Vol. 25 No. 2 2023 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. 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 Journal “Obrabotka Metallov – Metal Working and Material Science” is indexed in the world's largest abstracting bibliographic and scientometric databases Web of Science and Scopus. 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.
OBRABOTKAMETALLOV Vol. 25 No. 2 2023 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 Aff airs, 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. Korotkov, D.Sc. (Engineering), Professor, Kuzbass State Technical University, Kemerovo; 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. 25 No. 2 2023 5 CONTENTS OBRABOTKAMETALLOV TECHNOLOGY Kisel’ A.G., Churankin V.G. Predicting the coolant lubricating properties based on its density and wetting eff ect.................................................................................................................................................................... 6 Berezin I.M., Zalazinsky A.G., Kryuchkov D.I. Analytical model of equal-channel angular pressing of titanium sponge.............................................................................................................................................. 17 EQUIPMENT. INSTRUMENTS Kuts V.V., Chevychelov S.A. Theoretical study of the curvature of the treated surface during oblique milling with prefabricated milling cutters....................................................................................................................... 32 Skeeba V.Yu., Zverev E.A., Skeeba P.Yu., Chernikov A.D., Popkov A.S. Hybrid technological equipment: on the issue of a rational choice of objects of modernization when carrying out work related to retrofi tting a standard machine tool system with an additional concentrated energy source................................................ 45 MATERIAL SCIENCE 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. In-situ analysis of ZrN/CrN multilayer coatings under heating................................................................................................................................................................. 68 Kornienko E.E., Gulyaev I.P., Kuzmin V.I., Tambovtsev A.S., Tyryshkin P.A. Structure and properties of WC-10Co4Cr coatings obtained with high velocity atmospheric plasma spraying.................................... 81 Balanovsky A.E., Nguyen V.V., Astafi eva N.A., Gusev R.Yu. Structure and properties of low carbon steel after plasma-jet hard-facing of boron-containing coating............................................................................. 93 Emurlaeva Yu.Yu., Lazurenko D.V., Bataeva Z.B., Petrov I.Yu., Dovzhenko G.D., Makogon L.D., Khomyakov M.N., Emurlaev K.I., Bataev I.A. Evaluation of vacancy formation energy for BCC-, FCC-, and HCP-metals using density functional theory................................................................................................ 104 EDITORIALMATERIALS 117 FOUNDERS MATERIALS 127 CONTENTS
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 In-situ analysis of ZrN/CrN multilayer coatings under heating Andrey Vorontsov 1, a, Andrey Filippov 1, b,*, Nikolay Shamarin 1, c, Evgenij Moskvichev 1, d, Ol’ga Novitskaya 1, e, Evgenii Knyazhev 1, f, Yuliya Denisova 2, g, Andrei Leonov 2, h, Vladimir Denisov 2, i 1 Institute of Strenght Physics and Materials Sciences SB RAS, 2/4 pr. 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.filippov@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. 2023 vol. 25 no. 2 pp. 68–80 ISSN: 1994-6309 (print) / 2541-819X (online) DOI: 10.17212/1994-6309-2023-25.2-68-80 ART I CLE I NFO Article history: Received: 15 March 2023 Revised: 22 March 2023 Accepted: 28 March 2023 Available online: 15 June 2023 Keywords: Coating Nitrides Phase composition RSA CTE Stresses Funding The work was carried out with the financial support of the Russian Federation represented by the Ministry of Science and Higher Education (project No. 075-15-2021-1348) 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. Advanced hard coatings combine different properties such as high hardness, wear resistance, corrosive resistance. At present, layer-by-layer deposited zirconium and chromium nitrides are promising hard coating materials. Currently, the multilayer coating process is not sufficiently described in the literature to understand all the processes involved. The problem is the complexity of depositing thick layers of multilayer, multicomponent coatings with different physical characteristics of the coating components. First and foremost this concerns the coefficient of linear thermal expansion (CTE). Since the coating and operating processes consist in