Vol. 24 No. 1 2022 3 EDITORIAL COUNCIL EDITORIAL BOARD EDITOR-IN-CHIEF: Anatoliy A. Bataev, D.Sc. (Engineering), Professor, Rector, Novosibirsk State Technical University, Novosibirsk, Russian Federation DEPUTIES EDITOR-IN-CHIEF: Vladimir V. Ivancivsky, D.Sc. (Engineering), Associate Professor, Department of Industrial Machinery Design, Novosibirsk State Technical University, Novosibirsk, Russian Federation Vadim Y. Skeeba, Ph.D. (Engineering), Associate Professor, Department of Industrial Machinery Design, Novosibirsk State Technical University, Novosibirsk, Russian Federation Editor of the English translation: Elena A. Lozhkina, Ph.D. (Engineering), Department of Material Science in Mechanical Engineering, Novosibirsk State Technical University, Novosibirsk, Russian Federation The journal is issued since 1999 Publication frequency – 4 numbers a year Data on the journal are published in «Ulrich's Periodical Directory» Journal “Obrabotka Metallov” (“Metal Working and Material Science”) has been Indexed in Clarivate Analytics Services. We sincerely happy to announce that Journal “Obrabotka Metallov” (“Metal Working and Material Science”), ISSN 1994-6309 / E-ISSN 2541-819X is selected for coverage in Clarivate Analytics (formerly Thomson Reuters) products and services started from July 10, 2017. Beginning with No. 1 (74) 2017, this publication will be indexed and abstracted in: Emerging Sources Citation Index. Journal “Obrabotka Metallov” (“Metal Working & Material Science”) has entered into an electronic licensing relationship with EBSCO Publishing, the world's leading aggregator of full text journals, magazines and eBooks. The full text of JOURNAL can be found in the EBSCOhost™ databases. Novosibirsk State Technical University, Prospekt K. Marksa, 20, Novosibirsk, 630073, Russia Tel.: +7 (383) 346-17-75 http://journals.nstu.ru/obrabotka_metallov E-mail: metal_working@mail.ru; metal_working@corp.nstu.ru
OBRABOTKAMETALLOV Vol. 24 No. 1 2022 4 EDITORIAL COUNCIL EDITORIAL COUNCIL CHAIRMAN: Nikolai V. Pustovoy, D.Sc. (Engineering), Professor, President, Novosibirsk State Technical University, Novosibirsk, Russian Federation MEMBERS: The Federative Republic of Brazil: Alberto Moreira Jorge Junior, Dr.-Ing., Full Professor; Federal University of São Carlos, São Carlos The Federal Republic of Germany: Moniko Greif, Dr.-Ing., Professor, Hochschule RheinMain University of Applied Sciences, Russelsheim Florian Nürnberger, Dr.-Ing., Chief Engineer and Head of the Department “Technology of Materials”, Leibniz Universität Hannover, Garbsen; Thomas Hassel, Dr.-Ing., Head of Underwater Technology Center Hanover, Leibniz Universität Hannover, Garbsen The Spain: Andrey L. Chuvilin, Ph.D. (Physics and Mathematics), Ikerbasque Research Professor, Head of Electron Microscopy Laboratory “CIC nanoGUNE”, San Sebastian The Republic of Belarus: Fyodor I. Panteleenko, D.Sc. (Engineering), Professor, First Vice-Rector, Corresponding Member of National Academy of Sciences of Belarus, Belarusian National Technical University, Minsk The Ukraine: Sergiy V. Kovalevskyy, D.Sc. (Engineering), Professor, Vice Rector for Research and Academic Affairs, Donbass State Engineering Academy, Kramatorsk The Russian Federation: Vladimir G. Atapin, D.Sc. (Engineering), Professor, Novosibirsk State Technical University, Novosibirsk; Victor P. Balkov, Deputy general director, Research and Development Tooling Institute “VNIIINSTRUMENT”, Moscow; Vladimir A. Bataev, D.Sc. (Engineering), Professor, Novosibirsk State Technical University, Novosibirsk; Vladimir G. Burov, D.Sc. (Engineering), Professor, Novosibirsk State Technical University, Novosibirsk; Aleksandr N. Gerasenko, Director, Scientifi c and Production company “Mashservispribor”, Novosibirsk; Sergey V. Kirsanov, D.Sc. (Engineering), Professor, National Research Tomsk Polytechnic University, Tomsk; Aleksandr N. Korotkov, D.Sc. (Engineering), Professor, Kuzbass State Technical University, Kemerovo; Evgeniy A. Kudryashov, D.Sc. (Engineering), Professor, Southwest State University, Kursk; Dmitry V. Lobanov, D.Sc. (Engineering), Associate Professor, I.N. Ulianov