of their electrical transport properties by inclusions of foreign materials. However, the changes in electrical transport are often difficult to assess. Here, we propose that the analysis of resistance–temperature dependencies of modified fibres supported by a recently developed theoretical model may aid research in this area and accelerate real life applications of the fibres.

The process of conjugated polymer deposition on the surface of horizontally aligned multi-walled carbon nanotube, HA-CNT, electrode is described. Poly(3,4-ethylenedioxythiophene), PEDOT, was grown electrochemically under variable conditions in both aqueous and non-aqueous solutions of selected electrolytes. It is shown that the mechanism of nucleation highly depends on the reaction environment. The presence of a surfactant or non-aqueous medium favors the process of progressive nucleation in which the polymer growth is uniform and a homogeneous film of PEDOT is formed. It is demonstrated that the conditions make it is possible to cover the outer walls of individual HA-CNTs instead of forming thick polymer layer. The application of overpotential is proven to be a necessary condition to generate radical cations and cause relatively fast growth of polymer layer.

The electrical transport of a carbon nanotube assembly is determined by its morphology and composition. These vary with the assembly production processes and post-process treatments applied. Here, we present the study of the electrical – structural dependence of wire like assemblies of carbon nanotubes i.e. carbon nanotube fibres produced via floating catalyst chemical vapour deposition processes. We propose that the analysis of resistance – temperature characteristics of the fibres provides vast amount of information for the assessment of the quality of the fibres and thus the efficacy of fibre production and post-production processes. To aid qualitative and quantitative analysis of the experimental results we propose a new universal model which allows the fitting of experimental data in the full range of temperatures and a straightforward comparison of the recorded characteristics.

Improving the interface between copper and carbon nanotubes (CNTs) offers a straightforward strategy for the effective manufacturing and utilisation of Cu–CNT composite material that could be used in various industries including microelectronics, aerospace and transportation. Motivated by a combination of structural and electrical measurements on Cu–M–CNT bimetal systems (M = Ni, Cr) we show, using first principles calculations, that the conductance of this composite can exceed that of a pure Cu–CNT system and that the current density can even reach 1011 A cm−2. The results show that the proper choice of alloying element (M) and type of contact facilitate the fabrication of ultra-conductive Cu–M–CNT systems by creating a favourable interface geometry, increasing the interface electronic density of states and reducing the contact resistance. In particular, a small concentration of Ni between the Cu matrix and the CNT using either an “end contact” and or a “dot contact” can significantly improve the electrical performance of the composite. Furthermore the predicted conductance of Ni-doped Cu–CNT “carpets” exceeds that of an undoped system by ∼200%. Cr is shown to improve CNT integration and composite conductance over a wide temperature range while Al, at low voltages, can enhance the conductance beyond that of Cr.

We have demonstrated fire-retardancy properties of a polymer matrix-free CNT film for the first time. As compared with classical fire-retardant materials such as Kevlar, Twaron or Nomex, the CNT film showed a spectrum of advantages. The material is lightweight, flexible and well-adherent to even the most complicated shapes. The results have showed that by using CNTs for fire-retardancy we can extend the operational time almost two-fold, what makes CNTs a much better protection than the solutions employed nowadays. We believe that among other great properties of CNT, their macroscopic assemblies such as CNT films show significant potential for becoming a fire protective coating, which exhibits high performance in not sustaining fire.

Carbon nanotubes are very promising materials for many electrical and electronic application. Particularly, it is expected that macroscopic assemblies made purely of carbon nanotubes may form highly efficient and reliable electrical conductors for the next generation of electrical wires. It has already been demonstrated that wire-like nanotube assemblies—carbon nanotube fibres can successfully work as electrical wires, however, their performance needs further research and development. This paper presents the possible method of enhancement of electrical conductivity and current-carrying capacity of the carbon nanotube fibres via incorporation of silver nanoparticles into the nanotube network and formation of a hybrid carbon nanotube fibre–silver conductor.

Aligned carbon nanotube (CNT) polymer composites are envisioned as the next-generation composite materials for a wide range of applications. In this work, we investigate the erosive wear behavior of epoxy matrix composites reinforced with both randomly dispersed and aligned carbon nanotube (CNT) arrays. The aligned CNT composites are prepared in two different configurations, where the sidewalls and ends of nanotubes are exposed to the composite surface. Results have shown that the composite with vertically aligned CNT-arrays exhibits superior erosive wear resistance compared to any of the other types of composites, and the erosion rate reaches a similar performance level to that of carbon steel at 20° impingement angle. The erosive wear mechanism of this type of composite, at various impingement angles, is studied by Scanning Electron Microscopy (SEM). We report that the erosive wear performance shows strong dependence on the alignment geometries of CNTs within the epoxy matrix under identical nanotube loading fractions. Correlations between the eroded surface roughness and the erosion rates of the CNT composites are studied by surface profilometry. This work demonstrates methods to fabricate CNT based polymer composites with high loading fractions of the filler, alignment control of nanotubes and optimized erosive wear properties.