heating, coating components with different CTE will be susceptible to cracking, further failure and product failure over time. The purpose of work is in-situ study of multilayer ZrN/CrN coatings by X-ray analysis using synchrotron radiation and qualitative microstress behavior of multilayer coatings formed by plasmaassisted vacuum-arc method on substrate of alloy VK8 (92% WC–8% Co) under heating up to 750°С. Research methodology. Samples of coatings made of chromium and zirconium nitrides deposited on a substrate of the hard alloy VK8 are investigated. The basic method is the X-ray analysis using synchrotron radiation. We used the most common techniques to study the characteristics of multilayered coatings such as the coefficient of linear thermal expansion and the qualitative measurement of microstresses. Results and discussion. The result is the ability to determine changes in the characteristics of multilayer coatings during heating, such as changes in the crystal lattice parameter of each of the coating components separately, the possibility to determine the coefficient of linear thermal expansion of the coating components and the qualitative measurement of microstresses, as well as providing the opportunity, based on the analysis, to form recommendations for further application of the technology of applying multilayer coatings with given characteristics. For citation: VorontsovA.V., FilippovA.V., Shamarin N.N., Moskvichev E.N., Novitskaya O.S., Knyazhev E.O., DenisovaYu.A., LeonovA.A., Denisov V.V. In-situ analysis of ZrN/CrN multilayer coatings under heating. Obrabotka metallov (tekhnologiya, oborudovanie, instrumenty) = Metal Working and Material Science, 2023, vol. 25, no. 2, pp. 68–80. DOI: 10.17212/1994-6309-2023-25.2-68-80. (In Russian). ______ * Corresponding author Vorontsov Andrey V., Ph.D. (Engineering), Junior researcher Institute of Strenght Physics and Materials Sciences SB RAS, 2/4 pr. Academicheskii, 634055, Tomsk, Russian Federation Tel.: 8 (983) 239-34-17, e-mail: vav@ispms.ru
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 Introduction With the development of materials production technology for cutting tools, press molds, engine components, and other mechanical components, mainly hard coatings are used [1, 2]. Metal nitrides such as chromium, niobium, zirconium, tantalum, titanium, or its combinations are primarily used as coating materials [3–5]. Such coatings are able to withstand the high load and temperature that characterize the operation of the cutting tool. It is worth noting that coatings are used not only to provide the necessary characteristics of cutting tools; as studies show, some coatings such as CrN can be used as a coating for zirconium alloy for use in fuel accident-resistant materials [6, 7], and ZrC/TaC, Ru-Al/Ru-Si-Zr finds applications in the aviation industry and gas turbine blades [8, 9]. In this regard, the main methods of coating deposition can be named as reactive magnetron sputtering [3, 10], vacuum brazing [11], thermal spraying [12], high-speed physical vapor deposition [13, 14], and pulsed electro deposition [15]. In this work, the vacuum arc plasma deposition method is used [16]. Despite the wide use of nitride coatings in the cutting tools manufacture, the limits of its application, and properties acquired after exposure to certain conditions are being investigated. In most cases, corrosion resistance [17] and oxidation processes [10, 18] at temperatures above 1,000 °C are studied. The authors [17] found that multilayer Cr/CrN coatings on a Zr-4 zirconium alloy substrate exhibit good resistance to steam oxidation with a decrease in the thickness of the multilayer coating layers. In turn, the primary task of characterizing the coating process is not described in the literature. The problem lies in the complexity of depositing thick multilayer, multicomponent coatings with different physical characteristics. First of all, this concerns the coefficient of linear thermal expansion (CLTE) of the components of the multilayer coating. Since the process of deposition and operation of coatings involves temperature exposure, the components of the coating with different CLTEs will eventually be prone to cracking, further destruction, and failure of the products. The aforementioned works suggest that it is important not only to understand the characteristics and properties of nitride coatings, but also the kinetics of the structural behavior of multilayer coatings obtained through thermal action in air. Therefore, the purpose of this work is to in-situ study the patterns of structural changes in CrN/ZrN multilayer coatings deposited on a 92 wt.% Co-8 wt.