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Funding Information: A.A.M. and A.G.N. thanks RFBR research project ? 20-32-90233 for support in experimental part of the work. D.V.K. thanks Russian Science Foundation grant No. 20-73-10256 for support in synthesis of aerosol SWCNT films. V.D. thanks the Russian Science Foundation (Grant No. 17-72-30006) for the support in characterization of pulse laser generation. Funding Information: A.A.M. and A.G.N. thanks RFBR research project № 20-32-90233 for support in experimental part of the work. D.V.K. thanks Russian Science Foundation grant No. 20-73-10256 for support in synthesis of aerosol SWCNT films. V.D. thanks the Russian Science Foundation (Grant No. 17-72-30006 ) for the support in characterization of pulse laser generation. Publisher Copyright: © 2021 Elsevier Ltd Single-walled carbon nanotubes (SWCNTs) are widely explored for the ultrashort pulse generation in the fiber lasers enabled by pronounced saturable absorption (SA) effect. Despite many remarkable results demonstrated in the area, degradation of the samples inside the laser cavity limits the widespread use of SWCNT-SA. In the present work, we investigate the degradation mechanism by measuring the temperature of the carbon nanotubes in an operating laser cavity in accordance with the Raman G-band position. We identify the process behind the sample degradation by comparing the burning temperature of the sample with results of thermogravimetric analysis. We apply this approach for the SWCNTs in polyvinyl alcohol polymer matrix and polymer-free SWCNT thin film and demonstrate that these samples undergo different degradation mechanism. Proposed technique provides a useful instrument for optimization of SWCNT-SA for desired ultrafast laser generation.

The architecture of transparent contacts is of utmost importance for creation of efficient flexible light-emitting devices (LEDs) and other deformable electronic devices. We successfully combined the newly synthesized transparent and durable silicone rubbers and the semiconductor materials with original fabrication methods to design LEDs and demonstrate their significant flexibility. We developed electrodes based on a composite GaP nanowire-phenylethyl-functionalized silicone rubber membrane, improved with single-walled carbon nanotube films for a hybrid poly(ethylene oxide)-metal-halide perovskite (CsPbBr3) flexible green LED. The proposed approach provides a novel platform for fabrication of flexible hybrid optoelectronic devices.

Films of single-walled carbon nanotubes are promising for various electro-optical applications. Their engineering at the nanoscale requires a robust method of the contactless, non-invasive determination of structural properties. Here we present a study that uses specular reflectometry for this purpose, namely to determine the film thickness. Analysis of the reflection coefficient of neutrons, as well as X-rays, makes it possible to obtain a normal density profile and thereby trace the effect of densification of films of single-walled carbon nanotubes by ethanol drop casting. The paper summarizes the first experience of using combined neutron and X-ray approach in relation to low-density carbon films. Further steps for the development of the technique are discussed.

We propose a novel approach to enhance optoelectronic performance of single-walled carbon nanotubes (SWCNTs) for transparent conducting film applications. The method provides fine and reversible tuning of optoelectrical properties of SWCNT films over a wide range of parameters. Using imidazolium-based ionic liquid with a wide electrochemical window (BMIM-PF6), we achieved the film sheet resistance as low as 53 Ω/sq at the 90% transmittance, thereby shifting the SWCNT Fermi level up to 1.4 eV. We believe the results to promote collateral research of adjustable tuning of the electronic structure of carbon nanomaterials as promising components for future electronics, electrochromic devices, and ionotronics.

We demonstrate a simple and resource-efficient approach for rapid purification of single-walled carbon nanotube (SWCNT) films from catalyst impurities by Joule heating in a vacuum. As a result, the catalyst concentration decreases by a factor of 27 (from 17 to 1600 °C for 2 min. Moreover, the nanotube structure remains almost intact as the purified films show a high ratio of intensities of G to D bands of Raman spectrum IG/ID = 180. The technique perfectly fits for the devices based on free-standing carbon nanotube films such as protective membranes, infrared detectors, and sound generators. For purified SWCNT films, we show the signal-to-noise ratio for the bolometers to increase by a factor of 2.5 and 24% sound pressure gain for the air-coupled thermophones. The method can be easily extended to other applications, for instance, the SWCNT-based devices of limited liquid and harsh reagent tolerance like nanotube aerogels and drug delivery systems.

