Dmitry V. Krasnikov

Direct Vapor-Phase Bromination of Multiwall Carbon Nanotubes

We present the simple procedure of the vapor-phase bromination of multiwall carbon nanotubes (MWNTs) at moderate temperatures. MWNTs with average diameter 9±3 nm were treated with Br2 vapors 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.

Investigation of defectiveness of multiwalled carbon nanotubes produced with Fe–Co catalysts of different composition

Abstract. We have performed a study of CVD multiwalled carbon nanotubes (MWCNTs) produced with Fe–Co catalysts with a variable ratio of active metals. The Raman data were considered in combination with the temperature dependence of MWCNT conductivity. The data analysis is based on the point that the value of I2D/ID ratio correlates with the graphene fragment size. The fragments are considered as building blocks of MWCNTs. We showed that MWCNT defectiveness depends on the ratio of bimetallic active components in the Fe–Co catalyst. Thus, the ratio of I2D/ID increases and the D-mode intensity decreases while the Fe content in the catalyst increases. This also points to the reduction of defect number in the bigger graphene fragments. These results correlate with the data on conductivity temperature dependence. Namely, the increase of Fe content in the active component of the Fe–Co catalyst results in the increase of charge carrier concentration, which, in turn, indicates a decrease in MWCNT defectiveness.

Investigation of Fe-Co catalyst active component during multi-walled carbon nanotube synthesis by means of synchrotron radiation X-ray diffraction

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.

Structure and Properties of Multiwall Carbon Nanotubes/Polystyrene Composites Prepared via Coagulation Precipitation Technique

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.

Simulation of transient processes of the catalytic synthesis of carbon nanotubes in a fluidized bed

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.

Towards the optimization of carbon nanotube properties via in situ and ex situ studies of the growth mechanism

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.

Modification of the surface of carbon fibers with multi-walled carbon nanotubes and its effect on mechanical characteristics of composites with epoxy resin

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.