We determine the three-dimensional structure of melt-mixed carbon nanotube (CNT) networks in an amorphous polymer matrix via confocal microscopy and image analysis. We find that the CNT networks consist of ramified clusters whose size distribution scales with cluster mass according to exponents typical of percolating systems. Remarkably, these scaling relationships hold over a wide range of concentrations, processing operations (squeezing, shearing, annealing) and subsequent electrical conductivity levels. Our results suggest that the power law scaling of cluster mass with size and frequency might be an important principle governing multi-wall carbon nanotube (MWCNT) structure in processed composites. We suggest that subtle changes in MWCNT-polymer interface structure may play a significant role in composite electrical direct current DC conductivity. Also, we find that residual flow plays a key role in the phenomenon of conductivity recovery during post-process annealing.

The excellent electrical and mechanical performance of individual carbon nanotubes combined with their extremely low weight make these structures highly interesting materials for electrical wiring applications. The recent manufacture of macroscopic wire-like assemblies made purely of carbon nanotubes – carbon nanotube fibres – has opened up new prospects in this area. The extensive research on the optimization of the morphology of the fibres indicates that it will be soon possible to produce carbon nanotube fibres exceeding both the electrical and mechanical performance of conductive metals currently used in electrical engineering. To enable the application carbon nanotube fibres as wires in everyday electrical circuits it is necessary to provide them with electrical insulation. This paper proposes, for the first time, a method of insulation of the fibres and analyses the parameters which control the successful development of insulating coating on the surface of these highly porous carbon materials. It is shown that the applied insulation does not compromise either the electrical or mechanical performance of the fibres. The proposed insulation method is inexpensive, easy to integrate into a production process for the carbon nanotube fibres and it can be scaled up.

A melt processing route was successfully applied in the manufacturing of aligned multi-wall carbon nanotube/isotactic polypropylene (MWCNT-iPP) composites. As high as 25 wt% content of the catalytic Chemical Vapour Deposition (c-CVD) derived nanotube filler could be introduced into the iPP matrix. The composite was characterised by a practically retained nanotube alignment as well as an enhanced crystallisation of iPP. Analysis of the phase iPP composition in the composite using XRD and DSC revealed a dominating α-phase with polymer molecules uniaxially oriented in the same direction as the nanotube alignment. Furthermore, kinetic in situ Synchrotron XRD studies verified that the enhanced crystallisation was induced mainly by shear stress occurring in the initial stage of infiltration MWCNT arrays by flowing molten polymer and, to a lesser extent, by the template-based growth of iPP crystallites.

For electromagnetic absorbing and shielding applications, carbon nanotubes (CNT) are widely used due to their excellent electrical and physical properties. Fabrication of microwave absorbing materials involves the use of compounds capable of generating dielectric and/or magnetic losses when impinged by an electromagnetic wave. The presence of lattice defects e.g. vacancies and dislocations contributes to the loss and attenuation in the electromagnetic waves, which in turn remarkably enhance the absorption ability of the material. With the CVD technique which is known to produce several lattice defects in the final product, aligned MWCNTs were successfully synthesized by pyrolizing toluene and ferrocene in an inert argon environment. The morphology analysis of the aligned MWCNTs was conducted via FESEM and TEM analysis, to reveal the average length of approximately 295 μm, with diameters in the range of 60-200 nm. EDS analysis indicates the high yield of CNTs, with more than 90% in weight composition, with less than 5 % Fe impurities presence. Textural properties of MWCNTs were studied by measuring pore size and BET surface area. To understand the response of CNTs to an electromagnetic field, permeability and permittivity measurement were conducted in the frequency range of 100 Hz to 110 MHz. In conclusion, the presence of defects in MWCNTs is desirable for enhanced electromagnetic absorption ability.

