Aleshin, S.V.

Andreev, A.A.

Gorban, V.F.

Grigorev, S.N.

Sobol, О.V.

Stolbovoy, V.A.

Volosova, M.A.

Electronic Sumy State University Institutional Repository

88                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I              STUCTURE AND MECHANICAL CHARACTERISTICS OF VACUUM ARC TiN COATINGS DEPOSITED WITH  HIGH-VOLTAGE HIGH FREQUENCY PULSES ON THE SUBSTRATE 1*Sobol O.V., 2Andreev A.A., 3Grigorev S.N., 4Gorban V.F., 3Volosova M.A., 3Aleshin S.V., 2Stolbovoy V.A.  1 National Technological University “Kharkov Polytechnic Institute”, Frunze St., 21, Kharkov, 61002, Ukraine 2 National Science Center “Kharkov Institute of Physics and Technology”, Akademicheskaya St., 1, Kharkov, 61108, Ukraine 3 Moscow State Technological University "Stankin",  Vadkovskij per., 3a, 127055, Moscow, Russia 4 Frantsevich Material Science Problem Institute, Krzhizhanovsky St., 3, Kiev, 03142, Ukraine  In order to improve the functional properties of the most currently used in industry TiN vacuum arc coating in this paper we used plasma-based ion implantation with deposition (PBIID) method. In this method a high pulse negative potential is applied to a surface immersed in plasma which provides the necessary conditions for significant atom restructuring in the area of collision and therefore initial stresses relaxation in coating. Such stresses relaxation (and associated deformed state) is necessary, because due to a large ionization degree characteristic of vacuum arc method and accordingly high flux density of accelerated particles, great compressive stresses in the coating can occur, which causes significant stretching of substrate and loss of required functional properties of the system. Samples were obtained with the help of vacuum-arc plant "Bulat-6" extra supplied with a high-voltage pulse generator. We used a stainless steel substrates with dimensions 20*20*3 mm and a copper foil 0.2 mm thick. Negative bias value of Us = - 5 V (“floating” potential),  40 V and 230 V was applied on a substrate during deposition process. In some cases negative pulse potential (Upi) with amplitude of 2 kV, 10 ms duration and repetition frequency  of   7  kHz  was  applied  on  a  substrate  along  with  a  constant  bias  during deposition. Evaporator arc current (Id) was 100..110 A, nitrogen pressure was PN = 0,53 ... 0,66 Pa. Composition and structure were studied by X-ray diffraction on a diffractometer DRON-3M in Cu-KĮ radiation using a secondary beam graphite monochromator. Determination of residual macroscopic stresses in the TiN coatings with a cubic (NaCl structural type) crystal lattice was carried out by X-ray strain                                                * e-mail: sool@kpi.kharkov.ua Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I              89  gauging ("a-sin2ȥ" method) and its modification in the case of strong axial texture type. Hardness test was performed using "Micron-Gamma" indenter with Berkovich pyramid and load up to 20 g. Wear resistance test was carried out on cutting plates from a high-speed steel with TɿN coating on the front surface by turning of constructional steel  at  speed of 103 m/min., feed 0.15 mm/rev. and cutting depth of 3 mm.  X-ray diffraction analysis of composition and structure have shown that the diffraction spectra (Fig.  1, curves 2 and 3) obtained under "floating" potential bias -5 V revealed reflections from two phases. The most intense are the main phase of TiN with Bl-NaCl cubic crystal structure and significantly less intense for Į-Ti phase with the relative volume content less than 5%. The crystallite size determined from the Selyakova-Scherrer ratio is 27-30 nm. X-ray diffraction spectra revealed single-phase state - TiN phase with a cubic crystal structure and average crystallite size of 20-21 nm in the case of coatings obtained under additional pulse action (Fig. 1, curve 1).   30 40 50 60 70 80050000100000150000 321TiN (222)TiN (311)TiN (220)TiN (200)TiN (111)I, a.u.2T,deg       30 40 50 60 70 80010002000300040005000600070008000900010000 321TiN (222)TiN (311)TiN (220)TiN (200)TiN (111)Ti (101)Ti (002)SabstSabstSabstI, a.u.2T,degSabst                                  a)                                                                  b) Fig. 1 - Plots of the diffraction spectra of titanium nitride coatings for Us = -5 V with high-voltage pulses (curve 1), without high-voltage pulses (curves 2 and 3), coatings thickness of 7 microns (curves 1 and 3) and 3.5 microns (curve2). General view (a) and detail of low intensity diffraction peaks (b).  