The features and patterns of self-organization processes in the diffusion-limited conditions (method of
drops) of carbon-containing compounds and carbon nanotubes have been studied. The results of the research
influence of the substrate temperature and solvent on the formation of nanoscale fractal structures
in sediments of colloidal solutions are provided

Chan Nyein, Aung

Chervyakov, L.M.

Dobromyslov, M.B.

Emelyanov, S.G.

Kuzmenko, A.P.

Myo Min, Than

Thet Phyo, Naing

English

SocioEconomic Challenges Journal (Sumy State University)

JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ 
Vol. 7 No 4, 04014(3pp) (2015) Том 7 № 4, 04014(3cc) (2015) 
 
 
2077-6772/2015/7(4)04014(3) 04014-1  2015 Sumy State University 
Self-assembly and Self-organization Processes of Carbon Nanotubes in the Colloidal Systems 
 
A.P. Kuzmenko1, Thet Phyo Naing1, Myo Min Than1, Chan Nyein Aung1,  
M.B. Dobromyslov2, S.G. Emelyanov1, L.M. Chervyakov1 
 
1 Southwest State University, 94, 50 let Oktyabrya St., 305040 Kursk, Russia 
2 Pacific State University, Khabarovsk, Russia 
 
(Received 28 September 2015; published online 10 December 2015) 
 
The features and patterns of self-organization processes in the diffusion-limited conditions (method of 
drops) of carbon-containing compounds and carbon nanotubes have been studied. The results of the re-
search influence of the substrate temperature and solvent on the formation of nanoscale fractal structures 
in sediments of colloidal solutions are provided. 
 
Keywords: Self-organization, The carbon-containing colloidal solution, Multi-walled carbon nanotubes, 
Fractal structures, Benzene ring. 
 
 PACS numbers: 81.05.U –, 61.48.De 
 
 
1. INTRODUCTION 
 
Transition in nanorange is accompanied by a dis-
play of the new dimensional of physicochemical effects 
and phenomena, in particular, self-organization and 
self-assembly [1]. There is no alternative in terms of 
their implementation for new generations of both elec-
tronics and nanostructured materials. An important 
role in the processes of self-organization and self-
assembly are played by the substrate temperature and 
solvent composition of colloidal system, whose role at 
fractals formation under the diffusion-limited condi-
tions (method from the drop – wedge dehydration) has 
has not been studied enough with the use of standard 
measurement techniques [2, 3], that have a significant 
effect on the processes themselves. Previously in a col-
loidal solution of carbon nanotubes, methods of atomic-
force microscopy (AFM), confocal microscopy (CM) and 
fluorescence microscopy allowed to find out the variety 
and development of structural formations of the den-
drite type in the form of fractals [3]. Application of Ra-
man scattering of light (RSL), FT-IR analysis, low-
voltage SEM and fluorescence microscopy and energy-
dispersive analysis allowed establishing that the sedi-
mentation of CNTs has a central-axis structure which 
is made up of a pinning ring, areas of stagnation and 
formation of fractals [4]. Also, that made it possible to 
develop a qualitative physical model of fractals for-
mation in those colloidal solutions that considers com-
pensation of Rayleigh-Benard streams and surface ca-
pillary Marangoni streams proposed in [5], and also to 
add data concerning volume convection. Of interests 
are investigations of structures formed from single- and 
multi-walled carbon nanotubes (SWCNTs and 
MWCNTs). However, their application involves great 
difficulties due to natural aggregation, which is charac-
teristic for such nano-dimensional systems [6]. 
The present work considers, with nano instrumen-
tal techniques, including CM with the help of AFM 
coordinate scanning heated up to 160 С, with AFM, 
SEM, UV-spectrophotometry, FT-IR analysis, RSL ef-
fect of the substance temperature and the solvent com-
position on the self-organization processes and the re-
arrangements of structure after evaporation of drop 
(SAED) of colloidal solutions with CNTs.  
2. TECHNIQUES AND INVESTIGATION 
RESULTS 
 
