Nanocomposite coatings based on Ti, O, C and H thickness of 70 – 200 microns with hardness of
1015 250 HV0.05 and porosity 2 – 5% were deposited on aluminium samples by using the cumulativedetonation
equipment. The nanocomposite coatings were examined by scanning electron microscopy
(SEM), transmission electron microscopy (TEM) with diffraction, X-ray phase analysis, hardness measurements.
It is shown that the area of the coating that adjoins to the substrate contains a transition layer
of intermetallic TiAl and the nanocomposite coatings based on Ti, O, C and H are characterized by the
presence of titanium nanocrystalline grains with face-centered close-packed lattice, amorphous phases and
nanoamorphous oxide of titanium. It was found that the main phases of the composite coatings are Ti, TiO,
rutile, anatase, Ti2O3. In the composite coatings formed from the hydrogenated powder was recorded the
presence of -TiH phase and TiH2.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3488

Arseenko, M.Y.

Kolisnichenko, O.V.

Kovaleva, M.G.

Prozorova, M.S.

Tyurin, Y.N.

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 1 No 2, 02NFC19(4pp) (2012) 
 
 
2304-1862/2012/1(2)02NFC19(4) 02NFC19-1  2012 Sumy State University 
Structure and Properties of Nanocomposite Coatings Based on Titanium, Oxygen, Carbon 
and Hydrogen Obtained by the Cumulative-Detonation Device 
 
M.G. Kovaleva1,*, M.Y. Arseenko1, M.S. Prozorova1, Y.N. Tyurin2,†, O.V. Kolisnichenko2 
 
1 Belgorod State University, 85, Pobedy Str., 308015 Belgorod, Russia 
2 Paton Electric Welding Institute NANU, 11, Bozhenko, 03650 Kyiv, Ukraine 
 
(Received 16 June 2012; published online 22 August 2012) 
 
Nanocomposite coatings based on Ti, O, C and H thickness of 70 – 200 microns with hardness of 
1015  250 HV0.05 and porosity 2 – 5% were deposited on aluminium samples by using the cumulative-
detonation equipment. The nanocomposite coatings were examined by scanning electron microscopy 
(SEM), transmission electron microscopy (TEM) with diffraction, X-ray phase analysis, hardness meas-
urements. It is shown that the area of the coating that adjoins to the substrate contains a transition layer 
of intermetallic TiAl and the nanocomposite coatings based on Ti, O, C and H are characterized by the 
presence of titanium nanocrystalline grains with face-centered close-packed lattice, amorphous phases and 
nanoamorphous oxide of titanium. It was found that the main phases of the composite coatings are Ti, TiO, 
rutile, anatase, Ti2O3. In the composite coatings formed from the hydrogenated powder was recorded the 
presence of -TiH phase and TiH2. 
 
Keywords: cumulative-detonation technology, aluminium alloys, nanostructured composite coatings, la-
mellas. 
 
  PACS numbers: 68.37.Hk, 68.37.Lp, 68.37.Yz, 68.47.De 
 
 
                                                          
