The paper describes the nanostructured coatings produced by C-PVD method at various deposition conditions. Samples with thickness of 2, 3 mm and diameter 10, 42 mm were constructed of steel 0.55 % Fe, 0.45 % C with polished surface. The samples were tested by XRD (small angle X-Ray diffraction), SEM with EDX, AFM, scratch – tester REVETEST, tests of wear resistance and acoustic emission, nanoindenter before annealing. It was discovered that the size of nanograins varied from 3,3 nm to 8 nm by annealing at 500°, 800° and 1000°C. By dint of μ- PIXE were discovered the segregation process of impurities at the junctions of interfaces and at nanograin boundaries. Moreover as a result of the thermal annealing hardness of coatings increased on 18- 20 %.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3523

Demianenko, A.A.

Rogoz, V.M.

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2No 1, 01NTF38(5pp) (2013)   2304-1862/2013/2(1)01NTF38(5) 01NTF38-1  2013Sumy State University Influence of Thermal Treatment on the Structure, Physical and Mechanical Properties of Nanostructured Coatings (Ti, Hf, Nb, Si)N Deposited by C-PVD Method  A.A. Demianenko*, V.M. Rogoz†  Sumy State University, 2, Rymsky Korsakov Str., 40007 Sumy, Ukraine  (Received 05 July 2013; published online 03 September 2013)  The paper describes the nanostructured coatings produced by C-PVD method at various deposition conditions. Samples with thickness of 2, 3 mm and diameter 10, 42 mm were constructed of steel 0.55 % Fe, 0.45 % C with polished surface. The samples were tested by XRD (small angle X-Ray diffraction), SEM with EDX, AFM, scratch – tester REVETEST, tests of wear resistance and acoustic emission, nanoindenter before annealing. It was discovered that the size of nanograins varied from 3,3 nm to 8 nm by annealing at 500°, 800° and 1000°C. By dint of μ- PIXE were discovered the segregation process of impurities at the junctions of interfaces and at nanograin boundaries. Moreover as a result of the thermal annealing hardness of coatings increased on 18- 20 %.  Keywords: Nanostructured Coatings, Thermal Treatment, C- PVD, μ- PIXE, Nanocrystallites, X-Ray Diffraction, (Ti, Hf, Nb, Si) N.   PACS numbers: 61.05.cm, 61.46.Hk, 62.20.Qp.68.37.Hk, 81.15.-z                                                           * artem.demyanenko@gmail.com † v.rogoz@yandex.ru 1. INTRODUCTION  Multicomponent and nanostructured coatings are being nowadays one of the most promising protective materials because of their high hardness, high abrasion, corrosion and fatigue resistance as well as high temperature of oxidation, etc. [1-10]. It is well known that binary - TiN, CrN, MoN, triple - TiNAl, TiCrN, and quaternary - Ti-Zr-Si-N, Ti-Hf-Si-N [2-4] compounds are commonly used for wear protection, corrosion protection, and possess high thermal stability even up to (900 ÷ 1000)°C.  Recently published works [2-5] have shown that nanostructured (nanocomposite) (Ti-Hf-Si-N) coatings, obtained by C-PVD method may have two-phases: (Ti, Hf)N - solid solution phase and α-Si3N4 - amorphous phase at the same time these coatings exhibit high hardness up to 48 GPa (superhardness), along with low friction coefficient of 0.12 to 0.45 and thermal stability up to 900 C. Therefore, it is of particular interest to add to such system Nb, which has (as Hf) a high enthalpy of mixing, for improving the resistance to high temperature oxidation and possibly to improve other physical and mechanical properties of coatings such as abrasion resistance and elastic modulus. For providing of studies multielement coatings (Ti, Hf, Nb, Si)N were selected. According to the proposed and experimentally proven concept of high entropy multicomponent alloys such coatings significantly improve thermal stability of the material [1]. Therefore, the creation of new types of nanocomposite (nanostructured) coatings on the basis of (Ti, Hf, Nb, Si) N by means of cathode vacuum arc evaporation (CAVD) and subsequent study of their physical and mechanical properties is an important task of modern materials science.  