The results of experimental studies of the interface of "dielectric liquid  -  nanostructured metal electrode" after electroconvection is presented. It is discovered the patterns of structuring of areas of polymerization showing disruption of the diffusion layer and the processes of charge injection from the tops of structures.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3636

Belov, P.A.

Emelyanov, S.G.

Kuzmenko, A.P.

Kuz’ko, A.E.

Kuz’ko, A.V.

Electronic Sumy State University Institutional Repository

ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ JOURNAL OF NANO- AND ELECTRONIC PHYSICS  Том 6 № 3, 03057(3cc) (2014) Vol. 6 No 3, 03057(3pp) (2014)  The article was reported at the International Conference «The Advanced Technology, Equipment and Analytical Systems for Materials», Kursk, 13-14 May, 2014 2077-6772/2014/6(3)03057(3) 03057-1  2014 Sumy State University Induction of Polymerization of the Surface Nanostructures of the  Electrodes by Electric Field  S.G. Еmelyanov1, A.E. Kuz’ko1, A.V. Kuz’ko1, A.P. Kuzmenko1, P.A. Belov2  1 South West State University, 94, 50 let Oktyabrya Str., 305040 Kursk, Russia 2 Scientific Research Center (Kursk), the Federal State Unitary Enterprise "18 Central Research University" of the Ministry of Defense of the Russian Federation, 23, Blinova Str., 305040 Kursk, Russia  (Received 19 May 2014; published online 15 July 2014)  The results of experimental studies of the interface of "dielectric liquid - nanostructured metal elec-trode" after electroconvection is presented. It is discovered the patterns of structuring of areas of polymeri-zation showing disruption of the diffusion layer and the processes of charge injection from the tops of struc-tures.  Keywords: Surface nanostructures, Microelectroconvection, Charge injection, Electric double layer, Polymerization.   PACS numbers: 47.65. – d, 61.46.Df   1. INTRODUCTION  Studying of dimensional effects and self-organizing of nanostructures on surfaces of interfaces under the influence of force fields is currently the popular direc-tion of scientific and technological progress [1-2]. The studying of conditions of emergence, properties and application of the self-organized ordered structures is very interesting. The nanostructured ensembles with their unusual properties are created by the nature at dissipation of energy of impact on system. The "dielec-tric liquid-a metal electrode" interface being under the influence of high-voltage electric fields is important for the practical application. Properties of this interface predetermine the charge formation processes. Possibil-ity of control of the charge formation is a basis for pro-gress in using of electrohydrodynamic currents in effec-tive devices of mass- and heat exchange and chemical industries where the electric field is used as the activa-tor of chemical processes. It is shown in work [3] that numerical calculation which takes as a basis of regularity of the autoelectron-ic emission (AEE) current (Fowler-Nordheim equation) is confirmed by experimental data of electrohydrody-namic currents with the macroscale peak electrodes. Therefore the AEE model can be used adequately for calculations in the "dielectric liquid - electrode" system. Possibility of control by the charge formation in the area of the nanometer sizes according to geometry of the surfaces structures of electrodes is shown in works [4, 5]. The above description is incomplete therefore it is necessary to consider the existence of the nanoscale electric double layers and also the adsorption and the oxidation processes on a surface of electrodes.  2. EXPERIMENTAL RESULTS   A number of processes is observed at course of the developed electrohydrodynamic currents (for Е  1 kV/cm) in system of the plane-parallel copper electrodes polished with quality of 20 nanometers and polymethylsiloxane liquid with degree of polymeriza-tion of 50 (PMS-50).These processes are formation of microelectroconvective currents on the tops nanostruc-tures, different types of polymerization, electroerosive degradation of a surface of electrodes [6]. The surface of the anode is shown in figure 1. Microelectroconvection on tops of nanostructures leads to emergence of the porous polymerized layers of molecules of the polyme-thylsiloxan liquid (fig. 1).    