*Kovaleva@bsu.edu.ru 
† ytyurin@i.com.ua 
1. INTRODUCTION 
 
One of the priorities of science and technology is the 
creation of new materials, in particular, multi-, nano-
composite coatings with a typical grain size of less than 
100 nm [1,2]. 
One of the new technologies for applying protective 
coatings, composites and other functions is the cumula-
tive-detonation technology of coatings. Multifunctional 
nanocrystalline material on the surface of products with 
a wide range of controlled composition, structure and 
properties can be used to protect them from wear and 
corrosion, as well as to improve the thermal stability [3]. 
For example, to protect from wear and corrosion of alu-
minum products have a fairly thin layer of composite 
coatings based on Ti, O, C and H, which does not affect 
significantly the weight of the structure [4]. 
Taking into account high physical-mechanical prop-
erties of titanium and titanium ability to form stable 
solid solutions and a series of compounds with different 
types of chemical bonds with the combustion products, 
which contain oxygen, nitrogen, hydrogen and carbon, is 
of interest to the creation and study of multicomponent 
composite materials based on titanium surface produc-
tion of light alloys [5]. The combination of such diverse 
components leads to the formation of a new material 
whose properties are quantitatively and qualitatively 
different from the properties of each of its components, 
and superior to traditional materials for their mechani-
cal properties [6]. 
At present the titanium coatings are produced by 
plasma spraying of wire VT1-0. The coatings are porous 
and have low adhesion. The maximal values of adhesion 
(up to 80 MPa) are achieved at a substrate temperature 
of 500 C. The substrates are made from alloys VT6 and 
VT20 [7]. Much work is underway now on using upgrad-
ed HVOF [8,9], as well as a helium jet under a pressure 
of 24 atm. and temperature of 450 – 550 C [11], or a ni-
trogen jet under a pressure of 30 atm. and temperature 
of up to 600 C [12]. The titanium coatings are produced 
by using plasmatrons [10]. It can be noted that all the 
coatings are porous, their adhesion strength is not in 
excess of 30 – 50 MPa, and they comprise local phases 
with hardness of HV 700 – 1500. These phases contain 
nitrogen, oxygen and carbon. 
The purpose of this study is to investigate the inter-
action of titanium powder obtained from titanium 
sponge, with the components of the combustion products 
in the shaped-charge cumulative-detonation device and 
its effect on the structure of protective nanocomposite 
coatings based on Ti, O, C and H. 
 
2. EXPERIMENTAL PROCEDURE 
 
2.1 Feedstock material, deposition process, and 
conditions 
 
An essential difference of the cumulative-detonation 
device from the detonation one is that it combines the 
energy from several, specially profiled detonation cham-
bers. This provides an efficient energy transfer to the 
powder materials. In addition, it is characterized by a 
wide possibility of controlling the velocity and tempera-
ture of the powder materials. The device operates at a 
frequency of up to 30 Hz, this allowing the use of stand-
ard powder and gas control devices, simplification of the 
equipment, reduction of its price, and improvement of its 
operational reliability. 
The cumulative-detonation technology has of a pulse 
character. This makes it possible to form the composite 
coatings from a small distance (10 – 60 mm) in a shield-
 M.G. KOVALEVA, M.Y. ARSEENKO, M.S. PROZOROVA, ET AL. PROC. NAP 1, 02NFC19 (2012) 
 
 
02NFC19-2 
ing gas atmosphere. As a result, oxidation and losses of 
spraying materials are reduced. The titanium powder 
utilization factor in deposition of the composite coatings 
is 85 – 90 %. The velocity of the powder material is 800 –
 900 m/s. 
In this work, coatings were deposited on the surface 
of samples by the cumulative-detonation device [4]. The 
samples of aluminum alloy 1545 K of the system Al-Mg-
Sc were used as a substrate. 
Composite coatings of titanium powder were deposit-
ed (the results of fragmentation of titanium sponge) in 
the environment of the combustion products, which con-
tain oxygen, nitrogen, hydrogen and carbon. Titanium 
sponge was saturated with hydrogen before the disper-
sion. Obtained powder filter out and held in a vacuum 
oven at 900 C for 4 hours. 
Four types of powder were used: 1 – titanium (Ti), 2 –
 hydrogenated titanium (Ti/H), 3 – a mechanical mixture 
of powders of titanium and boron amorphous (Ti/B), 4 - a 
hydrogenated mechanical mixture of powders of titani-
um and boron amorphous (Ti/B/H) (see. Table 1 and, for 
example, Fig. 1). The particle size was measured by the 
laser scattering method and confirmed by electron mi-
croscopy. 
Since a mechanical mixture of such materials during 
the deposition of the coatings is easily splits, powder 
feeder with a rotating bunker and a dynamic mixer of 
powders was used. Composite coatings were deposited 
with a frequency of 20 Hz of the snake with a transverse 
displacement 4 mm and a three-time repetition. Speed of 
moving was 3000 mm/min, distance from the sample – 
65 – 70 mm. The powders of Ti and Ti/H are sprayed by 
a two-chamber device with an output nozzle of 16 mm. 
Powders from a mechanical mixture of Ti/B and Ti/B/H 
were deposited on a single chamber device with an out-
put nozzle of 20 mm. 
 