Field emission (FE) measurements are reported from carbon nanotube (CNT) fibers and laser-patterned free standing films fabricated by direct online condensation from a floating catalyst chemical vapor deposition reactor. Fiber and film cathodes showed stable emission in the 1–2 mA current (I) range at maximum cathode temperatures less than 1000 °C; film cathodes show localized heating at the triangular tips and higher maximum temperatures than the fibers. Fowler-Nordheim (FN) analysis indicated a change in the morphology of the emitters with increasing external electrical field (Eext). Fiber cathode I-Eext data are interpreted as FN emission from the fiber tip which is eventually limited by space-charge effects. At higher Eext, FN emission from the fiber sidewall occurs. The single fiber cathode stopped emitting abruptly when field induced self-heating effects became significant. For CNT films, self-heating effects can destroy a portion of the film, but FE can still occur from other areas.

We developed carbon nanotube wires (CNWs) and monitored in situ their electrical properties at high temperature conditions for the first time. The dominant type of CNTs present in the material and packing density of thereof proved to have a dominant effect on the thermal stability of CNWs. Furthermore, we showed that kinetics of CNW oxidation plays an important role and slow heating rates or prolonged heating times are essential for the proper determination of thermal stability of CNTs. To enhance the stability at high temperatures, we applied SiC coating onto the CNWs, what allowed a 300 °C improvement to the operational window, eventually reaching 700 °C in the long-haul. Correlation of the change in electrical properties with thermogravimetric response showed that the loss of electrical percolation takes place at 100 °C lower temperature than the last observed weight loss in CNTs content. Finally, we demonstrated feasibility of SiC-coated CNWs under high temperature conditions, by creating a heating device out of them. The presence of SiC layer gave rise to a significant improvement to the thermal stability of the CNT heaters, which now offer unprecedented range of operation reaching 700 °C, as compared to 400 °C when uncoated.

The production of an innovative, high-performance graphene-based polymer nanocomposite using cost-effective techniques was pursued in this study. Well-dispersed and uniformly distributed graphene platelets within a polymer matrix, with strong interfacial bonding between the platelets and the matrix, provided an optimal nanocomposite system for industrial interest. This study reports on the reinforcement of high molecular weight multimodal-high-density polyethylene reinforced by a microwave-induced plasma graphene, using melt intercalation. The tailored process included designing a suitable screw configuration, paired with coordinating extruder conditions and blending techniques. This enabled the polymer to sufficiently degrade, predominantly through thermomechanical-degradation, as well as thermo-oxidative degradation, which subsequently created a suitable medium for the graphene sheets to disperse readily and distribute evenly within the polymer matrix. Different microscopy techniques were employed to prove the effectiveness. This was then qualitatively assessed by Raman spectroscopy, X-ray diffraction, rheology, mechanical testing, density measurements, thermal expansion, and thermogravimetric analysis, confirming both the originality as well as the effectiveness of the process.

A novel chemical approach was established to produce carbon nanotube/Nylon-6,6 hybrid materials from readily available substrates, that is, Nylon-6,6 salt and oxidized multiwall carbon nanotubes (O-MWCNTs). The key synthetic precursor hexane-1,6-diaminium adipate and “carbon nanotubate”—“Binary nanotube salt”—was obtained and isolated as stable and easy-to-handle solid in over 80% yield and with no nanotube losses. The final hybrid materials of various nanotube loadings were synthesized at 270°C and were easily purified from the homopolymer. Purified hybrids were comprehensively analyzed (yields and grafting ratios, SEM, TEM, FT-IR) revealing a two-phase characteristics—individually grafted nanotubes and cross-linked nanotube material. Isothermal TGA kinetic studies showed that in the “binary salts” diamine and diacid molecules were anchored to the nanotube outer shells and then held electrostatically enabling growth of polymer immobilized on O-MWCNTs (“grafting-from” mechanism). Depending on the density and type of nanotube functionalities and filler concentration in the “binary salt,” the O-MWCNT/Nylon-6,6 hybrids can be treated as hybrid material of a proportion of aliphatic polyamide and polyaramide properties. POLYM. COMPOS., 35:523–529, 2014. © 2013 Society of Plastics Engineers

We synthesized highly porous composite films of vertically aligned carbon nanotubes (CNTs) and polypyrrole (PPy) by employing a simple in situ electropolymerisation process from aqueous pyrrole solutions. By contacting the entire CNT array, each CNT acts as a highly active anode that facilitates uniform deposition and immediate polymerization of pyrrole directly on the CNT surface. As a result, each individual CNT was coated with a thin layer of PPy with a tunable thickness between 4 and 38 nm. At the same time the vertical array structure of the CNTs was preserved. A major advantage of this route is that the resulting composite film is highly porous and can be post-filled with other polymers, metals or ceramics to create new multifunctional composites and hybrid structures.

