Production of the Ti-Zr-Nb biomedical alloy powder and its application in the metal cored wire for DED-Arc-M process

Production of the Ti-Zr-Nb biomedical alloy powder and its application in the metal cored wire for DED-Arc-M process | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Production of the Ti-Zr-Nb biomedical alloy powder and its application in the metal cored wire for DED-Arc-M process Serhiy Schwab, Roman Selin, Mykhailo Voron, Taras Yanko, Maksym Khokhlov This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5043610/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 5 You are reading this latest preprint version Abstract The use of biomedical titanium alloys is gaining more and more interest and attention. In this work, the Ti-Zr-Nb system alloy was produced and studied, as well as its powder, that was obtained by the Hydrogenation-Dehydrogenation method. The problem of using powders obtained by this method is shown. Based on obtained powder, an experimental metal powder wire was made, which was used as filler material for TIG surfacing. As a result, a multilayer deposited detail was obtained, of which the microstructure and properties (modulus of elasticity and microhardness) were investigated. Biomedical titanium alloy electron-beam casting Ti-Zr-Nb titanium powder HDH cored wire DED-Arc-M Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 Figure 17 1. Introduction The use of titanium alloys in endoprosthetics has been intensively developing during the last thirty years due to its unique biocompatibility and the combination of mechanical and biomechanical properties [ 1 ]-[ 3 ]. The study of titanium and its alloys as materials for endoprosthetics has achieved excellent results, which is proven by many years of positive experience in their use. At the same time, new alloys are constantly being developed, which are getting better and better in terms of their operational properties than the existing ones. Solving the problem of finding the optimal compositions of titanium alloys for endoprostheses allows to significantly improve most types of endoprostheses - reduce the risk of rejection reaction, reduce toxicity, increase service life, adjust mechanical properties, etc. Biocompatibility is considered the most important among all parameters of medical alloys. From this point of view, the presence of a number of alloying elements in titanium alloys is undesirable. Vanadium in the Ti6Al4V alloy, for example, which, although it was recognized as non-toxic as early as 1986, is still being avoided in use due to the possibility of its penetration into the body through friction products of pairs of endoprostheses (friction pair "femur - hip joint"), when the integrity of the TiO2 oxide film is broken. According to [ 3 ], vanadium, entering the body, damages the reproductive system, causes kidney diseases and causes a general toxic reaction of cells upon contact. For this reason, in many countries, as early as the 80s, researches were conducted on the possibility of creating and using vanadium-free compositions [ 3 ]-[ 5 ], which led to the development of alloys known today as Ti-6Al-7Nb, Ti-5Al-2 ,5Fe, Ti-12Mo-6Zr-2Fe, Ti-15Mo-2.8Nb-0.2Si, Ti-11Mo-11Nb, Ti-35Nb-2Ta-3Zr, etc. The problems of ensuring full biocompatibility of alloys for endoprosthetics and their solution are the main driving force of research in the development of new titanium alloys. As a result of these studies around the world, many experts have come to the conclusion that the most effective alloying elements are the ones that do not reduce the biocompatibility of titanium and are safe for the human body. Among them are Nb, Ta, Zr, Sn and to some extent - Mo [ 3 ], [ 5 ]-[ 6 ]. Titanium-zirconium alloys and Ti-Zr-Nb alloys have the most promising combination of strength and modulus. Double Ti-Zr alloys are characterized by strength in the range of 600...1450 MPa and modulus of elasticity of 72...110 GPa, while Ti-Zr-Nb compositions have strength in the range of 600...1000 MPa and modulus of elasticity in the range of 58...80 GPa, which is much better than the combination of the same parameters in the Ti6Al4V alloy [ 7 ]. Having analyzed the relevance of using low-modulus titanium alloys for endoprosthetics and the technology of manufacturing finished products from them, which involve the presence of rods for fixation, or other loaded and massive elements, it was concluded that the DED-Arc (Direct Energy Deposition-Arc) Additive Manufacturing (AM) technique, which is also known as Wire and Arc AM (WAAM), method is appropriate as an alternative to existing additive manufacturing methods. Despite the large number of studies on the production of parts by the DED-Arc-M, the majority of