Funding Information: V.N. thanks the Russian Foundation for Basic Research (RFBR project No. 19-32-60040) for PDMS/MW membrane fabrication and optical measurements. V.F. thanks the Russian Foundation for Basic Research (RFBR project No. 19-32-60037) for the support of the MBE growth. V.N. and F.K. thank the support from the Russian Foundation for Basic Research (grant 20-32-90182) for electrical measurements. V.N., F.K., R.I. and I.M. thank the Russian Scientific Foundation (RSF project No. 20-19-00256) for chemical treatment of PDMS. V.N., V.F., A.M., F.K. and K.S. thank the Ministry of Science and Higher Education of the Russian Federation (FSRM-2020-0005) for the general support. E.M. thanks the Basic Research Program at the National Research University Higher School of Economics (HSE University) in 2021 for optical measurements. N.A.-M. and M.T. thank ITN Marie Curie project INDEED (grant No. 722176) for GaPAs NW/PDMS membrane investigation. This work received financial support from Partenariats Hubert Curien Kolmogorov project No. 43784UJ and Indo French Centre for the Promotion of Advanced Research (CEFIPRA) Project No. 6008-1. A.G.N. acknowledges the Russian Scientific Foundation (RSF project No. 21-72-20050) for synthesis of SWCNTs. Funding Information: Funding: V.N. thanks the Russian Foundation for Basic Research (RFBR project No. 19-32-60040) for PDMS/MW membrane fabrication and optical measurements. V.F. thanks the Russian Foundation for Basic Research (RFBR project No. 19-32-60037) for the support of the MBE growth. V.N. and F.K. thank the support from the Russian Foundation for Basic Research (grant 20-32-90182) for electrical measurements. V.N., F.K., R.I. and I.M. thank the Russian Scientific Foundation (RSF project No. 20-19-00256) for chemical treatment of PDMS. V.N., V.F., A.M., F.K. and K.S. thank the Ministry of Science and Higher Education of the Russian Federation (FSRM-2020-0005) for the general support. E.M. thanks the Basic Research Program at the National Research University HigherSchool of Economics (HSE University) in 2021 for optical measurements. N.A.-M. and M.T. thank ITN Marie Curie project INDEED (grant No. 722176) for GaPAs NW/PDMS membrane investigation. This work received financial support from Partenariats Hubert Curien Kolmogorov project No. 43784UJ and Indo French Centre for the Promotion of Advanced Research (CEFIPRA) Project No. 6008-1. A.G.N. acknowledges the Russian Scientific Foundation (RSF project No. 21-72-20050) for synthesis of SWCNTs. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. We demonstrate flexible red light-emitting diodes based on axial GaPAs/GaP heterostruc-tured nanowires embedded in polydimethylsiloxane membranes with transparent electrodes involv-ing single-walled carbon nanotubes. The GaPAs/GaP axial nanowire arrays were grown by molecular beam epitaxy, encapsulated into a polydimethylsiloxane film, and then released from the growth substrate. The fabricated free-standing membrane of light-emitting diodes with contacts of single-walled carbon nanotube films has the main electroluminescence line at 670 nm. Membrane-based light-emitting diodes (LEDs) were compared with GaPAs/GaP NW array LED devices processed directly on Si growth substrate revealing similar electroluminescence properties. Demonstrated membrane-based red LEDs are opening an avenue for flexible full color inorganic devices.

Rubber materials are the key components of flexible optoelectronic devices, especially for the light-emitting diodes based on arrays of inorganic nanowires (NWs). This paper reports on polydimethylsiloxane-graft-polystyrene (PDMS-St) as a new flexible substrate of GaP NW array structures. The NWs were encapsulated by the newly introduced G-coating method to substitute the inefficient mainstream spin-coating. To further exploit the flexibility and the stretchability of the NW/PDMS-St structures, the ferrocenyl-containing polymethylhydrosiloxane was synthesized and successfully used as an electrode for the NWs. In order to make an alternative highly efficient transparent electrode, a new application of conductive single-walled carbon nanotubes was demonstrated. The novel materials and methods demonstrated unsurpassed mechanical stability of the fabricated flexible electronic devices.