Table 1 – The morphology and composition of the powders 
 
Powders 
Wt% 
Size of powder particles 
Ti O B Zr 
Ti 99.40 - - 0.60 6 – 70 
Ti/H 97.09 2.91 - - 1 – 50 
Ti/B 77.40 1.09 21.51  0.6 – 60 
Ti/B/H 81.91 3.88 14.21 - 0.7 – 19 
 
Table 2 – The elemental composition of nanocomposite coatings 
 
Coatings 
Wt% 
Ti Al O C Ca Si B Zr Fe 
Ti 83.23 0.49 14.17 0.61 1.50 - - - - 
Ti/H 61.34 0.48 33.63 1.31 - 3.23 - - - 
Ti/B 60.16 0.54 22.51 3.21 - 1.73 10.63 0.57 0.64 
Ti/B/H 61.23 0.42 22.28 1.94 0.29 1.84 10.95 0.40 0.64 
 
 
 
 
 
a 
 
   
 
b 
 
Fig. 1 – SEM (a) and TEM image (b) of the hydrogenated tita-
nium powder 
 
2.2 Microstructure Observation 
 
Examinations of microstructure and elemental 
composition of the titanium powders and the nanocom-
posite coatings based on Ti, O, C, and H were carried 
out by using electron ion microscope Quanta 600 
equipped with integrated microanalysis system Pega-
sus 2000. Local phase and diffraction analysis of the 
titanium powder and the nanocomposite coatings was 
conducted by using transmission electron field emission 
microscope Tecnai G2 20F S-T (FEI) with microdiffrac-
tion and X-ray powder diffractometer ARL X’TRA, 
providing integrated information on a layer of several 
microns thick. 
 
3. RESULTS AND DISCUSSION 
 
3.1 SEM observation of the system «nanocompo-
site coatings - substrate» 
 
The study of the microstructure and elemental com-
position of the transverse sections of samples with com-
posite coatings showed that were obtained uniform coat-
ings with thickness of 70 – 200 microns and good adhe-
sion to the substrate, the bulk of the coating material is 
deformed and tightly packed (see, for example, Fig. 2a). 
Porosity of the coatings was determined by metallo-
graphic method was 2 – 5%. 
 STRUCTURE AND PROPERTIES OF NANOCOMPOSITE COATINGS BASED … PROC. NAP 1, 02NFC19 (2012) 
 
 
02NFC19-3 
The visible boundary of the coating-substrate inter-
face has no defects. Fig. 2 shows that in the contact area 
of coating and substrate is mixed structure consisting of 
islands covering the substrate a very different shapes 
and sizes. Part of the powder material penetrated deeply 
and firmly connected to the substrate material (see. 
Fig. 2). At impact a large powder particles, it corrects 
and deforms the surface layer of the substrate. There are 
"splashes" of the substrate material, which are located in 
surface (see. Table 2). Area of the coating that adjoins to 
the substrate contains a transition layer of intermetallic 
TiAl (see. Fig. 2b). Total this layer has a high density of 
dislocations caused by the shock effect of plasma-
detonation wave. 
 
 
 
a 
 
  
 
b 
 
Fig. 2 – SEM image of cross section of the nanocomposite Ti/H 
coating layer and substrate (a), TEM image of the coating-
substrate interface (b), diffraction TEM photographs of a tran-
sition layer of intermetallic TiAl 
 
Furthermore, it was established that the hardness of 
nanocomposite coatings is 1015  250 HV0.05, which is 15 
times higher than the hardness of the substrate material 
85  5 HV0.05. A wide range of hardness values of the 
composite coatings caused by their different phase com-
position and porosity. According to the theory [13] during 
the deposition, the small fraction of the powder is almost 
completely melted, while larger particles of the nucleus 
remain in the solid state. In practice, this leads to the 
formation of material with local differences in mechani-
cal properties. The maximum hardness of the coating is 
associated with the formation of regions containing TiO 
and TiO2 [14]. It is known [15], oxygen forms a large 
number of compounds with titanium, and their composi-
tions are located within the lower and higher valence 
oxides, titanium dioxide (TiO up on TiO2). Titanium is 
oxidized with greater speed compared to its interaction 
with other gases. The formation of solid solution of oxy-
gen in titanium related to the strong distortion of the 
crystal lattice and, therefore, related to significant 
changes in the mechanical properties of titanium. In-
creasing the oxygen content leads to a sharp increase in 
strength, hardness and lower ductility of titanium. 
Hydrogen is also absorbed by the titanium in ex-
tremely large quantities that can be explained by the 
formation, along with the introduction of solid solution, 
hydrogen compounds hydrides of titanium. Even at very 
low concentrations of hydrogen in titanium can be 
formed hydride of titanium. The increase of the concen-
tration of hydrogen could lead to a sharp decrease in 
ductility. Further increase of the content of hydrogen 
could lead to a catastrophic decrease in ductility at room 
temperature [16]. Carbon dissolves in titanium in small 
quantities. Due to the low solubility of carbon in titani-
um content in the metal fraction of a percent of carbon 
causes a selection of metal carbide and fragile. A marked 
decrease in ductility and increase of strength and hard-
ness of the metal take place at content of more than 0.1 –
 0.2% C [17]. On further increase of the content of carbon 
due to the appearance of the carbide phase, the mechan-
ical properties of titanium are more or less stabilized. 
 