research is confined only to the production of parts using solid wires. There are practically no studies on the use of flux-cored wire for obtaining parts from titanium alloys by this method. The use of flux-cored wire in the production of parts by the DED-Arc-M makes it possible to produce parts from titanium alloys of various compositions and significantly increase the range of titanium alloys that can be used to produce parts by this method. Based on above mentioned, the following tasks were set: obtaining an alloy based on the Ti-Zr-Nb system, manufacturing a powder from obtained alloy, developing a metal powder wire based on this alloy, using it in multilayer surfacing, and studying the structure and properties of the obtained samples. 2. Materials and methods 2.1. Obtaining the Ti-Zr-Nb system alloy Obtaining finished products from the Ti-Zr-Nb system alloy remains a multi-stage, complex and very expensive process. According to the conventional technological cycle, such production involves multiple (at least two times) vacuum-arc remelting, deformation of the ingot, and its subsequent mechanical and thermal treatment [8]. As an alternative, you can consider atomizing the ingot to obtain powder and subsequent 3D printing from it, but the most profitable way from an economic point of view is obtain products using casting technologies. The most versatile and multifunctional casting method for obtaining castings from titanium and its alloys is the electron-beam casting technology (electron-beam garnish melting), developed at the Physical and Technological Institute of Metals and Alloys of the NAS of Ukraine, [9]-[10]. This method allows for the preparation of the wide range of alloy melts based on refractory and highly reactive metals, alloys based on intermetallics, special and complex titanium alloys, which include the biomedical alloy of Ti-Zr-Nb systems. Under the conditions of electron-beam garnish melting, melts are prepared in a vacuum inside a copper water-cooled crucible and the skull is frozen on its inner walls. In the process of melting, the charge is placed inside the skull, melted to form a liquid metal surface and exposed to electromagnetic stirring (EMS). The power of electron beam heating (EBH) should increase gradually in the process of melting and electromagnetic stirring. In this way, an increase in the volume of liquid metal is achieved, which is controlled by measuring the temperature of the water that cools the crucible. When the temperature stops rising, the corresponding increase in the volume of the liquid metal also stops. All experimental melting was carried out in a mode that provided for gradual melting of the charge for 30-40 minutes at an electron-beam heating power of 12-24 kW. Then, for 20-30 minutes under the action of EMS, the EBH gradually increased to 60 kW until the cooling water temperature growth stopped. After that, for 5-10 minutes, the final stage of preparing the melt was carried out at the EBH power around 70 kW and the melt was poured into the mold. Next, the chemical composition of the resulting castings was investigated. Dual alloys of the Ti-Zr and Ti-Nb systems had relatively minor deviations from the expected chemical composition. The results of experimental melts showed that zirconium in titanium is absorbed completely, and small deviations from the exact chemical composition are mostly associated with the dissolution of the skull metal. Niobium, due to its greater density, is absorbed worse and settles to a greater extent on the walls and bottom of the garnish. The simultaneous fusion of titanium, zirconium and niobium in almost equal proportions showed the predominant role of niobium in the process of preparing the melt. All three metals are infinitely soluble in each other. At the same time, niobium has the highest density, heat capacity and melting point. These factors most likely contribute to the formation of the melt volume precisely on the basis of niobium. In the process of melting this alloy, there was an active growth of the "garnishment collar" - a metal ring above the level of the liquid metal bath. The chemical composition of this formation contained mainly titanium and zirconium. Differences in the chemical composition in the different parts of each of the castings were less than 1%. For a preliminary assessment of their quality, a visual inspection and mechanical processing were carried out (Fig. 1). The microstructure study of the alloys was carried out simultaneously with the analysis of the distribution of chemical elements (Fig. 2). The presented structures are homogeneous and clearly reflect the dependence of the structural phase state of titanium alloys on their chemical composition. Thus, in the cast state, the Ti-13Zr-13Nb alloy has the smallest amount of β-phase. The conditions of crystallization of the casting and its chemistry do not allow recording the β-structure. Instead, there are hardening type structures. EDX analysis of the sample shows a uniform distribution of elements. Thus, it can be stated that in the EBM conditions, the production of titanium alloys castings with a high content of zirconium and niobium in wide concentration ranges allows to achieve high quality alloys, their uniform structure and chemical composition. 