Vol. 26 No. 4 2024 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. 26 No. 4 2024 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, V.P. Larionov Institute of the Physical-Technical Problems of the North of the Siberian Branch of the RAS, Yakutsk; Alexander S. Yanyushkin, D.Sc. (Engineering), Professor, I.N. Ulianov Chuvash State University, Cheboksary
Vol. 26 No. 4 2024 5 CONTENTS OBRABOTKAMETALLOV TECHNOLOGY Manikanta J.E., Ambhore N., Shamkuwar S., Gurajala N.K., Dakarapu S.R. Investigation of vegetable-based hybrid nanofl uids on machining performance in MQL turning........................................................................................... 6 Dama Y.B., Jogi B.F., Pawade R., Kulkarni A.P. Impact of print orientation on wear behavior in FDM printed PLA Biomaterial: Study for hip-joint implant...................................................................................................................... 19 GrinenkoA.V., ChumaevskyA.V., Sidorov E.A., Utyaganova V.R.,AmirovA.I., Kolubaev E.A. Geometry distortion, edge oxidation, structural changes and cut surface morphology of 100mm thick sheet product made of aluminum, copper and titanium alloys during reverse polarity plasma cutting...................................................................................... 41 Somatkar A., Dwivedi R., Chinchanikar S. Comparative evaluation of roller burnishing of Al6061-T6 alloy under dry and nanofl uid minimum quantity lubrication conditions............................................................................................... 57 Karlina Yu.I., Konyukhov V.Yu., Oparina T.A. Assessment of the quality and mechanical properties of metal layers from low-carbon steel obtained by the WAAM method with the use of additional using additional mechanical and ultrasonic processing..................................................................................................................................................... 75 EQUIPMENT. INSTRUMENTS Yusubov N.D., Abbasova H.M. Systematics of multi-tool setup on lathe group machines............................................... 92 Toshov J.B., Fozilov D.M., Yelemessov K.K., Ruziev U.N., Abdullayev D.N., Baskanbayeva D.D., Bekirova L.R. Increasing the durability of drill bit teeth by changing its manufacturing technology......................................................... 112 Pospelov I.D. Investigation of the distribution of normal contact stresses in deformation zone during hot rolling of strips made of structural low-alloy steels to increase the resistance of working rolls..................................................... 125 Ablyaz T.R., Blokhin V.B., Shlykov E.S., Muratov K.R., Osinnikov I.V. Manufacturing of tool electrodes with optimized confi guration for copy-piercing electrical discharge machining by rapid prototyping method.......................... 138 MATERIAL SCIENCE Shubert A.V., Konovalov S.V., Panchenko I.A. A review of research on high-entropy alloys, its properties, methods of creation and application.................................................................................................................................................. 153 Syusyuka E.N., Amineva E.H., Kabirov Yu.V., Prutsakova N.V. Analysis of changes in the microstructure of compression rings of an auxiliary marine engine.......................................................................................................... 180 Dudareva A.A., Bushueva E.G., Tyurin A.G., Domarov E.V., Nasennik I.E., Shikalov V.S., Skorokhod K.A., Legkodymov A.A. The eff ect of hot plastic deformation on the structure and properties of surface-modifi ed layers after non-vacuum electron beam surfacing of a powder mixture of composition 10Cr-30B on steel 0.12 C-18 Cr-9 Ni-Ti............................................................................................................................................................................. 192 Boltrushevich A.E., Martyushev N.V., Kozlov V.N., Kuznetsova Yu.S. Structure of Inconel 625 alloy blanks obtained by electric arc surfacing and electron beam surfacing........................................................................................... 206 Sablina T.Y., Panchenko M.Yu., Zyatikov I.A., Puchikin A.V., Konovalov I.N., Panchenko Yu.N. Study of surface hydrophilicity of metallic materials modifi ed by ultraviolet laser radiation........................................................................ 218 EDITORIALMATERIALS 234 FOUNDERS MATERIALS 243 CONTENTS