Research of MWCNTs synthesized by catalytic py-
rolysis method of ethanol (95 % purity nickel nanocata-
lyst installation Domna) – MWCNTs I, and also ob-
tained by the CCVD method (purity 90 %, nanocatalyst 
cobalt oxide, Nanocyl Belgium) MWCNTs II has re-
vealed that the diameter of the all MWCNTs was the 
same d  1020 nm, however, the CCVD characterized 
tube has the length (L) of up to 10 m, whereas L of 
MWCNTs I was up to 500 nm. An aspect ratio L/d for 
MWCNTs I and II reached  25  50 and  103, respec-
tively. 
SAED of both types of MWCNTs have been exam-
ined with the drop method (3 l) on the coverslip, sili-
con single crystal and cleavage of mica depending on 
the concentration of CS with different solvents. Addi-
tionally, as a colloidal solution of silica – SiO2 was also 
used. 
MWCNTs underwent purification and chemical oxi-
dation, during which the following procedures were 
subsequently conducted: mixing in an USB of 
MWCNTs with H2SO4and HNO3 in ratio of 3 : 1, cool-
ing, and addition of deionized water, filtration, washing 
and drying, in accordance with [7]. Mechanochemical 
treatment causes the dimension reductions, functional-
ization, prevented from agglomeration of MWCNTs. 
Analysis of CM images of SAED in CS of various com-
position with MWCNTs has revealed: benzene rings 
(BR), piecewise linear structures (PLS), fractal struc-
ture (FS), BR of particles, clusters. 
The most typical CM images (Fig. 1) are demon-
strated diversity of structural forms. These results 
have been selected solvents, from mixture of acids, tol-
uene, pyridine, DMFA were used. For example, the 
formation of FS in SAED of MWCNTs in toluene 
(Fig. 1a, b) occurred only at thermo activation, starting 
at the temperature from 313 K. It is characteristic that 
the length of FS branches with further heating did not 
changed, but they became less in thickness (Compare 
Fig. 1a and b). However, even at 343 K FS were de-
stroyed, individual fragments of MWCNTs became 
larger in size, and the space between them was filled 
 A.P. KUZMENKO, THET PHYO NAING, ET AL. J. NANO- ELECTRON. PHYS. 7, 04014 (2015) 
 
 
04014-2 
with a heavily corrugated surface (Fig. 1b). In SAED of 
CS with MWCNTs, in distinction to [4], the central-axis 
symmetry was not explicitly occurred. Nevertheless, at 
drop evaporation the formation of the pinning ring, the 
stagnation region, and also the central region were 
always observed. Structuration, including fractal for-
mation, took place mainly near the pinning ring, as is 
seen from Fig. 1a. However, when heating, the corruga-
tion structure appeared over the whole surface of the 
evaporated droplet (Fig. 1b). 
 
  
a b 
 
c 
Fig 1 – Temperature effect on the FS formation in the CS of tolu-
ene + MWCNTs: a – 313,  b – 343 Киc – CS SiO2 + MWCNTs 
 
Fractal structure was also found in composition 
(Fig. 1c) that presented MWCNTs in CS ofSiO2 with a 
ratio of 1 : 1 with an addition of H2O. SAED represent-
ed a crystallized film with a thickness of not more than 
5 m where MWCNTs were uniformly distributed 
throughout by volume. As seen from shown in Fig. 1c, 
in CM images of several fragments such sectors sepa-
rated by cracks, within them FSs were formed through 
all thickness of the SiO2 film. Thus, if the previously  
 
  
a b 
  
c d 
 
Fig 2 – Structuration of CS of MWCNTs + H2SO4 and HNO3: 
a – 4 % USD 5 min; 0.4 % with USD, b  – 5 min; and also c –
 55 min; d – C5H5N 1 : 1, USD 50 min 
 
 
a 
  
b 
 
 c 
 
Fig 3 – Structuration of CS of MWCNTs + H2SO4 and 
HNO3 with 0.4 % and USD 55 min according to: а – КМ,  
b and c – SEM 
 
FSs formed, generally only on the substance surface 
[3], including the formation of 3D structures [4], here 
FS became abundant and distributed throughout 
thickness film of the silica (Fig. 1). 
When MWCNTs treated with USD by the mixture 
of H2SO4 and HNO3, in SAED the formation of either 
regular «benzene rings» BR (Fig. 2a) or deformed BR 
was found, which is illustrated in Fig. 4b. It is seen 
that, there are also areas in which FSs are observed. 
When the concentration of acids was reduced by an 
order of magnitude at a constant time of USD treat-
ment (5 min), BRs became sharper and larger practi-
cally by two times (Compare Fig. 2a and b). When the 
time of USD treatment increased at a constant concen-
tration, both the increase in size of BR (up to 50 %) and, 
beginning with 10 min of USD, the appearance of a 
piecewise linear structures (PLS) (Fig. 2c) was observed. 
This inference is in accord with the conclusions about 
the fracture of MWCNTs at an ultrasonic cavitation [6]. 
Besides that, for SAED of CS (MWCNTs + mixture 
of H2SO4 and HNO3) with a concentration of 4 % at 
USD for 40 min, regions with practically mutually-
 SELF-ASSEMBLY AND SELF-ORGANIZATION PROCESSES… J. NANO- ELECTRON. PHYS. 7, 04014 (2015) 
 