3.2 TEM observation of the system «nanocom-
posite coatings - substrate» 
 
Local phase and structure analysis of the composite 
coatings based on Ti, O, C and H showed that lamellas in 
the coatings consisted of the mixture of titanium nano-
crystalline grains with face-centered close-packed lattice 
and amorphous phases, and nanoamorphous oxide of 
titanium (see. Fig. 3). This is confirmed by results of dif-
fraction analysis of the nanocomposite coatings (see. 
Fig. 4). This structure could be caused by a high-
temperature cycle in formation of composite coatings 
[18,19]. 
Therefore, it can be assumed that the values of hard-
ness in fine lamellae of the nanocomposite coatings are 
attributable to the absence of dislocations inside the 
crystalline grains and ratio of the volume contents of 
nanocrystalline to amorphous phases of metallic and 
non-metallic titanium compounds. 
Strength of intermediate and near-interface layers 
leads to increase of deformation resistance of nanocom-
posite coatings. The absence of dislocations inside the 
crystalline grains leads to increase in elasticity and, at 
the same time, in plasticity of nanocomposite coatings. It 
was detected for the first time ever [19], as far back as 
20 – 25 years ago, that ceramic materials of titanium 
oxides acquire superplastic properties at room tempera-
ture at the characteristic sizes of crystals equal to sever-
al nanometers. 
 
3.3 XRD analysis of the nanocomposite coatings 
 
Carried out phase analysis showed that the main 
phase of the coating layer, which is located at a dis-
tance of about 1 – 2 mm from the free surface was Ti 
with a face-centered close-packed lattice (a  2.965 Å) 
(see. Fig. 4). The calculated interplanar distances re-
flections suggest the presence in the coatings and the 
following phases: TiO with a cubic lattice (a  4.197 Å), 
rutile TiO2 with tetragonal lattice (a  b  4.585 Å, 
c  2.972 Å), anatase TiO2 with tetragonal lattice 
(a  b  3.775 Å, c  9.492 Å), Ti2O3 with a hexagonal 
lattice (a  b  5.129 Å, c  13.815 Å). In the nanocom-
posite coatings formed from the hydrogenated powder, 
 M.G. KOVALEVA, M.Y. ARSEENKO, M.S. PROZOROVA, ET AL. PROC. NAP 1, 02NFC19 (2012) 
 
 
02NFC19-4 
recorded the presence of -TiH phase with a cubic lat-
tice (a  4.415 Å) and TiH2 with tetragonal lattice 
(a  b  3.148 Å, c  4.140 Å). The studies did not report 
the presence of boron in the coatings. Apparently this is 
due to the fact that micron particles of amorphous bo-
ron overheat and evaporate in the environment of the 
combustion products. 
 
 
      
 
Fig. 3 – TEM image and diffraction photographs of material of nanocomposite coating of TiH powder: mixture of titanium nano-
crystalline grains with face-centered close-packed lattice and amorphous phases (1), amorphous phases (C, Ti, Al, O) (2), 
nanoamorphous oxide of titanium (3) 
 
 
 
Fig. 4 – XRD analysis of the nanocomposite coatings: 1 – Ti/H, 
2 – Ti, 3 – Ti/B, 4 – Ti/B/H 
 
4. CONCLUSIONS 
 
Cumulative-detonation technology provides formation 
of dense composite coatings based on Ti, O, C, H thickness 
of 70 – 200 microns with hardness of 1015  250 HV0.05. 
The porosity of coatings was 2 – 5%, which correlates 
with the technological requirements of industrial coat-
ings. The apparent limit of adhesion of the coating to the 
substrate is free of defects. It was found a transition re-
gion coating/substrate consisting of a nanocrystalline 
TiAl. The main phases of the composite coatings are Ti, 
TiO, rutile, anatase, Ti2O3. In the composite coatings 
formed from the hydrogenated powder was recorded the 
presence of -TiH phase and TiH2.  
Based on the results of the study could be offered en-
ergy-saving technology for deposition of composite coat-
ings based on Ti, O, C, H on substrates of aluminum 
alloy. 
 