Chuvash State University, Cheboksary; Aleksey V. Makarov, D.Sc. (Engineering), Corresponding Member of RAS, Head of division, Head of laboratory (Laboratory of Mechanical Properties) M.N. Miheev Institute of Metal Physics, Russian Academy of Sciences (Ural Branch), Yekaterinburg; Aleksandr G. Ovcharenko, D.Sc. (Engineering), Professor, Biysk Technological Institute, Biysk; Yuriy N. Saraev, D.Sc. (Engineering), Professor, Institute of Strength Physics and Materials Science, Russian Academy of Sciences (Siberian Branch), Tomsk; Alexander S. Yanyushkin, D.Sc. (Engineering), Professor, I.N. Ulianov Chuvash State University, Cheboksary
Vol. 23 No. 2 2021 5 CONTENTS OBRABOTKAMETALLOV TECHNOLOGY Kuznetsov V.P., Makarov A.V., Skorobogatov A.S., Skorynina P.A., Luchko S.N., Sirosh V.A., Chekan N.M. Normal force infl uence on smoothing and hardening of steel 03Cr16Ni15Mo3Ti1 surface layer during dry diamond burnishing with spherical indenter............................................................................ 6 Gubin D.S., Kisel’A.G. Calculation of temperatures during fi nishing milling of a nickel based alloys.......... 23 EQUIPMENT. INSTRUMENTS Bratan S.M., Roshchupkin S.I., Chasovitina A.S., Gupta K. The effect of the relative vibrations of the abrasive tool and the workpiece on the probability of material removing during fi nishing grinding................. 33 MATERIAL SCIENCE OzolinA.V., Sokolov E.G. Effect of mechanical activation of tungsten powder on the structure and properties of the sintered Sn-Cu-Co-W material................................................................................................................. 48 Korobov Yu.S., Alwan H.L., Makarov A.V., Kukareko V.A., Sirosh V.A., Filippov M.A., Estemirova S. Kh. Comparative study of cavitation erosion resistance of austenitic steels with different levels of metastability................................................................................................................................................... 61 Vologzanina S.A., IgolkinA.F., PeregudovA.A., Baranov I.V., Martyushev N.V. Effect of the deformation degree at low temperatures on the phase transformations and properties of metastable austenitic steels.......... 73 Filippov A.V., Shamarin N.N., Moskvichev E.N., Novitskaya O.S., Knyazhev E.O., Denisova Yu.A., Leonov A.A., Denisov V.V. Investigation of the structural-phase state and mechanical properties of ZrCrN coatings obtained by plasma-assisted vacuum arc evaporation..................................................................... 87 EDITORIALMATERIALS Guidelines for Writing a Scientifi c Paper ............................................................................................................ 103 Abstract requirements ......................................................................................................................................... 107 Rules for authors ................................................................................................................................................. 111 FOUNDERS MATERIALS 119 CONTENTS
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 Investigation of the structural-phase state and mechanical properties of ZrCrN coatings obtained by plasma-assisted vacuum arc evaporation Andrey Filippov 1, а,*, Nikolay Shamarin 1, b, Evgenij Moskvichev1, с, Ol’ga Novitskaya1, d, Evgenii Knyazhev1, e, Yuliya Denisova2, f, Andrei Leonov2, g, Vladimir Denisov2, h 1 Institute of Strenght Physics and Materials Sciences SB RAS, 2/4, pr. Akademicheskii, Tomsk, 634055, Russian Federation 2 Institute of High Current Electronics SB RAS, 2/3 Akademichesky Avenue, Tomsk, 634055, Russian Federation a https://orcid.org/0000-0003-0487-8382, andrey.v.fi lippov@yandex.ru, b https://orcid.org/0000-0002-4649-6465, shnn@ispms.ru, c https://orcid.org/0000-0002-9139-0846, em_tsu@mail.ru, d https://orcid.org/0000-0003-1043-4489, nos@ispms.tsc.ru, e https://orcid.org/0000-0002-1984-9720, zhenya4825@gmail.com, f https://orcid.org/0000-0002-3069-1434, yukolubaeva@mail.ru, g https://orcid.org/0000-0001-6645-3879, laa-91@yandex.ru, h https://orcid.org/0000-0002-5446-2337, volodyadenisov@yandex.ru Obrabotka metallov (tekhnologiya, oborudovanie, instrumenty) = Metal Working and Material Science. 