The formation of oriented to the axis [110] (in the case of coating thickness 2.5 mm) and [100] (coating thickness 7 mm) crystallites mainly occurs in coatings obtained under "floating" bias without any additional effects of high-voltage pulse (Fig. 1a). In the case of coating deposition at “floating” bias and high-voltage pulse action preferred crystallite orientation is practically absent, which indicates a high disorienting ability of such exposure. The tendency to formation of two-phase coating (TiN phase and Į-Ti) also remains at bias increase (Us) to -230 V and absence of high-voltage pulse (Fig. 2,  curve 1). At the same time with an increase of Us crystallite size decreases, accounting for Us = - 230 V average value 24-25 nm and 15 nm for TiN and Į-Ti phases respectively.  90                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I              Single-phase crystal-line state of TiN coating is characterized by substan-tially smaller crystal size up to 12 nm when high-voltage pulses are applied.  In the case of relative-ly  high  Us =  230  V  the  formation of preferred crystalline orientation with the axis of the axial texture [111] perpendicular to the plane of the growth surface is observed in spite of presence or absence of high-voltage pulses (Fig. 2). Comparison of the diffraction spectra of coatings obtained by applying high-voltage pulses and different constant bias (Fig.  3) shows that at “floating” bias (curve 1, Fig.  3), and at relatively low potential Us = - 40 V(curve 2, Fig. 3) polycrystalline coatings without significant preferred orientation plane of crystallite growth are formed, and  only  applying  of  relatively  high  Us =  -  230  V  leads  to  preferential  orientation of crystallites growth, expressed in the diffraction spectra as redistribution of peaks intensity (curve 3, Fig. 3). For investigating the elastically stressed state, the X-ray tensometry tech-nique (“Į-sin2ȥ”  method)  was  used,  and  in  the  case  of  an  axial-type  strong  texture a modified version of the method was used, based on the measurement of interplanar spacings from different planes at certain crystallographically preset tilt angles ȥ of the sample. From the “Į-sin2ȥ” plot given in fig. 4 it can be seen that with an increase in the constant bias potential on the substrate residual stresses and the titanium nitride lattice constant increase, this being apparently the result of an increased intensity of ion bombardment during depo-sition.  30 35 40 45 50 55 60 65020004000600080001000012000  TiN (111)TiN (220)TiN (200)Ti (002)Ti (101)21I, a.u.2T, deg  Fig. 2 - Plots of the diffraction spectra of titanium nitride coatings for Us =- 230 without high-voltage pulses (curve 1), with high-voltage pulses (curve 2). General view (a) and detail of low intensity diffraction peaks (b) 30 40 50 6005000100001500020000  TiN (220)TiN (200)TiN (111)321I, a.u.2T,deg  Fig. 3 - Plots of the diffraction spectra of titanium nitride coatings with high-voltage pulses and bias – 5 V (curve 1), -40 (curve 2) and -230 (curve 3) Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I              91  0,00 0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,454,2354,2404,2454,2504,2554,2604,2654,2704,2754,2804,285  54321a,10-1, nmsin2\   Fig. 4 - The function “Į-sin2ȥ” for TiN coatings: 1 – without pulses, Us = -5 V; 2 – with pulses, Us = -5 V; 3 – with pulses, Us = -40 V; 4 – without pulses, Us = -230 V;  5 – with pulses, Us = -230 V Fig. 5 - Cutting bit flank wear (h3) versus turning time(t). 1 – uncoated bit, 2 – with coating with no HVP (Us=-230V), 3 – with coating and with HVP(Us=-20V),  4 -  with coating and HVP (Us=-200V).  A special feature of the effect of high-voltage pulses on the properties of the coating during its deposition is the deformation reduction of the material. Note, however, that, in this case, irrespective of the absence or presence of high-voltage pulses, the increase in the constant voltage Us leads to the increase in elastic deformation. The characteristic property of the coatings deposited under the action of high-voltage high-frequency pulses is the increase in their hardness from 38 … 45 GPa at floating and low (less than – 100V) bias potentials up to a superhard state (60 … 62 GPa) at a high bias potential ranging from -150V to -230V.  Another important performance parameter of TiN coatings is their wear resistance. The strength tests of TiN-coated cutting tips from high-speed steel R6M5 by turning steel 45 have demonstrated that the cutting bits having the coatings deposited under the action of high-voltage pulses (HVP) are more efficient even at a low constant potential Us (fig. 5).     