AKNOWLEDGEMENTS 
 
Work is carried out by Joint Research Center of Bel-
gorod State University in the framework of the federal 
target program under Grant application 
№ 14.740.11.1017. 
 
 
 
REFERENCES 
 
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4. Y.N. Tyurin, O.V. Kolisnichenko, I.M. Duda, Strength. 
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2005’ (May 2-4, 2005) (Switzerland, Basel). 
13. P.A. Vitayaz, D.N. Dubrovsky, L.M Kirilyuk, Gas-phase 
deposition of coatings of titanium nitride (Minsk: Science 
and technology: 1983). 
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Sci. 172, 242 (2005). 
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Heat Treat. No5, 49 (1977). 
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English

Structure and Properties of Nanocomposite Coatings Based on Titanium, Oxygen, Carbon and Hydrogen Obtained by the Cumulative-Detonation Device

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 1 No 2, 02NFC19(4pp) (2012)   2304-1862/2012/1(2)02NFC19(4) 02NFC19-1  2012 Sumy State University Structure and Properties of Nanocomposite Coatings Based on Titanium, Oxygen, Carbon and Hydrogen Obtained by the Cumulative-Detonation Device  M.G. Kovaleva1,*, M.Y. Arseenko1, M.S. Prozorova1, Y.N. Tyurin2,†, O.V. Kolisnichenko2  1 Belgorod State University, 85, Pobedy Str., 308015 Belgorod, Russia 2 Paton Electric Welding Institute NANU, 11, Bozhenko, 03650 Kyiv, Ukraine  (Received 16 June 2012; published online 22 August 2012)  Nanocomposite coatings based on Ti, O, C and H thickness of 70 – 200 microns with hardness of 1015  250 HV0.05 and porosity 2 – 5% were deposited on aluminium samples by using the cumulative-detonation equipment. The nanocomposite coatings were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) with diffraction, X-ray phase analysis, hardness meas-urements. It is shown that the area of the coating that adjoins to the substrate contains a transition layer of intermetallic TiAl and the nanocomposite coatings based on Ti, O, C and H are characterized by the presence of titanium nanocrystalline grains with face-centered close-packed lattice, amorphous phases and nanoamorphous oxide of titanium. It was found that the main phases of the composite coatings are Ti, TiO, rutile, anatase, Ti2O3. In the composite coatings formed from the hydrogenated powder was recorded the presence of -TiH phase and TiH2.  Keywords: cumulative-detonation technology, aluminium alloys, nanostructured composite coatings, la-mellas.    PACS numbers: 68.37.Hk, 68.37.Lp, 68.37.Yz, 68.47.De                                                             *Kovaleva@bsu.edu.ru † ytyurin@i.com.ua 1. INTRODUCTION  One of the priorities of science and technology is the creation of new materials, in particular, multi-, nano-composite coatings with a typical grain size of less than 100 nm [1,2]. One of the new technologies for applying protective coatings, composites and other functions is the cumula-tive-detonation technology of coatings. Multifunctional nanocrystalline material on the surface of products with a wide range of controlled composition, structure and properties can be used to protect them from wear and corrosion, as well as to improve the thermal stability [3]. For example, to protect from wear and corrosion of alu-minum products have a fairly thin layer of composite coatings based on Ti, O, C and H, which does not affect significantly the weight of the structure [4]. Taking into account high physical-mechanical prop-erties of titanium and titanium ability to form stable solid solutions and a series of compounds with different types of chemical bonds with the combustion products, which contain oxygen, nitrogen, hydrogen and carbon, is of interest to the creation and study of multicomponent composite materials based on titanium surface produc-tion of light alloys [5]. The combination of such diverse components leads to the formation of a new material whose properties are quantitatively and qualitatively different from the properties of each of its components, and superior to traditional materials for their mechani-cal properties [6]. At present the titanium coatings are produced by plasma spraying of wire VT1-0. The coatings are porous and have low adhesion. The maximal values of adhesion (up to 80 MPa) are achieved