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 Study of surface hydrophilicity of metallic materials modifi ed by ultraviolet laser radiation Tatyana Sablina a, *, Marina Panchenko b, Ilya Zyatikov c, Aleksey Puchikin d, Ivan Konovalov e, Yurii Panchenko f Institute of High Current Electronics of the Siberian Branch of the Russian Academy of Sciences, 2/3 Akademichesky Avenue, Tomsk, 634055, Russian Federation а https://orcid.org/0000-0002-5941-5732, sabltat@mail.ru; b https://orcid.org/0000-0003-0236-2227, panchenko.marina4@gmail.com; c https://orcid.org/0000-0003-3219-9299, zyatikov@lgl.hcei.tsc.ru; d https://orcid.org/0000-0001-6931-9800, puchikin@lgl.hcei.tsc.ru; e https://orcid.org/0000-0002-1166-1416, ivan@lgl.hcei.tsc.ru; f https://orcid.org/0000-0001-8017-7268, yu.n.panchenko@mail.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. 2024 vol. 26 no. 4 pp. 218–233 ISSN: 1994-6309 (print) / 2541-819X (online) DOI: 10.17212/1994-6309-2024-26.4-218-233 ART I CLE I NFO Article history: Received: 24 September 2024 Revised: 05 October 2024 Accepted: 14 October 2024 Available online: 15 December 2024 Keywords: Ultraviolet laser radiation Surface Laser treatment Hydrophilicity TiNi alloy Stainless steel Contact angle Funding This work was carried out with the fi nancial support of Russian Federation represented by Ministry of Science and Higher Education (project No. 075-152021-1348). ABSTRACT Introduction. Surface modifi cation using laser radiation is a promising direction in the fi eld of creating new technologies for treatment metal materials, including those for medical purposes. The ability of lasers to change the surface characteristics of a material and, consequently, its interaction with the environment has attracted great interest among researchers. Despite numerous recommendations for the use of laser surface treatment, there is still lack of systematic and detailed studies on the infl uence of parameters on the structural-phase state and properties of the modifi ed surface, especially concerning ultraviolet laser exposure. The purpose of this work is to study the hydrophilicity of the surface of TiNi alloy and stainless steel after UV laser treatment. Materials and methods of the study: experimental samples made of TiNi (TN-10) alloy and 12KH18N9T (AISI 321) stainless steel were locally (beam diameter 0.5 cm) exposed to a solid-state Nd:YAG laser at the wavelength of 266 nm, with a pulse duration of ~ 5 ns, and pulse repetition rate of 10 Hz. The material was exposed to a constant output radiation energy density of 0.1 J/cm2, with a change in the exposure duration from 10 to 600 s. Before and after UV laser treatment, the wettability of the material surface and free surface energy were determined. The structure, elemental and phase composition, and surface topography of TiNi and steel were studied using scanning electron microscopy with the determination of the elemental composition by energy-dispersive spectroscopy, X-ray phase analysis, and profi lometry. Results and discussion. Ultraviolet laser treatment of the surface of TiNi alloy and steel samples leads to an increase in their hydrophilicity. In the initial state, the contact angle of wetting is ≈75° for both materials, and after ultraviolet laser treatment it decreases to ≈11-13° for TiNi and to ≈22° for steel. The phase composition of steel does not change during laser treatment, and phases belonging to oxides are recorded on the surface of TiNi after 420 seconds of treatment. Ultraviolet laser treatment of TiNi alloy and steel leads to an increase in free surface energy, a change in the ratio of its components (a decrease in the dispersed component and a signifi cant increase in the polar component), an increase in the oxygen content on the surface of both materials. With long laser exposure times (more than 300 seconds), microcracking occurs on the surface of the processed material, leading to an increase in roughness. The change in the surface topography (roughness) of TiNi alloy does not have a noticeable eff ect on the wettability of the surface of metal materials, and for steel samples, there is an insignifi cant tendency to reduce the contact wetting angle with increasing roughness. The degree of hydrophilicity of metal materials, characterized by the contact wetting angle, increases with an increase in the duration of laser exposure due to saturation of the surface with free oxygen and an increase in free surface energy (its polar component). Based on the studies, it can be concluded that ultraviolet laser treatment is an eff ective way to change the wettability of metal materials. For citation: Sablina T.Y., Panchenko M.Yu., Zyatikov I.A., Puchikin A.V., Konovalov I.N., Panchenko Yu.N. Study of surface hydrophilicity of metallic materials modifi ed by ultraviolet laser radiation. Obrabotka metallov (tekhnologiya, oborudovanie, instrumenty) = Metal Working and Material Science, 2024, vol. 26, no. 4, pp. 218–233. DOI: 10.17212/1994-6309-2024-26.4-218-233. (In Russian). ______ * Corresponding author Sablina Tatyana. Yu., Ph.D. (Engineering), Engineer Institute of High Current Electronics of the Siberian Branch of the Russian Academy of Sciences, 2/3 Akademichesky Avenue, 634055, Tomsk, Russian Federation Tel.: +7 913 843-21-78, e-mail: sabltat@mail.ru Introduction The main methods of changing the surface properties of metallic materials, used both in technology and medicine, are various types of surface treatment [1–5]. Surface modifi cation using concentrated energy fl ows is one of the promising areas in the fi eld of creating new technologies for treating metallic materials,
