Microstructure and residual stresses of ZrN/CrN multilayer coatings formed by the plasma-assisted vacuum-arc method

Vol. 24 No. 3 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. 3 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. 24 No. 3 2022 5 CONTENTS OBRABOTKAMETALLOV TECHNOLOGY Permyakov G.L., Davlyatshin R.P., Belenkiy V.Y., Trushnikov D.N., Varushkin S.V., Pang S. Numerical analysis of the process of electron beam additive deposition with vertical feed of wire material...................... 6 Ilinykh A.S., Banul V.V., Vorontsov D.S. Theoretical analysis of passive rail grinding.................................. 22 Chinchanikar S. Modeling of sliding wear characteristics of Polytetrafl uoroethylene (PTFE) composite reinforced with carbon fi ber against SS304........................................................................................................ 40 EQUIPMENT. INSTRUMENTS Abbasov V.A., Bashirov R.J. Features of ultrasound application in plasma-mechanical processing of parts made of hard-to-process materials...................................................................................................................... 53 MATERIAL SCIENCE Stolyarov V.V., Andreev V.A., Karelin R.D., Ugurchiev U.Kh., Cherkasov V.V., Komarov V.S., Yusupov V.S. Deformability of TiNiHf shape memory alloy under rolling with pulsed current....................... 66 Vorontsov A.V., Filippov A.V., Shamarin N.N., Moskvichev E.N., Novitskaya O.S., Knyazhev E.O., Denisova Yu.A., Leonov A.A., Denisov V.V. Microstructure and residual stresses of ZrN/CrN multilayer coatings formed by the plasma-assisted vacuum-arc method........................................................................... 76 Ivanov I.V., Safarova D.E., Bataeva Z.B., Bataev I.A. Comparison of approaches based on the WilliamsonHall method for analyzing the structure of an Al0.3CoCrFeNi high-entropy alloy after cold deformation....... 90 Kryukov D.B. Structural features and technology of light armor composite materials with mechanism of brittle cracks localization.......................................................................................................................... 103 EDITORIALMATERIALS 112 FOUNDERS MATERIALS 123 CONTENTS

