Metallurgist, Vol. 54, Nos. 9–10, 2011
MULTILAYER NANOSTRUCTURED HEAT-GENERATING COATINGS. PREPARATION AND CERTIFICATION OF MECHANICAL AND TRIBOLOGICAL PROPERTIES
E. A. Levashov,1 M. I. Petrzhik,1 M. Ya. Tyurina,1 F. V. Kiryukhantsev-Korneev,1 P. A. Tsygankov,2 and A. S. Rogachev1,3
UDC 621.793.18:630.22-419.8-492
The state of problems for preparing and using multilayer nanostructured heat-generating films and coatings is considered. A method is proposed for preparing binary Ti/Al coatings. The composition, structure, adhesion and tribological properties of coatings on substrates of various materials are studied. It is shown that the hardness of a Ti/Al coating increases with a reduction in single layer thickness. Key words: coating, layer, structure, composition, titanium, aluminum, magnetic deposition, hardness, elasticity modulus, adhesion, friction.
Creation of multilayer (nanolayer) films and coatings for different functional purposes is a rapidly developing area of nanotechnology. There is a considerable interest in multilayered nanostructured films and coatings, within which an exothermic reaction between the components of the layered systems propagates independently in a heating regime due to the generation of heat during reaction with external heating sources. Multilayered nanostructured heat-generating films and coatings (MNHC) are alternating nanosize layers of elements or compounds, with a capacity for exothermic reaction with the generation of a considerable amount of heat. They are used for preparing solid joints during soldering of materials that are not compatible [1–8], and also for protecting information stored in an electronic device [9]. For the first time in [1] there was information about a self-supporting reaction in a multilayer nanofilm of nickelaluminum (overall thickness up to 300 nm) separated from the substrate. An important role in developing research was played by [2] (USA patent of 1996 within which simultaneously the preparation method for nanostructured multilayer films and the wave reaction process within them were protected). In the next ten years, there was an increase in the number of scientific publications in various countries, and also development of practical applications. Since this area of research is at the junction of chemical physics of combustion processes, chemistry and materials science, many results have been published in physical and chemical journals and others in materials science journals. Protection of information stored in an electronic device and the construction of the device itself from unauthorized access is currently very important. In contemporary electronic information devices, there is some level of protection from 1
National Research Technological University – Moscow Institute of Steel and Alloys (NITU MISiS), Moscow, Russia; e-mail:
[email protected]. 2 Bauman Moscow State Technical University, Moscow, Russia. 3 Institute of Structural Macrokinetics and Materials Science Problems, Russian Academy of Sciences, Chernogolovka, Moscow Oblast, Russia. Translated from Metallurg, No. 9, pp. 66–74, September, 2010. Original article submitted July 21, 2010.
0026-0894/11/0910-0623 ©2011 Springer Science+Business Media, Inc.
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unauthorized access to information stored within them: software, equipment and technology [10]. The software level is realized by means of the operating system. The operating level of protection prevents the possibility of the use of information in non-standard operating regimes prescribed by the developer. The technology of the level of protection is aimed at preventing reproduction of the structure and the electronic circuit of a device and prevents breakdown of units in the case of their unauthorized and unregulated opening or examination. Heat-generating multilayered nanostructured films and coatings have considerable promise for application in information protection at a technological level. These MNHC are often prepared with layer-by-layer magnetron deposition, which makes it possible to deposit a layer of uniform composition over a prolonged time with a constant rate of layer growth, and this is very important if depositing hundreds and thousands of alternating layers. The deposition method for multilayer reaction nanofilms [2, 11–13] is similar to that developed previously [14, 15] for depositing multilayer coatings. Atomization of reagents occurs from two or more simultaneously operating sources (magnetron targets), the substrate is fastened on a rotating holder and it is alternately exposed to a stream of deposited substance from one and then another target. The number of layers equals the number of holder rotations, and the thickness of each layer is determined by the exposure time (rotation rate), power of the source and distance from the source to the substrate. As a rule, the process is accomplished in an atmosphere of especially pure rarified argon with a pressure up to several tens of Pa (previously a high vacuum is created in the deposition chamber). A necessary condition is maintenance of a low substrate temperature, in order to exclude reaction between the layers and suppress mutual