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 including materials for medical purposes (biomaterials) [1, 6–10]. The main purpose of surface treatment of metallic biomaterials is to obtain a modifi ed layer with specifi c properties on the material surface. Such surface characteristics as wettability, surface energy, roughness, phase and chemical composition have a signifi cant impact on the biocompatibility of materials in a physiological environment. In this case, both the corrosion properties and the ability to integrate biomaterials into living biological tissues largely depend on the wettability of these materials with biological fl uids, aqueous solutions of salts and acids [4, 6, 7, 9, 11, 12]. In terms of interaction with biological fl uids, cells and tissues, a hydrophilic surface is more preferable than a hydrophobic one. Unlike conventional materials, the surface of implants with increased hydrophilicity provides higher rates of osseointegration, i.e. interaction of biomaterial with bone tissue without the participation of connective tissue [13]. The ability of lasers to change the surface characteristics of material and, consequently, its interaction with the environment has attracted great interest among researchers in using this unique feature to improve the material behavior in biological environments [9, 11, 12, 14–17]. The advantage of using laser radiation for modifying the surface of various materials is that laser treatment is an environmentally friendly, noncontact and relatively fast method, and this method of treatment is characterized by high accuracy and the possibility of local infl uence. By adjusting the parameters of laser treatment, it is possible to selectively change the surface of the material without aff ecting its internal structure and volumetric properties. Nowadays, lasers are increasingly used as a tool for modifying the surface of various metallic materials and devices which are used as biomedical materials in cardiology, orthopedics and dentistry and other areas [11, 18–20]. The works [1, 5, 9, 11, 14, 18–22] note that lasers are mainly used to modify the surface of metal implants in order to improve osseointegration, corrosion resistance and hydrophilicity. Metallic biomaterials based on titanium and its alloys, as well as stainless steel, are used in the manufacture of artifi cial heart valves, pacemakers, stents for blood vessels, bone and joint endoprostheses (shoulder, knee, hip, elbow), for auricles reconstruction, in facial surgery, and also as dental implants. These biomaterials prevail over other classes of biomaterials due to the synergistic combination of excellent mechanical properties, corrosion resistance and wear resistance, as well as long-term biocompatibility [12, 14, 19, 20, 23, 24]. Recently, controlled laser treatment has been actively studied to change the topography, morphology, and physicochemical properties of the surface of biomaterials, including with the aim of reducing bacterial adhesion on the surface of implants and, thus, tuning its biological and other surface properties [11, 16, 17, 20, 22, 25]. In vitro and in vivo studies have been conducted to estimate the eff ect of laser treatment on adhesion, cell growth and proliferation, wettability, surface hardness, mechanical properties, surface morphology, antibacterial properties, and biofi lm formation on the surface of implants [13, 15–17, 20, 23, 25, 26]. It should be noted that basically all studies on laser treatment on materials surface aimed at changing the morphology, topography and properties of the materials surface were carried out using radiation with a wavelength of λ = 1,064 nm or λ = 532 nm with high values of energy density or power [10, 15, 17, 25, 27]. Works on the study of the eff ect of ultraviolet (UV) laser radiation (λ < 400 nm) on the surface of materials are not many [20, 28, 29]. However, despite numerous recommendations on using laser surface treatment, there is still lack of systematic and detailed studies of the eff ect of laser radiation parameters on the structural-phase state and properties of the modifi ed surface of metallic materials. The purpose of this work is to study the hydrophilic behavior of the surface of TiNi alloy and stainless steel after UV laser treatment. The objective of this study is to conduct a comparative analysis of the contact angle, structure, topography, phase and chemical composition of the surface of TiNi and steel specimens before and after laser treatment with a change in the exposure duration. Materials and methods of investigation The experimental specimens in the form of plates with dimensions of 10×10×1.5 mm (length × width × thickness) made of an alloy based on titanium nickelide TiNi (TN-10), developed at the Research institute of