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 Microstructure and residual stresses of ZrN/CrN multilayer coatings formed by the plasma-assisted vacuum-arc method Andrey Vorontsov 1, a, Andrey Filippov 1, b,*, Nikolay Shamarin 1, c, Evgenij Moskvichev1, d, Ol’ga Novitskaya1, e, Evgenii Knyazhev1, f, Yuliya Denisova2, g, Andrei Leonov2, h, Vladimir Denisov2, i 1 Institute of Strenght Physics and Materials Sciences SB RAS, 2/4 per. Academicheskii, Tomsk, 634055, Russian Federation 2 Institute of High Current Electronics SB RAS, 2/3 per. Academicheskii, Tomsk, 634055, Russian Federation a https://orcid.org/0000-0002-4334-7616, vav@ispms.ru, b https://orcid.org/0000-0003-0487-8382, andrey.v.fi lippov@yandex.ru, c https://orcid.org/0000-0002-4649-6465, shnn@ispms.ru, d https://orcid.org/0000-0002-9139-0846, em_tsu@mail.ru, e https://orcid.org/0000-0003-1043-4489, nos@ispms.tsc.ru, f https://orcid.org/0000-0002-1984-9720, zhenya4825@gmail.com, g https://orcid.org/0000-0002-3069-1434, yukolubaeva@mail.ru, h https://orcid.org/0000-0001-6645-3879, laa-91@yandex.ru, i https://orcid.org/0000-0002-5446-2337, volodyadenisov@yandex.ru Obrabotka metallov - Metal Working and Material Science Journal homepage: http://journals.nstu.ru/obrabotka_metallov Obrabotka metallov (tekhnologiya, oborudovanie, instrumenty) = Metal Working and Material Science. 2022 vol. 24 no. 3 pp. 76–89 ISSN: 1994-6309 (print) / 2541-819X (online) DOI: 10.17212/1994-6309-2022-24.3-76-89 ART I CLE I NFO Article history: Received: 16 May 2022 Revised: 31 May 2022 Accepted: 18 June 2022 Available online: 15 September 2022 Keywords: Coating TEM investigation Nitrides X-Ray analysis Phase composition Funding The work was carried out with the fi nancial support of the Russian Federation represented by the Ministry of Science and Higher Education (project No. 075-15-20211348) 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. The current state of the art in the fi eld of hard coatings application requires the formation of nanostructured compositions using different chemical elements. Modern hard coatings are able to combine different properties such as high hardness, wear resistance, corrosion resistance. At present, coatings formed by layer-by-layer deposition of zirconium and chromium nitrides are promising. When depositing combinations of chemical elements on various substrates, studies are required aimed at investigating its microstructure and, mainly, residual stresses formed during the deposition of multilayer coatings. The purpose of this work is to investigate the structural-phase state and residual stresses of ZrN/CrN system coatings formed by plasma-assisted vacuum-arc method from the gas phase. Research methods. Samples with coatings of zirconium and chromium nitrides deposited on substrates of hard alloy VК8 are investigated. Transmission electron microscopy is used to study the microstructural characteristics of multilayered coatings and X-ray diffraction analysis is used to quantify macroscopic stresses. Results and discussion. Based on the experimental results obtained it is found that changing the modes of deposition of multilayer ZrN/CrN coatings with regard to rotation speeds of table and substrate holder leads to variations in microstructure, morphology and internal stresses of surface layers of multilayer coatings. It is shown that by changing conditions for the multilayer coating deposition the possibilities of forming ZrN/CrN coatings on the substrate made of VK8 alloy with nanoscale thickness of coating layers open up. X-ray diffraction analysis indicates mainly insignifi cant stresses, and at high table and substrate rotation speeds – high compressive stresses in the multilayer coating. Transmission electron microscopy revealed that CrN and ZrN coatings have a common multilayer coating growth texture at low rotation speeds, and at high speeds a textural misorientation of the phases of the coating layers is observed. Based on the results obtained it is possible to recommend coatings of ZrN/CrN system as hard coatings. For citation: Vorontsov A.V., Filippov A.V., Shamarin N.N., Moskvichev E.N., Novitskaya O.S., Knyazhev E.O., Denisova Yu.A., Leonov A.A., Denisov V.V. Microstructure and residual stresses of ZrN/CrN multilayer coatings formed by the plasma-assisted vacuumarc method. Obrabotka metallov (tekhnologiya, oborudovanie, instrumenty) = Metal Working and Material Science, 2022, vol. 24, no. 3, pp. 76–89. DOI: 10.17212/1994-6309-2022-24.3-76-89. (In Russian). ______ * Corresponding author Vorontsov Andrey V., Ph.D. (Engineering), Research assistant Institute of Strenght Physics and Materials Sciences SB RAS, 2/4 per. Academicheskii, 634055, Tomsk, Russian Federation Tel.: 8 (983) 239-34-17, e-mail: vav@ispms.ru