% WC substrate by vacuum-arc plasma deposition after thermal testing in air with an exposure temperature of 30 to 750 °C. The conducted research will be useful for developing knowledge on the behavior of materials with various physical properties in multilayer coatings at elevated operating temperatures in engineering applications, such as cutting tools. The study is based on the task of investigating the structural-phase composition in CrN/ZrN multilayer coatings during the heating of the substrate of 92 wt.% Co-8 wt.% WC alloy with a multilayer coating consisting of alternating nitride layers of CrN and ZrN. The aim of this study is to conduct in-situ investigation of ZrN/CrN multilayer coatings using X-ray structural analysis with synchrotron radiation and to qualitatively assess the behavior of microstrains in multilayer coatings obtained by plasma-assisted vacuum arc method on a substrate made of 92 wt.% Co-8 wt.% WC alloy under temperature exposure up to 750 °C. The result is to provide the opportunity to determine changes in the characteristics of multilayer coatings during heating, such as the change in the lattice parameter of each component of the coating separately, the possibility of determining the coefficient of thermal expansion of the coating components, and the qualitative determination of microstrains, as well as the possibility of forming recommendations for further application of multilayer coating deposition technology with specified characteristics based on the conducted analysis. Methods and materials Experimental specimens subjected to heating during synchrotron investigations were used with ZrN/CrN multilayer coatings applied to a substrate of 92 wt.% Co-8 wt.% WC alloy using a plasma-assisted vacuum arc method, obtained at different rotation speeds of the table and substrate holder in the planetary coating deposition scheme shown in Fig. 1. For the experiment, two coating deposition modes were selected: table rotation speed of 0.5 rpm (ZrN/CrN-0.5 specimen) and 8.0 rpm (ZrN/CrN-8 specimen).
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 In chamber 1, substrates made of 92 wt.% Co-8 wt.%WC alloy for the deposition of multilayer coatings are attached to a rotating holder 2, installed on a rotating table 3. A turbomolecular pump 4 creates a vacuum in chamber 1, and after reaching a vacuum of 10-4 Pa, inert filling gas puffing occurs through a plasma source 5 to create the required working pressure in the chamber. When the gas discharge is ignited with a current of 40 A and a bias voltage of 700 V is applied to the substrate holder with the specimens, the substrates are heated to 400 °C. After cleaning the surface of the objects under investigation by ion bombardment and its chemical activation, a mixture of nitrogen and argon gases (90/10) puffing occurs to the desired pressure, and the arc evaporator discharges are ignited with a current of 80 A for each of it. One cathode made of the deposited material (positions 6 and 7) was installed in each evaporator, in our case these were Cr (99.9%) and Zr (99.5%). Specimens with multilayer coatings were circular in shape, 15 mm in diameter, and 3 mm thick, with a thickness of coatings. The thickness of the coatings was in all cases 5 μm. The most appropriate method for the research task is in-situ synchrotron characterization of multilayer coatings during temperature exposure to a multilayer coating deposited on a substrate. Coatings applied to the 92 wt.% Co-8 wt.% WC alloy substrate were investigated using X-ray diffraction analysis (XRD) with synchrotron radiation (work was carried out at VEPP-3 synchrotron). The wavelength during synchrotron experiments was 1.54 Å. For in-situ studies, the sample with a multilayer coating was placed on a heated holder in an air atmosphere. Then the initial XRD pattern was obtained using an asymmetric measurement method, i.e., with a fixed angle of incidence of radiation in the range of angles 2Θ, selected depending on the material of the multilayer coating (31–48). In the next stage, the sample was heated at a given rate, providing exposure time sufficient for step-by-step construction of the XRD pattern of the sample with the multilayer coating using synchrotron radiation. The temperature range of heating was determined by the real operating conditions of the coatings. Simultaneous registration and recording of XRD patterns with a step ensuring sufficient accuracy of identification the phase transitions and structural changes occurring during heating of the coating in the temperature range from 50 to 750 °C was made. To ensure the necessary measurement accuracy, a part of the 2Θ angle range was registered, in which one reflection of each phase of the multilayer coating was presented. The sample with the