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 medical materials and implants with shape memory (Tomsk) (identifi cation mark — TiNi) and stainless steel 0.12 C-18 Cr-9 Ni-Ti (GOST 5632-72) (AISI 321) (identifi cation mark — steel) were taken for the study. The specimens were previously polished on SiC grinding paper of various grits P600–2500 (ISO6344) and then polished to gloss with diamond pastes ASM or ASN 3/2, 2/1, 1/0. To remove surfactant contamination after polishing, the specimens were washed in an ultrasonic bath (VGT-1620QTD, China) successively in alcohol and acetone for 10 minutes. Ultraviolet laser treatment was carried out in air at normal atmospheric pressure and room temperature (22 ± 3 °C). Experimental specimens were exposed to radiation of the 4th harmonic of Q-smart 850 Nd:YAG laser (Quantel, France) at the wavelength of 266 nm. Pulse duration was ~ 5 ns, pulse repetition rate was 10 Hz. Experimental scheme of laser treatment is shown in Fig. 1, a. The material was treated stationary, without moving the specimen and laser beam, at a constant radiation energy density of 0.1 J/cm2, and the duration of treatment was varied from 10 to 600 s. The area of exposure on the surface of the experimental specimens was limited by the diameter of the laser beam d = 0.5 cm (Fig. 1, b). a b Fig. 1. Experimental scheme of UV laser treatment of specimen surface Before and after UV laser treatment, the wettability of the materials surface was determined using the sessile drop method of test liquids (deionized water, glycerin) with known properties of surface energy at the contact angle. Contact angle was measured by photographing a drop on the surface of the material. To do this, a 3 μl drop of liquid from a micropipette was applied to the horizontal surface of the metallic material, after which the drop was photographed so that the optical axis coincided with the plane of the material surface and the drop. The height h and the length of the baseline 2r of the drop were measured from the obtained photographs (Fig. 2), and the contact angle (Θ) was calculated using the semi-angle method using formulas (1, 2): 1 1Þ Þtan / , h r − Θ = (1) 1, Þ Þ 2 Θ= Θ (2) where h is the height; r is the half of baseline length. At least 5 series of contact angle measurements were carried out for the original surface and for each treatment mode. Fig. 2. Scheme of measuring the wetting contact angle
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 The free surface energy γs of the material before and after laser treatment was determined by the Owns – Wendt – Rabel – Kjelble (OWRK) method [30], using known reference data on surface tension, dispersed γd and polar γp components of the test liquids (water and glycerin) and the obtained data on the contact angle. The surface topography of TiNi alloy and steel before and after laser treatment was studied using the contact method with a profi lometer for tribological tests (Tt-Tribotechnic, France) equipped with a high resolution diamond needle (7.55 nm along the Z axis) without a sliding element. The roughness Ra, averaged over the entire length of the baseline equal to 3 mm, was measured in accordance with GOST 2789-73. At least 5 measurements were performed for each specimen. The structure and elemental composition of the materials surface before and after treatment were estimated using data obtained using a scanning electron microscope (SEM) (VEGA 3 TESCAN, Czech Republic) equipped with an energy dispersive analyzer (EDS). The phase composition of TiNi and steel specimens in the initial state and after laser treatment was determined from diff raction patterns obtained on a DRON-type X-ray diff ractometer (Burevestnik, St. Petersburg, Russia) with fi ltered CuKα radiation in the range of scanning angles 2Θ 30°–110°. Qualitative and quantitative analysis of X-ray diff raction (XRD) patterns was carried out using the PDWin and CDA software packages (OJSC Burevestnik, St. Petersburg, Russia). Results and discussion Measuring and determining the contact angle with deionized water is the simplest method for studying the wettability of material surfaces. Fig. 3 shows the graphs of the dependence of the contact angle of TiNi and steel surfaces and the duration of UV laser treatment. The insets (Fig. 3) show typical images of water droplets on the specimen surfaces before and after laser treatment. In the initial state, the contact wetting angles for TiNi and steel specimens are similar, measuring 75.0 ± 5.1° for TiNi and 75.4 ± 5.4° for steel. Ultraviolet laser treatment alters the hydrophilicity of both