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 Introduction Nitride coatings made of either ZrN or CrN possess high mechanical corrosion-resistant and tribological characteristics and therefore are widely used in applications where protection of the base underlying materials against the above mentioned factors is required [1, 2]. In particular, this is especially true for CrN coatings that begin occupying more and more attention of the researchers [3, 4]. Chromium nitride coatings can be obtained using either vapor deposition or arc-ion plating [2]. Zirconium nitride coatings can be used in aero-space applications as thermal or erosion barriers as well as for extending the service life of the metal cutting tools [5]. Cathodic arc ZrN coatings may be used for protection of radioactive waste storage tanks against corrosion [6]. The research literature search shows that there are multilayer coatings containing combinations of alternating metallic, ceramic and amorphous layers. Such an approach allows combining various strength and functional characteristics of the constituent layers for achieving improved synergistic performance of the entire coating. For instance, addition of a CrN layer when preparing the multilayer AlTiN/CrN/ ZrN coatings allowed reducing the residual stresses depending on the CrN layer thickness [7]. Vapor deposition of nanosize thickness CrN/ZrN and CrN/CrAlN layers on stainless steel substrates was carried out to improve the corrosion resistance of the fuel proton exchange membrane cells [8]. It was found that corrosion resistance of CrN/ZrN multilayer coatings proved to be much higher than that of less chemically stable CrN/CrAlN ones. Vacuum-arc deposited ZrN/CrN multilayer coatings with ZrN/CrN bi-layer of different thickness were prepared [9] to show that the thickness reduction allowed increasing the coating hardness while maintaining acceptable the other mechanical characteristics. In addition, the effect of nitrogen atomic concentration on the microhardness and microstructure characteristics of the multilayer coatings was revealed. Summarizing the information reported in the relevant literatures sources it could be stated that the multilayer nitride coatings allow improving mechanical, anti-corrosion and anti-wear characteristics of the substrates [8, 10–15]. Such a conclusion allowed us to suggest that deposition of multilayer ZrN/CrN coatings on the WC-8 wt.%Co cermet has potential for improving the tribological and anti-wear characteristics of the metal processing tools. The objective of this work can be formulated as follows: study texturing and residual macrostresses in the of multilayer plasma-assisted vacuum-arc deposited ZrN/CrN coatings as well as evaluate the applicability of the deposition method inviting both earlier obtained [16] and below disclosed results. Methods and materials A scheme of the plasma-assisted vacuumarc deposition shows the WC-8 wt%Co substrate (Fig. 1, pos. 1) mounted successively on the sample holder (Fig. 1, pos. 2) and table (Fig. 1, pos. 3) inside the vacuum chamber (Fig. 1, pos. 4). Sample holder and table were independently rotated during the deposition as shown by corresponding arrows (Fig. 1, pos. 5) and (Fig. 1, pos. 6), respectively. Such a planetary rotation of the sample was chosen to adapt the deposition of multilayer coatings so that the total sample’s rotation rate was directly proportional to that of the table. The internal vacuum chamber volume was evacuated using a turbomolecular pump (Fig. 1, pos. 7) as shown by the arrow (Fig. 1, pos. 8). An inert gas was then supplied via a plasma torch Fig. 1. Scheme of the plant for a ZrN/CrN multilayer nanostructured coating deposition

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 (Fig. 1, pos. 9) as shown by arrow (Fig. 1, pos. 10) to provide the residual working pressure. On fi lling the chamber, a gas discharge was ignited at 40 A and bias voltage 700 V with simultaneous preheating the sample to 400°C. The sample’s temperature was controlled using a thermocouple (Fig. 1, pos. 11). A thermal shield (Fig. 1, pos. 12) was mounted to avoid the excess heating of the chamber elements. Ion bombardment cleaning and chemical activation of the sample’s surface was carried out and then an argon and nitrogen (90/10) gas mixture was supplied into the chamber up to reaching the working pressure level. Next step was igniting the 80 A arc discharges on both evaporators (Fig. 1, pos. 13). Each of the evaporators contained a single cathode made of the deposited material (Fig. 1, pos. 14 and 15), i.e. either 99.5% purity Zr or 99.9 % purity Cr. A chamber door (Fig. 1, pos. 16) served for extracting the sample holder and samples after fi nishing the deposition. The table rotation rate was varied during the deposition as follows: 0.5 RPM, 3.5 RPM and 8.0 RPM for samples ZrN/CrN-0.5, ZrN/CrN-3.5 and ZrN/CrN-8, respectively. The resulting sample’s holder rotation rates were then as follows: 20; 140; 320 RPM. The deposited layers were characterized using TEM and synchrotron XRD (Synchrotron Source VEPP-3). TEM allowed characterizing phases formed and inter-layer boundary misorientation. The XRD allowed obtaining the residual stress magnitudes and nitride phase contents. The synchrotron radiation with wavelength 1.540598 Å was used for performing quantitative sin2Ψmethod analysis of residual stresses formed in the multilayer coatings during deposition and cooling. The required for the analysis data on elasticity modulus were obtained from nanoindentation experiments on these multilayer ZrN/CrN-0.5, ZrN/CrN-3.5 and ZrN/CrN-8 coatings and were at the level of 364, 359 and 436 GPa, respectively [16]. The Poisson ratio values for ZrN and CrN were assumed as 0.24 and 0.28, respectively [17, 18]. Results and discussion TEM studies allowed revealing both morphological and orientation differences among the multilayer coatings as depended on the sample’s planetary rotation rates. Fig. 2 shows the bright-fi eld TEM images of the ZrN/CrN-0.5, ZrN/CrN-3.5 and ZrN/CrN-8 multilayer coatings obtained at different rotation rates of the holder. All ZrN/CrN coatings are composed of alternating nitride layers but at least two different layer types can be observed in the ZrN/CrN-0.5 coating. The fi rst one shows formation of nanoscale thickness layers the same as those in the ZrN/CrN-3.5 and ZrN/CrN-8 coatings. The nanoscale layer thicknesses are shown in the TEM images as denoted by the “h” letter). Accelerating both table and holder rotation rate resulted in reducing the nitride layer thicknesses (Fig. 2 d) and it could be suggested from the plot that there is a linear dependence between the holder rotation rate and layer thickness. A regression equation was reconstructed to describe such a dependence that allowed observing the layer thickness tended to zero if the rotation rate approached to the ordinate axis at 592±58 RPM where both nitrides would be homogeneously distributed across the coating. In such a situation it would be plausible formation of either mixed ZrCrN nitride or amorphous layer as discussed below. The second type of layers are submicron thickness ones that are formed at low rate rotations of both table and holder (Fig. 2, a). These submicron layers are composed of the alternating nitride nanoscale ones. The EDS element profi les were obtained on the ZrN/CrN-0.5 coating deposited at the holder rotation rates of 20 RPM (Fig. 3, a). Periodic element concentration dependencies along the line in Fig. 3 a allow suggesting that these submicron layers are of 120±8 nm mean thickness. SAED analysis of phases formed in the coatings showed the presence of both nitrides (Fig. 3). However, there are some specifi c features as those identifi ed from the bright fi eld images (see circles in Fig. 2, a–c). First of all, this relates to crystallite orientations in the layers. Samples of ZrN/CrN-0.5 and ZrN/CrN-3.5 were characterized by the presence of an [111] axis zone common for the ZrN and CrN SAED patterns (Fig. 3 a, b). On the contrary, the SAED pattern from ZrN/CrN-8 sample exposes a common ZrN/CrN axis zone [0-11] as well as extra SAED pattern from the ZrN with different axis zone [1–21]. In other words, there is