diffusion in the deposition stage. Normally the substrate temperature should be close to room temperature for the whole film deposition time. A multilayer reaction system exhibits excess chemical energy, elastic energy of stressed layers and free energy of interphase boundaries [16]. This excess creates a thermodynamic moving force, that may destroy a layer, lead to their movement or separation (formation of a continuous layer of individual islands). In addition, each layer is polycrystalline, i.e., it consists of a mosaic of flat grains, the boundaries of which are perpendicular to the boundary between layers. As analysis of MNHC stability has shown from the point of view of excess energy of an interface [16], a layer is flatter if the specific (per unit area) energy of the boundary between grains is much less than the energy of the boundary between layers. With a reverse ratio at the intersection of intergranular and interlayer boundaries typical troughs develop, which may lead to layer separation. Excess energy over a grain boundary leads to the situation that the center of the grain grows more rapidly than its periphery, as a result of which the surface becomes dome shaped. Features of layer roughness change in relation to the system, single layer thickness, substrate properties and other parameters. It is hardly possible to predict precisely the microstructure of a layer, and for each system it is necessary to determine it by experiment. Finally, a feature of layers deposited by means of a magnetron is the texture, i.e., in the crystal structure there are individual grains of which the polycrystalline film consists, and the same atomic planes are orientated predominantly along layers. This phenomenon is well known from the practice of thin film preparation [11]. Thus, in spite of the apparent simplicity of the geometry of multilayer films, they exhibit a complex microstructure, or considering the size of layers it is possible to say a complex nanostructure. Its most important characteristics, that are provided in almost all work in this field, is the spacing of the structure, i.e., the overall thickness of two adjacent layers (subsequently this is value d), and the overall film thickness (subsequently H). Recently magnetron deposition has been used to prepare and study reaction films in the systems Ni/Al [17, 18], Ti/Al [12, 19–25], Nb/Al [21, 26, 27], Ta/Al [27], Cu/Al [27], Nb/Si [2, 28], CuO/Al [29, 30], etc. It may be stated that this method is the main one in studying self-supporting reactions in nanofilms. Currently the method of magnetron deposition is used to prepare films with continuous alternating layers with a thickness 3–4 nm, and the number of layers in the film may exceed 5000 [24]. Deposition of vapor in a high vacuum (PVD method) also makes it possible to obtain very thin, up to several angstrom, layers of prescribed composition. However, with use of it there is difficulty in obtaining a constant evaporation rate over a prolonged period, that is required for deposition of hundreds or thousands of layers. Therefore this method has so far been used fro preparing films with a relatively small number of layers. In a number of works [31, 32], two-layer films of the systems Al/Ni, Al/Fe, and Al/Co have been studied with a thickness of each layer within the limits 30–100 nm, and here the thickness of the whole film does not exceed 200 nm. Layers were applied by evaporation, i.e., deposition in a vacuum of 10–4 Pa. In a earlier work [1], for studying combustion in a multilayer Ni/Al system films were prepared of several 624
Fig. 1. Composition of thin layer section and deposition scheme: 1) magnetron, 2) accelerator with anodic layer; 3) substrate with deposited multilayer coating; 4) rotary water-cooled substrate holder.
tens of layers by electron beam evaporation and deposition in a vacuum of 10–6 Pa, and the overall thickness of the film was as a rule 300 μm. Vacuum deposition has been used to prepare multilayer films of the Pt–Co system [33], containing from 60 to 90 pairs of layers with a thickness of 0.40–0.44 nm for Co and 0.51–0.55 nm for Pt. Electron beam evaporation in a high vacuum (10–6 Pa) has also been used for preparing multilayer reaction films in the Ti–Si system [34] with a layer thickness of Ti of 14–18 nm and Si 16–42 nm, and the number of layers was, as a rule, ten (five layers of each reagent). Often layers deposited in a vacuum have an amorphous atomic structure. An important fundamental and practical question is initiation of combustion in multilayered heat-generating systems. For this in order to initiate a self-propagating reaction wave local heating of a small area of film is necessary to a certain temperature. As is well known from combustion theory [35], the ignition temperature is a kinetic quantity, i.e., it depends both on the composition of a given mixture and on the heating rate, rate of heat generation in the course of a reaction, and the level of heat lost to the surroundings. In powder mixtures, the ignition temperature of the systems in question is often close to the phase transition temperature, for example melting of a readily melting reagent since at this point there is rapid