Processes of self-organization in diffusive and limited conditions of colloidal solutions of carbon nanotubes under the influence of constant electric fields are studied. It is established that functionalized MCNT – COOH in a drop of colloidal solution is oriented in an electric field in a controllable way, which is of great practical value

Dobromyslov, M.B.

Kutsenko, A.V.

Kuzko, A.E.

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. 8 No 3, 03035(3pp) (2016) Том 8 № 3, 03035(3cc) (2016) 
 
 
2077-6772/2016/8(3)03035(3) 03035-1  2016 Sumy State University 
Structure of Carbon Nanotubes in Colloidal Solutions under the Influence of a Constant 
Electric Field 
 
A.P. Kuzmenko1, Thet Phyo Naing1, A.E. Kuzko1, Myo Min Than1, A.V. Kutsenko1, M.B. Dobromyslov2 
 
1 Southwest State University, 94, 50 let Oktyabrya st., 305040 Kursk, Russia 
2 Pacific National University, 136, Tikhookeanskaya st., 680035 Khabarovsk, Russia 
 
(Received 04 May 2016; published online 03 October 2016) 
 
Processes of self-organization in diffusive and limited conditions of colloidal solutions of carbon nano-
tubes under the influence of constant electric fields are studied. It is established that functionalized 
MCNT – COOH in a drop of colloidal solution is oriented in an electric field in a controllable way, which is 
of great practical value. 
 
Keywords: Multiwalled carbon nanotubes, Colloidal solutions, Ordered structures 
 
DOI: 10.21272/jnep.8(3).03035 PACS numbers: 61.48.De,  82.70.Dd 
 
 
1. INTRODUCTION 
 
The high mechanical durability, heat conductivity 
and electrical conductivity, very low voltage of field 
emission, which are characteristic of carbon nanotubes 
(CNTs), along with high chemical and mechanical sta-
bility are substantially due to abnormally high aspect 
ratio l/d , which amounts to 106 [1]. All of these proper-
ties, and also abundance and availability of methods 
and ways of synthesis of CNTs both in the form of sin-
gle-walled (SWCNTs) and multi-walled carbon 
(MWCNTs), cause their application promising in differ-
ent fast-developing areas of engineering [2]. However, 
the application of SWCNTs and MWCNTs involves 
difficulties in stabilization and the set orientation. The 
alternative decision when SWCNTs and MWCNTs are 
structured can use the phenomena of self-assembly and 
self-organization [3]. The present work considers the 
influence of electric fields on self-organization process-
es of preliminary functionalized with carboxyl groups – 
MWCNTs – COOH [4, 5] with a different concentration 
in colloidal solutions of sodium dodecyl sulfate (SDS) 
with the deionized water (DW) and without SDS. 
As samples for research were MWCNTs (Nanocyl 
production, Belgium) synthesized by CCVD method 
with nanocatalysts on the basis of CoO. The level of 
functionalization of MWCNTs was determined by the 
use of FT-IR spectra (Nicolet iS50, 0,125 cm – 1). The 
intensity of all lines in the range of measurements from 
3435 to 624 cm – 1 is noted to have changed by an order 
of magnitude. From MWCNTs – COOH, which feature 
high stability, the colloidal solutions (CSs) either 
MWCNTs – COOH + SDS + DW (0.69 mg/ml) or 
MWCNTs – COOH + DW (0.2 mg/ml) were prepared. 
An exponential change of the sizes of the initial ag-
glomerates MWCNTs – COOH as a function of disper-
sion time (t) is found: D  D0exp(– kt), where D0 is the 
largest diameter of agglomerate MWCNTs – COOH in 
an initial state; k is time characteristic of a dispergator. 
The minimum diameter of the agglomerate, coincident 
with or multiple to MWCNTs diameter d  20 nm, was 
probably the limit from below. 
The produced CS was put with the drop method 
within the interelectrode space of the film chip pre-
sented in Fig. 1, a. Structurization of CS during evapo-
ration at a constant voltage (from 10 to 50 V) is stud-
ied. The motion of particles in an electric field in the 
evaporation was recorded with a video camera. By us-
ing video files, the dynamic analysis of particle behav-
ior was conducted. 
 