2.2. Production of Ti-13Zr-13Nb alloy powders The creation of metal powder wires based on titanium alloys for various purposes solves an urgent problem in the field of modern additive technologies, namely, their use allows obtaining high-quality multilayer samples [11]. One of the important and complex technological processes in the production of metal powder wires is the preparation of their core - the metal component, that is, the powder itself. Today, we have the opportunity to use two methods of producing titanium-based powders: Hydrogenation-DeHydrogenation (HDH) and Plasma Rotating Electrode Process (PREP). 2.2.1. Production of Ti-13Zr-13Nb alloy powder by HDH method HDH technology (Fig. 3) is based on the property of hydrogen to reduce the strength of metallic titanium (brittleness). The essence of the process is described by the reverse reaction of hydrogenation-dehydrogenation Ti + H2 ↔ TiH2 [12]-[13]. Under certain conditions (temperature, pressure), titanium and its alloys are saturated with hydrogen. The obtained titanium hydride is easily crushed into fractions in the range of 5...250 μm. Next, the resulting powder is subjected to high-temperature processing in a vacuum to remove hydrogen. This technology for the production of titanium powders by the HDH method includes the following main technological operations: - preparation and loading of primary charge materials (sponge titanium, ingots, blanks, scrap, etc.); - hydrogenation of titanium material; - grinding of titanium hydride; - screening of hydride titanium powder; - degassing of titanium powder The main advantages of the technology for the production of titanium powders by the HDH method: - the use of hydrogen technology allows obtaining titanium powders with a low content of impurities; - obtaining a wide range of powder particle sizes from 250 to 5 μm; - a closed cycle for the use of water and gases allows to organize ecologically clean production; - HDH technology allows processing a wide range of materials containing titanium (sponge titanium, titanium scrap, shavings, waste, etc.) into powders. To obtain Ti-13Zr-13Nb alloy powder, the method of hydrogenation of the cast alloy was used. In the process of hydrogenation, the workpiece was heated to a temperature of about 900 ºС, followed by hydrogen treatment. In the process of hydrogen saturation, deformation of crystal lattices took place, which led to embrittlement of the material. Due to this, it was possible to grind the alloy into powder. After grinding the alloy, the powder was classified into fractions. The fraction (5...50 μm) required for the research was subjected to thermal vacuum treatment to remove hydrogen from the powder (Fig. 4). 2.2.2. Obtaining of Ti-13Zr-13Nb alloy powder by the PREP method The PREP method [14] is as follows: the sputtering alloy electrode rotates around a horizontal axis, and its free end is melted using a plasma torch. Drops of molten metal break off from the rotating electrode and crystallize in free flight before hitting the walls of the spray chamber. In the chamber where the electrode rotates and spraying takes place, there must be an environment protecting against oxidation. This makes it possible to obtain powders with high surface purity (Fig. 5). The powder particles are smooth, spherical in shape, the average particle size is 200 μm, the yield of particles with sizes from 50 to 500 μm is 75%. One of the advantages of powders obtained by this method is their high fluidity and purity (low oxygen content). The disadvantage of this material when used as a core is the spherical shape of the granules - during welding, they are not tightly held in the formed tube and fly apart under the pressure of the welding arc. In order to avoid such problems, it is necessary to carry out preliminary work on changing the shape of particles, namely their deformation, which is a rather long process and requires special equipment (Fig. 6). For the above reasons, it is of interest to use the metal component of the core of metal powder wires obtained by another method. That is why further experiments on obtaining a wire were carried out with powder obtained by the HDH method, with a