Stucture and mechanical characteristics of vacuum arc TiN coatings deposited with high-voltage high frequency pulses on the substrate

SocioEconomic Challenges Journal (Sumy State University)

88                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I             
 
STUCTURE AND MECHANICAL CHARACTERISTICS OF 
VACUUM ARC TiN COATINGS DEPOSITED WITH  
HIGH-VOLTAGE HIGH FREQUENCY PULSES ON THE 
SUBSTRATE 
1*Sobol O.V., 2Andreev A.A., 3Grigorev S.N., 4Gorban V.F., 3Volosova M.A., 
3Aleshin S.V., 2Stolbovoy V.A. 
 
1 National Technological University “Kharkov Polytechnic Institute”, Frunze St., 21, Kharkov, 
61002, Ukraine 
2 National Science Center “Kharkov Institute of Physics and Technology”, Akademicheskaya St., 
1, Kharkov, 61108, Ukraine 
3 Moscow State Technological University "Stankin",  Vadkovskij per., 3a, 127055, Moscow, 
Russia 
4 Frantsevich Material Science Problem Institute, Krzhizhanovsky St., 3, Kiev, 03142, Ukraine 
 
In order to improve the functional properties of the most currently used in 
industry TiN vacuum arc coating in this paper we used plasma-based ion 
implantation with deposition (PBIID) method. In this method a high pulse 
negative potential is applied to a surface immersed in plasma which provides 
the necessary conditions for significant atom restructuring in the area of 
collision and therefore initial stresses relaxation in coating. 
Such stresses relaxation (and associated deformed state) is necessary, 
because due to a large ionization degree characteristic of vacuum arc method 
and accordingly high flux density of accelerated particles, great compressive 
stresses in the coating can occur, which causes significant stretching of 
substrate and loss of required functional properties of the system. 
Samples were obtained with the help of vacuum-arc plant "Bulat-6" extra 
supplied with a high-voltage pulse generator. We used a stainless steel 
substrates with dimensions 20*20*3 mm and a copper foil 0.2 mm thick. 
Negative bias value of Us = - 5 V (“floating” potential),  40 V and 230 V 
was applied on a substrate during deposition process. In some cases negative 
pulse potential (Upi) with amplitude of 2 kV, 10 ms duration and repetition 
frequency  of   7  kHz  was  applied  on  a  substrate  along  with  a  constant  bias  
during deposition. Evaporator arc current (Id) was 100..110 A, nitrogen pressure 
was PN = 0,53 ... 0,66 Pa. 
Composition and structure were studied by X-ray diffraction on a 
diffractometer DRON-3M in Cu-KĮ radiation using a secondary beam graphite 
monochromator. 
Determination of residual macroscopic stresses in the TiN coatings with a 
cubic (NaCl structural type) crystal lattice was carried out by X-ray strain 
                                               