  
 
а 
 
b 
  
 
c 
 
d 
Fig. 1 – Images of a chip (a) and microstructures of a deposit 
from CS on polycrystalline glass for MWCNTs – COOH + DW: 
FS U  15 V (b) and DS U  16 V (c); for MWCNTs –
 COOH + SDS + DW LPFs U  45 V (d) 
 
Fragments of instant confocal images of the struc-
ture at reorganization shown are in Figs. 1, b – d (with 
a distance between electrodes of 1500 µm; from below –
 the cathode, from above – the anode). The structures 
MWCNTs + DW observed at U  15 and 16 V were sys-
tematized on the multilevel fractal structures (FSs) 
and the diffusion structures (DSs), respectively (see 
Fig. 1, b and c). And in MWCNTs + SDS + DW, the 
origination of piecewise linear (threadlike) structures 
(PLSs) (Fig. 1, d) was observed. Video control of parti-
cle motions revealed that the formation of FSs and 
PLSs occurred in one direction, namely, from the nega-
tive to the positive electrode. 
Restructurings of MWCNTs – COOH + in a drop 
with electric influence according to the atomic force 
microscopy (AFM) are illustrated in Fig. 2, a, b. At a 
 A.P. KUZMENKO, THET PHYO NAING, A.E. KUZKO, ET AL. J. NANO- ELECTRON. PHYS. 8, 03035 (2016) 
 
 
03035-2 
voltage of 16 V, in some areas the formation of rectilin-
ear enough structures of PLSs up to 450 nm long (Fig. 
2, a) was observed, which were composed of three sepa-
rate agglomerates with a diameter of 150 nm. It was 
found that when the voltage increased the diameter of 
the components of PLSs substantially reduced. So, at a 
voltage of 23 V, this diameter actually became equal to 
the MWCNTs diameter of 20 nm. Along with areas 
having PLSs, AFM made it possible to find the for-
mation of spherical shape agglomerates with a diame-
ter on the order of 230 nm, which were made of sepa-
rate MWCNTs with sizes, multiple 20 nm. The for-
mation from plaits of PLSs was also confirmed with the 
scanning electron microscopy (Fig. 2, c). 
The analysis of dynamic behavior of particles in CS 
MWCNTs –COOH + DW according to video data re-
vealed that the formation of FSs from CS in DW solu-
tion began with 10 V and proceeded up to 20 V. PLSs 
originated only at a voltage of 16 V, and at greater 
voltage, the formation of areas with DS was observed. 
For CS from MCNTs – COOH + SDS + DW the growth 
of structures began starting with over 20 V. At the first 
stage, there appeared DSs and only then PLSs origi-
nated. 
 
  
 
a 
 
b 
 
 
                         c 
 
Fig. 2 – AFM-images of PLSs structures from CS MWCNTs –
 COOH + DW in an electric field: a – 16V; b – 23 V with sizes 
of 20 nm, c – the electronic microscopic image of PLSs struc-
tures 
 
It was established that from CS in DW solution the 
formation of FSs started with 10 V and continued up to 
20 V. PLSs arose only at 23 V, and at a bigger voltage 
the formation of areas with DSs was observed. For CS 
from a SDS with the deionized water (MWCNTs –
 COOH + SDS + DW) structures began to grow with a 
voltage over 20 V when at the first stage there were 
DSs, and then PLSs. PLSs grew with acceleration  
(Fig. 3, a) and was also followed by the reduction in the 
sizes of the forming particles (Fig. 3, b). 
The chemical composition of structures observed 
was studied by Raman scattering (RS) (Scope™ omega 
the Raman microspectrometer, 532 nm, 0.8 cm – 1). A 
spot of 500 nm diameter produced by focused radiation 
with a confocal microscope allowed one to obtain RS 
spectra from DSs, FSs and PLSs. The content of 
MWCNTs in them was confirmed by D  1336-1353 
cm – 1 and G  1567-1600 cm – 1 lines in the RS spec-
trum and by radial breathing modes (RBM)  200-
600 cm – 1. Typical RS spectra are presented in Fig. 4. 
In them, CS MWCNTs – COOH + SDS + DW from 
PLSs featured the greatest intensity (ID and IG. For 
MWCNTs – COOH + DW it was 4 times lower in the 
field of DSs, and in the FSs area, the intensity of these 
lines decreased by an order of magnitude. The amount 
of the relation ID/IG determining the deficiency level 
was for structures of PLSs 1,27; for DSs increased  up 
to 1,4, and for FSs amounted to 1,5. Essential changes 
in RS spectra in the RBM were observed. All of this 
confirmed that PLSs, DSs and FSs from MWCNTs –
 COOH were created. 
 