multilayer coating was heated in the temperature range from 30 °C to 750 °C with a temperature increase rate not exceeding 5 °C/min, providing exposure time sufficient for the construction of the XRD pattern of the sample, and with a step of 10 °C, XRD patterns were registered and recorded using synchrotron radiation in the X-ray range of radiation with a scanning step of 0.05 degrees and a range of angular position scanning of 2Θ from 31 to 48 degrees. After obtaining the necessary number of X-ray diffraction patterns at different temperatures, the obtained profiles were approximated with the determination of such characteristics of the reflections of the present phases as interplanar spacings (d), the full width at half maximum intensity (FWHM) and identification of all phases in the multilayer coating within the diffraction patterns selected from the entire array of obtained patterns after visual assessment of the temperature at the phase transformations beginning. To obtain the characteristics of the reflections presented in the coating phases, the obtained X-ray diffraction profiles were approximated by the Pseudo-Voigt function [19]. After determining all the necessary parameters of the diffraction pattern profile, the lattice parameter (a) was calculated for the cubic symmetry of the CrN and ZrN phases presented in the multilayer coating, as Fig. 1. Multilayer nanostructured ZrN/CrN coating application unit scheme
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 well as the coefficient of thermal expansion (CLTE) for each phase at all stages of the heating temperature range. Based on the obtained data, a dependence of the lattice parameter (a) for each phase of the multilayer coating on the temperature of exposure was constructed for each stage of the heating temperature range of the sample with a multilayer coating, as well as the dependence of the change in the lattice parameter (Δa) and graphical determination of the CLTE using the last coefficient of thermal expansion. Quantitative determination of the crystal lattice parameter (a) was carried out after approximation and determination of interplanar distances (d) using equation 1 [20]: 2 2 2 a d H K L = ⋅ + + , (1) where d is the interplanar distance [Å]; H, K, L are the Miller indices of the analyzed reflection. Based on the calculated crystal lattice parameters of the multilayer coating components using equation 1, it is possible to calculate the linear coefficient of thermal expansion (CLTE) of each component of the multilayer coating separately using equation 2: , a a T ∆ β = ∆ (2) where β is the CLTE (K-1); a is the crystal lattice parameter in nm; Δa is the change in the crystal lattice parameter in nm when the sample with the multilayer coating is subjected to a temperature change (ΔT [K]). To assess the temperature at which microstresses may occur, the full width at half maximum intensity (FWHM) of the coating phases was plotted against temperature. As it is known from literature [21] that the magnitude of microstresses is directly proportional to FWHM, comparing the FWHM of at least two samples with multilayer coatings allows for conclusions to be drawn about the degree of microstresses present in multilayer coatings. Results and discussion The heating was carried out in an air medium on a holder with a platinum heating element. The initial state of the multilayer coating material was characterized by obtaining an X-ray diffraction pattern at a temperature of 30 °C. In our case, for the CrN and ZrN coating phases, the X-ray diffraction pattern registration range was 31–48 2Θ. Figure 2 shows an array of X-ray diffraction patterns obtained at a heating rate of 5°C/min, by the asymmetric scanning method using synchrotron radiation transformed into monochromatic radiation with a wavelength of 1.54 Å, during the heating ZrN/CrN-coated samples in the temperature range from 30 °C to 750 °C. The array consists of 71 projections of X-ray diffraction patterns obtained from both the substrate surface and the layers of the deposited multilayer coating, where each projection of the diffraction pattern represents a gradation of pseudo-color, shown in Fig. 2, indicating the intensity of the obtained signal during the X-ray diffraction pattern construction. Such data visualization is convenient for a qualitative analysis of phase transformations. The graphs presented in Fig. 2 (a, b) allow assessing the final stage of phase transitions in multilayer coatings. In the case of the CrN/ZrN coating applied at a table rotation speed of 0.5 rpm, the coating phase completely disappears at 575 °C, while the CrN/ZrN multilayer coating applied at a table rotation speed of 8 rpm completely loses its phase only at 635 °C. Fig. 3 shows selected X-ray diffraction patterns from the array shown in Fig 2. The temperature interval, initial and final points of temperature exposure are chosen for the sake of readability of a smaller data array and considerations of the end of phase transformations. As shown in Fig. 2, coating phases in multilayer coatings completely disappear after 650 °C, and it is advisable to limit the temperature range from 30 °C to 650 °C. In Table 1, the calculated values of interplanar spacing (d, Å), the width of the reflection at FWHM (in degrees), as well as the lattice parameter of the crystalline structure for the components of the CrN/ZrN