acceleration of the reaction. A more precise value of the temperature for initiating reaction in the field of slow heating rates is obtained by the method of differential scanning calorimetry [36]. Data obtained for exothermic systems Ti–Al, Ni–Al, Nb–Al show that in nanonfilms reaction commences with a temperature 300–400 degrees below the aluminum melting temperature (933 K). For example, with a heating rate of 40 K·min–1 for the composition Ni/3Al the reaction is initiated at 480–540 K [17, 18, 36], and for compositions Nb/Al, Nb/3Al, 2Nb/Al, and 3Nb/Al this temperature is 600–650 K [27, 37]. In films of Ti/Al and Ti/3Al, intense heat generation commences at 600–700 K [24, 25]. It is also noted that the reaction initiation temperature depends on film thickness. Multilayer heat-generating coatings are nevertheless nanostructured materials, which in a nonequilibrium condition should be characterized by temporary stability in a certain temperature range in air, and technological reproducibility. Here the upper limit of the temperature range selected should be considerably lower than the temperature for the start of chemical reaction and it often corresponds to room temperature. A key question of MNHC commercialization is creation of standard procedures and standardized provision of unification of property measurement, that will make it possible to accomplish control of the temporary stability and reproducibility of properties. This relates to structure-sensitive mechanical and tribological properties of coatings: hardness, elasticity modulus, elastic recovery, adhesive strength with the substrate, and friction coefficient [37–39]. Therefore, in this work studies are performed for mechanical and tribological properties of the well studied and developed binary system Ti/Al. Measurements were carried out in the accredited test laboratory of functional surfaces at the Moscow Institute of Steel and Alloys (MISiS) using the metrological complex, including modern equipment: nano hardness meter (nano indenter); scratch tester (adhesion meter); friction machine (tribometer); scanning probe microscope; contact and 625
Fig. 2. Elemental profile of Ti/Al multilayer coating after deposition (SIMS method) during first week (a) and after holding a specimen in air for six months (b).
optical profilometers. This complex provides measurement over a wide range of values and uncertainties of measurements fro physical quantities in the nano range. Preparation of Ti/Al multilayer binary coatings. In order to form a layered binary structure, two sections of thin-film deposition are used, each of which consists of a magnetron atomizing device, operating in a pair with an ion source based on accelerator with an anodic layer. The operating principle of this section is explained in Fig. 1. For generation of material vapor a face magnetron 1 is used with a cathode-target diameter of 51 mm and a magnetic system based on permanent magnets. In this work, cathodes of Al (AVR-99.95%) and Ti (VT1-0) were used, i.e., each for its own section. The electrical supply system provided voltage to the magnetron up to 1200 V with a discharge current up to 2 A, which provided a material film growth rate on a substrate of 0.5–1.5 nm/sec. The ion source 2, operating simultaneously with the magnetron in an assistant regime, generates an expendable annular beam with an original diameter of 50 mm with an average current density at the substrate of 0.3–0.8 mA/cm2 and an ion energy of 120 eV. It is arranged so that the substrate 3 at the input to the section first passes over one of the beam (zone I), where the surface is cleaned and activated, and then to the zone of intense access of material vapor atomized by the magnetron (zone II), where another part of the ion beam fulfils an assistant action. Parameters of the ion beam for deposition were selected in order on one hand to provide good adhesion of a film to a substrate, including fuzed quartz, and to reduce the residual stresses in a coating, and on the other not to provide marked blurring and movement of an interlayer boundary. Each section of deposition was located in a sector of 180° and separated from its neighbor by a metal screen. A multilayer coating was applied to specimens, fastened on a rotating water-cooled drum 4 (see Fig. 1) rotating at a constant rate with a drive from a stepped motor. The substrate subsequently enters the application zone for each of the materials, which provides formation of a layered system. During one drum rotation, two layers of coating are applied to a substrate, i.e., Ti and Al. The thickness of each layer is determined by the productivity of the atomizing device and the angular velocity of drum rotation. Magnetrons operate with volt-ampere characteristics providing the same thickness of Ti and Al layers, and by selecting the drum rotation rate with the substrate it is possible to control the binary layer thickness over wide limits. A multilayer coating was applied in an argon atmosphere with a working pressure of 0.3 Pa. The substrate temperature did not exceed 80°C. 626
Fig. 3. Elemental profile of Ti/Al multilayer coating (OESGD method) with a layer thickness of 25/25 nm (a) and 50/50 nm (b).