We propose to use artificial neural networks to process the experimental data and to predict the performance of the aerosol CVD synthesis of single-walled carbon nanotubes based on Boudouard reaction. We employ five key input parameters of the growth (pressures of CO, CO2 and ferrocene as well as the residence time and the growth temperature) to control the performance of produced nanotube films (yield, mean and standard deviation of the diameter distribution, and defectiveness). The prediction errors were found to be comparable with the corresponding experimental errors. We believe the proposed approach is of great interest for the synthesis of nanocarbons with tailored characteristics.

We have designed and built an exhaust-free spark discharge generator for robust aerosol CVD synthesis of single-walled carbon nanotubes. The systematic study has shown the generator to provide a facile and repeatable route to precisely control the size of the catalyst particle and, therefore, carbon nanotube growth. Using a comprehensive set of methods (the analysis of differential mobility of the aerosol particles, optical spectroscopy, scanning and transmission electron microscopy, Raman spectroscopy, and atomic force microscopy) we have revealed the relation between the defectiveness, length, diameter distribution of carbon nanotubes and specific features of a generator such as electrode characteristics (breakdown voltage, composition, and current) as well as the nature of the surrounding media (carrier gas nature, flow rate). The design used has resulted in separation of the nanoparticle formation and carbon nanotube nucleation processes. This provides a mutual independence of the growth parameters and the diameter distribution of the single-walled carbon nanotubes enhancing the scalability of the process. For instance, the breakdown voltage has been shown to have nearly zero effect on diameter and length distribution of carbon nanotubes produced while strictly governing the yield. We focus here on producing specifically short carbon nanotubes (l < 500 nm) of pronounced defectiveness for drug delivery and transistor applications.

The influence of the surface modification of multi-walled carbon nanotubes (MWCNT) with nitrogen-containing compounds on the performance of 40 wt% Pt/MWCNT catalysts in the oxygen electroreduction reaction (ORR) was investigated using a rotating disk electrode (RDE) at 10–35 °C in 0.1 M HClO4 as electrolyte in electrochemical cell, and in a hydrogen–oxygen polymer electrolyte membrane fuel cell (PEMFC) at 82 °C. The catalysts were characterized by low-temperature nitrogen adsorption, XPS, TEM, gas-phase CO titration, electrooxidation of the adsorbed CO monolayer, and cyclic voltammetry. It was shown that the modification of MWCNT with melamine–formaldehyde resin leads to the surface nitrogen concentration up to 8.3 at.% (CNT-MF sample). The 40 wt% Pt/CNT-MF catalyst with 0.1 mg cm−2 Pt loading on the cathode showed a good performance in PEMFC (~ 0.61 W cm−2) and a high utilization ratio (0.84) of Pt in membrane electrode assembly as compared to Pt/CNT catalyst (~ 0.37 W cm−2 and utilization of 0.29). The higher power density of nitrogen-modified catalysts was ascribed to a higher utilization of Pt in the electrode layer.