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 preferential orientation relationship between ZrN and CrN during deposition at low rotation rates while it is violated at higher rotation rates with the common zone axis rotation and partial misorientation of the ZrN. Azimuthal ZrN/CrN layer misorientation is higher in samples ZrN/CrN-0.5 and ZrN/CrN-3.5, deposited at low rotation rates. For comparison, the azimuthal misorientation in these samples was about 18° as compared to 6° in the ZrN/CrN-8 (Fig. 3, b–d). Therefore, sample rotation during deposition has some effect on the coating microstructure, in particular, the orientation relationship between the layers. Such an effect may be the reason behind the residual stresses formed in the coatings during cooling. Residual stress level is one of the most important characteristics that determine mechanical and functional characteristics of the multilayer coatings. Therefore, the research can not be limited only by studying the microstructures only. Residual stress levels were studied using the well-known sin2Ψ-method but with utilizing the synchrotron X-ray radiation. Quantitative stress level can be estimated using expression 1 as follows [19]: 0 2 (2 ) ctg [MPa], 2(1 ) 180 (sin ) x x ÌÏ E             (1) Fig. 2. Bright fi eld image of multilayer coating formed at ZrN/CrN-0.5 (a), ZrN/CrN-3.5 (b), ZrN/ CrN-8 (c) and linear approximation of the table and substrate holder rotation speeds as a function of the thickness of nanometer coating layers (d) a b c d