Before coating deposition, the substrate, fastened to the rotary drum, was previously cleaned in order to remove absorbed admixtures, oxide layers and in order to activate the surface for 20 min with the accelerators of each section, operating in a highvoltage regime with which an ion beam is generated with an energy of 320 eV with a current density of 0.2–0.5 mA/cm2. It should be noted that the ion sources used operate without systems of individual gas supply (argon), and therefore their energy and voltampere characteristics are determined by the overall working pressure in the chamber, which in the preliminary cleaning regime is 0.1–0.15 Pa. Parameters of the ion beam in this work were controlled with a probe diagnostic unit [40]. A two-section system for application of binary multilayer coatings is placed in the dome space of a vacuum device grade URM-3. The residual vacuum in the chamber at the level of 1 MPa is provided by a turbomolecular pump 01AB-1500-004 with a nitrogen productivity of 720 liters/sec. Pressure control of the residual atmosphere is accomplished by a vacuum gauge VIT-3 with an ionization pump PMI-2. Creation and support of the working pressure of argon is accomplished by a piezostrictive flow regulator SNA-2. The argon working pressure within the limits of 0.1–1.0 Pa was controlled by a thermostatically controlled barometric converter MKS Baratron 627. Within the scope of this work, multilayer coatings were deposited on a substrate of single-crystal silicon (for studying composition and structure), and on a substrate of fuzed quartz, sapphire, microstructured (m/s) titanium Grade 4, and also nanostructured (n/s) titanium with an average grain size of less than 200 nm (for studying mechanical and tribological properties). The latter were prepared by intense plastic deformation, i.e., equal-channel angular rolling (ECAR) in the Ufa State Aviation Technical University [41]. Multilayer coatings prepared in this work consisted of a different number (from 8 to 280) alternating layers, and the layer thickness for different specimens was 3.8–125 nm. Study of the composition and structure of multilayer coatings. In order to obtain concentration profiles for element distribution over the depth of layers secondary ion mass spectrometric (SIMS) and optical emission spectroscopic glow discharge (OESGD) were used. Analysis of the structure by the SIMS method was performed in a PHI-6600 instrument (Physical Electronics, USA) with a voltage of 7 kV and a current strength of 150 nA. OESGD was carried out in a Profiler 2 spectrometer (Hiriba Jobin Yvon, France). The depth of the craters obtained was determined by means of an optical profilometer WYKO-NT1100 (Veeco, USA). Analysis of transverse coating fractures in on silica substrates was carried out by scanning electron microscopy in JSM-6700F instrument (JEOL, Japan) with a accelerating voltage of 15 kV. An elemental profile of a multilayer Ti/Al coating is shown in Fig. 2a in the first week after deposition, obtained by means of SIMS. It may be seen that the layer thickness is 10 nm, and the spacing is 20 nm. Repeated studies by the SIMS method were carried out after holding a specimen in air for six months. The profile for element distribution is shown in Fig. 2b. In the aluminum profile there is a drop in intensity, connected with presence of a layered coating structure. At the 627
Fig. 4. Structure of a Ti/Al Coating transverse fracture with layer thickness 25/25 nm and total thickness 2.250 μm.
Fig. 5. Structure of a Ti/Al coating transverse fracture with layer thickness 50/50 nm and total thickness 2.110 μm.
same time, the intensity for titanium in the profile does not depend on deposition time, i.e., titanium is distributed uniformly throughout the whole coating thickness. The most probable explanation of this difference is the possible occurrence of a reaction between titanium and aluminum at the interface of layers during holding with formation of Ti3Al intermetallic. Here all the titanium is consumed in the reaction, and excess aluminum retains a layered structure, close to the original. Elemental profiles are shown in Fig. 3 obtained by the OESGD method for a coating with a layer thickness of 25/25 and 50/50 nm, respectively (the results are presented in relative units for clarity). The concentration was also determined for the main elements and impurities in each of the layers. It may be seen from Fig. 3a that the overall coating thickness was 2 μm. In the initial stage of etching, the layer is well developed, then there is lowering of profiles, connected with the effect of the signal from sloped walls of a crater with considerable etching depth. This effect appears particularly strongly in multilayer coatings with a small layer thickness. With an increase in elemental profile, it will be seen that the spacing for these coatings is about 50 nm, and the thickness of layers is close to the calculated value of 25 nm. For a coating with layers 50/50 nm thick (see Fig. 3b), there is also good conformity of the data obtained from OESGD calculated thickness. In addition, for this coating the distribution of impurities was analyzed. It may be seen from Fig. 3b that impurities (nitrogen and carbon atoms) are predominantly in the titanium layers, and the oxygen impurity is distributed uniformly in titanium and aluminum layers. Most probably oxygen and carbon impurities fall into the coating composition from the precursor, i.e., the titanium target. At the same time, a specific amount of oxygen is connected with the effect of residual gases in the 628
Fig. 6. Experimental curves for the dependence of the depth of hardness indenter immersion for Ti/Al multilayer coatings on fuzed quartz substrates with layer thickness: 1) 3.8 nm; 2) 7.5 nm; 3) 15 nm; 4) 35 nm; 5) 125 nm.