2. EXPERIMENTAL AND DETAILS  A Cathodic - Arc - Vapor - Deposition "Bulat - 3T" with HF generator [3, 5] was applied. Potential bias was applied to the substrate from the HF generator of pulsed damped oscillations with a frequency of < 1 MHz. The duration of each pulse of 60 us, with a repetition rate of ~ 10 kHz. The amount of negative self-bias potential of the substrate caused by HF diode effect was 2 + 3 kV. Cathodes of the multicomponent alloys (Ti, Hf, Nb, Si) N were prepared by vacuum-arc melting in an atmosphere of high purity argon. The bonding state’s were determined using photoelectron spectroscopy (XPS, Kratos Axis Ultra) with a nanochromatic Alkα (1486,71 eV, X-ray emission/radiation 15 kV/10 mA). The elemental composition, was studied with scanning electron microscope (SEM) with EDX - mocroanalysis JEOL - 7000F (Japan). To perform the element analysis over a sample depth, we employed the Rutherford backscattering (RBS) method with He+ ions of 1.7 MeV (the scattering angle was θ  170°) with a normal fall of probing ions to the surface of coated samples. The energy resolution of detector was 13 keV. A dose of helium ions was 5 µ Ci. To interpret the RBS spectra and to obtain the element profiles over the coatings depth, we employed standard software. The phase composition and structural studies were performed on the X-ray diffractometer DRON-3M and Rigaku RINT-2500 - MDG Japan, in the filtered radiation of Cu-Ka using in the secondary beam graphite monochromator. The diffraction spectra were surveyed in the point-by-point scanning mode with a step 2θ  0.05 - 0.1°. We also employed the diffraction of X - rays using a grazing incidence beam, in Cr  A.A. DEMIANENKO, V.M. ROGOZ PROC. NAP 2, 01NTF38 (2013)   01NTF38-2 emission, at angle 3°. In order to study the stress-strain state of the coatings, we employed the method of X - ray strain measurements («α - sin2 φ» - method) and its modifications, which are commonly applied to the coatings with strong axial texture [10 - 14]. The distribution of elements in nanostructured coatings has been studied by micro-proton beam induced X-ray emission (µ-PIXE) measurements at an initial particle energy of 1,4 MeV – these measurements were performed using an IAPC (Sumy) electrostatic accelerator with a beam diameter of 0,4 µm the raster was  50?50 at a step of 0,5 µm and a change of 3÷10-10C/pixel. To determine the adhesive/cohesive strength, scratch resistance, and also to study the fraction mechanism the scratch tester REVETEST see (CSM Instruments) [6] was used (Fig. 1). The scratches were applied to the coating surface at continuously increasing load by diamond spherical indenter "Rockwell C" with a radius of curvature of 200 µm. Simultaneously the power of acoustic emission, friction coefficient and the penetration depth of the indenter and the value of the normal load (FN) were recorded. Three scratches were applied to each sample.    Fig. 1 – Experimental setup for the determination of the adhesive/cohesive strength.   Tests were carried out under the following conditions: the load on the indenter increased from 0.9 to 70 N, speed of the indenter movement was 1 mm/min, scratch length – 10 mm, the loading rate -6.91 N / min, the frequency of a digital signal – 60 Hz, acoustic emission – 9 Db. Tests determined the minimum (critical) load LC1, which corresponds to the beginning of the indenter penetration into the coating; LC2 - top when the first cracks appear; LC3 - the peel of some parts of coating; LC4 - plastic abrasion of the coating to the substrate. Registration, during a test, (a relatively large number of different physical parameters) improves the reliability and accuracy of the method the critical load determination. The deformation of the coating by the diamond indenter was investigated further using the integrated optical microscope and electron-ion scanning microscope Quanta 200 3D, equipped with an integrated system of Pegasus 2000 for microanalysis.   3. RESULTS AND DISCUSSION  Coatings deposition was performed by vacuum-arc method on set up Bulat-6. A constant negative potential Us = (-40 - 200) V was applied to the substrate, the residual gas pressure was 0.0066 Pa and arc current did not exceed 85 A. Figure 2 shows image of a coating (Ti, Hf, Nb, Si) N in the initial state.    Fig. 2 - The image of surface of nanocomposite combined coatings obtained by scanning electron microscopy.  Before turning to the analysis of X- ray data, it should be noted that, for understanding of the sequence of processes occurring in the surface region during the deposition, it is necessary to compare the heat of formation of possible nitrides.  