Funding Information: The authors J.E., C.D. and A.K. would like to thank Jean Dussaud for his work on the MOVPE setup. V.N. would like to thank Maria Baeva for her assistance with the stretchable LED transparency measurements.J.E., C.D. and A.K. thank French National Labex GaNeX (ANR-11-LABX-0014) for MW synthesis and CL measurements. V.N. thanks the Russian Foundation for Basic Research (RFBR project no. 19-32-60040) for PDMS/MW membrane fabrication and optical measurements. I.S.M., V.N., F.M.K. thank the support from the Russian Science Foundation (grant 20-19-00256) for PDMS synthesis and electrical measurements. D.K. and A.G.N. thank Russian Foundation of Basic Research project no. 20-03-00804 for the synthesis of carbon nanotubes. F.E.K. thanks the support from the Russian Science Foundation (grant 19-79-00313) for the LED array encapsulation and membrane transfer. I.S.M., F.M.K., V.N., V.A.M., S.M., A.A.V., A.V.U., and D.A.M. thank the Ministry of Science and Higher Education of the Russian Federation (FSRM-2020-0005) for the general support. N.A. and M.T. acknowledge the financial support from the ITN Marie Curie project INDEED (grant no. 722176), by the Indo-French Centre for the Promotion of Advanced Research (IFCPAR/CEFIPRA project no. 6008-1) for MW/PDMS membrane processing and characterization. Funding Information: Funding: J.E., C.D. and A.K. thank French National Labex GaNeX (ANR-11-LABX-0014) for MW synthesis and CL measurements. V.N. thanks the Russian Foundation for Basic Research (RFBR project no. 19-32-60040) for PDMS/MW membrane fabrication and optical measurements. I.S.M., V.N., F.M.K. thank the support from the Russian Science Foundation (grant 20-19-00256) for PDMS synthesis and electrical measurements. D.K. and A.G.N. thank Russian Foundation of Basic Research project no. 20-03-00804 for the synthesis of carbon nanotubes. F.E.K. thanks the support from the Russian Science Foundation (grant 19-79-00313) for the LED array encapsulation and membrane transfer. I.S.M., F.M.K., V.N., V.A.M., S.M., A.A.V., A.V.U., and D.A.M. thank the Ministry of Science and Higher Education of the Russian Federation (FSRM-2020-0005) for the general support. N.A. and M.T. acknowledge the financial support from the ITN Marie Curie project INDEED (grant no. 722176), by the Indo-French Centre for the Promotion of Advanced Research (IFCPAR/CEFIPRA project no. 6008-1) for MW/PDMS membrane processing and characterization. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. We propose and demonstrate both flexible and stretchable blue light-emitting diodes based on core/shell InGaN/GaN quantum well microwires embedded in polydimethylsiloxane membranes with strain-insensitive transparent electrodes involving single-walled carbon nanotubes. InGaN/GaN core-shell microwires were grown by metal-organic vapor phase epitaxy, encapsulated into a polydimethylsiloxane film, and then released from the growth substrate. The fabricated free-standing membrane of light-emitting diodes with contacts of single-walled carbon nanotube films can stand up to 20% stretching while maintaining efficient operation. Membrane-based LEDs show less than 15% degradation of electroluminescence intensity after 20 cycles of stretching thus opening an avenue for highly deformable inorganic devices.

Dual-wavelength ultra-short pulses generation in the dumbbell-shaped thulium fiber laser was demonstrated. The mode-locking regime was achieved by using single-walled carbon nanotubes in the laser cavity. Output power was up to 6 mW and the main repetition rate was around 5.3 MHz.

In this work, we evaluate the effect of ferrocene delivery in the reactor on the growth of single-walled carbon nanotubes (SWCNTs) in an aerosol CVD utilizing carbon monoxide as a feedstock. For this purpose, we assess the reactor output parameters varying a gas flow rate through a ferrocene vapor injector in the hot zone with other conditions (temperature, total flow rate, and reactant concentration) being fixed. Our experimental results reveal the adjustment of the ferrocene injection strategy (injector flow rate) to cause a 9-fold improvement in the synthesis yield while preserving the SWCNT properties. We show the catalyst injection optimization to enhance catalyst activation degree as a result of a streamline catalyst delivery, preventing particle over-growth; the experimental data are supported by the computational fluid dynamics. We believe our work to highlight the importance of appropriate aerosol CVD reactor engineering and to facilitate the optimization of reactor productivity, which is one of the fundamental milestones towards SWCNT-based technology.

We investigate a complex relationship between structural parameters of single-walled carbon nanotubes (namely, mean length, diameter, and defectiveness) and optoelectrical properties (equivalent sheet resistance) of thin films composed of the nanotubes. We obtained a systematic dataset describing the influence of CO2 concentration and growth temperature. On the basis of the experimental results, we prove the high Raman peak ratio (IG/ID), length, and diameter of the nanotubes to decrease the equivalent sheet resistance of the nanotube-based film. The approach employed highlights the change in the nanotube growth mechanism at the temperature coinciding with the phase transition between α-Fe and γ-Fe catalyst phases. We believe this work to be of high interest for researchers working not only in the field of transparent and conductive films based on nanocarbons, but also for those who reveals the fundamentals of the nanotube growth mechanism.