Sonication-induced scission was used to obtain carbon nanotubes (CNTs) with aspect ratios averaging 50 (short CNTs) and 500 (long CNTs). A series of carbon nanotube/epoxy nanocomposite samples with CNT content up to 1.0 wt.% were prepared using these tubes. Electrical and thermal characterisation was conducted to identify changes in such properties and the extent of these changes as a function of aspect ratio and CNT content. Results show significantly enhanced electrical conductivities and a modest increase in the thermal conductivities in both sets of samples. Further analysis of electrical conductivity of the long CNT and short CNT-based epoxy nanocomposites was carried out in order to understand their viability for EMI shielding and electrostatic dissipation applications. The processing behaviour of the long and short CNT-based composites and the corresponding electrical properties is also discussed which will help the researchers to select the right type of carbon nanotube aspect ratio achieve specific electrical properties as well as good processing behaviour.

The design of biocompatible implants for neuron repair/regeneration ideally requires high cell adhesion as well as good electrical conductivity. Here, we have shown that plasma-treated chitin carbon nanotube composite scaffolds show very good neuron adhesion as well as support of synaptic function of neurons. The addition of carbon nanotubes to a chitin biopolymer improved the electrical conductivity and the assisted oxygen plasma treatment introduced more oxygen species onto the chitin nanotube scaffold surface. Neuron viability experiments showed excellent neuron attachment onto plasma-treated chitin nanotube composite scaffolds. The support of synaptic function was evident on chitin/nanotube composites, as confirmed by PSD-95 staining. The biocompatible and electrically-conducting chitin nanotube composite scaffold prepared in this study can be used for in vitro tissue engineering of neurons and, potentially, as an implantable electrode for stimulation and repair of neurons.

Sea bed logging is new technique for the detection of hydrocarbon reservoir. Magnitude of EM waves is important for the detection of deep target hydrocarbon reservoir below 4000 m from the sea floor. A new aluminium based EM transmitter is developed and NiZn (Ni 0.8 Zn 0.2 Fe 2 O 4 ) ferrite with and with out multiwall carbon nano tubes (MWCNTs) polymer composites as magnetic feeders are used in a scaled tank. Nickel zinc ferrite plays an important role in many applications due to its best magnetic properties. Nanocrystalline NiZn (Ni 0.8 Zn 0.2 Fe 2 O 4 ) ferrite and novel Ni 0.8 Zn 0.2 Fe 2 O 4 -MWCNTs composites were prepared by sol–gel route. The samples were sintered at 750–950 °C and were characterized by XRD, FESEM, HRTEM and Raman spectroscopy. Single phase of Ni 0.8 Zn 0.2 Fe 2 O 4 having [3 1 1] major peak was obtained by sol–gel method at 750 °C and 950 °C. FESEM micrographs show that grain size increases with the increase of sintering temperature and ranges from 24 to 60 nm. FESEM and HRTEM results showed coating of Ni 0.8 Zn 0.2 Fe 2 O 4 on MWCNTs and show better morphology at the sintering temperature of 750 °C. The magnetic properties measured from impedance vector network analyzer showed that sample (Ni 0.8 Zn 0.2 Fe 2 O 4 -MWCNTs) sintered at 750 °C have higher initial permeability (20.043), Q -factor (50.047), and low loss factor (0.0001) as compared Ni 0.8 Zn 0.2 Fe 2 O 4 -MWCNTs sintered at 950 °C. Due to better magnetic properties, Sample (Ni 0.8 Zn 0.2 Fe 2 O 4 -MWCNTs sintered at 750 °C) composites were used as magnetic feeders for the EM transmitter. It was found that magnitude of EM waves from EM transmitter increased up to 243% by using Ni 0.8 Zn 0.2 Fe 2 O 4 -MWCNTs polymer composites.

In situ polymerisation provides a route to polystyrene (PS) matrix composites reinforced with aligned multi-walled carbon nanotubes (MWNTs). As shown, fully densified composites can be prepared; by varying the number of layers of aligned MWNT arrays, desired thickness of the composite can be manufactured. These aligned composites have characteristic anisotropic electrical and thermal properties.

