The article presents the results of the studies related to the development of hardening, antifriction, heat-resistant, corrosion-resistant coatings. There have been considered the models of concentration supercooling associated with the presence of a radial concentration gradient of metal nitride impurity; Benard cells, the occurrence of which is caused by the presence of a vertical temperature gradient; a cellular dislocation structure associated with the presence of plastic deformations in the coating; the emergence of auto-waves in the most diverse environments, including living beings. From the studies presented in the work, it follows that self-organization of forming coatings can occur only under conditions of a large value of the surface energy

Alkina, A. D.

Mekhtiyev, A. D.

Syzdykova, A. Sh.

Yurov, V. M.

English

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443METALURGIJA 62 (2023) 3-4, 443-446A.SH. SYZDYKOVA, V.M. YUROV, A.D. MEKHTIYEV, A.D. ALKINAFORMATION OF THE STRUCTURE AND PROPERTIES  OF MULTI-ELEMENT ION-PLASMA COATINGSReceived – Primljeno: 2023-02-11Accepted – Prihvaćeno: 2023-03-25Preliminary Note – Prethodno priopćenjeThe article presents the results of the studies related to the development of hardening, antifriction, heat-resistant, corrosion-resistant coatings. There have been considered the models of concentration supercooling associated with the presence of a radial concentration gradient of metal nitride impurity; Benard cells, the occurrence of which is caused by the presence of a vertical temperature gradient; a cellular dislocation structure associated with the presence of plastic deformations in the coating; the emergence of auto-waves in the most diverse environments, including living beings. From the studies presented in the work, it follows that self-organization of forming coatings can occur only under conditions of a large value of the surface energy.Keywords: multi-element coating, x-ray research, metal nitride, corrosion, hardnessISSN 0543-5846METABK 62(3-4) 443-446 (2023)UDC – UDK 621.793: 593.26: 661.55: 620.193: 620.178.1=111INTRODUCTIONPresent day industrial production that is faced with the limitation of material resources in the development of structural materials, resorts to new technological so-lutions. New technologies lie in the fact that instead of expensive materials made of iron and refractory ele-ments obtained in metallurgy, there are used hardening, antifriction, heat-resistant, corrosion-resistant coatings [1]. Increasing the coating thickness is accompanied by increasing internal mechanical stresses, which results in decreasing the adhesion strength. Increasing the dura-bility of surfaces with the help of special coatings is still one of the most effective methods of improving the functional and operational characteristics of products and parts for various purposes [2].At present, instead of single-phase coatings, such as titanium nitrides or carbides, multi-element coatings have been used, which have a number of unique proper-ties and cannot be obtained by traditional metallurgy. Such an alloy based on a multi-element composition, including such elements as Fe, Cr, Ni, Ti, Al, was stud-ied in [3, 4]. Some investigators [5] have claimed that multilayer nanoscale structures are more effective com-pared to single-layer coatings, in particular, in increas-ing hardness and strength. A more complete presenta-tion of multi-element coatings can be found in [6]. In this work, it is shown that ion-plasma coatings deposit-A.D. Mekhtiyev, e-mail: barton.kz@mail.ru, Kazakh AgroTechnical University, Astana, Republic of Kazakhstan.A.Sh. Syzdykova, Polytechnic College of Kazakhmys Corporation, Balkhash, Republic of Kazakhstan.V.M. Yurov, Buketov Karaganda State University, Karaganda, Repub-lic of Kazakhstan.zsA.D. Alkina, Karaganda Technical University, Karaganda, Republic of Kazakhstaned on a modernized HNV-6.6I1 installation have the following technological parameters: the optimal sub-strate temperature for all the applied coatings is 400 0C; with increasing the arc current of the evaporator, the surface energy of the coating decreases, which is ex-plained by a rapid increasing of its thickness that leads to increasing the dislocation density in the formed coat-ing; coatings obtained at nitrogen pressure Р = 10-6 Pa have the most uniformly distributed fine dense struc-ture, the minimum content of the droplet phase, pores, sags, delaminations and the highest values of surface tension and microhardness. These parameters wil bel adhered to in this work. In recent years, atomic force microscopy (AFM) has been used very often in connec-tion with a complete study of the morphology and sur-face properties of coatings, metal and other films, as well as in the synthesis of new materials, including bio-materials and living beings.The purpose of the work is studying the properties of coatings that contain copper and applying them to steel surfaces of mining equipment parts in order to pro-tect them against corrosion.RESEARCH OBJECTS AND METHODSOur studies of the surface morphology of coatings