size of 5...50 μm. 2.3. Production of metal cored wire based on Ti-13Zr-13Nb alloy The development and production of metal cored wire based on Ti-13Zr-13Nb titanium alloy was carried out by the metal dragging method on the installation (Fig. 7), which is designed for the production of titanium cored wires [15]. VT1-00 titanium foil with a thickness of 0.2 mm was used as the shell. It was established that the optimal linear speed during dragging after forming is a speed of 0.4 m/min, which ensures optimal pouring of the charge into the formed chute, and also eliminates the curvature of the output tube. Pulling was carried out using a set of dies with a step of 0.1 mm. The wire was fed into the spinneret in such a way that it is placed on the reel with the seam outward, since the stretching of the outer fibers leads to additional closure of the seam, and also eliminates distortion (corrugation). As the result, the wire with 3.0 mm diameter was obtained, with a filling factor of 65% (Fig.8). 2.4. Multi-layer deposition process with filler metal cored wire (DED-Arc-M) Multilayer TIG surfacing with the obtained metal cored wire based on medical titanium alloy was carried out on the equipment designed for TIG welding and surfacing of titanium-based alloys (Fig. 9). The process was carried out on a pre-determined mode: I W , = 210 A, Uarc = 12,7 V, Vweld = 8 m/h, Vwire = 34 m/h, Larc = 3,5 mm. 2.5. Methods used in research Flaw detection was carried out on the X-ray machine RAP 150/300 (of constant action) in transmission mode: I = 10 mA, F = 1000 mm, U = 110 kV, t = 2 min, control sensitivity: 0,16 mm, the image quality indicator is wired 10TIEN, film is FujiFilm IX800. The content of oxygen, nitrogen and hydrogen was determined by the method of reduction melting in the flow of the carrier gas. The oxygen content was determined on LECO RO-316 determinator, measurement sensitivity - 10–5 wt%; nitrogen content was determined on LECO TN-114 determinator, measurement sensitivity - 10–5 wt%; hydrogen content was determined on LECO RH-2 determinator, measurement sensitivity - 10-5–5 wt%. Microstructure studies were performed by electron microscopy on Tescan Vega 3 scanning electron microscope. It allows to obtain a topographic image in the mode of detection of secondary electrons (SE - secondary electrons) and an image by contrast according to the atomic weight of the components in the mode of detection of reflected electrons (BSE - backscattered electrons). Preference was given to the second mode. During microscopic studies, local chemical analysis of phases and EDX-mapping (color elemental distribution by their atomic weight) were determined by Bruker detector, installed on microscope. Studies of microhardness were carried out on a microhardness tester PMT-3 with a load on the indenter of 100 g. To study micromechanical properties of the obtained sample, microindentation testing was used on the “Micron-Gamma” device [16]-[18], which works according to the Oliver and Farr method of "An Improved technique for determining the hardness (H) and elastic modulus (E) using load displacement sensing indentation experiments" to determine microhardness, Young's modulus and plasticity coefficient by indentation diagrams, which are automatically recorded and processed during continuous loading/unloading of a diamond trihedral pyramidal Berkovich indenter according to ISO/FDIS 14577-1: 2015; Metallic materials - Instrumented indentation test for hardness and material parameters - Part 1: Test method (ISO Central Secretariat, Geneva, Switzerland). Testing was carried out with a 100 g load on the indenter which is a good general-purpose value for titanium alloys [16] and allows to eliminate possible size effect of such measurements and to obtain values which are more of an integral characteristic of a whole material and not of a particular structural element [17]-[18]. The step between each indentation is determined by the load value to eliminate the influence of adjacent measurements and was 100 μm. The sample was studied along all of the layers by its entire height and layer by layer for more detail and statistics. The step between measurements of each of the deposited layers was 1000 μm and they were done in their middle parts to eliminate the effect of interlayer boundaries. Typical diagrams of indentation show that curves for each measurement are similarly shaped and fall into a narrow value range which indicates that obtained layers have high uniformity and defects if any are negligible. 