* e-mail: sool@kpi.kharkov.ua 
Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I              89 
 
gauging ("a-sin2ȥ" method) and its modification in the case of strong axial 
texture type. 
Hardness test was performed using "Micron-Gamma" indenter with 
Berkovich pyramid and load up to 20 g. Wear resistance test was carried out on 
cutting plates from a high-speed steel with TɿN coating on the front surface by 
turning of constructional steel  at  speed of 103 m/min., feed 0.15 mm/rev. and 
cutting depth of 3 mm.  
X-ray diffraction analysis of composition and structure have shown that 
the diffraction spectra (Fig.  1, curves 2 and 3) obtained under "floating" 
potential bias -5 V revealed reflections from two phases. The most intense are 
the main phase of TiN with Bl-NaCl cubic crystal structure and significantly 
less intense for Į-Ti phase with the relative volume content less than 5%. The 
crystallite size determined from the Selyakova-Scherrer ratio is 27-30 nm. X-
ray diffraction spectra revealed single-phase state - TiN phase with a cubic 
crystal structure and average crystallite size of 20-21 nm in the case of coatings 
obtained under additional pulse action (Fig. 1, curve 1). 
 
 
30 40 50 60 70 80
0
50000
100000
150000
 
3
2
1
Ti
N
 (2
22
)
Ti
N
 (3
11
)
Ti
N
 (2
20
)
Ti
N
 (2
00
)
Ti
N
 (1
11
)
I, 
a.
u.
2T,deg       
30 40 50 60 70 80
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
 3
2
1
Ti
N
 (2
22
)
Ti
N
 (3
11
)
Ti
N
 (2
20
)
Ti
N
 (2
00
)
Ti
N
 (1
11
)
Ti
 (1
01
)
Ti
 (0
02
)
S
ab
st
S
ab
st
S
ab
st
I, 
a.
u.
2T,deg
S
ab
st
  
                                a)                                                                  b) 
Fig. 1 - Plots of the diffraction spectra of titanium nitride coatings for Us = -5 V with 
high-voltage pulses (curve 1), without high-voltage pulses (curves 2 and 3), coatings 
thickness of 7 microns (curves 1 and 3) and 3.5 microns (curve2). General view (a) and 
detail of low intensity diffraction peaks (b). 
 
The formation of oriented to the axis [110] (in the case of coating 
thickness 2.5 mm) and [100] (coating thickness 7 mm) crystallites mainly 
occurs in coatings obtained under "floating" bias without any additional effects 
of high-voltage pulse (Fig. 1a). In the case of coating deposition at “floating” 
bias and high-voltage pulse action preferred crystallite orientation is practically 
absent, which indicates a high disorienting ability of such exposure. 
The tendency to formation of two-phase coating (TiN phase and Į-Ti) also 
remains at bias increase (Us) to -230 V and absence of high-voltage pulse (Fig. 
2,  curve 1). At the same time with an increase of Us crystallite size decreases, 
accounting for Us = - 230 V average value 24-25 nm and 15 nm for TiN and Į-
Ti phases respectively.  
90                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I             
 