Fig. 1 – Topography of the nanostructured surface of the anode  Charge injection and microconvection in the pres-ence of the double electric layer (DEL) leads to the complex branched porous structure on an electrode surface. The images obtained by the confocal micro-scope are presented at the focusing to the plane of a surface of an electrode (fig. 2a) and above (fig. 2b). It is visible that structures (callouts of figures 2a, b) for the same area differ at the change of focusing on height. Obviously, the small pores (callout of figures 2a) corre-spond to movement of charges from tops of protruding nanostructures and the corresponding larger pores (callout of figures 2b) show the areas of the microelec-troconvective currents above the tops of nanostruc-tures. It is understood that ion motion takes place through the pores to the highest nanostructures of the copper surface. The polymerized layer between areas of a charge formation creates an obstacle for movement and a discharge of ions to a surface and therefore the mechanism of transport of charges from an electrode occurs in this case only through a time. Calculation of relative surface area that is occupied by the pores in comparison to the whole area respectively gives value 0.033 for callout 2a and 0.117 for callout 2b. Thus the  S.G. EMELYANOV, A.E. KUZKO, ET AL. J. NANO- ELECTRON. PHYS. 6, 03057 (2014)   03057-2                а b  Fig. 2 – Formation of a film with the centers of charge formation at EC in PMS-50 on the anode  filling of area of callouts by the pores in figure 2b is 3.5 times greater than 2a. We can assume that the counted pore area will determine the surface areas of tops of nanostructures from which charge injection at AEE occurs. Moreover, the let-through current without re-turnable streams is possibly formed in the pores of fig-ure 2a and the microvortices with processes of polymer-ization are occurred in a figure 2b. The charge injection at electroconvection begins with the highest peaks of nanostructures polished to 20 nm in our case. A number of mechanisms [7] involved in the electroconvection in charge formation process. Injection of electrons from tops of structures is facilitated by three factors: 1) when the potential barrier is lowered the high-voltage local electric field generated by an external field [8] (as well as on the "vacuum-metal" border), 2) when the molecules of the electric double layer directly adjacent to the top of the structure increase the field, 3) when the electron acceptor impurities are added in dielectric liquid. Therefore, molecules of the liquid or the impurities mole-cules immediately capture an electron, leading to ionic charge injection. On the flip side the molecule of electric double layer of liquid reduce a poten-tial barrier for an exit of ions of a crystal lattice of metal that at the devel-oped electro convection and the combination of redox reac-tions leads to emergence of the erosive structures. The erosion of metal proceeds in space under the oxide film of a surface of metal if the oxide film isn't metallized at the current destruction of structure. The double electric layer has the same nanometer sizes [9] as well as the considered    Fig. 3 – the emergence of the organized cluster structures  above nanostructures.  If the sizes of structure exceed the thickness of the diffusion layer the breakaway of a diffusive layer in the field of top of structure and nanostructures is the most probable that is accompanied by resonant neutraliza-tion, ionization and an exit of the ions of crystal lattices (erosion). Decrease of thickness of the diffusion layer induces the erosion even below the main surface of the metal (of the horizontal oxide film). It is shown the clusters formed in the breakdown  INDUCTION OF THE SURFACE NANOSTRUCTURES… J. NANO- ELECTRON. PHYS. 6, 03057 (2014)   03057-3 region in figure 3 (a other kind of polymerization). The clusters during its growth come in close contact so that their shape is deformed and becomes similar to the pentagon. Clusters are not of the same nature, they differ in color. The light clusters are formed around the charged core (copper crystallites), and the dark clusters are formed around the adsorbed particles of the iodine ejected at the breakdown moment in the volume of liq-uid. Next the resulting clusters are concentrated at the exposed surface of the metal.   REFERENCES  1. V.I. Roldughin, Russ. Chem. Rev. 73 No 2, 115 (2004).  2. Yu.D. Tretyakov, Russ. Chem. Rev. 72 No 8, 651 (2003). 3. Yu.K. Stishkov, V.A. Chirkov, Tech. Phys. 58 No 12, 1822 (2013). 4. A.I. Zhakin, A.P. Kuzmenko, A.E. Kuzko, Proc. South-West State University 40 No 1, 60 (2012). 5. A.P. Kuz'menko, A.E. Kuz'ko, D.I. Timakov, Tech. Phys. 58 No 2, 239 (2013). 6. A.I. Zhakin, A.E. Kuz'ko, A.V. Kuz'ko, P.V. Abakumov, J. Nano- Electron. Phys. 5 No 4, 04030 (2013). 7. A.I. Zhakin, Phys. Usp. 49 No3, 275 (2006). 8. B.V. Stetsenko, A.I. Shchurenko, Plasma Physics No 1, 136 (2009). 9. O.A. Petrii, G.A. Tsirlina, Russ. Chem. Rev. 70 No4, 285 (2001). 