2022 vol. 24 no. 1 pp. 87–102 ISSN: 1994-6309 (print) / 2541-819X (online) DOI: 10.17212/1994-6309-2022-24.1-87-102 Obrabotka metallov - Metal Working and Material Science Journal homepage: http://journals.nstu.ru/obrabotka_metallov ART I CLE I NFO Article history: Received: 10 December 2021 Revised: 28 December 2021 Accepted: 28 January 2022 Available online: 15 March 2022 Keywords: Coating Morphology Nitrides Structure Phase composition Funding The work was carried out with fi nancial support from the Russian Federation represented by Ministry of Science and Higher Education (Project No. 075-152021-1348) within the framework of event No. 1.1.16. Acknowledgements Research were partially conducted at core facility “Structure, mechanical and physical properties of materials” ABSTRACT Introduction. Modern technologies allow the synthesis of nanostructured coatings from multiple chemical elements to combine different physical, mechanical, and chemical properties in one coating. Promising in this respect are coatings formed via layer-by-layer deposition of zirconium and chromium nitrides. The deposition of various chemical elements on various substrates requires separate studies in order to produce high-strength and wear-resistant coatings. The purpose of this work is to study the structuralphase state and mechanical properties of ZrCrN coatings formed by plasma-assisted vacuum arc evaporation. Materials and methods. The investigation is performed on specimens comprising VK8 hard alloy substrates with zirconium and chromium nitride coatings as well as with multilayer ZrCrN coatings. The methods used are confocal laser scanning microscopy, X-ray diffraction analysis, high-resolution scanning electron microscopy, nanoindentation, and scratching. Results and discussion. The experimental results obtained showed that the mode of multilayer ZrCrN coating evaporation greatly affects the structure, morphology, surface roughness, and mechanical properties of the coatings. In particular, by varying the substrate rotation speed during coating deposition it is possible to control the deposition time of each coating layer and thereby modify the layer properties. Conclusions. The investigation results showed that variation of the evaporation conditions allows one to obtain a ZrCrN coating with a high nanohardness of 45 GPa on a VK8 alloy substrate. Analysis of mechanical test results indicate good adhesion between the studied coatings and the substrate. Scratch tests revealed that fracture of CrN and ZrN coatings occurs by the cohesive mechanism, and the surface of ZrCrN coatings exhibits uniform scratches without any signs of fracture. Based on the results obtained, ZrCrN-2…ZrCrN-4 coatings can be recommended for use as hard and wear-resistant coatings. For citation: Filippov A.V., Shamarin N.N., Moskvichev E.N., Novitskaya O.S., Knyazhev E.O., Denisova Yu.A., Leonov A.A., Denisov V.V. Investigation of the structural-phase state and mechanical properties of ZrCrN coatings obtained by plasma-assisted vacuum arc evaporation. Obrabotka metallov (tekhnologiya, oborudovanie, instrumenty) = Metal Working and Material Science, 2022, vol. 24, no. 1, pp. 87–102. DOI: 10.17212/1994-6309-2022-24.1-87-102. (In Russian). ______ * Corresponding author Filippov Andrey V., Ph.D. (Engineering), Senior Researcher Institute of Strenght Physics and Materials Sciences SB RAS 2/4, pr. Akademicheskii, 634055, Tomsk, Russian Federation Tel.: 8 (999) 178-13-40, e-mail: andrey.v.fi lippov@yandex.ru