X-ray scattering is used to measure particle orientation in concentrated multiwalled carbon nanotube (MWNT) suspensions under shear flow. MWNTs were dispersed in a Newtonian suspending fluid (uncured epoxy). The dispersions exhibit shear thinning, approaching the matrix viscosity at high shear rates. This is accompanied by progressive development of MWNT orientation along the flow direction with increasing shear rate. The impact of MWNT aspect ratio and concentration on steady-state orientation is explored. In one sample (2 wt. % dispersion of short MWNTs), orientation was measured in both the flow-gradient (1-2) and flow-vorticity (1-3) planes of shear flow to provide a more complete picture of the three-dimensional orientation state. Also in this sample, 1-3 plane measurements were conducted using both small- and wide-angle x-ray scattering (SAXS and WAXS). While the two methods produce qualitatively similar results, WAXS-derived measures of flow-induced anisotropy are consistently larger than SAXS data...

Highly aligned carbon nanotube/polystyrene (HACNT/PS) composites were prepared conveniently via polymer impregnation of aligned arrays, avoiding conventional solution or melt processes that involve high-shear blending. Detailed scanning electron microscopy (SEM), X-Ray diffraction (XRD) and differential scanning calorimetry (DSC) studies show that the alignment of the multi-wall nanotubes is retained after polymer impregnation. A range of key parameters were investigated, including the amount of molten polymer required for complete infiltration, the maximum mass fraction of CNTs in dense composites, and the effect of CNTs on the glass transition temperature ( T g ) of the polymer. This approach may be adapted to the fabrication of large scale, highly anisotropic, thin or multilayer CNT composites using other molten polymers.

Multiwalled carbon nanotube (MWNT)/poly(vinyl butyral) (PVB) composite nanofibers were prepared by electrospinning, successive twisting and heat treatment. The MWNTs were highly oriented in an electrified thin jet during electrospinning. The heat treatment of the twisted electrospun nanofiber yarns produced the characteristics of the CNT in the composite nanofiber yarns and enhanced their electrical properties, mechanical properties, and thermal properties. The electrical conductivity of the heated yarn was significantly enhanced and showed the maximum value of 154 S cm(-1) for the yarn heated at 400 °C. It is an order of magnitude higher than other electrospun CNT composite materials. These results demonstrated that the novel top-down process based on electrospinning, twisting, and heat treatment provide a promising option for simple and large-scale manufacture of CNT assemblies.

The control of the structure of carbon nanotubes remains a central issue in rapidly developing science and technology. Of the various structural parameters of nanotubes, namely, diameters, number of walls, length, and chirality, it is the control of chirality which presents significant challenges as well as opportunities. It is known from our earlier work that the addition of nitrogen as a heterocyclic compound in the hydrocarbon feedstock leads to the growth of carpets of multiwall nanotubes in which all the walls are either of the armchair or zigzag structure. The research here shows the role of nitrogen in stabilizing iron carbide catalyst particles, the belt nucleation of the nanotubes, the orientational relationship between particle and nanotube structure, and the reconstruction of the surface layers of the carbide in contact with the growing ends of the tubes. By combining the various pieces of new experimental evidence it has proved possible to suggest why such unique types of nanotubes should form...

Addition of just 0.0025 mass fraction of highly aligned multiwall carbon nanotubes (MWCNTs) showed a 45% reduction in the peak mass loss rate (PMLR) during gasification of epoxy/MWCNT composites; this 45% decrease in PMLR at such a low loading (0.0025mass fraction) of MWCNTs, is much better than that reported previously with either MWCNTs (0.02 mass fraction) or SWCNTs (0.005 mass fraction). We attribute this effect to the use of highly aligned MWCNTs which easily exfoliate, or debundle, using high shear mixing. In addition, 0.005 mass fraction MWCNTs showed significant reduction in the initial mass loss rate as compared to other epoxy/MWCNT, epoxy montmorillonite (MMT) and pure epoxy samples. Reduced PMLR was also observed for epoxy/MMT nanocomposites, but required much higher MMT content. The epoxy/MWCNTs composites residue/char integrity (no visible cracks on the char surface of MWCNTs/epoxy samples) appeared to be superior to that for epoxy/MMT samples. The rheological characterization of the epoxy composites was carried out in order to study the effect of nanoparticle network formation on the rheological properties and flammability. Significant increase in thermal conductivity (k) was observed for epoxy/MWCNTs composite with high loadings of MWCNTs. This gasification mass loss behavior of the nanocomposites was investigated using a model that combines a continuum description of the transport of thermal energy with Ahrrenius kinetics for the decomposition of the polymer. The enhanced thermal conductivity for the epoxy/MWCNT composites appears to be responsible for the initial mass loss reduction.