Single-phase crystal-
line state of TiN coating is 
characterized by substan-
tially smaller crystal size up 
to 12 nm when high-
voltage pulses are applied.  
In the case of relative-
ly  high  Us =  230  V  the  
formation of preferred 
crystalline orientation with 
the axis of the axial texture 
[111] perpendicular to the 
plane of the growth surface 
is observed in spite of 
presence or absence of 
high-voltage pulses (Fig. 
2). 
Comparison of the 
diffraction spectra of 
coatings obtained by 
applying high-voltage 
pulses and different 
constant bias (Fig.  3) 
shows that at “floating” 
bias (curve 1, Fig.  3), and 
at relatively low potential 
Us = - 40 V(curve 2, Fig. 3) 
polycrystalline coatings 
without significant preferred orientation plane of crystallite growth are formed, 
and  only  applying  of  relatively  high  Us =  -  230  V  leads  to  preferential  
orientation of crystallites growth, expressed in the diffraction spectra as 
redistribution of peaks intensity (curve 3, Fig. 3). 
For investigating the elastically stressed state, the X-ray tensometry tech-
nique (“Į-sin2ȥ”  method)  was  used,  and  in  the  case  of  an  axial-type  strong  
texture a modified version of the method was used, based on the measurement 
of interplanar spacings from different planes at certain crystallographically 
preset tilt angles ȥ of the sample. From the “Į-sin2ȥ” plot given in fig. 4 it can 
be seen that with an increase in the constant bias potential on the substrate 
residual stresses and the titanium nitride lattice constant increase, this being 
apparently the result of an increased intensity of ion bombardment during depo-
sition.  
30 35 40 45 50 55 60 65
0
2000
4000
6000
8000
10000
12000
 
 
Ti
N
 (1
11
)
Ti
N
 (2
20
)
Ti
N
 (2
00
)
Ti
 (0
02
)
Ti
 (1
01
)
2
1
I, 
a.
u.
2T, deg  
Fig. 2 - Plots of the diffraction spectra of titanium 
nitride coatings for Us =- 230 without high-voltage 
pulses (curve 1), with high-voltage pulses (curve 2). 
General view (a) and detail of low intensity 
diffraction peaks (b) 
30 40 50 60
0
5000
10000
15000
20000
 
 
Ti
N
 (2
20
)
Ti
N
 (2
00
)
Ti
N
 (1
11
)
3
2
1
I, 
a.
u.
2T,deg  
Fig. 3 - Plots of the diffraction spectra of titanium 
nitride coatings with high-voltage pulses and bias – 5 
V (curve 1), -40 (curve 2) and -230 (curve 3) 
Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part I              91 
 
0,00 0,05 0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45
4,235
4,240
4,245
4,250
4,255
4,260
4,265
4,270
4,275
4,280
4,285
 
 
5
4
3
2
1
a,
10
-1
, n
m
sin2\   
Fig. 4 - The function “Į-sin2ȥ” for TiN 
coatings: 1 – without pulses, Us = -5 V; 2 – 
with pulses, Us = -5 V; 3 – with pulses, Us = 
-40 V; 4 – without pulses, Us = -230 V;  
5 – with pulses, Us = -230 V 
Fig. 5 - Cutting bit flank wear (h3) versus 
turning time(t). 1 – uncoated bit, 2 – with 
coating with no HVP (Us=-230V), 3 – 
with coating and with HVP(Us=-20V),  
4 -  with coating and HVP (Us=-200V). 
 
A special feature of the effect of high-voltage pulses on the properties of 
the coating during its deposition is the deformation reduction of the material. 
Note, however, that, in this case, irrespective of the absence or presence of 
high-voltage pulses, the increase in the constant voltage Us leads to the increase 
in elastic deformation. 
The characteristic property of the coatings deposited under the action of 
high-voltage high-frequency pulses is the increase in their hardness from 38 … 
45 GPa at floating and low (less than – 100V) bias potentials up to a superhard 
state (60 … 62 GPa) at a high bias potential ranging from -150V to -230V.  
Another important performance parameter of TiN coatings is their wear 
resistance. The strength tests of TiN-coated cutting tips from high-speed steel 
R6M5 by turning steel 45 have demonstrated that the cutting bits having the 
coatings deposited under the action of high-voltage pulses (HVP) are more 
efficient even at a low constant potential Us (fig. 5).  
 
  


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Stucture and mechanical characteristics of vacuum arc TiN coatings deposited with high-voltage high frequency pulses on the substrate

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