 
04014-3 
perpendicular PLSs were found (Fig. 3a). It can be as-
sumed that the regions with similar structurization 
from MWCNTs are clustered congregations of rectan-
gular structural elements (Fig. 2c). In this case, as seen 
from the figure, equal size elements multiples of 1/2 
became ordered in parallel. This fact, as already noted, 
is in line with conclusions [6] about fracture of initial 
MWCNTs at cavitation in USD. Determined from 
Fig. 3a PLS from MWCNTs noted with arrows take on 
values: А  48, B  24, C  12, D  6, E  3, really, mul-
tiples of 1/2. At AFM measurement, the part of wall of 
BR or PLS was up to 7 m in height and made up of 
ordered entities of about 1 m in length.According to 
SEM results, the minimal PLSs diameter reached 
250 nm (Fig. 3b). These were constructed from the in-
dividual MWCNTs (Fig. 3c) combined into bundles. 
In SAED of CS from pyridine, BRs from MWCNTs 
were also found. The formation of BR was reached after 
50 min of USD treatment when the initial size of 
MWCNTs was dramatically reduced. In this case, BRs 
were constructed on the dramatically different basis, 
namely, made up of individual micro and nanoparti-
cles, which is shown in Fig. 2d. As a result, in distinc-
tion from BRs in Fig. 2a-c, only hexagonal shape char-
acteristic of BR repeated. The size of such BR was sig-
nificantly dependent on the substrate material. For 
example, the structure in Fig. 2d was obtained at the 
mica substrate. Similar structures were observed at a 
glass substrate, whereas the sizes of structures at the 
single silicon were greater roughly by two times. 
 
3. DISCUSSION OF RESULTS 
 
Discussing the results of SAED of CS with 
MWCNTs described in the second part, pay close atten-
tion to their considerable distinction in terms of sample 
dissection for studying and diversity of the observed 
structures, among which highlighted were BR, PLS 
and FS. Besides qualitative selection of solvents for CS 
of MWCNTs, it was established that the length of the 
side (a) that forms BR is a linear function of the USD 
time (tUSD): а  ktUSD. In doing so, the rate of growth of 
a, as well as the length of the component L of PLS –
k  da, L/dtUSD increases with MWCNTs concentration 
in CS. At the same time, the length of the branch of FS 
at such variations of concentration and time of USD 
reduces.  
Implementation of BR, PLS, and FS in SAED of CS 
is determined by quantities  and , including, with con-
sideration for (Т) and (Т) from the condition of mini-
mum free energy in such a system with an external en-
ergy source at the expense of the drop evaporation. 
 
4. CONCLUSION 
 
After evaporation of a droplet colloidal solution (on 
the basis of H2SO4 + HNO3, pyridine, toluene, dime-
thylformamide, or silica) of purified and functionalized 
multi-walled carbon nanotubes as a result of self-
assembly and/or self-organization structures appear as 
benzene rings, piecewise linear structures, or fractals.
 
 
REFERENCES 
 
1. G.B. Sergeev, Rus. Chem. J. No 5, 22 (2002). 
2. Hua Hu, G. Ronald, Phys.-Chem. J. Lett. B 7090 (2006). 
3. A.P. Kuzmenko, Chan Nyein Aung, V.V. Rodionov, 
M.B. Dobromyslov, J. Nano- Electron. Phys. 6 No 3, 03022 
(2014). 
4. A.P. Kuzmenko, Chan Nyein Aung, V.V. Rodionov, Tech. 
Phys. 60 No 6, 903 (2015). 
5. P.V. Lebedev-Stepanov, R.M. Radushnikov, S.P. Molchanov, 
N.I. Rubin, N.A. Shturkin, M.V. Alfimov, Nano Tech. 1-2 
No 6, 79 (2011). 
6. Yan Yan Huang, Eugene M. Terentjev, Polymers 4, 275 
(2012). 
7. V. Datsyuk, M. Kalyva, K. Papagelis, J. Parthenios, 
D. Tasis, A. Siokou, I. Kallitsis, C. Galiotis, Carbon 46, 
833 (2008). 
 


Self-assembly and Self-organization Processes of Carbon Nanotubes in the Colloidal Systems

https://essuir.sumdu.edu.ua/bitstream/123456789/43205/1/Kuzmenko.pdf

Self-assembly and Self-organization Processes of Carbon Nanotubes in the Colloidal Systems

Abstract

Similar works

Full text

Available Versions

SocioEconomic Challenges Journal (Sumy State University)