vacuum chamber. Quantitative evaluation of OESGD data showed that the concentration of impurities is, at.%: oxygen less than 0.3; carbon less than 1; nitrogen less than 0.2. Transverse fractures of a Ti/Al coating with a layer thickness of 20/20 and 50/50 nm, respectively, are shown in Figs. 4 and 5. Here layers of titanium and aluminum of the same thickness are clearly seen. Within coatings with thinner layers in a fracture there are columnar elements, passing through the whole thickness of a layered coating. Formation of a columnar structure is typical for single- and two-component coatings, deposited by means of magnetron deposition and other methods of physical deposition from a vapor. It should be noted that the number of layers observed in microphotographs does not correspond to the calculated values. This is explained by the fact that in a fracture, located at a small slope, often the silica substrate falls within the field of view and shields the lower part of a coating. The difference in sharpness of an image for the edge of a substrate and a coating itself confirms this explanation. Study of mechanical and tribological properties. In recent years in order to determine the hardness and elasticity modulus of surface layers there is extensive use of the method of continuous indentation measurement (IM) [37, 38, 42–47]. According to ASTM E 2456–07 [45] by indentation measurement we understand a test indentation, with which the force applied to an indenter, and as a result movement of an indenter into the depth of a specimen during loading-unloading, serves for working out the hardness value (according to its indentation) and elasticity modulus (according to its expulsion). With the use of very small loads (several mN), nano-indentation is used as a special case of IM, and this is a process of controlled introduction of a calibrated superhard tip of specific shape (indenter) under the action of an increasing load into the flat surface of an immobile specimen to a depth of several tens of nanometers. With ultra-low loads, immersion of an indenter proceeds to depths of several tens of nanometers. The method is irreplaceable in studying thin nanostructured films and multilayer nanosize structures. Consideration of these measurements of coating hardness is also considered correct (without the effect of a substrate), with which the depth of immersion is not more than 8–12% of its thickness [47]. Experimental curves are presented in Fig. 6 for the dependence of hardness on depth of indenter immersion, obtained with nano-indenters in a Nano-Hardness Tester (CSM Instruments, Switzerland) instrument for multilayer Ti/Al coatings with a different layer thickness, deposited on a fuzed quartz substrate. Here the overall coating thickness varied from 1 to 2 μm. Comparative analysis of nano-indentation data made it possible to establish that for all specimens low loads on the indenter give relatively low values of hardness (30
>30
Coating delamination (adhesive failure)
14.0
>30
>30
>30
ASTM C 1624–05 consists of sliding the indenter over a coating surface. In the course of indenter movement with a prescribed rate and with an increasing load there is a record in a computer of readings from several sensors; loading force, acoustic emission intensity, friction force, friction coefficient, scratch depth. Data are stored on a hard disk of a computer and subsequently from analyzing the shape of the property–load curves and observation of coating breakdown traces in an optical microscope the minimum (critical) load is established with which failure occurs. Testing of specimens of multilayer Ti/Al coatings on substrates of fuzed quartz, sapphire, m/s titanium Grade 4 and n/s titanium were carried out with the following conditions: load increased from 0.9 to 30 N at a rate of about 5 N/min, scratch length was 5 mm. A Rockwell C type diamond indenter with a rounding radius of 200 μm was used to apply three scratches and the average values of critical load were determined. Generation of acoustic emission (AE) on titanium substrates (Fig. 8, 3, 4) is at the level of the background. With scratching of a coating on a sapphire substrate (2), the AE burst is marked with a load of ≈22 N, and with scratching a coating on a fuzed quartz substrate (1) the AE burst is with a smaller load (about 4.5 N). Microscope observation showed that an AE burst is connected with formation of transverse cracks in a coating on scratching, which points to a cohesive mechanism for coating failure on oxide (sapphire and fuzed quartz) substrates with the loads used. Adhesive failure of a coating on a substrate of fuzed quartz sets in with a load of ~14 N (Fig. 9a). Adhesive failure of multilayer Ti/Al coatings on other substrates does not occur in this load range (1–30 N). From the results of analyzing the intensity of acoustic emission in a measurement scratch of test coatings and microscope observation of the scratch formed during a test, critical loads were determined that cause cohesive and adhesive failure of a test coating, deposited on a substrate of fuzed quartz, sapphire, m/s titanium Grade 4 and n/s titanium (see Table 1). 631
Fig. 10. Experimental dependence of friction coefficient on amount of travel for Ti/Al multilayer coatings about 1.8 μm thick on various substrates: a) fuzed quartz (1) and sapphire (2); b) m/s titanium Grade 4 (3) and n/s titanium (4). Counterbody material WC–Co.