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 a b Fig. 2. Projections of X-ray diffraction patterns, in pseudocolor gradation, denoting the signal intensity when taking X-ray diffraction patterns: a – ZrN/CrN 0.5 rpm; b – ZrN/CrN 8 rpm а b Fig. 3. A series of X-ray diffraction patterns of an experimental sample with a multilayer ZrN/CrN coating, obtained by asymmetric imaging using synchrotron radiation when heating from 30°C to 750°C: a – ZrN/CrN 0.5 rpm; b – ZrN/CrN 8 rpm Ta b l e 1 Characteristics of phase reflections in the sample with multilayer coating of CrN/ZrN obtained at a substrate holder rotation speed of 0.5 rpm depending on the temperature of exposure Temperature, °C Reflection, phase d, Å FWHM, deg. a, nm 50 (111) ZrN 2.654 1.0131 4.5965 (111) CrN 2.45 1.5584 4.2426 100 (111) ZrN 2.653 1.0433 4.5956 (111) CrN 2.44 1.3269 4.2265 200 (111) ZrN 2.658 0.9849 4.6030 (111) CrN 2.45 1.4758 4.2428 400 (111) ZrN 2.662 0.9586 4.6105 (111) CrN 2.456 1.5005 4.2540 500 (111) ZrN 2.664 0.915 4.6145 (111) CrN 2.454 1.4635 4.2511 550 (111) ZrN 2.662 0.8375 4.6103 (111) CrN 2.455 1.5585 4.2516
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 multilayer coating, obtained at a substrate holder rotation speed of 0.5 rpm, are presented according to the known Equation (1) [20]. The calculation of CLTE was performed using Equation 2 for each temperature point presented in Table 1. The X-ray diffraction pattern (Fig. 3) shows the reflections (111) of the CrN and ZrN phases of the multilayer coating in the selected temperature range. The dependence of the lattice parameter on the temperature is shown in Fig. 4, a. The graph shows that the lattice parameter of the coating materials (CrN and ZrN) increases, indicating an increase in material volume, which occurs according to a linear law with some error. The dependence of the lattice parameter on the exposure temperature is shown in Fig. 4, b. a b Fig. 4. Dependence of the crystal lattice parameter of the ZrN/CrN multilayer coating phases on temperature – a; dependence of the changes in the crystal lattice parameter (Δa) of the phases of the ZrN/CrN multilayer coating on temperature – b Equation 2 is applied as follows. Obviously, Figure 4b is a modified graph shown in Figure 4a, such that Δa = aT - a0, where aT is the lattice parameter at a higher temperature (in the case of Figures 4a, b, the highest values on the linear segments: 50–550 °C), and a0 is the lattice parameter at the beginning of the linear segments (in the case of Figures 4a, b, the lowest values on the linear segments: 50–550 °C). That is, for the heating range from 50 °C to 550 °C, the CLTE (β) of the ZrN phase of the multilayer coating will be calculated as: 6 1 4, 6145 4,5965 7,83 4,5965(550 50) 10 ZrN - - - β = ⋅ = - Ê . For the linear heating range from 50 °C to 550 °C, the lattice constant (β) of the CrN phase of the multilayer coating will be calculated as: 6 1 4, 2516 4, 2426 4, 2426 4 (550 50 24 10 ) , CrN - - - ⋅ β = = - Ê . Equation 2 can be represented graphically as a dependence of the change in the lattice parameter (Δa) on the temperature of exposure, as shown in Fig. 4, b. The slope of the tangent in this case is the rate of change of the lattice parameter value (nm) per 1 °C during heating. The thermal expansion coefficient (TEC) over the entire temperature range of exposure from 50 °C to 650 °C will be positive for both phases of the multilayer coating: 2.28249×10-14 K-1 for the CrN phase and 3.54878×10-14 K-1 for the ZrN phase. Fig. 5 shows the dependence of the FWHM of the (111) reflections of the CrN and ZrN phases on the temperature of exposure. Based on the possibility of the occurrence of microstrains with an increase in the FWHM value, it can be concluded that the increase in microstrains is possible in the temperature range