Table 1 – Crystallite size and the lattice period at different temperatures of annealing  № Annealing temperature °C а, nm Crystallite size, nm 1 - 0,4344 5,0 2 1000 0,42752 7,7 3 500 0,44398 5,9 4 800 0,4352 6,4  Table 2 - The enthalpies of formation ( H) of the five binary nitrides   TiN HfN NbN Si3N4 H, KJ/mole -337,7 -373 -234,7 -738.1  In accordance with [7] the enthalpies of formation ( H) of the four binary nitrides are shown in Table 2. It means that the heat of formation of all systems is a relatively large and negative, indicating that there is a high probability of the formation of such systems through the transfer of material from the target to the substrate. In this case, the proximity of the values of the heat of formation of TiN and HfN creates conditions for the formation of sufficiently homogeneous solid solution (Ti, Hf, Nb) N. Figure 3 and Table 2 shown study the X-ray diffraction. The first annealing (Fig. 3 curve 2) leads to an abrupt relaxation of compressive stresses, which is accompanied by a decrease of lattice period in direction perpendicular to the plane of growth. This annealing leads to a considerable recrystallization processes.  INFLUENCE OF THERMAL TREATMENT ON THE STRUCTURE… PROC. NAP 2, 01NTF38 (2013)   01NTF38-3 Then, annealing up to 800 C (Fig. 3 curve 4) has practically no effect on the stress state, leaving period of lattice the same. A significant relaxation processes were detected after annealing up to 1000 C, which leads to the sharp decrease of the lattice period in the direction perpendicular to the plane of growth. At the same time the average size of the crystallites are exposed to the increase throughout the all temperature range of annealing and reaches maximum size of 7.7 nm at 1000°C, i.e. increases for more than 60 % compared to the initial state.    Fig. 3 - Diffraction spectra of coatings obtained by GXRD: 1- as deposited 2 – annealed at 1000?C, 3 - annealed at 500°C, 4 - annealed at 800°C.  The following figure 4 shows the energy spectra of backscattered 4He+, obtained from samples coated with (Ti, Hf, Nb, Si) N on a steel substrate.    Fig. 4 - Energy RBS spectra obtained for coatings (Ti, Hf, Nb, Si) N, at the initial state and after annealing at T = 500°C, 800°C, 1000°C for 30 min. in air  As it is seen from the figure, the concentration of Ti, Hf, Nb, Si elements after annealing at T = 500°C and 800 C is comparable to concentration of these elements before annealing, which indicates the uniformity of distribution of elements through the thickness of the coating. Annealing of samples up to 1000 C for 30 min. led to formation of oxide film on the surface of coating and to redistribution of the elements in the form of films. Preliminary results obtained by μ-PIXE microbeam in depth and on the surface of nanostructured coatings showed that the annealing to 800°C leads to the segregation of impurities (for example, the elements Hf and Nb) in nanograins. A siliconitride layer which is formed as a result of the thermal diffusion of Si along nano-grain boundaries leads to the formation of SiNx - amorphous phase. It is also reflected in the results of XPS (peak in radon 101.9 KeV) wherein Si concentration in this compound estimated as (4.9 ~ 5.2) at %. Figure 5 a shows the results of tests performed on the scratch tester REVETEST of sample Ti- Hf- Nb- Si) N at the minimum (critical) load LC1 = 2,46 H and at the load at which the first cracks appear LC2 = 10,25 N.    а    b  Fig. 5 - Results of adhesion of tests system coatings (Ti, Hf, Nb, Si) N steel substrate: a - dependence AE (1), μ (2), and the depth of penetration (3); b - structure of the coating in the fracture zone at loads in the range 0.9 - 90.0 N  It should be noted that when the load increases, the curve describing the dependence of friction coefficient on the load gets an oscillatory character. The increase of the friction coefficient is accompanied by a surge of acoustic emission. The above described behavior of all recorded parameters in these experiments (coefficient of friction, hardness) shows that the hard coating with thickness of ≤ 1μm deposited on a surface of softer material (steel) shows a substantial resistance to diamond indenter to almost its full abrasion under high loads. [15-16].  