Induction of Polymerization of the Surface Nanostructures of the  Electrodes by Electric Field

SocioEconomic Challenges Journal (Sumy State University)

ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ JOURNAL OF NANO- AND ELECTRONIC PHYSICS  
Том 6 № 3, 03057(3cc) (2014) Vol. 6 No 3, 03057(3pp) (2014) 
 
The article was reported at the International Conference «The Advanced Technology, Equipment and Analytical Systems for Materials», Kursk, 13-14 May, 2014 
2077-6772/2014/6(3)03057(3) 03057-1  2014 Sumy State University 
Induction of Polymerization of the Surface Nanostructures of the  
Electrodes by Electric Field 
 
S.G. Еmelyanov1, A.E. Kuz’ko1, A.V. Kuz’ko1, A.P. Kuzmenko1, P.A. Belov2 
 
1 South West State University, 94, 50 let Oktyabrya Str., 305040 Kursk, Russia 
2 Scientific Research Center (Kursk), the Federal State Unitary Enterprise "18 Central Research University" of the 
Ministry of Defense of the Russian Federation, 23, Blinova Str., 305040 Kursk, Russia 
 
(Received 19 May 2014; published online 15 July 2014) 
 
The results of experimental studies of the interface of "dielectric liquid - nanostructured metal elec-
trode" after electroconvection is presented. It is discovered the patterns of structuring of areas of polymeri-
zation showing disruption of the diffusion layer and the processes of charge injection from the tops of struc-
tures. 
 
Keywords: Surface nanostructures, Microelectroconvection, Charge injection, Electric double layer, 
Polymerization. 
 
 PACS numbers: 47.65. – d, 61.46.Df 
 
 
1. INTRODUCTION 
 
Studying of dimensional effects and self-organizing 
of nanostructures on surfaces of interfaces under the 
influence of force fields is currently the popular direc-
tion of scientific and technological progress [1-2]. The 
studying of conditions of emergence, properties and 
application of the self-organized ordered structures is 
very interesting. The nanostructured ensembles with 
their unusual properties are created by the nature at 
dissipation of energy of impact on system. The "dielec-
tric liquid-a metal electrode" interface being under the 
influence of high-voltage electric fields is important for 
the practical application. Properties of this interface 
predetermine the charge formation processes. Possibil-
ity of control of the charge formation is a basis for pro-
gress in using of electrohydrodynamic currents in effec-
tive devices of mass- and heat exchange and chemical 
industries where the electric field is used as the activa-
tor of chemical processes. 
It is shown in work [3] that numerical calculation 
which takes as a basis of regularity of the autoelectron-
ic emission (AEE) current (Fowler-Nordheim equation) 
is confirmed by experimental data of electrohydrody-
namic currents with the macroscale peak electrodes. 
Therefore the AEE model can be used adequately for 
calculations in the "dielectric liquid - electrode" system. 
Possibility of control by the charge formation in the 
area of the nanometer sizes according to geometry of 
the surfaces structures of electrodes is shown in works 
[4, 5]. The above description is incomplete therefore it 
is necessary to consider the existence of the nanoscale 
electric double layers and also the adsorption and the 
oxidation processes on a surface of electrodes. 
 
2. EXPERIMENTAL RESULTS  
 
A number of processes is observed at course of the 
developed electrohydrodynamic currents 
(for Е  1 kV/cm) in system of the plane-parallel copper 
electrodes polished with quality of 20 nanometers and 
polymethylsiloxane liquid with degree of polymeriza-
tion of 50 (PMS-50).These processes are formation of 
microelectroconvective currents on the tops nanostruc-
tures, different types of polymerization, electroerosive 
degradation of a surface of electrodes [6]. The surface of 
the anode is shown in figure 1. Microelectroconvection 
on tops of nanostructures leads to emergence of the 
porous polymerized layers of molecules of the polyme-
thylsiloxan liquid (fig. 1). 
 
 
 
Fig. 1 – Topography of the nanostructured surface of the anode 
 
Charge injection and microconvection in the pres-
ence of the double electric layer (DEL) leads to the 
complex branched porous structure on an electrode 
surface. The images obtained by the confocal micro-
scope are presented at the focusing to the plane of a 
surface of an electrode (fig. 2a) and above (fig. 2b). It is 
visible that structures (callouts of figures 2a, b) for the 
same area differ at the change of focusing on height. 
Obviously, the small pores (callout of figures 2a) corre-
spond to movement of charges from tops of protruding 
nanostructures and the corresponding larger pores 
(callout of figures 2b) show the areas of the microelec-
troconvective currents above the tops of nanostruc-
tures. It is understood that ion motion takes place 
through the pores to the highest nanostructures of the 
copper surface. The polymerized layer between areas of 
a charge formation creates an obstacle for movement 
and a discharge of ions to a surface and therefore the 
mechanism of transport of charges from an electrode 
occurs in this case only through a time. Calculation of 
relative surface area that is occupied by the pores in 
comparison to the whole area respectively gives value 
0.033 for callout 2a and 0.117 for callout 2b. Thus the 
 S.G. EMELYANOV, A.E. KUZKO, ET AL. J. NANO- ELECTRON. PHYS. 6, 03057 (2014) 
 