Fig. 11. Relative wear of a multilayer Ti/Al coating about 1.8 μm thick on various substrates: 1) n/s titanium; 2) m/s titanium Grade 4; 3) fuzed quartz; 4) sapphire.
Tribological tests of functional surfaces by a rod–disk scheme were performed in an automated TRIBOMETER (CSM Instruments, Switzerland) friction machine [37, 38, 46–48] in air. These tests corresponded to the international standard (ASTM G99-959 and DIN 50324) and may be used for evaluating the wear resistance of a specimen and counterbody. The friction coefficient of a sliding friction pair is determined directly in a test: a coating and a counterbody in the form of a sphere of certified material. In a test a sphere is fixed in a holder made of stainless steel, that transfers a prescribed load to it, and is connected with a friction force sensor. Important information about the failure mechanism of a coating is given by analysis of wear products, and the structure of wear groove. The structure of the wear groove (in disks) and the diameter of wear spot (for spheres) is observed in an optical microscope. A profilometer is used to measure the area of the vertical cross section of a wear groove and its average cross sectional area and depth are determined. Test results are provided in Figs. 10 and 11 for tribological properties (friction coefficient and relative wear) of multilayer nanostructured Ti/Al coatings with a thickness of about 1.8 μm, deposited on substrates of fuzed quartz, sapphire, m/s titanium Grade 4, and n/s titanium. 632
For relatively hard oxide substrates there is total coating wear after about 200 revolutions (see Fig. 10a). The intensity of these processes is indicated by the increased amplitude of friction coefficient at the start of an experiment. A sharp reduction in amplitude points to contact of the counterbody with the solid polished oxide substrate. The amplitude of the friction coefficient for a coating on metal substrates is about the same during a whole test (see Fig. 10b). This indicates that a coating is retained up to the end of testing. According to experimental data (see Fig. 11), the greatest relative wear is typical for coatings on a sapphire substrate, and the least on titanium substrates, which is due to the greater adhesion of a coating to a metal (titanium) substrate (see Table 1). Conclusion. Different methods have been considered for preparing multilayer nanostructured heat generating coatings. For practical application, a method of magnetron deposition is proposed for a multilayer nanostructured binary Ti/Al coating that has production reproducibility. Compositions and coating structures have been studied, precise measurements have been made for mechanical, adhesion and tribological properties of binary coatings on substrates of fuzed quartz, sapphire and titanium Grade 4. The hardness of a Ti/Al coating 3 μm thick increases with an increase in layer thickness. It has been shown that contemporary methods for measuring mechanical and tribological properties of functional surfaces under mechanical contact conditions with indentation, scratching and sliding of a counterbody make it possible to obtain information about the structure-sensitive properties using extremely small (nanosize) volumes of materials for study. Determination of these properties plays a primary role in the construction of new coatings, making it possible to predict possible failure mechanisms, controlled by the structural state of a surface. Further progress in the field of creating MNHC is connected both with assimilation of industrial technology for their preparation, and with certification of procedures for measuring the properties of nanomaterials, and development of state standard specimens. The work was carried out within the scope of the Federal Targeted Program on Development of the Infrastructure of Nano-Industry in the Russian Federation for 2008–2010 (State Contract No. 154-6/334 of 10.24.2008) and also the Federal Targeted Program on Scientific and Teaching Staff for an Innovative Russia for 2009–2013 (State Contract No. 02.740.11.0859).
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