obtained by ion-plasma and magnetron sputtering in vacuum was carried out on a JEOL AFM JSPM – 5400. Our coating has a cellular (“pencil”) microstructure. This is especially evident in the section of the coating made by the Quanta 200 3D system that directs a fo-cused ion beam that allows precise removing the mate-rials by determining the coating thickness (Figure 1).Figure 2 shows the cellular (columnar, “pencil”) mi-crostructure of the coating (FeCuCrMnNiTi)N.444  METALURGIJA 62 (2023) 3-4, 443-446A.SH. SYZDYKOVA et al.: FORMATION OF THE STRUCTURE AND PROPERTIES OF MULTI-ELEMENT…In work [7] there are considered the models of con-centration supercooling associated with the presence of a radial gradient of the metal nitride impurity concen-tration; of Benard cells, the occurrence of which is caused by the presence of a vertical temperature gradi-ent; a cellular dislocation structure associated with the presence of plastic deformations in the coating. All these models correspond to the processes of self-organ-ization, including the formation of coatings. Self-organ-ization processes include the emergence of auto-waves in various media, including living beings [8, 9]. In this work, the following experiment was carried out: it was assumed that the cellular structure “in static” or “in fro-zen form” corresponds to a wave process. In this case, the coating microhardness was measured on a micro-hardness tester HVS - 1000 A with the use of the Vick-ers method along, across and diagonally of the samples.The cathodes made of pure copper Cu metals and steel X10CrNiTi18 – 10 (European Union) were made using cylinders with the diameter of 100 – 120 mm on a lathe, Figure 3.The deposition was carried out simultaneously from two cathodes on a modernized ion-plasma chamber vacuum installation HNV-6.6I1 in the nitrogen atmos-phere. If the electrodes are turned on in alternation, then multiphase flows and multilayer coatings will occur.X-ray fluorescent quantitative analysis (XPS) of the coating composition carried out on a JEOL JSM – 5 910 electron microscope, is shown in Figure 4. The quanti-tative analysis of the elemental composition of coatings has the following distribution: Fe – 47,4 %; Cu – 22,5 %; Cr – 15,0 %; N – 13,1 %; Mn – 4,0 %; Ni- 3,5 %; Ti – 0,9 %.Figure 1 Cross section of the (FeCuCrMnNiTi)N coatingFigure 2  Cellular (columnar) structure of a crystal that is formed during its growth from a meltFigure 3 Cu and X10CrNiTi18 – 10 cathodesFigure 4 XPS of the (FeCuCrMnNiTi)N coatingRESEARCH RESULTSStudying the phase composition and structural pa-rameters of the samples was carried out on an XRD – 6 000 diffractometer using CuKα radiation. As a result, two phases were found: BCC and FCC. These phases are formed due to nitrides and copper. Figure 5 shows the microstructure of coatings measured with a Tescan Vega LSU scanning electron microscope (SEM). The study shows that the alloy of the (FeCuCrMnNiTi)N system consists of large elongated grains with the aver-Figure 5  SEM of microstructure of the (FeCuCrMnNiTi)N coating445A.SH. SYZDYKOVA et al.: FORMATION OF THE STRUCTURE AND PROPERTIES OF MULTI-ELEMENT…METALURGIJA 62 (2023) 3-4, 443-446age width of (100 – 150) µm and an average length of (200 – 300) µm.To determine the resulting coatings nanohardness, there was used the Ntegra probe laboratory with a Berk-ovich indenter. The result is shown in Figure 6.Coatings were tested for hardness using an HVC-1000A electronic microhardness tester. The hardness of the (FeCuCrMnNiTi)N coating and some steels: (FeCu-CrMnNiTi)N coating microhardness 884,6 МPа; (Fe-CuCrMnNiTi)N coating nanohardness 995,6 МPа; Stainless steel 316 microhardness 189 МPа.In the scientific work, there were used computer modeling methods, numerical studies were carried out using the ANSYS program. This program had already been used before, and examples of computer models and simulation results were presented in [10]. Simulat-ing made it possible to exclude cumbersome and expen-sive full-scale tests of experimental samples.INDUSTRIAL TESTING OF COATINGSParts of mining equipment are exposed to corrosion primarily due to the impact of mine water. Mine water is called groundwater that penetrates into the under-ground space worked out during the extraction of min-erals and passes through the drainage system of the mine. The most acidic and highly mineralized mine wa-ters are formed on the upper levels and mine workings on the territory of the first hydrochemical zone from the surface. The most acidic mine waters are formed in an-thracite mines to depths of (250 – 300 m), at low angles of incidence of rocks when the content of total sulfur in the coal is more than 2,5 %, with a long length of work-ings and a large area of mined-out space.At deeper levels (300 – 400 m), sulfate-chloride so-dium or sodium-calcium waters are generated. At the depth of more than 400 m, chloride-sulfate waters are formed. Thus, in mine waters, the content of SO42-, Ca2+, Mg2+ decreases with depth and the content of K+, Na+, Cl-, HCO3- increases. But at the same depths, mine wa-ters contain more calcium and magnesium