at a substrate temperature of 500 C. The substrates are made from alloys VT6 and VT20 [7]. Much work is underway now on using upgrad-ed HVOF [8,9], as well as a helium jet under a pressure of 24 atm. and temperature of 450 – 550 C [11], or a ni-trogen jet under a pressure of 30 atm. and temperature of up to 600 C [12]. The titanium coatings are produced by using plasmatrons [10]. It can be noted that all the coatings are porous, their adhesion strength is not in excess of 30 – 50 MPa, and they comprise local phases with hardness of HV 700 – 1500. These phases contain nitrogen, oxygen and carbon. The purpose of this study is to investigate the inter-action of titanium powder obtained from titanium sponge, with the components of the combustion products in the shaped-charge cumulative-detonation device and its effect on the structure of protective nanocomposite coatings based on Ti, O, C and H.  2. EXPERIMENTAL PROCEDURE  2.1 Feedstock material, deposition process, and conditions  An essential difference of the cumulative-detonation device from the detonation one is that it combines the energy from several, specially profiled detonation cham-bers. This provides an efficient energy transfer to the powder materials. In addition, it is characterized by a wide possibility of controlling the velocity and tempera-ture of the powder materials. The device operates at a frequency of up to 30 Hz, this allowing the use of stand-ard powder and gas control devices, simplification of the equipment, reduction of its price, and improvement of its operational reliability. The cumulative-detonation technology has of a pulse character. This makes it possible to form the composite coatings from a small distance (10 – 60 mm) in a shield- M.G. KOVALEVA, M.Y. ARSEENKO, M.S. PROZOROVA, ET AL. PROC. NAP 1, 02NFC19 (2012)   02NFC19-2 ing gas atmosphere. As a result, oxidation and losses of spraying materials are reduced. The titanium powder utilization factor in deposition of the composite coatings is 85 – 90 %. The velocity of the powder material is 800 – 900 m/s. In this work, coatings were deposited on the surface of samples by the cumulative-detonation device [4]. The samples of aluminum alloy 1545 K of the system Al-Mg-Sc were used as a substrate. Composite coatings of titanium powder were deposit-ed (the results of fragmentation of titanium sponge) in the environment of the combustion products, which con-tain oxygen, nitrogen, hydrogen and carbon. Titanium sponge was saturated with hydrogen before the disper-sion. Obtained powder filter out and held in a vacuum oven at 900 C for 4 hours. Four types of powder were used: 1 – titanium (Ti), 2 – hydrogenated titanium (Ti/H), 3 – a mechanical mixture of powders of titanium and boron amorphous (Ti/B), 4 - a hydrogenated mechanical mixture of powders of titani-um and boron amorphous (Ti/B/H) (see. Table 1 and, for example, Fig. 1). The particle size was measured by the laser scattering method and conﬁrmed by electron mi-croscopy. Since a mechanical mixture of such materials during the deposition of the coatings is easily splits, powder feeder with a rotating bunker and a dynamic mixer of powders was used. Composite coatings were deposited with a frequency of 20 Hz of the snake with a transverse displacement 4 mm and a three-time repetition. Speed of moving was 3000 mm/min, distance from the sample – 65 – 70 mm. The powders of Ti and Ti/H are sprayed by a two-chamber device with an output nozzle of 16 mm. Powders from a mechanical mixture of Ti/B and Ti/B/H were deposited on a single chamber device with an out-put nozzle of 20 mm.  Table 1 – The morphology and composition of the powders  Powders Wt% Size of powder particles Ti O B Zr Ti 99.40 - - 0.60 6 – 70 Ti/H 97.09 2.91 - - 1 – 50 Ti/B 77.40 1.09 21.51  0.6 – 60 Ti/B/H 81.91 3.88 14.21 - 0.7 – 19  Table 2 – The elemental composition of nanocomposite coatings  Coatings Wt% Ti Al O C Ca Si B Zr Fe Ti 83.23 0.49 14.17 0.61 1.50 - - - - Ti/H 61.34 0.48 33.63 1.31 - 3.23 - - - Ti/B 60.16 0.54 22.51 3.21 - 1.73 10.63 0.57 0.64 Ti/B/H 61.23 0.42 22.28 1.94 0.29 1.84 10.95 0.40 0.64      a      b  Fig. 1 – SEM (a) and TEM image (b) of the hydrogenated tita-nium powder  2.2 Microstructure Observation  Examinations of microstructure and elemental composition of the titanium powders and the nanocom-posite coatings based on Ti, O, C, and H were carried out by using electron ion microscope Quanta 600 equipped with integrated microanalysis system Pega-sus 2000. Local phase and diffraction analysis of the titanium powder and the nanocomposite coatings was conducted by using transmission electron field emission microscope Tecnai G2 20F S-T (FEI) with microdiffrac-tion and X-ray powder diffractometer ARL X’TRA, providing integrated information on a layer of several microns thick.  