A.A. DEMIANENKO, V.M. ROGOZ PROC. NAP 2, 01NTF38 (2013)   01NTF38-4 When testing coatings it can be can clearly distinguished different threshold values of critical load which lead to different typed of destruction. What is more only a minimum (critical) LC1 load and a load at which the first crack appears LC2 can be associated with the adhesive destruction of coatings. Destruction of the coating begins with the appearance of chevron cracks at the bottom of wear groove, which causes the increase of local stresses and friction. This leads to the subsequent rapid abrasion of coating (Fig. 5b). According to the results of adhesion tests, cohesive destruction of the coatings (as-deposited) (Ti- Hf- Nb- Si) N appears at the minimal (critical) load LC1  2.38 H and adhesion destruction occurs at a load when the first crack appears LC2 = 9.81 N. Figure 6 (a, b, c) shows the results of scratch tests of samples after annealing at 500, 800 and 1000°C. according to obtained results it can be argued that the greatest resistance to wear is demonstrated by coatings after high-temperature annealing up 1000°C (lowest takeout of coating material (c)). Accordingly, the degree of wear resistance decreases with decreasing stresses, and perhaps this is also associated with an increase of friction coefficient (although as can be seen from the results of EDX analysis there is an oxide film with thickness of 60 – 75 nm).  4. CONCLUSIONS   It is shown that high temperature annealing leads to increase of the nanocrystallites size of the solid solution from 3 nm to 7.7 nm and to different recrystallization processes. High macro- and microdeformation occurring in the coating seems to be related to an “atomic peening” effect resulting to non-ordered distribution of titanium atoms implanted to the film during its growth. In the course of annealing, the macro- and micro-deformation relaxed. The relaxation was accompanied by formation of deformation packing defects in a metallic sublattice of (Ti, Hf) N, (Ti, Nb) N solid solution.   a    b    c  Fig 6 - The results of wear resistance tests obtained by scratch tester REVETEST of samples (Ti, Hf, Nb, Si,) N: a – after annealing 500°C, b – after annealing 800°C, с – after annealing 1000°C  INFLUENCE OF THERMAL TREATMENT ON THE STRUCTURE… PROC. NAP 2, 01NTF38 (2013)   01NTF38-5 ACKNOWLEDGMENTS  Ministry  of Eucation and Science of Ukraine (state program, order №. 411), and in collaboration with NIMS (Tsukuba, Japan) and Martin-Luther University (Dresden, Germany). The work was supported by Ministry of Education and Science of Ukraine (project № 0112U005920) and Ministry of Education and Science of Russia (grant № 12-08-31060). Authors are grateful to the staff of the Joint Reserch Center “Diagnostics of Structure and Properties of Nanomaterials” (Belgorod State University, Russia) for their assistance with instrumental analysis. And authors acknowledge Dr. Sc. F.F.Komarov(Belarusian State University, Minsk, Belarus) for their help in performance of these experiments.   REFERENCES  1. A.D. Pogrebnjak, A.G. Ponomarev, A.P. Shpak, Yu.A. Kunitskii, Physics-Uspekhi 55 No3, 270(2012).  2. A.D. Pogrebnjak, A.P. Shpak, N.A. Azarenkov, V.M. Beresnev, Physics-Uspekhi 52 No1, 29 (2009). 3. A.D. Pogrebnjak, E.A. Bazyl, Vacuum 64 No1, 1 (2001). 4. A.D. Pogrebnyak, V.M. Beresnev, D.A. Kolesnikov, M.V. Kaverin, A.P. Shypylenko, K. Oyoshi, Y. Takeda, R. Krause-Rehberg, A.G. Ponamarev, Technical Physics Letters 39 No3, 280 (2013). 5. A.D. Pogrebnjak, O.V. Sobol, V. M. Beresnev, P.V. Turbin, G.V. Kirik, N.A. Makhmudov, M.V Il'yashenko, A.P. Shypylenko, M.V. Kaverin, M.Yu. Tashmetov, A.V. Pshyk Ceramic Engineering and Science Proceedings, 31, 127 (2010). 6. O.V. Sobol, A.D. Pogrebnyak, V.M. Beresnev, The Physics of Metals and Metallograph, 112 No2, 199 (2011). 7. J. Musil, P. Zeman, Advances in Applied Ceramics 107 No3, 148 (2008). 8. A.D. Korotaev, V.D. Borisov, V.Y. Moshkov, S.V. Ovchinnikov, J.P. Pinzhin, A.N. Tyumentsev, “Elastic stress state in superhard multielement coatings”, Physical Mesomechanics 12 No5-6, 269 (2009). 9. A.D. Pogrebnyak, V.M. Beresnev, D.A. Kolesnikov, M.V. Kaverin, A.P.Shypylenko, K.Oyoshi,Y. Takeda, R. Krause-Rehberg, A.G. Ponamarev, Technical Physics Letters 39 No3, 280 (2013). 10. O.V. Sobol', A.A. Andreev, V.F. Gorban, N. Krapivka, V.A. Pole, I.V. Serdyuk, V.E. Filchikov, Technical Physics Letters 38 No7, 616 (2012). 11. I.V. Blinkov, S.A. Volkhonsky, V.N. Anikin, M.I. Petrzhik, D.E. Derevtsova, Physics and Chemistry of Materials Pro-cessing  4, 37 (2010) (in Russian). 12. Shao-Yi Lin, Shou-Yi Chang, Yi-Chung Huang, Fuh-Sheng Shieu, Jien-Wei Yeh, Surface and Coatings Tech-nology, 206 No24, 5096 (2012). 13. J. Musil, Surface and Coatings Technology 207, 50 (2012). 14. A.D. Pogrebnjak, A.P. Shpak, V.M. Beresnev, D.A. Kolesnikov, Yu.A. Kunitsky, O.V. Sobol, V.V. Uglov, F.F. Komarov, A.P. Shypylenko, A.A. Demyanenko, V.S. Baidak, V.V. Grudnitskii, Journal of Nanoscience and Nanotechnology 12, 9213 (2012). 15. S.V. Rempel, A. Gusev, JETP Letters 88 No7, 508 (2008). 16. Nanomaterials, nanostructures and nanotechnology (Ed. A.I. Gusev) (Moscow: Fizmatlit:2005).  