Here we have studied the kinetics of the ethylene non-catalytic decomposition on the surface of multi-walled carbon nanotubes (MWCNTs) leading to the formation of lateral carbon deposits (LCD). Despite the comprehensive data on the gas-phase pyrolysis and a clear presence of surface impurities formed of carbon deposits, this process has not gained any proper attention. Within the temperature range studied (650–750 °C), we have found the rate of the reaction to be proportional to the MWCNT surface area and ethylene partial pressure. The activation energy of carbon deposition is close to that for the collision of two ethylene molecules to form C2H5· and C2H3· radicals. Based on the data obtained, we have proposed the radical mechanism of the formation of the deposits. High-resolution TEM, synchrotron radiation XRD, Raman spectroscopy, differential thermal analysis, temperature dependence of conductivity, and surface area measurements were used to characterize the structure and properties of the carbon-carbon composite produced. We have shown the deposition of lateral carbon to be a soft non-destructive technique for MWCNT surface functionalization allowing one to tune the properties of 3D-structured nanotube materials (e.g. arrays or aerogels). As an example, the LCD coating gradually changes the conductivity mechanism to 3D variable range hopping.

International audience; 59 Co NMR a b s t r a c t CoFe 2 /CaO catalysts for multi-walled carbon nanotubes (MWCNT) were characterized during the activation period (T = 670°C; C 2 H 4 /Ar = 1:1, 400 sccm) by internal field 59 Co nuclear magnetic resonance. During this induction period, although C 2 H 4 is already reacting, the MWCNT yield remains negligible. The NMR spectra of the catalysts revealed the occurrence of several structural and magnetic species. They were not detectable by conventional X-ray diffraction but the heterogeneity of the metal particles was corroborated by high-resolution transmission electronic microscopy coupled with energy dispersive X-ray spectroscopy. Two samples quenched at different activation time contained, beside non-reacted pure metal Co particles, strong and weak ferromagnetic alloys. During activation, the pure Co metal content dropped and an increase of the ordering of the cobalt-iron alloy in the catalyst was evidenced thus revealing a multistage activation mechanism for the reaction. We propose this ordering process during the induction period to be an intermediate step between the strong ferromagnetic Co rich alloy and the weak ferromagnetic Fe rich one and that it favors the onset of MWCNTs growth.

We demonstrate a short cavity passively mode-locked composite erbium-doped fiber laser with saturable absorber based on aerosol-synthesized single-walled carbon nanotubes. Optical pulses had a duration of 973 fs while an average output power – 6 mW. Using a shortened laser cavity, a stable soliton generation with a pulse repetition rate of 150 MHz at the output of the all-fiber linear cavity was obtained.

We examine an effect of residence time on the growth of single-walled carbon nanotubes (SWCNTs) in an aerosol (floating catalyst) chemical vapor deposition (CVD) process using CO as a carbon source and ferrocene as a catalyst precursor. The key feature of aerosol CVD reactors, namely stabilization of fine nanoparticles by an extreme dilution, limits the method for catalyst evolution studies. We show an approach to examine the role of the residence time while maintaining all the processes preceding the nanotube growth (catalyst formation, nanotube nucleation). Using the diameter distribution of nanotubes as a fingerprint of the SWCNT nucleation stage, we have proven the latter to be unaffected by changes in the residence time. Using SEM observations, we have revealed a quite intuitive but inspiring correlation between the carbon nanotube length and residence time. We have also found a decrease in the SWCNT yield caused by the drop in the aerosol concentration, which could be attributed to the gas-phase losses as well as the shift in the catalyst activation degree. Nevertheless, the trends observed allowed us to reach a tenfold decrease in an equivalent sheet resistance (sheet resistance of a film with 90% transmittance at 550 nm) by a threefold increase in the residence time at optimal CO2 concentration. SWCNT films with the equivalent sheet resistance as low as 245 Ω/□ and 51 Ω/□ (for pristine and doped carbon nanotubes, correspondingly) ensure the promising future of the proposed strategy for optimization of both aerosol CVD reactors and SWCNT-based films for optoelectronic applications.