3. RESULTS AND DISCUSSION  3.1 SEM observation of the system «nanocompo-site coatings - substrate»  The study of the microstructure and elemental com-position of the transverse sections of samples with com-posite coatings showed that were obtained uniform coat-ings with thickness of 70 – 200 microns and good adhe-sion to the substrate, the bulk of the coating material is deformed and tightly packed (see, for example, Fig. 2a). Porosity of the coatings was determined by metallo-graphic method was 2 – 5%.  STRUCTURE AND PROPERTIES OF NANOCOMPOSITE COATINGS BASED … PROC. NAP 1, 02NFC19 (2012)   02NFC19-3 The visible boundary of the coating-substrate inter-face has no defects. Fig. 2 shows that in the contact area of coating and substrate is mixed structure consisting of islands covering the substrate a very different shapes and sizes. Part of the powder material penetrated deeply and firmly connected to the substrate material (see. Fig. 2). At impact a large powder particles, it corrects and deforms the surface layer of the substrate. There are "splashes" of the substrate material, which are located in surface (see. Table 2). Area of the coating that adjoins to the substrate contains a transition layer of intermetallic TiAl (see. Fig. 2b). Total this layer has a high density of dislocations caused by the shock effect of plasma-detonation wave.    a     b  Fig. 2 – SEM image of cross section of the nanocomposite Ti/H coating layer and substrate (a), TEM image of the coating-substrate interface (b), diffraction TEM photographs of a tran-sition layer of intermetallic TiAl  Furthermore, it was established that the hardness of nanocomposite coatings is 1015  250 HV0.05, which is 15 times higher than the hardness of the substrate material 85  5 HV0.05. A wide range of hardness values of the composite coatings caused by their different phase com-position and porosity. According to the theory [13] during the deposition, the small fraction of the powder is almost completely melted, while larger particles of the nucleus remain in the solid state. In practice, this leads to the formation of material with local differences in mechani-cal properties. The maximum hardness of the coating is associated with the formation of regions containing TiO and TiO2 [14]. It is known [15], oxygen forms a large number of compounds with titanium, and their composi-tions are located within the lower and higher valence oxides, titanium dioxide (TiO up on TiO2). Titanium is oxidized with greater speed compared to its interaction with other gases. The formation of solid solution of oxy-gen in titanium related to the strong distortion of the crystal lattice and, therefore, related to significant changes in the mechanical properties of titanium. In-creasing the oxygen content leads to a sharp increase in strength, hardness and lower ductility of titanium. Hydrogen is also absorbed by the titanium in ex-tremely large quantities that can be explained by the formation, along with the introduction of solid solution, hydrogen compounds hydrides of titanium. Even at very low concentrations of hydrogen in titanium can be formed hydride of titanium. The increase of the concen-tration of hydrogen could lead to a sharp decrease in ductility. Further increase of the content of hydrogen could lead to a catastrophic decrease in ductility at room temperature [16]. Carbon dissolves in titanium in small quantities. Due to the low solubility of carbon in titani-um content in the metal fraction of a percent of carbon causes a selection of metal carbide and fragile. A marked decrease in ductility and increase of strength and hard-ness of the metal take place at content of more than 0.1 – 0.2% C [17]. On further increase of the content of carbon due to the appearance of the carbide phase, the mechan-ical properties of titanium are more or less stabilized.  