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 Fig. 5. Dependence of FWHM reflection of (111) CrN and (111) ZrN multilayer coating on temperature from 50 °C to 400 °C for the CrN phase. After reaching the temperature of 400 °C, the FWHM value increases and, accordingly, microstrains will also have an increasing dependence for the CrN phase. For the ZrN phase, the situation is reversed: the FWHM value decreases almost throughout the heating process, and accordingly, microstrains will only decrease. Table 2 presents the calculated values of interplanar distances (d, Å), the full width at half maximum (FWHM) values (degrees), as well as the calculated lattice parameter for the CrN/ ZrN multilayer coating obtained at a substrate holder rotation speed of 8 rpm using the known Equation 1 [20]. The CLTE calculations were performed using Equation 2 for each temperature point presented in Table 1. The X-ray diffraction pattern shows the reflections (111) of the CrN and ZrN phases of the multilayer coating in the selected temperature range. Ta b l e 2 Characteristics of reflections of all phases, presented in a sample with a multilayer CrN/ZrN coating, obtained at a substrate holder rotation speed of 8 rpm as a function of temperature Temperature, °C Reflection, phase d, Å FWHM, deg. a, nm 50 (111) ZrN 2.6596 1.1329 4.6065 (111) CrN 2.4595 1.5925 4.2599 100 (111) ZrN 2.6644 1.0414 4.6148 (111) CrN 2.4679 1.5137 4.2745 200 (111) ZrN 2.6671 1.0504 4.6195 (111) CrN 2.4633 1.6553 4.2665 400 (111) ZrN 2.6721 1.0941 4.6282 (111) CrN 2.4519 1.6526 4.2468 500 (111) ZrN 2.6732 1.0407 4.6301 (111) CrN 2.4595 1.6878 4.2599 550 (111) ZrN 2.6729 0.9904 4.6295 (111) CrN 2.4572 1.6518 4.25599524 600 (111) ZrN 2.6698 0.8949 4.62422925 (111) CrN 2.4739 1.652 4.28492049 The dependence of the crystal lattice parameter on the temperature is shown in Fig. 6, a. From the graph, it can be seen that the crystal lattice parameter of the coating materials (CrN and ZrN) increases, i.e., the material expands, and this occurs according to a linear law with some error. The dependence of the crystal lattice parameter change on the temperature of the coating materials (CrN and ZrN) is shown in Fig. 6, b. Equation 2 is applied as follows. Obviously, Fig. 6, b is a rearranged graph shown in Fig. 6, a, such that Δa = aT - a0, where aT is the lattice parameter at a higher temperature (in the case of Figures 6, a, b, the highest values on the linear segments: 50–550 °C), and a0 is the lattice parameter at the beginning of the linear segments (in the case of Figures 6, a, b, the lowest values on the linear segments: 50–550 °C). Thus,
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 a b Fig. 6. Dependence of the changes in the crystal lattice parameter of the phases of the ZrN/CrN multilayer coating on temperature – a; dependence of the changes in the crystal lattice parameter (Δa) of the phases of the ZrN/CrN multilayer coating on temperature – b for the heating range from 50°C to 550°C, the XRD (β) of the ZrN phase of the multilayer coating will be calculated as: 6 1 6, 99 4, 6065(600 50) 4, 6242 4, 6065 10 ZrN - - - β = = - ⋅ Ê . In the case of the CrN coating component, it can be seen from Fig. 3a that the dependence is not linear but consists of two linear segments. The first segment is 50–400 °C, and for it, the CLTE should be calculated separately. For the linear heating range from 50 °C to 550 °C, the lattice constant (β) of the CrN phase of the multilayer coating will be calculated as: 6 1 8,79 4, 2599(400 5 4, 2468 4 0) , 2599 10 CrN - - - β = = ⋅ - - Ê . In the temperature range from 50 °C to 400 °C, the component of the CrN multilayer coating undergoes compression. The second section, from 400 °C to 600 °C, should also be calculated separately. For this linear heating range, the lattice constant of the CrN phase of the multilayer coating (β) is calculated as: 5 1 4,2849 4,2468 4, 49 4,2468(600 400) 10 CrN - - - ⋅ β = = - Ê . In the temperature range of heating from 400°C to 600°C, the expansion of the component of the CrN multilayer coating occurs, but the CLTE of the CrN component is an order of magnitude higher than that of the ZrN component of the multilayer coating. For clarity, Equation 2 can be represented in graphical form as a dependence of the change in the lattice parameter (Δa) on the temperature of exposure, as shown in Fig. 6b. The tangent of the slope angle in this case is the rate of change in the value of the lattice parameter (nm) per 1 °C during heating. The CLTE value for ZrN phase in the temperature range of 50 °C to 600 °C is positive and equals 3.44×10–5 nm/K, as shown above the red straight line. For the CrN phase of the multilayer coating, in the temperature range of 50 °C to 400 °C, the CLTE value corresponds to a negative value of -5.55×10-5 nm/K. The positive CLTE value is observed in the temperature range of 400 °C to 600 °C, and it equals 1.61×10-4 nm/K for the CrN phase of the multilayer coating.