In the present study, we have developed a mathematic model describing quasi-continuous catalytic synthesis of multi-walled carbon nanotubes (MWCNTs) in a fluidized bed (FB) reactor. The special attention has been paid to the effects related to heat release or absorption during MWCNT synthesis. The heat of the reaction for MWCNT growth has been shown to significantly affect the thermal field in the reactor with the diameter as low as 6 cm. We attribute this to the extremely low thermal conductivity of aerogel-like MWCNT agglomerates (0.5–0.7 W/(m·K)), the basic units of the fluidized bed. According to the proposed model, the overheating up to 60 degrees takes place in the reactor with the diameter of D = 18 cm, the wall temperature of 943 K, and blown by 1:1 C2H4/Ar mixture. We have observed major changes caused by overheating: the activity of the catalyst and morphological properties of the produced MWCNTs (outer diameter, the structure of the walls, and fraction of impurities). The role of these thermal effects rises dramatically with increasing the reactor size and should be taken into account when designing reactors for large-scale production of MWCNTs.

A machine learning technique, namely, support vector regression, is implemented to enhance single-walled carbon nanotube (SWCNT) thin-film performance for transparent and conducting applications. We collected a comprehensive data set describing the influence of synthesis parameters (temperature and CO2 concentration) on the equivalent sheet resistance (at 90% transmittance in the visible light range) for SWCNT films obtained by a semi-industrial aerosol (floating-catalyst) CVD with CO as a carbon source and ferrocene as a catalyst precursor. The predictive model trained on the data set shows principal applicability of the method for refining synthesis conditions toward the advanced optoelectronic performance of multiparameter processes such as nanotube growth. Further doping of the improved carbon nanotube films with HAuCl4 results in the equivalent sheet resistance of 39 Ω/□-one of the lowest values achieved so far for SWCNT films.

We propose a novel, scalable, and simple method for aerosol doping of single-walled carbon nanotube (SWCNT) films. This method is based on aerosolization of a dopant solution (HAuCl4 in ethanol) and time-controlled deposition of uniform aerosol particles on the nanotube film surface. The approach developed allows fine-tuning of the SWCNT work function in the range of 4.45 eV (for pristine nanotubes) to 5.46 eV, controllably varying the sheet resistance of the films from 79 to 3.2 Ω/□ for the SWCNT films with 50% transmittance (at 550 nm). This opens a new avenue for traditional and flexible optoelectronics: both to replace existing indium-tin oxide electrodes and to develop novel applications of the highly conductive transparent films.

Effect of the catalyst composition on the structure of nanotubes layers obtained on the surface of carbon nanofibers was studied. We found the preliminary functionalization of the surface of carbon fibers to affect the coating uniformity and the thickness of synthesized nanotube layer. We determined the optimal surface concentration of the catalyst (Fe–Co) which provides uniform layer of nanotubes on the surface of carbon fibers. The effect of modification of the surface of carbon fibers with multi-walled carbon nanotubes on the mechanical properties of carbon fiber–epoxy resin composites was examined. The modification of the carbon fibers with multi-walled carbon nanotubes were shown to increase the flexural modulus and the flexural strength.

The synthesis conditions of multi-walled carbon nanotubes (MWCNTs) indirectly determine their application potential through the decisive role in the characteristics of individual tubes: diameter distribution, structure and defectiveness of graphene walls, the amount of metal impurities and amorphous carbon. In the present work, we have studied the influence of the catalyst composition and synthesis conditions on the diameter distribution and the structure of nanotube walls. We have observed the influence of the particle size for MWCNT synthesis (i.e. size effect) on catalytic activity by ex situ and in situ techniques: in situ X-ray diffraction on synchrotron radiation (SRXRD), gas chromatography, and ex situ transmission electron microscopy. The data obtained by in situ SRXRD are in agreement with the results collected using laboratory tubular fix-bed catalytic reactor allowing thereby extending the applicability of the approach. For the first time we have shown the increase of the fraction of graphene walls in the total MWCNT diameter with time.

We report a development of recently designed apparatus equipped with a spark discharge generator of catalytic nanoparticles for robust aerosol CVD synthesis of single-walled carbon nanotubes. We achieve a profound control over the diameter distribution and the defectiveness of carbon nanotubes produced. By providing a justified comparison of the apparatus with the most abundant aerosol CVD reactor utilizing ferrocene as a catalyst precursor, we reveal the role of the activation procedure: while spark-discharge generator provides aerosol of nanoparticles (ex situ route), the ferrocene vapor decomposes in the nanotube growth zone providing an in situ formation of the catalyst. With other parameters being equal, we reveal the differences in the nanotube growth (diameter and length distribution, yield, defectiveness) employing a comprehensive set of methods (the analysis of differential mobility of the aerosol particles, optical spectroscopy, scanning and transmission electron microscopy, Raman spectroscopy, and atomic force microscopy). We show the ex situ activation in the spark discharge reactor to provide a lower utilization degree of the nanoparticles due to over-coagulation. However, the same method provides an independence of the key performance parameters of the nanotubes opening a room for scaling the apparatus.