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 Fig. 3. Chemical element distribution in ZrN/CrN-0.5 multilayer coating (a), micro diffraction patterns of multilayer coatings formed at ZrN/CrN-0.5 (b), ZrN/CrN-3.5 (c) and ZrN/CrN-8 (d) modes a b c d where E is the effective elasticity modulus obtained from nanoindentation; νML is the Poisson ratio, Θ0 is the diffraction angle of incident synchrotron beam on a stress-free coating; ΘΨx is the diffraction angle of incident synchrotron beam on a coating with residual stress for crystalline planes normal to (Ψ) the incident beam axis. The fi rst stage was obtaining primary Bregg-Brentano diffraction patterns and 2Θ0 refl ection positions from the ZrN/CrN multilayer coatings according to symmetrical XRD procedure (Fig. 4). XRD FCC peaks such as (200)CrN and (222)ZrN were chosen for determining the residual stress taking into account the best accuracy reasons. An obstacle was that there were WC peaks shining from underneath substrate in the form of very narrow peaks. The XRD pattern in Fig. 4 allows observing some variation of a textured coating’s component. Thus, almost invisible at 2Θ=56.7° (220)ZrN peak in the ZrN/CrN-0.5 coating became very noticeable in samples ZrN/CrN-3.5 and ZrN/CrN-8, i.e at higher rotation rates. Such a fi nding allows suggesting that the ZrN crystallites have no preferential growth axis during deposition at faster rotation. Asymmetrical XRD were then carried out at Ψ angles 0°, 5°, 10°, 15°, 20°, 25°, 30° and a series of corresponding diffraction patterns in the vicinity of the (222)ZrN peak (red line) are shown in Fig. 5 for sample ZrN/CrN-0.5.

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 Fig. 5. Series of asymmetric synchrotron radiation surveys in the range of 2Θ 65° – 77° for the ZrN phase peak (222) of sample ZrN/CrN-0.5 with a variation of angle Ψ from 0° to 30° with a step of 5°. The angular range of the analyzed peak is highlighted in red Fig. 4. X-ray diagrams of the formed ZrN/CrN multilayer coated samples obtained by symmetrical imaging (Bragg-Brentano focusing) with marking of peaks subjected to further series of asymmetrical imaging to determine stresses by sin2Ψ method When the angle position of the XRD peaks was accurately determined, the data were represented in the 2ΘΨx-sin 2Ψ domain and then linearly approximated (Fig. 6). The residual stress levels σx can be obtained using equation 2: [ ], x MK MPa   (2)

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 Fig. 6. Linear dependence of diffraction maximum position (222) of ZrN phase on sin2Ψ for samples of multilayer coatings deposited at different rotational speeds of table and substrate holder where 0 ctg , MPa/grad, 2(1 ) 180 ÌÏ E M       (3) 2 (2 ) , grad (sin ) x K        (4) Consequently, quantitative determination of the residual stress in the multilayer coatings requires determining angle Θ0 of the stress-free material from the 2ΘΨx – sin 2Ψ plot, where 2Θ 0 is the extrapolation of linear approximation 2ΘΨx – sin 2Ψ [20]. Coeffi cient KΔ is determined from the 2Θ Ψx – sin 2Ψ approximation line slope as shown by equation 4. Stress coeffi cient M was calculated according to equation 3 using the earlier obtained values of νML, E, Θ0. The residual stress magnitudes in the multilayer coatings were obtained using equation 2 (see Table 1). Similar to the previous stages, the residual stress magnitudes were obtained from XRD patterns in the vicinity of (200)CrN angle position at 2Θ = 44° (Fig. 7). Angle positions of the (200)CrN are represented in the 2ΘΨx – sin 2Ψ domain in Fig. 8. Finally, some data as well as residual stress magnitudes were shown in Table 2. Ta b l e 1 Calculated values for determining the residual stresses and the result of calculating the residual stresses in the plane of the surface of the multilayer coating samples for the ZrN phase Coating 2Θ0, ° Coeffi cient M, MPa/grad Coeffi cient K, grad Residual stress, MPa ZrN/CrN-0.5 70.754 ± 0.017 –2.393×103 0.003 ± 0.001 –6.437 ZrN/CrN-3.5 70.808 ± 0.026 –2.235×103 –0.010 ± 0.001 22.000 ZrN/CrN-8 70.851 ± 0.057 –2.599×103 –0.008 ± 0.003 19.65

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 Fig. 7. Series of asymmetric surveys using synchrotron radiation in the range of angle 2Θ 38° – 50° for the peak (200) of the CrN phase with a variation of angle Ψ from 0° to 30° with a step of 5° Fig. 8. Linear dependence of diffraction maximum position (200) of CrN phase on sin2Ψ for multilayer coating samples deposited at different table and substrate rotation speeds The asymmetrical XRD patterns in Fig. 4 and 6 are shown as the examples that allow identifying the fact that residual stresses were rather low for all the coatings obtained using the plasma-assisted vacuumarc method. These stresses are either tensile or compressive as in case of CrN in the ZrN/CrN-8 coating (Table 2).

OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 24 No. 3 2022 Ta b l e 2 Results of quantitative determination of stress values in in the plane of the surface of the multilayer coating samples for the CrN phase during synchrotron studies Coating 2Θ0, ° Coeffi cient M, MPa/grad Coeffi cient, K, grad Residual stress, MPa ZrN/CrN-0.5 44.092 ± 0.084 –4.520×103 –0.019 ± 0.005 839 ZrN/CrN-3.5 44.096 ± 0.053 –4.301×103 –0.016 ± 0.003 674 ZrN/CrN-8 43.976 ± 0.041 9.441×105 –0.009 ± 0.002 –8,251 Taking into account the results of TEM one may conclude that increasing the rotation rates of table and holder is accompanied by misorientation and reorientation of the nitride layers, increasing its hardness and elasticity modulus [16] and transition from tensile to compressive residual stress. Despite microstructural characteristics of the coatings, specifi cs of texturing and residual stress indicate on the positive effect of increasing the rotation rate during the multilayer coating deposition, there are some aspects to be studied to determine the applicability of such a technique as well as its effect on the functional characteristics of the coatings. Conclusions Plasma-assisted vacuum-arc ZrN/CrN multilayer coatings were investigated for microstructure, hardness and residual stress. As shown, the rotation rates of both table and sample’s holder have its effect on the above noted characteristics. ZrN and CrN crystallites grow along the common axis with the interlayer misorientation about 18° at low rotation rates. Increasing the rotation rate resulted in breaking the orientation relationship with increased misorientation between the ZrN crystallites. The thickness of the alternating ZrN and CrN layers is almost linearly reduced when increasing the substrate rotation rate. The XRD shows that residual tensile stress in the ZrN/CrN-0.5 and ZrN/CrN-3.5 multilayer coatings are low whereas it becomes compressive in the fast rotated ZrN/CrN-8. References 1. Berríos-Ortíz J.A., La Barbera-Sosa J.G., Teer D.G., Puchi-Cabrera E.S. Fatigue properties of a 316L stainless steel coated with different ZrN deposits. Surface and Coatings Technology, 2004, vol. 179, pp. 145–157. DOI: 10.1016/S0257-8972(03)00808-9. 2. Zhang M., Li M.K., Kim K.H., Pan F. Structural and mechanical properties of compositionally gradient CrNx coatings prepared by arc ion plating. Applied Surface Science, 2009, vol. 255, pp. 9200–9205. DOI: 10.1016/J. APSUSC.2009.07.002. 3. Zhang M., Lin G., Lu G., Dong C., Kim K.H. High-temperature oxidation resistant (Cr, Al)N fi lms synthesized using pulsed bias arc ion plating. Applied Surface Science, 2008, vol. 254, pp. 7149–7154. DOI: 10.1016/J. APSUSC.2008.05.293. 4. Liu C., Bi Q., Ziegele H., Leyland A., Matthews A. Structure and corrosion properties of PVD Cr–N coatings. Journal of Vacuum Science and Technology A: Vacuum, Surfaces, and Films, 2002, vol. 20, pp. 772–780. DOI: 10.1116/1.1468651. 5. Mernagh V.A., Kelly T.C., Ahern M., Kennedy A.D., Adriaansen A.P.M., Ramaekers P.P.J., McDonnell L., Koekoek R. Adhesion improvements in silicon carbide deposited by plasma enhanced chemical vapour deposition. Metallurgical Coatings and Thin Films, 1991, vol. 1, pp. 462–467. DOI: 10.1016/B978-0-444-89455-7.50087-3. 6. Gruss K.A., Zheleva T., Davis R.F., Watkins T.R. Characterization of zirconium nitride coatings deposited by cathodic arc sputtering. Surface and Coatings Technology, 1998, vol. 107, pp. 115–124. DOI: 10.1016/S02578972(98)00584-2.

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