Influence of Thermal Treatment on the Structure, Physical and Mechanical Properties of Nanostructured Coatings (Ti, Hf, Nb, Si)N Deposited by C-PVD Method

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2No 1, 01NTF38(5pp) (2013) 
 
 
2304-1862/2013/2(1)01NTF38(5) 01NTF38-1  2013Sumy State University 
Influence of Thermal Treatment on the Structure, Physical and Mechanical Properties of 
Nanostructured Coatings (Ti, Hf, Nb, Si)N Deposited by C-PVD Method 
 
A.A. Demianenko*, V.M. Rogoz† 
 
Sumy State University, 2, Rymsky Korsakov Str., 40007 Sumy, Ukraine 
 
(Received 05 July 2013; published online 03 September 2013) 
 
The paper describes the nanostructured coatings produced by C-PVD method at various deposition 
conditions. Samples with thickness of 2, 3 mm and diameter 10, 42 mm were constructed of steel 
0.55 % Fe, 0.45 % C with polished surface. The samples were tested by XRD (small angle X-Ray 
diffraction), SEM with EDX, AFM, scratch – tester REVETEST, tests of wear resistance and acoustic 
emission, nanoindenter before annealing. It was discovered that the size of nanograins varied from 3,3 nm 
to 8 nm by annealing at 500°, 800° and 1000°C. By dint of μ- PIXE were discovered the segregation process 
of impurities at the junctions of interfaces and at nanograin boundaries. Moreover as a result of the 
thermal annealing hardness of coatings increased on 18- 20 %. 
 
Keywords: Nanostructured Coatings, Thermal Treatment, C- PVD, μ- PIXE, Nanocrystallites, X-Ray 
Diffraction, (Ti, Hf, Nb, Si) N. 
 
 PACS numbers: 61.05.cm, 61.46.Hk, 
62.20.Qp.68.37.Hk, 81.15.-z 
 
 
                                                        
* artem.demyanenko@gmail.com 
† v.rogoz@yandex.ru 
1. INTRODUCTION 
 
Multicomponent and nanostructured coatings are 
being nowadays one of the most promising protective 
materials because of their high hardness, high 
abrasion, corrosion and fatigue resistance as well as 
high temperature of oxidation, etc. [1-10]. It is well 
known that binary - TiN, CrN, MoN, triple - TiNAl, 
TiCrN, and quaternary - Ti-Zr-Si-N, Ti-Hf-Si-N [2-4] 
compounds are commonly used for wear protection, 
corrosion protection, and possess high thermal stability 
even up to (900 ÷ 1000)°C.  
Recently published works [2-5] have shown that 
nanostructured (nanocomposite) (Ti-Hf-Si-N) coatings, 
obtained by C-PVD method may have two-phases: 
(Ti, Hf)N - solid solution phase and α-Si3N4 - 
amorphous phase at the same time these coatings 
exhibit high hardness up to 48 GPa (superhardness), 
along with low friction coefficient of 0.12 to 0.45 and 
thermal stability up to 900 C. Therefore, it is of 
particular interest to add to such system Nb, which has 
(as Hf) a high enthalpy of mixing, for improving the 
resistance to high temperature oxidation and possibly 
to improve other physical and mechanical properties of 
coatings such as abrasion resistance and elastic 
modulus. 
For providing of studies multielement coatings (Ti, 
Hf, Nb, Si)N were selected. According to the proposed 
and experimentally proven concept of high entropy 
multicomponent alloys such coatings significantly 
improve thermal stability of the material [1]. 
Therefore, the creation of new types of nanocomposite 
(nanostructured) coatings on the basis of (Ti, Hf, Nb, 
Si) N by means of cathode vacuum arc evaporation 
(CAVD) and subsequent study of their physical and 
mechanical properties is an important task of modern 
materials science. 
 