TiNi alloy and steel surfaces. The contact angle decreases as the UV laser treatment duration increases. Already after 10 s of treatment, a signifi cant reduction in the contact angle is observed for both materials compared to its initial state. For TiNi specimens, the contact angle decreases more than twofold, while for steel specimens, it decreases by approximately 30 %. A sharp decrease in the contact angle is seen up to 120 s of treatment. With a further increase in the duration of treatment, the contact angle for TiNi specimens remains virtually unchanged at 11–13°, while for steel specimens, it continues to decrease gradually, reaching a minimum value of 22.6 ± 4.2° after 600 s of laser treatment. As observed in Fig. 3, increasing the duration of UV laser treatment reveals diff erences in the kinetics of contact angle changes for TiNi and steel specimens. The contact angle of TiNi decreases faster and more signifi cantly compared to steel as the treatment duration increases. Moreover, the minimum values of the contact angle also diff er. For the same duration of ultraviolet laser treatment, the contact angle of TiNi specimens is 1.5-2 times lower than that of steel ones. Therefore, ultraviolet laser treatment of TiNi and steel specimens’ surfaces eff ectively alters its hydrophilic behavior, making the TiNi alloy more hydrophilic than steel with the same laser treatment parameters. Since the wettability of materials is regulated by a thin surface layer (the fi rst atomic layers of the surface), any change in the physicochemical properties of this layer can signifi cantly aff ect it [31]. Currently, there is no consensus among researchers regarding the mechanisms of changing hydrophilicity through various surface modifi cation methods. Numerous hypotheses exist about the causes of changes in the degree of hydrophilicity of materials, and these hypotheses are often contradictory. Surface wettability is greatly infl uenced by the phase and chemical composition of the surface, the surface microgeometry factor, its texture, roughness, structure, as well as the surface polarity, which is one of the important characteristics aff ecting the affi nity for water [21, 22, 27, 32]. One hypothesis suggests that a decrease in the contact angle, indicating an increase in hydrophilicity, may result from cleaning the surface of materials from organic contaminants [4, 33–35]. On the one hand, it is known that contamination of the metal surface with organic compounds with a predominance of hydrocarbon groups in the molecule leads to surface hydrophobization, therefore, removal of these organic contaminants from the surface of materials can lead to a moderate increase in surface hydrophilicity [35]. At the same time, a number of studies report the absence of an eff ect
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 of cleaning the surface from organic contaminants on its hydrophilicity [36, 37]. On the other hand, metal oxides have increased hydrophilicity and can chemically alter the surface wettability due to its strong affi nity for hydroxylation [27, 38]. An increase in hydrophilicity can also result from the process of photooxidation during surface treatment [35]. In particular, titanium dioxide becomes superhydrophilic when exposed to UV radiation due to its photocatalytic activity [39]. Several studies [26, 40] have reported on the laser oxidation of metal surfaces both during irradiation in water and in air, which is associated with possible processes of excitation, ionization, and dissociation of atmospheric oxygen. It is known that laser treatment, which causes surface oxidation and increases the oxygen content on the treated surfaces, can enhance its hydrophilicity [27]. However, a thin oxide fi lm on the surface of metals does not prevent further interaction with oxygen [15, 41–43]. Therefore, in this study, a change in the hydrophilicity of metallic materials can also be attributed to the saturation of the surface with atmospheric oxygen and its subsequent oxidation. The data on the change in the amount of oxygen on the surface of TiNi and steel after UV laser treatment, obtained using EDS during SEM study and XRD analysis, presented in Figs. 4–7, indicate the saturation of metallic surfaces with oxygen and the formation of an oxide fi lm during ultraviolet laser treatment. Figs. 4 and 5 show SEM images of TiNi and steel specimens with the results of EDS analysis in the initial state and after laser treatment. According to the data obtained from scanning electron microscopy, the structure of the TiNi specimens consists of a TiNi matrix (light areas) and a small amount of TiC precipitates (dark areas) (Fig. 4, a). The elemental composition of the matrix primarily consists of Ti and Ni in a ratio that is close to equiatomic, and an insignifi cant amount of Mo and Fe. Additionally, the matrix contains carbon and a small