3. Results and discussion As a result of the experiments a 9-layer sample was obtained with metal cores wire based on the powder of the Ti-13Zr-13Nb alloy (Fig. 10). The wire melting process for this case was stable, the layers were deposited with a constant height (on average, the height of each layer is 1.6-1.8 mm), the width of the sample is about 11 mm and 15.2 mm high. The base is 6 mm thick pure titanium. The X-ray analysis did not reveal any significant defects, except for a small sized pores (up to 50 μm), which is allowed in welded titanium alloys. They are mostly located in the middle part of each layer (Fig. 11). Gas analysis was carried out for the ingot itself, for the powder and for the surfaced metal (Table 1). Table 1. Results of gas analysis of samples Research area [O], wt% [N] , wt% [H] , wt% Casting of the Ti-13Zr-13Nb alloy 0,82 0,034 0,026 HDH powder of Ti-13Zr-13Nb alloy 2,76 0,61 0,0157 The metal of the surfaced sample 1,35 0,072 0,0063 A significant increase in oxygen in the material is undoubtedly associated with a significant increase in the specific area of the material. Each particle of the alloy powder was covered with an oxide layer since titanium and zirconium are very prone to oxidation. It is possible that during the hydrogenation process, local overheating occurred during the exothermic hydrogenation reactions of titanium and zirconium. Some recrystallization of the alloy may have also occurred during grinding. This could've lead to local phase transitions with the formation of structures based on the Ti-Zr-Nb system, which have an increased affinity for oxygen. The decrease in oxygen content after the surfacing process is due to the fact that pure titanium foil was added to the content of the composite wire. A significant decrease in the specific surface area of the material also have occurred during the surfacing process. Presumably, this led to the migration of metal oxides to the surface, which led to reduced amount of total oxygen in the center of the detail. Oxygen alloying technologies of titanium alloys belong to the topic of economical alloying. Thanks to dosed alloying with elements such as oxygen, nitrogen and carbon, it is possible to increase the strength of alloys without the use of expensive alloying elements. The relatively low modulus of elasticity of the Ti-13Zr-13Nb alloy is accompanied by a decrease in strength. The technology of economical alloying with oxygen is proposed to eliminate this shortcoming [19-20]. This technology can be implemented by the method of passivation of the powder material after degassing. In the research process it was quite difficult to control the degree and speed of material passivation. Studies of the structural and phase characteristics and distribution of components of the surfanced metal were conducted. The macrostructure of the sample is represented by columnar grains that were formed during crystallization in the direction of the heat dissipation (Fig. 12). The fusion zone (zones 1 and 2) can be considered potentially the most problematic because of the longest path that the molten metal takes having time to cool down. This can lead to a poor connection between the volumes of solid and surfaced metal and cause the appearance of microdefects. The microstructure of this zone (Fig. 13) shows a high-quality continuous connection without cracks in the surfacing zone. On the lateral side, at a distance of 500-800 μm from the surfacing zone, the presence of small (up to 100 μm) surface defects is observed. The formation of a high-quality continuous connection with a diffusion zone of about 15-20 μm is observed closer to the edge, in which there is no clear structural gradient (Fig. 13 a). Closer to the center, there are inflows of deposited metal with twice as large diffusion zone approximately 20-40 μm. The first row of grains of the deposited metal is equiaxed, which is related to the conditions of heat removal. All subsequent rows of grains have a characteristic columnar structure. The central part of the fusion zone (region 2) is characterized by the largest diffusion zone with a width of 50-100 μm. The transition zone and the base metal above it have favorable characteristics – it is uniformed, fine-grained, with an absence of defective areas (Fig. 13 b). If the columnar grains in the structure of the previous zone had dimensions of about (80-120)x(200-300) μm, then the grains in the zone 3, that is closer to the center (Figure 14 a) are about 2-3 times larger, and the structure itself is less homogeneous It also has inclusions of equiaxed configuration, which are horizontally formed columnar crystals. The growth of such grains occurs due to the movement of the crystallization front along the axis of the deposited layer formation. Such structures are observed closer to the existing solid phase of previously deposited layers. The microstructure of zone 4 is characterized by the relatively