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 Introduction One of the methods for improving the performance of parts and components is to cover its elements with coatings that have higher physical, mechanical, and chemical properties than the base metal. A rational choice of the coating composition, deposition technique and conditions will determine the properties of the coatings and characteristics of the improved products. Modern technologies allow synthesizing coatings from multiple chemical elements in order to combine its different physical, mechanical and chemical properties in one coating. This is most often done through the formation of multilayer coatings with thin nanostructured layers [1]. The alternating layers provide an effective combination of various functional properties such as wear resistance, corrosion resistance, high hardness, etc. in one coating. Therefore, the choice of the composition of each layer will determine the resulting performance characteristics of the product. The most effective approach to the formation of multilayer coatings implies the deposition of one layer with high hardness and the other with the ability to absorb strain energy. This combination gives a coating with high hardness but not prone to brittle fracture at large strains, which is a desired goal of modern technology [2]. An important aspect is that modern types of equipment operate in high-power modes with high operating temperatures at which coatings must retain its properties. Thus, the high temperature resistance is also a necessary coating property in addition to the already mentioned ones. Chromium and zirconium nitride coatings correspond in some respects to the above requirements. It is known that ZrN coatings have high wear resistance and can effectively absorb mechanical strain energy during friction [3–8]. A single-layer CrN coating has low wear resistance due to columnar structure [9–12], while a multilayer coating of the same material has a much higher wear resistance [13–17], indicating a high structural sensitivity of the given material. Both of these types of coatings have high thermal stability and chemical resistance [14, 18]. Therefore, by alternating ZrN and CrN layers it is possible to obtain ZrCrN coatings with high physical and mechanical properties. Multilayer ZrCrN coatings can be applied by various methods [19]. The most widely known PVD techniques aremagnetron sputtering [20–25] andvacuumarc evaporation [26–30].The lattermethodprovides high adhesion between the coating and the substrate, and allows fl exible control over the composition and thickness of the deposited layer due to a wide-range variation of the energy of condensed ions. The literature reviews in [29, 30] indicate that the hardness of multilayer ZrCrN coatings deposited on TiC substrates strongly depends on its deposition conditions and, as a rule, does not exceed 30 GPa. A higher hardness (up to 42 GPa) was achieved in nanostructured multilayer ZrCrN coatings deposited on corrosion-resistant steel 12Cr18Ni10Ti [27]. Consequently, the substrate strongly affects the fi nal application properties of the coating. As far as we know there are no reports on multilayer ZrCrN coatings deposited on VK8 alloy, which is widely used for industrial metal forming and cutting tools. The purpose of this work is to study the structural-phase state and mechanical properties of ZrCrN coatings deposited by plasma-assisted vacuum arc evaporation on VK8 alloy substrates. Research methods Coatings were deposited by vacuum arc plasma evaporation. In the experiment, metal plasma was generated using two electric arc evaporators with 80-mm-diameter cylindrical cathodes made of E110 Zr alloy and 99.9% purity Cr. Gas plasma was generated by a plasma source with a thermionic and hollow cathode. The gas plasma source was used for cleaning, heating and chemical activation of the sample surfaces by gas ion bombardment, as well as for additional gas ionization and plasma-assisted coating deposition. VK8 hard alloy samples with a diameter of 10 mm and a thickness of 7 mm were mounted on a rotating planetary substrate holder at a distance of about 20 cm from the chamber axis at the exits of the plasma sources. Before the start of the experiment, the vacuum chamber with dimensions of about 650x650x650 mm3 was evacuated to a limiting pressure of 10-2 Pa using a TMP1000 turbomolecular pump. Argon plasma gas