amount of oxygen. The secondary phase precipitates contain Ti, C and Ni (Fig. 4, b). After 300 s of laser treatment, there is an observed increase in the oxygen content by approximately 10 times (Fig. 4, c), and a further increase in the treatment duration to 600 s results in an even more substantial increase in oxygen levels on the material’s surface (Fig. 4, d). For the steel specimens subjected to UV laser treatment durations of 60–300 s, only minor changes in the oxygen concentration on the surface are observed, whereas after 600 s of treatment, the oxygen content increases to approximately 13 at. % (Fig. 5). UV laser treatment results in an increase in the amount of oxygen on the surface. When comparing the oxygen levels on the surfaces of TiNi and steel specimens after UV laser treatment, it is evident that, under identical treatment conditions, the oxygen concentration on the TiNi specimens is signifi cantly higher than that on the steel specimens. This diff erence may be attributed to the presence of a substantial amount of Fig. 3. The dependence of contact wetting angle on the duration of UV laser treatment
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 а b c d Fig. 4. SEM images of Ni-Ti alloy specimens with the results of EDS analysis before (a, b) and after UV laser treatment for 300 s (c), 600 s (d) titanium in the TiNi alloy, which has a higher electronegativity and thus is considerably more chemically reactive in the presence of oxygen. Titanium is more prone to lose electrons and form oxides than iron, chromium, and nickel found in stainless steel. Additionally, titanium can lead to the formation of more stable oxides, such as TiO2, compared to the typical oxides formed in stainless steel. The oxide fi lm of TiO2 also exhibits a more ordered and compact structure than the oxides formed on stainless steel surfaces, such as chromium oxides. Figs. 4, d and 5, d illustrate that after 600 s of treatment, changes occur in the morphology of the TiNi and steel surfaces, leading to the formation of distinct surface textures on both materials. A crack network is observed on the TiNi surface, and the microcracking of a thin surface layer during long-term laser treatment is likely a consequence of the infl uence of the heat-aff ected zone caused by local heating during laser treatment, followed by rapid cooling after the end of treatment. This phenomenon is associated with the thermal gradient and stresses generated as a result of the rapid cooling of the treated material’s surface. Microcracking can also be caused by the diff erence in the coeffi cients of linear thermal expansion of the base material and the metal oxide formed on the metal surface during laser treatment. In contrast to the TiNi alloy, a granulated structure is developed on the surface of the steel specimens after 600 s of UV laser treatment. In [31], it was reported that similar granulated structures were observed on the surface of AISI 316L steel when subjected to laser irradiation at a wavelength of λ = 532 nm and a laser radiation power density of 1.1 J/cm². The formation of these structures was attributed to the rapid solidifi cation of the molten zone after ablation. The formation of such a structure on the steel surface under UV laser exposure can also be caused by thermal processes, such as melting and evaporation of the material. Diff erent surface morphology after UV laser treatment under identical conditions for TiNi and steel specimens is related to its diff erent thermophysical and chemical properties. Microcracking on the
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 surface of the TiNi alloy and the development of a granulated structure in steel contribute to an increase in the surface roughness Ra of the specimens, as indicated by the measurements of surface roughness of metallic materials before and after laser treatment. Initially, the Ra of the TiNi specimens is 40.9 ± 5.3 nm, while for the steel specimens, Ra is 27.7 ± 5.3 nm. Long-term UV laser treatment (600 s) results in a more than twofold increase in roughness: Ra increases to 82.3 ± 5.3 nm for TiNi and to 64.3 ± 6.2 nm for steel. Changes in surface topography (roughness) do not signifi cantly aff ect the wettability of the TiNi alloy surface, while for steel specimens, a slight tendency to decrease the contact angle with increasing roughness is noted. These results are consistent with the results presented in [20, 27], which emphasize the complex relationship between roughness and surface chemistry in changing hydrophilicity and biocompatibility. The formation of an oxide fi lm on the surface of TiNi specimens after UV laser treatment is further substantiated by data obtained through XRD. Figs. 6 and 7 illustrate the XRD patterns of TiNi and steel specimens both before and after laser treatment. The XRD pattern of the initial TiNi specimens (Fig. 6, a) and the XRD