Curved graphene fragments can be considered as building blocks of carbon nanotubes. Thus, the size of graphene fragments may be considered as one of the most important characteristics of their structural disorder. In this paper, we have performed a comparative Raman study of CVD multi-walled carbon nanotubes (MWCNTs) and graphene flakes deposited on MWCNTs. Raman data have been considered in combination with HRTEM characterization of nanotubes. The basic attention has been paid to the behavior of D (disorder-induced), G (tangential mode), and 2D (two-phonon scattering) bands in Raman spectra in order to use them for MWCNT characterization. A ratio of intensities of 2D and D bands (I2D/ID) demonstrates almost a linear dependence on the mean diameter of MWCNTs produced with two different types of catalysts (see abstract figure). It should be mentioned that each type of catalyst provides the linear dependence with its own specific slope. The graphene fragments have been proposed to form a mosaic structure of nanotube walls. I2D/ID ratio depends on the amount of graphene flakes deposited on nanotube surface via ethylene decomposition. A dependence of intensity ratio I2D/ID on the diameter of nanotubes produced with different types of catalysts.

In this paper electromagnetic properties of composite materials based on polymethylmethacrylate and multiwall carbon nanotubes (MWCNTs) are investigated. Carbon nanotubes are received with application of various types of catalysts and have various structural parameters. Calculation of dielectric permeability of the synthesised materials is carried out. Dependence of electromagnetic properties of composite materials on concentration and structure used multilayer carbon nanotubes is shown.

A transient model of the catalytic synthesis of multilayer carbon nanotubes in a fluidized bed under the condition of a sharp increase in its volume during synthesis has been developed. The model is based on experimental kinetic data of the synthesis of multiwalled carbon nanotubes on metallic catalysts and takes into account the induction period of the catalyst activation, its deactivation during the synthesis, changes in the bed’s height, and the mass transfer of the gas phase components. Various modes of the periodic discharge of the product and loading of the catalyst into a reactor have been considered and, under these conditions, the dynamics of changes in the process characteristics over time have been studied. Optimal controlling parameters that allow one to achieve maximum yields from the synthesis, a high conversion level of the gaseous carbon source, and high purity of the product have been determined for cyclic operation of the reactor.

The investigation of the catalyst active component formation during multi-walled carbon nanotube (MWCNT) synthesis was carried out by means of in situ and ex situ synchrotron radiation X-ray diffraction. The data on phase composition transformations obtained with 1 s time-resolution allows optimization the carbon nanotubes synthesis in industrial fluidized bed reactors.

The formation of active component of Fe–Mo and Co–Mo catalysts for carbon nanotube growth with variable Mo content is studied with in situ XRD, XPS, and STEM&EDX. The activation of bimetallic Fe–Mo catalysts under the growth conditions leads to the formation of Fe–Mo alloy particles in contrast to Co-containing catalysts in which active alloy incorporates only a small portion of Mo (

This paper is devoted to the influence of the multi-walled carbon nanotube (MWCNT) spatial distribution within a polymer matrix on the electrophysical properties of the composite. We have studied composites with MWCNT concentrations close to the percolation threshold upon variation in (i) the morphology of the reinforcing material using MWCNTs with different aspect ratio and nanotube aggregate size (up to the average size of ≈300 µm) that were isolated from each other by thin polymer layers, and (ii) the type of the polymer matrix. The composites obtained have been characterized using optical and scanning electron microscopy, and DC conductivity measurements. A study of the electromagnetic response in microwave (0.01–18 GHz) and terahertz (100–200 GHz) ranges was performed. In the region close to and above the percolation threshold, the electrophysical properties of the composites were found to be strongly affected by the spatial distribution of MWCNTs in the composite matrix. The effect of conductive fillers (NTs) size on the EMI reflectance of the composites was different for microwave and terahertz ranges.