small sizes of primary β-grains and the simultaneous presence of rather large needles of the α´-phase. The microstructure of zone 6 shows fairly large grains, similar to zone 4, but without the presence of horizontally formed grains, which is associated with proximity to the side of the surfacing and more intense cooling (Figure 14 b). The structure of the upper part of the surfacing (zone 5) shows the same grain size and shape as the previous zones, as well as the presence of pores at a depth of up to 1 mm from the surface (Fig. 15 a). Part of the surfacing from Fig.15 b (zone 7) shows the presence of both large and small grains, the width of which varies from 40 to 180 μm. Also, the presence of pores up to 5 μm deep from the edge up to 200 μm is noted. In all the figures given, you can see evenly distributed acicular structures inside the primary grain. The dimensions of needle-like structures can be visibly different within the same field of research. Taking into account the chemical composition of the surfacing, the question of the presence of separated α- and β-phases arises. Studies of the distribution of chemical elements by the EDX-mapping method showed high uniformity of the deposited metal (Fig. 16). Analysis of the chemical composition of the middle part of the sample (zone 3) shows the zirconium and niobium content of 6.53 and 6.67% by weight accordingly. The decrease in the number of these elements is due to the additional alloying with the pure titanium shell of the wire. Due to the high content of oxygen in the deposited metal, it is impossible to produce cylindrical samples for strength testing, since the deposited metal is very brittle and not amenable to lathe processing. It was also impossible to test flat samples made by the electrospark method. The fragility of the metal is also confirmed by the high values of microhardness - 4200-5000 MPa (Fig. 17). Summarizing the data that we observed from all the layers we can conclude that the higher values of microhardness and Young’s modulus are observed in the middle layers of the sample with layer #5 in particular having the highest H = 10,39 GPa and E = 133 GPa but with a plasticity coefficient k = 0,59 among the lowest (Table 2). Table 2. Properties of each layer Layer H, GPa E, GPa k 9 8,63 107 0,57 8 6,5 88 0,61 7 8,7 112 0,59 6 7,69 123 0,67 5 10,39 133 0,59 4 8,06 122 0,65 3 7,65 124 0,67 2 6,79 104 0,65 1 5,82 110 0,72 base metal 2,04 95 0,89 Average values for the sample (excluding base metal and layer 1) are: microhardness H = 8,05 GPa, Young’s modulus E = 114 GPa and plasticity coefficient k = 0,63. 6. Conclusions 1. Thanks to the electron-beam casting technology, it is possible to smelt complex titanium alloys with a high content of zirconium and niobium. Using this technology, a high-quality Ti-13Zr-13Nb alloy with a uniform structure and chemical composition was obtained. 2. Powders based on Ti-13Zr-13Nb alloy were obtained by HDH and PREP methods. The work was carried out using HDH powder with dimensions of 5...50 μm. 3. A metal cored wire with a diameter of 3.0 mm and a filling factor of 0.6 was developed based on the HDH powder of the Ti-13Zr-13Nb alloy. 4. Layer-by-layer TIG surfacing (DED-Arc-M technique) with filler metal cored wire based on Ti-13Zr-13Nb alloy was performed. As a result, a 9-layer sample with a height of 15.2 mm and a width of 11 mm was obtained. 5. There are almost no pores in the obtained sample by DED-Arc-M, the structure is homogeneous. The analysis of the chemical composition of the sample showed the homogeneity of the distribution of elements: Zr = 6.5% by weight, Nb = 6.7% by weight. The number of these elements decreased due to the presence of a pure titanium shell in the metal powder wire. 6. The amount of oxygen in the deposited sample exceeds the maximum values by several times, which is indicated by microhardness tests - 4200-5000 MPa. This, in turn, affected the fragility of the sample and made it impossible to determine its strength. Regulation of the oxygen content (reduction of its level) in the HDH powder to increase the strength of the samples is expected to be carried out in the next work, as well as the use of Ti-13Zr-13Nb alloy powders produced by the PREP method. 