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 was introduced through the plasma source to a working pressure of 0.3 Pa. By triggering a gas discharge with a current of about 40 A and applying a bias voltage of 700 V to the substrate holder with the hard alloy samples, the substrates were heated to a temperature of 400 ºC. After ion bombardment cleaning of the sample surfaces and its chemical activation, a nitrogen-argon mixture in a percentage ratio of 90/10 (N2:Ar) was injected to a pressure of 0.5 Pa and arc discharges with currents of 80 A were triggered in the evaporators. Along with multilayer ZrCrN coatings, ZrN and CrN coatings deposited under similar conditions, but using only one of the cathodes, were examined for a comparative analysis of the coating properties. The phase composition and properties of multilayer coatings were changed by varying the rotation speed of the sample holder. Four holder rotation speeds were used: 0.5 rpm (designation for ZrCrN-1 sample), 3.5 rpm (ZrCrN-2), 5 rpm (ZrCrN-3), and 8 rpm (ZrCrN-4). The holder rotation speed during the deposition of ZrN and CrN coatings was 0.5 rpm. Nanoindentation was performed on a NHT-TTX S nanoindentation tester (CSEM, Switzerland) with a linearly increasing load from 0 to 25 mN and a loading rate of 1.5 μm/min. The nanoindentation data were analyzed by the Oliver–Pharr method. Scratch indentation was performed on a Revetest RST macro scratch tester (CSM Instruments, USA) with a Rockwell diamond indenter, a scratching speed of 3 mm/min, a scratch length of 3 mm, and a linearly increasing load from 0 to 50 N. X-ray diffraction analysis was performed using a DRON-7 X-ray diffractometer (Burevestnik, Russia) in the angle range 2Θ = (20–90)° and with the X-ray wavelength λ = 1.54 A. The surface morphology of the samples was examined using an Apreo 2 S high-resolution scanning electron microscope (FEG SEM) (Thermo Fisher Scientifi c, USA). The cross section of the coatings was examined on fracture surfaces. The surface roughness was examined using an Olympus OLS LEXT 4100 confocal laser scanning microscope (Olympus, Japan). Results and discussion The surface images of the studied coatings are presented in Figure 1. One can see small black dots on the surface of all samples. Surface examination by confocal laser scanning microscopy revealed that these points are both droplet inclusions on the surface and pores. It appears visually similar and has comparable diameters of the order of 0.5–5 μm. The number and size of these dots are larger on the surface of multilayer ZrCrN coatings (Figs. 1c–1f) compared with ZrN (Fig. 1a) and CrN (Fig. 1b) coatings. Surface roughness analysis was performed with the Olympus LEXT software to quantify differences in the surface morphology of the coatings. The evaluation was carried out using two parameters Sa and Sz, which are the arithmetic mean and the maximum height of surface microroughness, respectively. The analysis data (Fig. 2) indicate that the roughness of multilayer ZrCrN coatings in terms of the Sa parameter is by a factor of 1.8–2.9 higher compared to CrN coating, and a factor of 1.1–1.8 than for ZrN coating. Amuch less increase in the roughness of multilayer ZrCrN coatings is observed in terms of the Sz parameter, which is by a factor of 1.5–1.8 higher compared to CrN and only 3–15 % higher compared to ZrN. It follows from the data obtained that surface roughness in terms of the Sa parameter increases monotonically from the sample with CrN coating to the sample with multilayer ZrCrN-4 coating. Increasing the substrate holder rotation speed from 0.5 to 8 rpm leads to an ~38% increase in surface roughness in terms of the Sa parameter. The surface roughness change due to variation in the deposition conditions for samples with multilayer ZrCrN-1…ZrCrN-4 coatings in terms of the Sz parameter is less signifi cant and does not exceed 12 %. Surface roughness measurements of the coatings by confocal laser scanning microscopy allow evaluating such parameters as the roughness amplitude and the number of roughness elements per unit area. This is done according to GOST R ISO 25178-2-2014 that involves the determination of the void volume, peak volume, and core material volume.