This study reports on the characterization of a carbon nanotube fibre using synchrotron radiation microbeam small- and wide-angle X-ray scattering in combination with microfluorescence. The fibre, spun directly from a chemical vapour deposition reaction zone, is imaged in terms of microstructural heterogeneities. The results reveal a fibre consisting of highly oriented nanotube bundles and unoriented carbonaceous material. Within the oriented component there is a variable orientation distribution and evidence of differences in nanotube packing. Single catalyst crystallites can be located within the fibre from their wide-angle X-ray scattering signal, and the particulate distribution imaged using X-ray microfluorescence. Whilst this study only constitutes a preliminary analysis, it demonstrates the application of existing fibre characterization methods to new materials. It also highlights the potential of synchrotron radiation micro- and nanobeam small- and wide-angle X-ray scattering and microfluorescence for the study of fibres of a few µm diameter.

Multiwall carbon nanotube (MWCNT)/cellulose composite fibers were processed from solutions in ethyl methylimidazolium acetate (EMIAc). Rheological percolation in MWCNT/Cellulose/EMIAc solution was observed above 0.01 mass fraction of MWCNT, while electrical percolation in oriented fibers was observed above 0.05 mass fraction of MWCNTs with respect to the weight of the cellulose. Cellulose orientation and crystal size were significantly higher in the composite than in the control cellulose fiber. In addition, in the composite fiber, carbon nanotube orientation was higher than cellulose orientation. At 0.05 mass fraction MWCNT, fiber tensile strength increased by about 25%, strain to failure increased by 100%, and modulus essentially remained unchanged. The composite fibers showed lower thermal shrinkage than the control cellulose fiber. The axial electrical conductivity at 0.1 mass fraction MWCNTs in these oriented fibers was more than 3000 S/m.

Electromagnetic characterization of CNT films fabricated by thermal decomposition of SiC has been performed. Purification and/or uncapping treatment conditions at an elevated temperature of 400 degrees C under flowing oxygen or carbon dioxide have been studied. A near field microwave microscope was used to measure the real and imaginary parts of the complex permittivity of CNT films through the frequency shift and the change in reciprocal quality factor between two extreme positions of an evanescent microwave probe-tip (in contact with the sample, and away from interaction with it). A theoretical two-point model was proposed to confirm experimental data, which showed poor conductivity of the CNT film as grown but has slight improvement after 40 min treatment.

Carbon nanotubes are regarded by many as being the next generation in high performance materials due to their unique properties. The Cambridge Process was developed to utilize these unique properties by directly spinning carbon nanotube fibres drawn from an aerogel sock. The sock is formed from carbon nanotubes grown via a catalytic chemical vapour deposition (CVD) process. Due to the nature of CVD, the process is readily scalable. Kilometres of fibre can be made at a rate of 20 m/min. Altering process parameters (catalyst concentration, feedstock injection rate, furnace temperature, and gas flow rate) allows the production of nanotubes of a desired morphology. The fibres have been characterized with scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman Spectroscopy in order to confirm nanotube composition and orientation. The fibre possesses mechanical and electrical properties that rival or exceed those of present-day materials. Mechanical properties can be enhanced by increasing the degree of orientation of the nanotubes with the long axis of the fibre and by overall densification. These effects can be accomplished through drawing the fibre and solvent treatment.

With their impressive individual properties, carbon nanotubes should form high-performance fibers. We explored the roles of nanotube length and structure, fiber density, and nanotube orientation in achieving optimum mechanical properties. We found that carbon nanotube fiber, spun directly and continuously from gas phase as an aerogel, combines high strength and high stiffness (axial elastic modulus), with an energy to breakage (toughness) considerably greater than that of any commercial high-strength fiber. Different levels of carbon nanotube orientation, fiber density, and mechanical properties can be achieved by drawing the aerogel at various winding rates. The mechanical data obtained demonstrate the considerable potential of carbon nanotube assemblies in the quest for maximal mechanical performance. The statistical aspects of the mechanical data reveal the deleterious effect of defects and indicate strategies for future work.

This paper describes rheological measurements and associated optical microstructural observations of multiwall carbon nanotubes (MWCNTs) suspended in an epoxy resin matrix. The base epoxy resin was found to be essentially Newtonian, and the progressive incorporation of nanotubes enhanced the low shear rate viscosity of the suspension by nearly two decades. At higher shear rates, the suspension viscosity asymptotically thinned to the viscosity of the matrix alone. The low shear rate viscosity enhancement was correlated with the optical observations of interconnected aggregates of carbon nanotubes, which themselves were induced by the low shear conditions. Intermediate shear rates resulted in a reduction in the size of the aggregates. High shear rates appeared to cause near-complete dispersal of the aggregates. From these results it is conjectured that for this suspension, shear thinning is connected with the breaking of the interconnected networks between nanotubes and or aggregates of nanotubes, and not b...