2. EXPERIMENTAL AND DETAILS 
 
A Cathodic - Arc - Vapor - Deposition "Bulat - 3T" 
with HF generator [3, 5] was applied. Potential bias 
was applied to the substrate from the HF generator of 
pulsed damped oscillations with a frequency of 
< 1 MHz. The duration of each pulse of 60 us, with a 
repetition rate of ~ 10 kHz. The amount of negative 
self-bias potential of the substrate caused by HF diode 
effect was 2 + 3 kV. 
Cathodes of the multicomponent alloys (Ti, Hf, Nb, 
Si) N were prepared by vacuum-arc melting in an 
atmosphere of high purity argon. 
The bonding state’s were determined using 
photoelectron spectroscopy (XPS, Kratos Axis Ultra) 
with a nanochromatic Alkα (1486,71 eV, X-ray 
emission/radiation 15 kV/10 mA). 
The elemental composition, was studied with 
scanning electron microscope (SEM) with EDX - 
mocroanalysis JEOL - 7000F (Japan). To perform the 
element analysis over a sample depth, we employed the 
Rutherford backscattering (RBS) method with He+ ions 
of 1.7 MeV (the scattering angle was θ  170°) with a 
normal fall of probing ions to the surface of coated 
samples. The energy resolution of detector was 13 keV. 
A dose of helium ions was 5 µ Ci. To interpret the RBS 
spectra and to obtain the element profiles over the 
coatings depth, we employed standard software. 
The phase composition and structural studies were 
performed on the X-ray diffractometer DRON-3M and 
Rigaku RINT-2500 - MDG Japan, in the filtered 
radiation of Cu-Ka using in the secondary beam 
graphite monochromator. The diffraction spectra were 
surveyed in the point-by-point scanning mode with a 
step 2θ  0.05 - 0.1°. We also employed the diffraction 
of X - rays using a grazing incidence beam, in Cr 
 A.A. DEMIANENKO, V.M. ROGOZ PROC. NAP 2, 01NTF38 (2013) 
 
 
01NTF38-2 
emission, at angle 3°. In order to study the stress-
strain state of the coatings, we employed the method of 
X - ray strain measurements («α - sin2 φ» - method) and 
its modifications, which are commonly applied to the 
coatings with strong axial texture [10 - 14]. 
The distribution of elements in nanostructured 
coatings has been studied by micro-proton beam 
induced X-ray emission (µ-PIXE) measurements at an 
initial particle energy of 1,4 MeV – these 
measurements were performed using an IAPC (Sumy) 
electrostatic accelerator with a beam diameter of 0,4 
µm the raster was  50?50 at a step of 0,5 µm and a 
change of 3÷10-10C/pixel. 
To determine the adhesive/cohesive strength, 
scratch resistance, and also to study the fraction 
mechanism the scratch tester REVETEST see (CSM 
Instruments) [6] was used (Fig. 1). The scratches were 
applied to the coating surface at continuously 
increasing load by diamond spherical indenter 
"Rockwell C" with a radius of curvature of 200 µm. 
Simultaneously the power of acoustic emission, friction 
coefficient and the penetration depth of the indenter 
and the value of the normal load (FN) were recorded. 
Three scratches were applied to each sample. 
 
 
 
Fig. 1 – Experimental setup for the determination of the 
adhesive/cohesive strength.  
 
Tests were carried out under the following 
conditions: the load on the indenter increased from 0.9 
to 70 N, speed of the indenter movement was 
1 mm/min, scratch length – 10 mm, the loading rate -
6.91 N / min, the frequency of a digital signal – 60 Hz, 
acoustic emission – 9 Db. Tests determined the 
minimum (critical) load LC1, which corresponds to the 
beginning of the indenter penetration into the coating; 
LC2 - top when the first cracks appear; LC3 - the peel of 
some parts of coating; LC4 - plastic abrasion of the 
coating to the substrate. Registration, during a test, (a 
relatively large number of different physical 
parameters) improves the reliability and accuracy of 
the method the critical load determination. The 
deformation of the coating by the diamond indenter 
was investigated further using the integrated optical 
microscope and electron-ion scanning microscope 
Quanta 200 3D, equipped with an integrated system of 
Pegasus 2000 for microanalysis. 
 