sulfates than groundwater. Pumping out mine water from mine work-ings leads to corrosion of metal parts of pumps, pipe-lines, fittings, etc. Mine supports are also subjected to significant corrosion, despite significant efforts to im-prove their corrosion resistance. To increase corrosion resistance of a number of mining equipment parts, the (FeCuCrMnNiTi)N coating was applied that showed the best results in preliminary studies. Table 1 shows the results of testing parts with such anti-corrosion  coatings.Figure 6  Measuring nanohardness of a sample with the (FeCuCrMnNiTi)N coatingTable 1  Anti-corrosion coatings properties on the mining equipment partsPart Coating Corrosion rate / g/m2∙hSteel 35 Without coating 3,21Steel 35 (FeCuCrMnNiTi)N 0,15Coupling, St. 35 (FeCuCrMnNiTi)N 0,15Clutch 12 s, St. 35 (FeCuCrMnNiTi)N 0,15Stopper HLG 30.002, St. 35 (FeCuCrMnNiTi)N 0,15Housing of gas distributor (FeCuCrMnNiTi)N 0,15H13.07.130-01, St. 35 (FeCuCrMnNiTi)N 0,12Plunger KSN01.311, St. SIH15 (FeCuCrMnNiTi)N 0,13Sleeve M130.07.149, St. 40 (FeCuCrMnNiTi)N 0,13Table 2  Corrosion rate of the most corrosion resistant steelsSteel grade Corrosion rate / g/m2∙hH23N28M3D3Т 0,21H23N27M3T 0,26H18H12М3Т 0,80Let’s compare the obtained results with the corro-sion rate of some corrosion-resistant stainless steels (Table 2).From this comparison it follows that our coating is not inferior to stainless steels in terms of corrosion but is much cheaper in cost. The following conclusion fol-lows from the above results: the greater the surface en-ergy σ of the coating, the greater its corrosion resist-ance. Thus, the tests carried out showed the economic feasibility of using multi-element ion-plasma coatings.CONCLUSIONMining machines for underground mining of coal and other minerals include winning machines, powered supports, drilling machines, loading and drilling-load-ing machines and auxiliary equipment of various types. The working tools of the mining machines are cutting and cone tools. Power subsystems of mining cutting machines contain auger, drum, chain, rotary and milling actuators. Shearers, road headers and plows also con-tain a large range of metal parts made of steels and al-loys of various grades.955,6 MPa446  METALURGIJA 62 (2023) 3-4, 443-446A.SH. SYZDYKOVA et al.: FORMATION OF THE STRUCTURE AND PROPERTIES OF MULTI-ELEMENT…The proposed (FeCuCrMnNiTi)N coating has prov-en itself as an anti-corrosion coating on most metal parts of mine production introduced in the mines of the Karaganda coal basin. This coating hardness is 2 – 3 times greater than hardness of stainless steels, which, alongside with low friction, leads to a significant in-creasing of the service life of mining machine parts. Such operational parameters have been achieved on coatings, the formation of which is conditioned to their self-organization at the high surface energy. The very process of self-organization of ion-plasma coatings re-quires further studies.AcknowledgementsIn the article there are used the materials of studies conducted within the framework of the dissertation for the degree of Candidate of Technical Sciences «Fea-tures of the formation of the structure and properties of multi-element ion-plasma coatings based on chromium-nickel steel» in specialty 05.16.09 - Materials Science (mechanical engineering).REFERENCES[1] Popov V., Sagalovych A., Sagalovych V. Hi-tech techno-logies based on advanced fundamental research. Tallin, Harju maakond, Estonia, (2020), 144.[2] Sevidova E.K., Gutsalenko Yu.G., Kryukova N.V. Increa-sed surface wear resistance nanostructured coatings. Elec-tronic processing of materials 50 (2014) 3, 92–94[3] Aliofkhazraei M., Nasar A., Chipara M., Laidani N., De Hosson J. Handbook of Modern Coating Technologies. Applications and Development. Elsevier (2021), 490.[4] Muboyajyan S.A. Erosion-resistant coatings for turbine compressor blades. Metals (2009) 3, 3–20.[5] Sheinman E. Superhard coatings from nanocomposites. Me-tal science and heat treatment of metals (2008) 12, 41–46[6] Yeremin E.N., Yurov V.M., Guchenko S.A., Syzdykova A.Sh. Structure and properties of steel coatings doped with aluminum. Eurasian Physical Technical journal 24 (2015) 2, 43-47.[7] Korotayev, A.D., Tyumentsev, A.N., Pinzhin, Yu.P., Ov-chinnikov, S.V., et al. Structural-phase state of nanocrystal-line coatings of metal nitrides. Physics and Chemistry of Materials Processing 32 (2006) 6, 32-40.[8] Gerasev A.P. Non-equilibrium thermodynamics of auto-wave processes in the catalyst layer. Success of Phys. Science 174 (2004) 10, 1061-1087.[9] Yelkin Yu.E. Autowave processes. Mathematical Biology and Bioinformatics 25 (2006) 1, 27-40.[10] Mekhtiyev, A.D., Bulatbayev, F.N., Taranov, A.V., Neshi-na, Y.G., Alkina, A.D. Use of reinforcing elements to im-prove fatigue strength of steel structures of mine hoisting machines (MHM). Metalurgija 59 (2020) 1, 121-124Note:  Translated from Russian into English by N. Drak, translator  of Karaganda Technical University

Formation of the structure and properties of multi-element ion-plasma coatings

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