There is considerable interest in the adhesion of polymers to carbon nanotubes for nanocomposite applications.(1-4) One example is multiwalled carbon nanotubes (MWCNTs) dispersed in nylon 6,6.(5) We will show that high-contrast tomographic reconstructions can be created from plasmon-loss electrons that show the three-dimensional structural complexity of the MWCNT-nylon composite at the nanoscale. Further, by recording a series of energy-loss images at successive tilts, it is possible to interrogate subvolumes to extract energy-loss spectra from the reconstructed "volume spectra".

The erosive wear behaviour of epoxy composites reinforced with aligned, as-produced carbon nanotube (CNT) films was investigated. The CNT film composites were fabricated in two different configurations, where the unidirectional (0°) and bi-directional (0°/90°) aligned CNT films were exposed to the particle stream. Results have shown that the unidirectional (0°) CNT film/epoxy composite exhibit superior erosive wear resistance compared to the unidirectional (0°) carbon fibre reinforced epoxy composite. Furthermore, the bi-directional (0°/90°) CNT film/epoxy composite shows even better resistance to erosion compared to the unidirectional (0°) CNT film/epoxy composite due to additional impact energy absorption resulted from CNT networks. Scanning Electron Microscopy (SEM) provides further insight into the erosive wear mechanisms of CNT film composites at different impingement angles. This work has successfully introduced aligned as-produced CNT films fabricating epoxy composites using traditional composite manufacturing processes with low erosive wear and high electrical performance which deliver potential for engineering applications.

The complex structure of the macroscopic assemblies of carbon nanotubes and variable intrinsic piezoresistivity of nanotubes themselves lead to highly interesting piezoresistive performance of this new type of conductive material. Here, we present an in-depth study of the piezoresistive effect in carbon nanotube fibers, i.e., yarnlike assemblies made purely of aligned carbon nanotubes, which are expected to find applications as electrical and electronic materials. The resistivity changes of carbon nanotube fibers were measured on initial loading, through the elastic/plastic transition, on cyclic loading and on stress relaxation. The various regimes of stress/strain behavior were modeled using a standard linear solid model, which was modified with an additional element in series to account for the observed creep behavior. On the basis of the experimental and modeling results, the origin of piezoresistivity is discussed. An additional effect on the resistivity was found as the fiber was held under load which led to observations of the effect of humidity and the associated water adsorption level on the resistivity. We show that the equilibrium uptake of moisture leads to the decrease in gauge factor of the fiber decrease, i.e., the reduction in the sensitivity of fiber resistivity to loading.

In seabed logging the magnitude of electromagnetic (EM) waves for the detection of a hydrocarbon reservoir in the marine environment is very important. Having a strong EM source for exploration target 4000 m below the sea floor is a very challenging task. A new carbon nanotubes (CNT) fibres/aluminium based EM transmitter is developed and NiZn ferrite as magnetic feeders was used in a scaled tank to evaluate the presence of oil. Resistive scaled tank experiments with a scale factor of 2000 were carried out. X-ray Diffraction (XRD), Raman Spectroscopy and Field Emission Scanning Electron Microscope (FESEM) were done to characterize the synthesized magnetic feeders. Single phase Ni0.76Mg0.04Zn0.2Fe2O4, obtained by the sol-gel method and sintered at 700 degrees C in air, has a [311] major peak. FESEM results show nanoparticles with average diameters of 17-45 nm. Samples which have a high Q-factor (approximately 50) was used as magnetic feeders for the EM transmitter. The magnitude of the EM waves of this new EM transmitter increases up to 400%. A curve fitting method using MATLAB software was done to evaluate the performance of the new EM transmitter. The correlation value with CNT fibres/aluminium-NiZnFe2O4 base transmitter shows a 152.5% increase of the magnetic field strength in the presence of oil. Modelling of the scale tank which replicates the marine environment was done using the Finite Element Method (FEM). In conclusion, FEM was able to delineate the presence of oil with greater magnitude of E-field (16.89%) and the B field (4.20%) due to the new EM transmitter.