patterns of the specimens after UV laser treatment for 10, 120, and 300 s (Fig. 6, a) contain only the peaks corresponding to the B2 phase of TiNi (Ti49.5-Ni50.5) and the phase TiC, which was formed during the material manufacturing process, with a volume fraction of 5–7 %. The XRD pattern obtained from TiNi specimens after 600 s of UV laser treatment (Fig. 6, a) indicates a change in phase composition. In addition to the primary B2 (TiNi) phase and TiC precipitates, peaks relating to the oxides TiO2 and Ti4Ni2Ox are also observed in the XRD pattern (Fig. 6, b). The oxide phases identifi ed on the surface of TiNi specimens after long-term laser treatment are most likely present on the surface of both the initial specimens and the specimens with a short duration of laser exposure, as evidenced by the data on the oxygen content on the surface obtained using EDS. Apparently, Fig. 5. SEM images of stainless steel specimens with the results of EDS analysis: initial surface (a), surface after UV laser treatment for 60 s (b), 420 s (c), 600 s (d) а b c d
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 the small thickness of the oxide fi lm (no more than 20 nm in accordance with [41–43]) and the insignifi cant amount of oxides, not exceeding 3 % of the sensitivity threshold of XRD method, do not allow to detect the oxides on the surface of TiNi by the XRD method. In the XRD patterns of steel (Fig. 7) before and after laser treatment, only phases identifi ed as austenite and ferrite in a ratio of 75:25 were recorded. Even with UV laser treatment for 600 s, phases belonging to oxides could not be detected in steel specimens by the XRD method, which may also be due to limitations of the XRD method. a b Fig. 6. XRD patterns of Ni-Ti alloy specimens in the initial state (a, 1) and after UV laser treatment for 60 s (a, 2), 120 s (a, 3), 300 s (a, 4) and 600 s (a, 5; b) Fig. 7. XRD patterns of stainless steel specimens before (a) and after UV laser treatment for 60 s (b), 420 s (c) and 600 s (d)
OBRABOTKAMETALLOV MATERIAL SCIENCE Vol. 26 No. 4 2024 It is assumed that revealed surface changes of the studied materials as a result of laser treatment aff ect the free surface energy. Fig. 8 shows the dependences of the free surface energy for TiNi (Fig. 8, a) and steel (Fig. 8, b) specimens on the duration of UV laser treatment. For both materials, with increasing duration of UV laser treatment, a signifi cant increase in free surface energy is observed. After laser exposure, a change in the ratio of dispersed γd and polar γp components of surface energy occurs. If in the initial state for both materials the ratio γp/γd was approximately 50/50, then after irradiation a decrease (more than 2 times) in the dispersed component and a signifi cant increase in the polar component are observed. With an increase in the duration of laser treatment, the value of dispersed component γd changes insignifi cantly and does not exceed 10 mJ/m2, while the value of polar component γ p increases by 2–5 times. a b Fig. 8. Free surface energy γs and its components (polar γp and dispersed γd) of Ni-Ti alloy (a) and stainless steel (b) depending on the duration of UV laser treatment Such a signifi cant increase in the polar component indicates the surface activation as a result of laser treatment and indicates the presence of polar functional groups on the surface (-OH, oxides, carboxyls), which are capable of forming hydrogen bonds with liquid molecules and contribute to increased hydrophilicity. Thus, an increase in free surface energy and a signifi cant increase in its polar component during UV laser treatment of both TiNi and steel specimens are associated with the saturation of metallic materials surface with atmospheric oxygen, its additional oxidation and the formation of an oriented layer on the surface, in which the polar groups of molecules responsible for the generation of the polar component are facing the air. Conclusion 1. The study demonstrates that ultraviolet laser treatment of the surfaces of TiNi and steel specimens enhance hydrophilicity. In the initial state, the contact wetting angle is ≈75° for both materials, but after UV laser treatment, it decreases to 11–13° for TiNi and ≈22° for steel. 2. An increase in the duration of UV laser treatment results in a tenfold or greater increase in the amount of oxygen on the surfaces of the metal materials compared to its initial state. The long-term laser treatment (600 s) causes changes in the surface morphology of the treated materials and an increase in roughness. 3. Ultraviolet laser treatment of the surfaces of metal materials leads to an increase in free surface energy from 32.4 mJ/m² to 76.5 mJ/m² for TiNi specimens and from 29.8 mJ/m² to 71.4 mJ/m² for stainless steel specimens, primarily due to a signifi cant increase in the polar component.
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