 
a 
 
 
b 
 
Fig. 3 – Changes of speed of the particles motion accord-
ing to video control (a) and the sizes of nanostructures 
with AFM images (b) versus the constant voltage ampli-
tude and their predicted dependences 
 
By UV-spectra (Shimadzu UV-1800, 190-1100 nm) 
the frequency of the plasmon resonance (PR) was de-
termined, and through an optical threshold of absorp-
tion when the dependence () was extrapolated, the 
width of the forbidden zone Eg was calculated which 
were on PR  259 and 257 nm, Eg  4.5 and 5.1 eV for 
MWCNTs – COOH + DW and MWCNTs –
 STRUCTURE OF CARBON NANOTUBES… J. NANO- ELECTRON. PHYS. 8, 03035 (2016) 
 
 
03035-3 
 COOH + SDS + DW, respectively. The coincidence of 
PR is completely due to the identical size of the main 
component of the CS. Under the assumption that the 
size of these complexes is an area of coherence (L) at a 
plasmon resonance the following condition will be satis-
fied: d  L  , from which it follows that the effective 
diameter of MWCNTs – COOH in CS amounts to about 
260 nm. 
 
 
 
Fig. 4 – Raman spectra of FSs, DSs, and PLSs 
 
The analysis of the AFM-images obtained (Fig. 2 a-c) 
revealed that with an increase in voltage the sizes d of 
particles forming FSs, DSs and PLSs decreased (Fig. 3, 
b) whereas the motion speed of particles, according to 
video control, as a function of the constant voltage am-
plitude increased (Fig. 3, а). At the same time, if d(U) 
corresponded to clearly hyperbolic dependence 
d(U)  A/U, then V(U)  BU2 – parabolic one, where A 
and B are the generalized dimensional and normalizing 
multipliers. 
For an explanation of the observed structuring pro-
cesses of MWCNTs – COOH in CS, probably, the most 
significant contribution will be made by an electric 
force and surface tension. In the described conditions, 
the electrophoretic force begins to affect particles in CS 
between electrodes, whose value [6] is proportional to 
the square of the gradient of the applied electric field 
amplitude E2 and to the cube of the particle radius R3: 
   3 212ЭФСF Л R E   , (1) 
where 1 is the dielectric permeability of CS (it is taken 
equal H2O  81; Re|K(0)| – with consideration for   0 
is taken equal to 1. The sizes of the particles forming 
FSs determined by AFM images vary depending on the 
amplitude of the applied voltage d(U) (Fig. 3) and are 
in accord with the dependence (1). 
It is possible to assume that MWCNTs – COOH in a 
drop in an electric field are polarized to form dipoles 
(Fig. 5) in the form of bundles (PLSs) of tubes with a 
radius (D) up to 150 nm (Fig. 2), with the number of 
the constituent tubes: D2/d2  50-100. When the drop 
will be evaporated, the surface tension will build these 
bundles vertically, and the electric force will create 
groups of three and cause the directed movement from 
«–» to «+». 
 
 
 
Fig. 5 – A schematic representation of the MWCNTs –
 COOH motion in an electric field 
 
Thus, functionalized MWCNTs – COOH within a 
drop of CS put in an electric field are capable to be ori-
ented in a controllable way, which is of great practical 
value. 
 
 
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3. A.P. Kuz’menko, Chan Nyein Aung, V.V. Rodionov, Tech. 
Phys.+ 60(6), 903 (2015). 
4. А.П. Кузьменко, Тет Пьо Наинг, Мьо Мин Тан, Изве-
стия Юго-Западного государственного университета. 
Серия: Техника и технологии 3(16), 39 (2015) 
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Structure of Carbon Nanotubes in Colloidal Solutions under the Influence of a Constant Electric Field

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Structure of Carbon Nanotubes in Colloidal Solutions under the Influence of a Constant Electric Field

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