 
3. RESULTS AND DISCUSSION 
 
Coatings deposition was performed by vacuum-arc 
method on set up Bulat-6. A constant negative 
potential Us = (-40 - 200) V was applied to the 
substrate, the residual gas pressure was 0.0066 Pa and 
arc current did not exceed 85 A. Figure 2 shows image 
of a coating (Ti, Hf, Nb, Si) N in the initial state. 
 
 
 
Fig. 2 - The image of surface of nanocomposite combined 
coatings obtained by scanning electron microscopy. 
 
Before turning to the analysis of X- ray data, it 
should be noted that, for understanding of the sequence 
of processes occurring in the surface region during the 
deposition, it is necessary to compare the heat of 
formation of possible nitrides. 
 
Table 1 – Crystallite size and the lattice period at different 
temperatures of annealing 
 
№ Annealing 
temperature °C 
а, nm Crystallite 
size, nm 
1 - 0,4344 5,0 
2 1000 0,42752 7,7 
3 500 0,44398 5,9 
4 800 0,4352 6,4 
 
Table 2 - The enthalpies of formation ( H) of the five binary 
nitrides 
 
 TiN HfN NbN Si3N4 
H, 
KJ/mole 
-
337,7 
-
373 
-
234,7 
-
738.1 
 
In accordance with [7] the enthalpies of formation 
( H) of the four binary nitrides are shown in Table 2. It 
means that the heat of formation of all systems is a 
relatively large and negative, indicating that there is a 
high probability of the formation of such systems 
through the transfer of material from the target to the 
substrate. In this case, the proximity of the values of 
the heat of formation of TiN and HfN creates 
conditions for the formation of sufficiently 
homogeneous solid solution (Ti, Hf, Nb) N. 
Figure 3 and Table 2 shown study the X-ray 
diffraction. The first annealing (Fig. 3 curve 2) leads to 
an abrupt relaxation of compressive stresses, which is 
accompanied by a decrease of lattice period in direction 
perpendicular to the plane of growth. This annealing 
leads to a considerable recrystallization processes. 
 INFLUENCE OF THERMAL TREATMENT ON THE STRUCTURE… PROC. NAP 2, 01NTF38 (2013) 
 
 
01NTF38-3 
Then, annealing up to 800 C (Fig. 3 curve 4) has 
practically no effect on the stress state, leaving period 
of lattice the same. A significant relaxation processes 
were detected after annealing up to 1000 C, which 
leads to the sharp decrease of the lattice period in the 
direction perpendicular to the plane of growth. At the 
same time the average size of the crystallites are 
exposed to the increase throughout the all temperature 
range of annealing and reaches maximum size of 7.7 
nm at 1000°C, i.e. increases for more than 60 % 
compared to the initial state. 
 
 
 
Fig. 3 - Diffraction spectra of coatings obtained by GXRD: 1- 
as deposited 2 – annealed at 1000?C, 3 - annealed at 500°C, 4 - 
annealed at 800°C. 
 
The following figure 4 shows the energy spectra of 
backscattered 4He+, obtained from samples coated with 
(Ti, Hf, Nb, Si) N on a steel substrate. 
 
 
 
Fig. 4 - Energy RBS spectra obtained for coatings 
(Ti, Hf, Nb, Si) N, at the initial state and after annealing at T 
= 500°C, 800°C, 1000°C for 30 min. in air 
 
As it is seen from the figure, the concentration of 
Ti, Hf, Nb, Si elements after annealing at T = 500°C 
and 800 C is comparable to concentration of these 
elements before annealing, which indicates the 
uniformity of distribution of elements through the 
thickness of the coating. Annealing of samples up to 
1000 C for 30 min. led to formation of oxide film on the 
surface of coating and to redistribution of the elements 
in the form of films. 
Preliminary results obtained by μ-PIXE microbeam 
in depth and on the surface of nanostructured coatings 
showed that the annealing to 800°C leads to the 
segregation of impurities (for example, the elements Hf 
and Nb) in nanograins. A siliconitride layer which is 
formed as a result of the thermal diffusion of Si along 
nano-grain boundaries leads to the formation of SiNx - 
amorphous phase. It is also reflected in the results of 
XPS (peak in radon 101.9 KeV) wherein Si 
concentration in this compound estimated as 
(4.9 ~ 5.2) at %. 
Figure 5 a shows the results of tests performed on 
the scratch tester REVETEST of sample Ti- Hf- Nb- Si) 
N at the minimum (critical) load LC1 = 2,46 H and at 
the load at which the first cracks appear LC2 = 10,25 N. 
 