3.2 TEM observation of the system «nanocom-posite coatings - substrate»  Local phase and structure analysis of the composite coatings based on Ti, O, C and H showed that lamellas in the coatings consisted of the mixture of titanium nano-crystalline grains with face-centered close-packed lattice and amorphous phases, and nanoamorphous oxide of titanium (see. Fig. 3). This is confirmed by results of dif-fraction analysis of the nanocomposite coatings (see. Fig. 4). This structure could be caused by a high-temperature cycle in formation of composite coatings [18,19]. Therefore, it can be assumed that the values of hard-ness in fine lamellae of the nanocomposite coatings are attributable to the absence of dislocations inside the crystalline grains and ratio of the volume contents of nanocrystalline to amorphous phases of metallic and non-metallic titanium compounds. Strength of intermediate and near-interface layers leads to increase of deformation resistance of nanocom-posite coatings. The absence of dislocations inside the crystalline grains leads to increase in elasticity and, at the same time, in plasticity of nanocomposite coatings. It was detected for the first time ever [19], as far back as 20 – 25 years ago, that ceramic materials of titanium oxides acquire superplastic properties at room tempera-ture at the characteristic sizes of crystals equal to sever-al nanometers.  3.3 XRD analysis of the nanocomposite coatings  Carried out phase analysis showed that the main phase of the coating layer, which is located at a dis-tance of about 1 – 2 mm from the free surface was Ti with a face-centered close-packed lattice (a  2.965 Å) (see. Fig. 4). The calculated interplanar distances re-flections suggest the presence in the coatings and the following phases: TiO with a cubic lattice (a  4.197 Å), rutile TiO2 with tetragonal lattice (a  b  4.585 Å, c  2.972 Å), anatase TiO2 with tetragonal lattice (a  b  3.775 Å, c  9.492 Å), Ti2O3 with a hexagonal lattice (a  b  5.129 Å, c  13.815 Å). In the nanocom-posite coatings formed from the hydrogenated powder,  M.G. KOVALEVA, M.Y. ARSEENKO, M.S. PROZOROVA, ET AL. PROC. NAP 1, 02NFC19 (2012)   02NFC19-4 recorded the presence of -TiH phase with a cubic lat-tice (a  4.415 Å) and TiH2 with tetragonal lattice (a  b  3.148 Å, c  4.140 Å). The studies did not report the presence of boron in the coatings. Apparently this is due to the fact that micron particles of amorphous bo-ron overheat and evaporate in the environment of the combustion products.          Fig. 3 – TEM image and diffraction photographs of material of nanocomposite coating of TiH powder: mixture of titanium nano-crystalline grains with face-centered close-packed lattice and amorphous phases (1), amorphous phases (C, Ti, Al, O) (2), nanoamorphous oxide of titanium (3)    Fig. 4 – XRD analysis of the nanocomposite coatings: 1 – Ti/H, 2 – Ti, 3 – Ti/B, 4 – Ti/B/H  4. CONCLUSIONS  Cumulative-detonation technology provides formation of dense composite coatings based on Ti, O, C, H thickness of 70 – 200 microns with hardness of 1015  250 HV0.05. The porosity of coatings was 2 – 5%, which correlates with the technological requirements of industrial coat-ings. The apparent limit of adhesion of the coating to the substrate is free of defects. It was found a transition re-gion coating/substrate consisting of a nanocrystalline TiAl. The main phases of the composite coatings are Ti, TiO, rutile, anatase, Ti2O3. In the composite coatings formed from the hydrogenated powder was recorded the presence of -TiH phase and TiH2.  Based on the results of the study could be offered en-ergy-saving technology for deposition of composite coat-ings based on Ti, O, C, H on substrates of aluminum alloy.  AKNOWLEDGEMENTS  Work is carried out by Joint Research Center of Bel-gorod State University in the framework of the federal target program under Grant application № 14.740.11.1017.    REFERENCES  1. H. Gleiter, Acta mater. 48, 1 (2000). 2. P.H. Mayrhofer, C. Mitterer, L. Hiltman, H. Clements, Prog. Mater. Sci. 51 No8, 1032 (2006). 3. Y.N. 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Structure and Properties of Nanocomposite Coatings Based on Titanium, Oxygen, Carbon and Hydrogen Obtained by the Cumulative-Detonation Device

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