 
03057-2 
             
 
 а b 
 
Fig. 2 – Formation of a film with the centers of charge formation at EC in PMS-50 on the anode 
 
filling of area of callouts by the pores in figure 2b is 3.5 
times greater than 2a. We can assume that the counted 
pore area will determine the surface areas of tops of 
nanostructures from which charge injection at AEE 
occurs. Moreover, the let-through current without re-
turnable streams is possibly formed in the pores of fig-
ure 2a and the microvortices with processes of polymer-
ization are occurred in a figure 2b. 
The charge injection at electroconvection begins with 
the highest peaks of nanostructures polished to 20 nm in 
our case. A number of mechanisms [7] involved in the 
electroconvection in charge formation process. Injection of 
electrons from tops of structures is facilitated by three 
factors: 1) when the potential barrier is lowered the high-
voltage local electric field generated by an external field 
[8] (as well as on the "vacuum-metal" border), 2) when the 
molecules of the electric double layer directly adjacent to 
the top of the structure increase the field, 3) when the 
electron acceptor impurities are added in dielectric liquid. 
Therefore, molecules of the liquid or the impurities mole-
cules immediately capture an electron, leading to ionic 
charge injection. On the flip side the molecule of electric 
double layer of liquid reduce a poten-tial barrier for an 
exit of ions of a crystal lattice of metal that at the devel-
oped electro convection and the combination of redox reac-
tions leads to emergence of the erosive structures. The 
erosion of metal proceeds in space under the oxide film of 
a surface of metal if the oxide film isn't metallized at the 
current destruction of structure. The double electric layer 
has the same nanometer sizes [9] as well as the considered 
 
 
 
Fig. 3 – the emergence of the organized cluster structures 
 
above nanostructures.  
If the sizes of structure exceed the thickness of the 
diffusion layer the breakaway of a diffusive layer in the 
field of top of structure and nanostructures is the most 
probable that is accompanied by resonant neutraliza-
tion, ionization and an exit of the ions of crystal lattices 
(erosion). Decrease of thickness of the diffusion layer 
induces the erosion even below the main surface of the 
metal (of the horizontal oxide film). 
It is shown the clusters formed in the breakdown 
 INDUCTION OF THE SURFACE NANOSTRUCTURES… J. NANO- ELECTRON. PHYS. 6, 03057 (2014) 
 
 
03057-3 
region in figure 3 (a other kind of polymerization). The 
clusters during its growth come in close contact so that 
their shape is deformed and becomes similar to the 
pentagon. Clusters are not of the same nature, they 
differ in color. The light clusters are formed around the 
charged core (copper crystallites), and the dark clusters 
are formed around the adsorbed particles of the iodine 
ejected at the breakdown moment in the volume of liq-
uid. Next the resulting clusters are concentrated at the 
exposed surface of the metal.  
 
REFERENCES 
 
1. V.I. Roldughin, Russ. Chem. Rev. 73 No 2, 115 (2004).  
2. Yu.D. Tretyakov, Russ. Chem. Rev. 72 No 8, 651 (2003). 
3. Yu.K. Stishkov, V.A. Chirkov, Tech. Phys. 58 No 12, 
1822 (2013). 
4. A.I. Zhakin, A.P. Kuzmenko, A.E. Kuzko, Proc. South-West 
State University 40 No 1, 60 (2012). 
5. A.P. Kuz'menko, A.E. Kuz'ko, D.I. Timakov, Tech. Phys. 
58 No 2, 239 (2013). 
6. A.I. Zhakin, A.E. Kuz'ko, A.V. Kuz'ko, P.V. Abakumov, 
J. Nano- Electron. Phys. 5 No 4, 04030 (2013). 
7. A.I. Zhakin, Phys. Usp. 49 No3, 275 (2006). 
8. B.V. Stetsenko, A.I. Shchurenko, Plasma Physics No 1, 
136 (2009). 
9. O.A. Petrii, G.A. Tsirlina, Russ. Chem. Rev. 70 No4, 285 
(2001).
 


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Induction of Polymerization of the Surface Nanostructures of the Electrodes by Electric Field

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