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 a b c d e f Fig. 1. Surface images of samples coated with: CrN (a), ZrN (b), ZrCrN-1 (c), ZrCrN-2 (d), ZrCrN-3 (e), ZrCrN-4 (f) ZrCrN coatings demonstrate a signifi cant increase in the dale void volume (Vvv increases by a factor of 2.25–3.75 compared with CrN coating and 1.13–1.88 compared with ZrN) and the core void volume (Vvc increases by a factor of 1.34–1.49 compared with CrN coating and 1.12–1.24 compared with ZrN). The peak and core material volumes also increase greatly for ZrCrN coatings (Vmp increases by a factor of 2.88–5.25 compared with CrN coating and 1.77–3.23 compared with ZrN; Vmc increases by a factor of 1.31–1.38 compared with CrN coating and 1.21– 1.29 compared with ZrN). The increase in the dale void volume (Vvv) and peak material volume (Vmp) indicates that ZrCrN coatings contain a larger number of peaks and valleys per unit area compared with CrN and ZrN coatings. This quantitatively agrees with the roughness measurement results. However, the obtained estimates show that the peak material volumes exceed the dale void volumes. As for the core, it is obvious that the core void volume (Vvc) exceeds the core material volume (Vmc). The coating surfaces were also examined by high-resolution scanning electron microscopy. It can be seen that the morphology of CrN (Fig. 4a) and ZrN (Fig. 4b) coatings differs signifi cantly. CrN coating has a nanocrystalline structure. ZrN Fig. 2. Surface roughness of coatings
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 a b Fig. 3. Void volume (a) and material volume (b) per unit area of coatings: CrN (1), ZrN (2), ZrCrN-1 (3), ZrCrN-2 (4), ZrCrN-3 (5), ZrCrN-4 (6) a b c d e f Fig. 4. SEM images of the coating surface: CrN (a), ZrN (b), ZrCrN-1 (c), ZrCrN-2 (d), ZrCrN-3 (e), ZrCrN-4 (f) coating exhibits no grains and has an inhomogeneous surface relief, which is consistent with the roughness studies. Multilayer ZrCrN-1 coating (Fig. 4c) is similar in surface morphology to ZrN, as its upper layer is of zirconium nitride. The surface morphology of ZrCrN-2…ZrCrN-4 coatings is represented by smaller elements, but it is diffi cult to classify it into independent elements due to its nanoscale size.
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 The cross-sectional image of the fracture surface of ZrCrN-1 coating (Fig. 5a) shows its multilayer structure with an average layer thickness of ~100 nm. The planarity of the layers is slightly distorted; no defects such as pores or delaminations are observed; the interface with the substrate is also free of defects. The total number of layers in the coating is 72. Fig. 5. Cross-sectional SEM images of the fracture surface of multilayer coatings: ZrCrN-1 (a), ZrCrN-2 (b), ZrCrN-3 (c), ZrCrN-4 (d) a b c d The SEM micrograph of the fracture surface of ZrCrN-2…ZrCrN-4 coatings (Figs. 5b–5d) also exhibits a nanosized structure, but without well-defi ned layers. The thickness of ZrCrN coatings is about 4.5±0.5 μm. The absence of signifi cant defects at the substrate–coating interface indicates a strong bond and good adhesion between the coating and the substrate. Otherwise, the coating would locally peel off as a result of cleavage. Analysis of X-ray diffraction profi les (Fig. 6) showed that the X-ray intensity is rather high and radiation reaches not only the coating but also the substrate, as confi rmed by the presence of refl ections belonging