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 25 No. 2 2023 Figure 7 shows the plot of the dependence of FWHM of (111) CrN and (111) ZrN phase reflections on the temperature. Based on the possibility of the occurrence of microstresses with an increase in the FWHM value, it can be concluded that microstresses can occur to a small extent for the CrN phase of the multilayer coating up to 200 °C. After reaching the temperature of 200 °C, the FWHM value remains, on average, at the same level. For the ZrN coating component, the FWHM value slightly increases up to the temperature of 400 °C, and then the FWHM value decreases, accordingly, microstresses will also have a decreasing dependence. As a result of the sequential actions with obtaining X-ray diffraction patterns of samples with coatings under temperature exposure, sampling and evaluation of X-ray diffraction patterns according to the proposed algorithm, recommendations for the application of coating technologies depending on the parameters of coating application can be made. The recommendations consist of a two-stage algorithm, consisting of: 1. Determining the CLTE of individual coating components; 2. Determining the FWHM and comparing it with the FWHM minimum of two samples with coatings. If the calculated CLTE values for some coating components exhibit differences, the deposition mode in which the CLTE of coating components exhibits the minimum differences at any temperature is selected as the optimal deposition mode. The temperature, at which the CLTE of coating components exhibits the minimum differences or is equal, is selected as the optimal mode of multilayer deposition, and the coating in which the FWHM values, as determined by the X-ray profile approximation, exhibit a decreasing dependency, is most suitable for prolonged use due to the minimal microstresses existing in the coating. Conclusions Based on the conducted research using the proposed algorithm, conclusions and recommendations can be made regarding the application and use of CrN/ZrN coatings: A multilayer coating of CrN/ZrN deposited at a table rotation speed of 0.5 revolutions per minute (rpm) had varying CLTE values throughout the entire thermal testing, with differences in CLTE between components exceeding 50%. For the multilayer coating deposited at a table rotation speed of 8 rpm, the CLTE dependence was found to be linear only for the CrN component, while the ZrN component exhibited an extremum in the temperature range of 400 °C. Prior to heating the coating to 400 °C, the CLTE was negative, and after reaching 400 °C, it changed sign to positive. This indicates that within a narrow temperature range around 400 °C, the CLTE of both coating components will not differ significantly. Therefore, the coating application mode with a table rotation speed of 8 rpm will be optimal. Based on the FWHM data, the occurrence of microstresses is possible for both coating application modes (0.5 and 8 rpm). However, for the coating application mode with a table rotation speed of 8 rpm, no microstresses were observed for the CrN component, even after exposure to 500 °C. This leads to the conclusion that this deposition mode for the multilayer coating is optimal. Fig. 7. Dependence of FWHM reflection of (111) CrN and (111) ZrN multilayer coating on temperature References 1. Liu J., Hao Z., Cui Z., Ma D., Lu J., Cui Y., Li C., Liu W., Xie S., Hu P., Huang P., Bai G., Yun D. Oxidation behavior, thermal stability, and the coating/substrate interface evolution of CrN-coated Zircaloy under hightemperature steam. Corrosion Science, 2021, vol. 185, p. 109416. DOI: 10.1016/j.corsci.2021.109416. 2. Pashkov D.M., Belyak O.A., Guda A.A., Kolesnikov V.I. Reverse engineering of mechanical and tribological properties of coatings: results of machine learning algorithms. Physical Mesomechanics, 2022, vol. 25, pp. 296–305. DOI: 10.1134/S1029959922040038.
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