Translating the remarkable mechanical properties of individual carbon nanotubes to macroscopic assemblies presents a unique challenge in maximizing the potential of these remarkable entities for new materials. Infinitely long individual nanotubes would represent the ideal molecular building blocks; however, in the case of length-limited nanotubes, typically in the range of micro- and millimeters, an alternative strategy could be based on the improvement of the mechanical coherency between bundles assembling the macroscopic materials, like fibers or films. Here, we present a method to enhance the mechanical performance of fibers continuously spun from a CVD reactor, by a postproduction processing methodology utilizing a chemical agent aided by UV irradiation. The treatment results in an increase of 100% in specific strength and 300% in toughness of the fibers with strength values rocketing to as high as 3.5 GPa SG(-1). An attempt has been made to explore the nature of the chemical modifications introduced in the fiber and the consequential effects on its properties.

The continuing momentum of carbon nanotube research is driven by a number of unresolved issues, particularly those associated with high-temperature synthesis, but also by the challenge of translating the exciting physical properties of the individual nanotubes into useful materials with new properties and applications. A process by which carbon nanotube fi bers can be spun directly from the chemical vapor deposition (CVD) reaction zone was fi rst reported in 2004. [ 1 ] The fi ber formed consisted of comparatively large diameter ( ≈ 7 nm) double-walled nanotubes that collapse to form stacks of graphene-like layers. [ 2 ] Also shown was the potential for exceptional axial mechanical properties. [ 3 , 4 ] The addition of sulfur in the right proportion is key to the formation of a cloud of entangled nanotubes that have suffi cient mechanical integrity to be drawn out of the reactor as a continuous fi ber. The major role of the sulfur has been seen as a “promoter” as suggested much earlier by Kiang et al. [ 5 , 6 ] In the continuous spinning process, sulfur has been identifi ed as segregating to the surface of the iron catalyst particles and the interface between the particle and the nanotube, [ 7 ] an effect recently simulated using molecular dynamics for Mo–S [ 8 ] and since confi rmed for Fe–S, [ 9 ] yet well known in the literature on cast irons. [ 10 ] The nanotubes produced by the process are exceptionally long, some 100 000 times their diameter, and their growth to this length over a few seconds at 1200 ° C seems associated with the promoting effect of added sulfur. Here we report the observation that if the sulfur is made available soon after the ferrocene is fi rst cracked to nucleate the fl oating iron catalyst particles, then it retards the growth of the particles so they nucleate single-walled nanotubes, which are then extracted as continuous ≈ 10 μ m diameter fi ber. Additionally, the fact that armchair (and thus metallic) nanotubes are dominant in the fi ber is surprising and adds further piquancy to their potential applicability. The process is described in Figure S1 (Supporting Information). We note (Supporting Information, Table S1) that the window of composition ratios for successful spinning is centred on Fe/C 0.008, the same as for successful spinning from thiophene, but the required Fe/S ratio is 0.080 for thiophene compared with 0.006 for the carbon disulfi de. Furthermore, the results provide additional input to the on-going debate as to the source of chirality preference in as-grown SWNTs [ 11–14 ] and is discussed in the context of three specifi c models: imprinting catalyst structure, [ 15 , 16 ] cap control of chirality, [ 17 , 18 ] and dislocation models of nanotube growth and reorientation. [ 18–20 ]

We report studies of the orientation state of multiwalled carbon nanotubes (MWNTs) dispersions in steady and transient shear flows. Uncured epoxy was used as a viscous Newtonian suspending medium and samples were prepared from "aligned" MWNTs using methods previously reported [S. S. Rahatekar et al., J. Rheol. 50, 599 (2006)]. Orientation measurements were performed in both the flow-gradient (1-2) and flow-vorticity (1-3) plane of simple shear flow using in situ x-ray scattering techniques. Steady state measurements in the 1-2 plane indicate that the MWNT orientation is shear rate dependent, with the MWNTs orienting closer to the flow direction at higher shear rates. During steady shear, anisotropy was measured to be higher in the 1-2 plane than in the 1-3 plane, demonstrating that the nanotube orientation state is not unaxially symmetric in shear. It is hypothesized that the steady state MWNT orientation is governed primarily by a rate-dependent state of nanotube aggregation/disaggregation, which was separately characterized by optical microscopy of the same samples under shear. High flux synchrotron radiation allowed for time-resolved structural studies in transient flows. A partial relaxation of flow-induced anisotropy was observed following flow cessation, despite the very small rotational diffusivity estimated for these nanotubes. Long transients are observed in step-down experiments, as the orientation state changes in response to the slow tube aggregation process.