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 Fig. 6. X-ray diffraction profi les of coatings: CrN (1), ZrN (2), ZrCrN-1 (3), ZrCrN-2 (4), ZrCrN-3 (5), ZrCrN-4 (6) to the WC phase. CrN and ZrN coatings have a pronounced (111) texture, which follows from the magnitude of the refl ections in the diffraction profi les and the almost complete absence of other phase refl ections for these coatings. Multilayer ZrCrN coatings have refl ections of both zirconium nitride and chromium nitride, but ZrN are more intense. The ZrN(220) refl ection is quite broad for ZrCrN-2…ZrCrN-4 samples. The ZrN(111) refl ection is shifted and its intensity is lower. These changes in the diffraction profi les may indicate the nanostructured state of the coating in these samples. The phase composition of ZrCrN-4 coating cannot be effectively assessed as, in addition to the above, there is a signifi cant shift and superposition of many refl ections. The mechanical properties of the coatings were studied by nanoindentation and scratching. Typical loading curves during nanoindentation are shown in Figure 7. The load was selected in such a way that the indentation depth was less than the coating thickness. At the fi rst glance, the plotted curves clearly demonstrate that the mechanical properties of the studied coatings are different. The values of nanohardness and reduced elastic modulus were obtained after data processing by the Oliver–Farr method using specialized software (Table 1). The H/E ratio is often used as a measure of the coating resistance to elastic deformation, with an H/E greater than or equal to 0.1 being considered to indicate high quality of the coating [31]. It follows from the data that only three multilayer coatings meet this characteristic; the chromium nitride coating has the worst properties. The quality of the zirconium nitride coating can also be considered insuffi cient in terms of H/E. It was shown in [26] that a decrease in the thickness of individual layers of multilayer ZrN/CrN coating from 300 to 20 nm allows increasing the hardness of the coating deposited on a 12Cr18Ni10Ti steel substrate from 33 to 42 GPa. The decrease in hardness is also attributed in [26] to the formation of solid solutions of (Zr,Cr)N and (Cr,Zr)N near the (200) refl ection. Such changes in the phase composition were not observed here, but, as in [26], the peaks of the ZrN and CrN refl ections were shifted. This indicates a microdistortion of the crystal lattice, which may be the cause of changes in the mechanical properties of the material. For the case considered in this work, refl ections in XRD profi les taken from ZrCrN coatings are also shifted (Fig. 6). It may also indicate lattice distortion that contributes to hardness enhancement. Similar results of the infl uence of lattice microdistortions on material hardness were earlier observed for austenitic steel produced by electron beam additive manufacturing [32]. The nanoindentation data are in qualitative agreement with the scratch test results. Figure 8 shows CLSM images of scratches on the surface of coatings. The fi rst thing to note is that CrN (Fig. 8a) and ZrN Fig. 7. Nanoindentation loading curves of coatings
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 Ta b l e 1 Nanoindentation test results Sample Nanohardness (H), GPa Reduced modulus of elasticity (E), GPa H/E CrN 21.6 335 0.06 ZrN 29.8 394 0.08 ZrCrN-1 34 364 0.09 ZrCrN-2 37.5 359 0.1 ZrCrN-3 39.3 382 0.1 ZrCrN-4 45 436 0.1 Fig. 8. Images of scratches on the surface of coatings: CrN (a), ZrN (b), ZrCrN-1 (c), ZrCrN-2 (d), ZrCrN-3 (e), ZrCrN-4 (f) a b c d e f coatings (Fig. 8a) were scratched with a linearly increasing load. Multilayer ZrCrN coatings exhibit rather uniform scratches without cracks and cleavage. For a more detailed analysis of the effect of indentation on the coatings, the scratch profi les in the region of the deepest pit using the microscope software were evaluated (Fig. 9). The depth of scratches near the cleavage (Table 2) shows that the fracture of CrN and ZrN coatings is cohesive, because the depth of pits is smaller than the thickness of these coatings. The CrN coating fracture begins at a normal indentation load of ~12 N and that of ZrN begins at ~45 N. The tangential force was ~0.8 N for CrN coating and ~2.3 N for ZrN. The change in the indentation depth during testing depends both on the coating properties and on the specifi ed load. The load was set to increase linearly. Therefore, in the ideal case, the penetration of the indenter into the coating should occur in the same manner. However, this quantity slightly fl uctuates in Fig. 10 (scratch length interval from 0 to ~2.3 mm), which is probably due to inhomogeneous surface