 
 
а 
 
 
 
b 
 
Fig. 5 - Results of adhesion of tests system coatings 
(Ti, Hf, Nb, Si) N steel substrate: a - dependence AE (1), μ (2), 
and the depth of penetration (3); b - structure of the coating in 
the fracture zone at loads in the range 0.9 - 90.0 N 
 
It should be noted that when the load increases, the 
curve describing the dependence of friction coefficient on 
the load gets an oscillatory character. The increase of the 
friction coefficient is accompanied by a surge of acoustic 
emission. The above described behavior of all recorded 
parameters in these experiments (coefficient of friction, 
hardness) shows that the hard coating with thickness of 
≤ 1μm deposited on a surface of softer material (steel) 
shows a substantial resistance to diamond indenter to 
almost its full abrasion under high loads. [15-16]. 
 A.A. DEMIANENKO, V.M. ROGOZ PROC. NAP 2, 01NTF38 (2013) 
 
 
01NTF38-4 
When testing coatings it can be can clearly 
distinguished different threshold values of critical load 
which lead to different typed of destruction. What is 
more only a minimum (critical) LC1 load and a load at 
which the first crack appears LC2 can be associated 
with the adhesive destruction of coatings. 
Destruction of the coating begins with the 
appearance of chevron cracks at the bottom of wear 
groove, which causes the increase of local stresses and 
friction. This leads to the subsequent rapid abrasion of 
coating (Fig. 5b). 
According to the results of adhesion tests, cohesive 
destruction of the coatings (as-deposited) (Ti- Hf- Nb-
 Si) N appears at the minimal (critical) load 
LC1  2.38 H and adhesion destruction occurs at a load 
when the first crack appears LC2 = 9.81 N. Figure 
6 (a, b, c) shows the results of scratch tests of samples 
after annealing at 500, 800 and 1000°C. according to 
obtained results it can be argued that the greatest 
resistance to wear is demonstrated by coatings after 
high-temperature annealing up 1000°C (lowest takeout 
of coating material (c)). Accordingly, the degree of wear 
resistance decreases with decreasing stresses, and 
perhaps this is also associated with an increase of 
friction coefficient (although as can be seen from the 
results of EDX analysis there is an oxide film with 
thickness of 60 – 75 nm). 
 
4. CONCLUSIONS  
 
It is shown that high temperature annealing leads 
to increase of the nanocrystallites size of the solid 
solution from 3 nm to 7.7 nm and to different 
recrystallization processes. High macro- and 
microdeformation occurring in the coating seems to be 
related to an “atomic peening” effect resulting to non-
ordered distribution of titanium atoms implanted to 
the film during its growth. In the course of annealing, 
the macro- and micro-deformation relaxed. The 
relaxation was accompanied by formation of 
deformation packing defects in a metallic sublattice of 
(Ti, Hf) N, (Ti, Nb) N solid solution. 
 
 
a 
 
 
 
b 
 
 
 
c 
 
Fig 6 - The results of wear resistance tests obtained by scratch tester REVETEST of samples (Ti, Hf, Nb, Si,) N: a – after 
annealing 500°C, b – after annealing 800°C, с – after annealing 1000°C 
 INFLUENCE OF THERMAL TREATMENT ON THE STRUCTURE… PROC. NAP 2, 01NTF38 (2013) 
 
 
01NTF38-5 
ACKNOWLEDGMENTS 
 
Ministry  of Eucation and Science of Ukraine (state 
program, order №. 411), and in collaboration with 
NIMS (Tsukuba, Japan) and Martin-Luther University 
(Dresden, Germany). The work was supported by 
Ministry of Education and Science of Ukraine (project 
№ 0112U005920) and Ministry of Education and 
Science of Russia (grant № 12-08-31060). 
Authors are grateful to the staff of the Joint Reserch 
Center “Diagnostics of Structure and Properties of 
Nanomaterials” (Belgorod State University, Russia) for 
their assistance with instrumental analysis. And 
authors acknowledge Dr. Sc. F.F.Komarov(Belarusian 
State University, Minsk, Belarus) for their help in 
performance of these experiments. 
 
 
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Influence of Thermal Treatment on the Structure, Physical and Mechanical Properties of Nanostructured Coatings (Ti, Hf, Nb, Si)N Deposited by C-PVD Method

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