Lightweight materials for efficient electromagnetic interference shielding over a wide range of frequency are of great interest. Aerogels of multi-walled carbon nanotubes (MWCNTs) distributed in a dielectric matrix may interact effectively with electromagnetic radiation. Moreover, being arranged in specific patterns, they can also provide metamaterial characteristics (e.g., negative refractive index). In the present paper, we have studied the interaction between two spheres of the carbon nanotube aerogels in order to obtain a comprehensive basis for producing periodic 2D and 3D structures of such aerogel spheres in a dielectric matrix. We have extended the open resonator technique to the case of two units of MWCNT aerogels in order to reveal the interaction between them. The performance of the system depends on the orientation of the electric field to the axis of the aerogel cluster: MWCNT aerogel spheres (d = 4.5 mm) interact considerably at the gap between spheres ∼0.2λ (11.6 GHz) for perpendicular orientation, while, in case of axial orientation, the interaction is negligible even at the distances close to the contact between aerogels (∼0.02λ). Additionally, the cluster of two carbon nanotube aerogel spheres provides the polarizability close to that of copper spheres while having only 1% of their weight.

The present paper is devoted to the influence of the growth temperature of multi-walled carbon nanotubes (MWCNTs) on their defective structure. The MWCNTs obtained within the range of 610–750 °C have been studied using two methods: Raman spectroscopy and the analysis of the temperature dependence of conductivity. This approach allows us to obtain independent data on the concentration of the defects within the MWCNTs via the intensity ratio of 2D and D bands, on one hand, and charge carrier concentration, on the other hand. The results obtained using Raman spectroscopy and the analysis of the conductivity have provided asymptotic and volcano-like curves, respectively, of defect concentration within the temperature range studied. This can be attributed to the difference in the probing depth of each method (∼50 nm for Raman spectroscopy, and ∼2–3 nm for conductivity measurements) providing different sensitivity to surface impurities or defects. The secondary factors (the size of the active component, the amount of the lateral carbon deposits) have been shown to mask the influence of the growth temperature. Nevertheless, as these secondary factors and the synthesis temperature independently affect the effective nanotube defectiveness, we have shown the defect concentration to fall with increasing MWCNT growth temperature.

We present the simple procedure of the vapor-phase bromination of multiwall carbon nanotubes (MWNTs) at moderate temperatures. MWNTs with average diameter9±3 nm were treated with Br2vapors at 250°C to produce Br-functionalized product. Transmission electron microscopy analysis was used to prove low damage of MWNT walls during bromination. X-ray photoelectron spectroscopy (XPS) and differential thermal analysis (DTA) were used to investigate chemical composition of the surface of initial and brominated nanotubes. The experimental results show that the structure of MWNTs is not affected by the bromination process and the total amount of Br-containing surface functions reaches 2.5 wt. %. Electrophysical properties of initial and brominated MWNTs were investigated showing decrease of conductivity for functionalized sample. Possible mechanism of the vapor-phase bromination via surface defects and oxygen-containing functional groups was proposed according to data obtained. Additional experiments with bromination of annealed low-defected MWNTs were performed giving Br content a low as 0.75 wt. % proving this hypothesis.

Coagulation technique was applied for preparation of multiwall carbon nanotube- (MWNT-)containing polystyrene (PSt) composite materials with different MWNT loading (0.5–10 wt.%). Scanning and transmission electron microscopies were used for investigation of the morphology and structure of produced composites. It was shown that synthesis of MWNT/PSt composites using coagulation technique allows one to obtain high dispersion degree of MWNT in the polymer matrix. According to microscopy data, composite powder consists of the polystyrene matrix forming spherical particles with diameter ca. 100–200 nm, and the surface of MWNT is strongly wetted by the polymer forming thin layer with 5–10 nm thickness. Electrical conductivity of MWNT/PSt composites was investigated using a four-probe technique. Observed electrical percolation threshold of composite materials is near to 10 wt.%, mainly due to the insulating polymer layer deposited on the surface of nanotubes. Electromagnetic response of prepared materials was investigated in broadband region (0.01–4 and 26–36 GHz). It was found that MWNT/PSt composites are almost radiotransparent for low frequency region and possess high absorbance of EM radiation at higher frequencies.