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 Fig. 9. Cross-sectional profi les of surface scratches on coatings: CrN (1), ZrN (2), ZrCrN-1 (3), ZrCrN-2 (4), ZrCrN-3 (5), ZrCrN-4 (6) Ta b l e 2 Scratch profi le parameters Sample Maximum scratch depth, μm Maximum scratch depth along the cleavage, μm CrN 3.52 4.50 ZrN 2.00 3.30 ZrCrN-1 1.88 – ZrCrN-2 1.42 – ZrCrN-3 1.32 – ZrCrN-4 1.31 – morphology of the coatings. This agrees with the surface roughness measurement results.Amore pronounced surface roughness of ZrCrN coatings (Fig. 2) leads to large indentation depth fl uctuations compared with smoother CrN and ZrN coatings. Ona can also see from Fig. 10 that the indentation depth sharply increases in CrN and ZrN coatings after ~2.3 mm of the scratch length, indicating signifi cant damage to these coatings. The data obtained show that the nanohardness measurement results (Table 1) are consistent with the scratch test results (Table 2). The hardest coatings are less susceptible to scratch damage. Note that none of the presented ZrCrN coatings showed signs of complete detachment, which implies its good adhesion to the substrate material.
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 1 2022 Fig. 10. Indentation depth variation profi les during scratching coatings: CrN (1), ZrN (2), ZrCrN-1 (3), ZrCrN-2 (4), ZrCrN-3 (5), ZrCrN-4 (6). CrN coating, judging from the greatest scratch depth along the cleavage (Table 2), locally detached from the substrate during fracture, which can be explained by its high brittleness against diamond indentation. ZrN coating, judging from the same value (Table 2), was not damaged over the entire thickness, as it has higher mechanical properties compared to CrN. The review of literature in [19] provides similar information on the fracture of ZrN, CrN, and CrN/ZrN coatings, showing that multilayer CrN/ZrN coatings have better properties compared to ZrN and CrN coatings. Conclusions Experimental studies were performed to investigate the structure, phase composition, and mechanical properties of CrN, ZrN, and ZrCrN coatings. It was found that the structure, morphology, surface roughness, and mechanical properties of multilayer ZrCrN coatings are greatly affected by changes in the deposition conditions. X-ray diffraction analysis data indicate the absence of pronounced texture in ZrCrN-2…ZrCrN-4 coatings, and the broadening of the refl ections is testimony to the nanostructured state of the layers. An increase in the rotation speed of the substrate holder relative to the Cr and Zr cathodes leads to a more pronounced surface microroughness. Increasing the holder rotation speed from 0.5 to 8 rpm during coating deposition causes an ~38 % monotonic increase in surface roughness in terms of the Sa parameter. The change in terms of the Sz parameter is less signifi cant and does not exceed 12 %. The investigation results showed that by varying the deposition conditions it is possible to obtain a ZrCrN coating (ZrCrN-4 sample) with a high nanohardness of 45 GPa on VK8 alloy. The nanohardness of multilayer ZrCrN coatings is by a factor of 1.14–2.1 higher than that of CrN and ZrN coatings. The H/E ratio values indicate that ZrCrN-2…ZrCrN-4 coatings are more resistant to mechanical loads. Scratch tests revealed that fracture of CrN and ZrN coatings occurs by the cohesive mechanism. The surface of multilayer ZrCrN coatings exhibits uniform scratches without signs of coating fracture. The results obtained confi rmed good adhesion of all the studied coatings to the substrate. Based on the study results, ZrCrN-2…ZrCrN-4 coatings can be recommended for use as hard and wearresistant coatings. The results obtained will be used for more detailed XRD studies of multilayer coatings using synchrotron radiation from the VEPP-3 storage ring of the Siberian Synchrotron Radiation Center at the Budker Institute of Nuclear Physics SB RAS.
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