7. Average values for the sample (without base metal and first layer) are: Young's modulus E = 114 GPa and plasticity coefficient k = 0.63. Declarations Conflict of Interest The author declares that there exists no competing financial interest or personal relationships that could have appeared to influence the work reported in this paper. Funding The work was carried out within the framework of a grant received from the National Academy of Sciences of Ukraine to research laboratories/groups of young scientists of the National Academy of Sciences of Ukraine to conduct research in the priority directions of the development of science and technology on the topic: " Investigation of the structure and quality of products made of titanium alloys for biomedical purposes, obtained by the WAAM method using a new class of metal powder wires" (State registration number: 0122U002067) References Vadiraj A, Kamaraj M (2010) Fretting fatigue behavior of surface modified biomedical titanium alloys. Trans Indian Inst Met 63: 217–223. https://doi.org/10.1007/s12666-010-0030-0 Müller-Heupt LK, Schiegnitz E, Kaya S, Jacobi-Gresser E, Wolfgang Kämmerer P, Al-Nawas B (2022) Diagnostic tests for titanium hypersensitivity in implant dentistry: a systematic review of the literature. 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Materials and Manufacturing Processes, 11(2): 185–197. https://doi.org/10.1080/10426919608947472 Cite Share Download PDF Status: Under Review Version 1 posted Reviewers agreed at journal 12 Nov, 2024 Reviewers invited by journal 12 Nov, 2024 Editor invited by journal 22 Sep, 2024 First submitted to journal 16 Sep, 2024 Editor assigned by journal 09 Sep, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5043610","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":377254294,"identity":"6dda8199-a321-4edd-9dfb-557932691b9a","order_by":0,"name":"Serhiy 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Ukraini","correspondingAuthor":false,"prefix":"","firstName":"Roman","middleName":"","lastName":"Selin","suffix":""},{"id":377254296,"identity":"b3c3854d-5939-43f6-876c-592858221e5e","order_by":2,"name":"Mykhailo Voron","email":"","orcid":"","institution":"Physical and Technological Institute of Metals and Alloys NASU: Fiziko-tehnologiceskij institut metallov i splavov Nacional'na akademia nauk Ukraini","correspondingAuthor":false,"prefix":"","firstName":"Mykhailo","middleName":"","lastName":"Voron","suffix":""},{"id":377254297,"identity":"495b2ff1-7e07-458e-8cbc-b91806327e8c","order_by":3,"name":"Taras Yanko","email":"","orcid":"","institution":"PJSC Titanium Institute/Underslab LLC","correspondingAuthor":false,"prefix":"","firstName":"Taras","middleName":"","lastName":"Yanko","suffix":""},{"id":377254298,"identity":"4f09dc61-6c9e-4956-8d8b-58011b5bd0ca","order_by":4,"name":"Maksym Khokhlov","email":"","orcid":"","institution":"Institut elektrozvaruvanna imeni E O Patona Nacional'na akademia nauk Ukraini","correspondingAuthor":false,"prefix":"","firstName":"Maksym","middleName":"","lastName":"Khokhlov","suffix":""}],"badges":[],"createdAt":"2024-09-06 10:31:50","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5043610/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5043610/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":70217763,"identity":"fab3d09e-f9d2-4114-b2e2-ab34d486b678","added_by":"auto","created_at":"2024-11-29 16:06:35","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":388609,"visible":true,"origin":"","legend":"\u003cp\u003eAppearance of the ingot: a – after casting, b – in longitudinal section, c – in cross section\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/8c3119fd6c272c9975ecf0c2.png"},{"id":70216715,"identity":"d3d08ee1-b797-4024-b87a-432db45369d1","added_by":"auto","created_at":"2024-11-29 15:50:35","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":726092,"visible":true,"origin":"","legend":"\u003cp\u003eMicrostructure (a) and chemical distribution (b) of Ti-13Zr-13Nb alloy samples\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/d1a62f85b6408f70bfc5a3c4.png"},{"id":70219168,"identity":"5b867c1d-6194-4285-a1cf-80560d331cc2","added_by":"auto","created_at":"2024-11-29 16:22:35","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":318097,"visible":true,"origin":"","legend":"\u003cp\u003eDiagram of obtaining powder by HDH method\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/493977a517b63f4498073b2e.png"},{"id":70216717,"identity":"dcf136bc-51e5-4e8e-a7b5-13bb83a55308","added_by":"auto","created_at":"2024-11-29 15:50:35","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":201709,"visible":true,"origin":"","legend":"\u003cp\u003ePowder obtained by HDH\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/138f28b08b56245eee5ac406.png"},{"id":70216712,"identity":"c51489c3-da18-456f-8dc7-a689683080a5","added_by":"auto","created_at":"2024-11-29 15:50:35","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":110454,"visible":true,"origin":"","legend":"\u003cp\u003eDiagram of obtaining powder by PREP method\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/8dc5210202c81ef20e3fe09c.png"},{"id":70218612,"identity":"1f69e140-6b51-4599-91c9-6491b0150e0a","added_by":"auto","created_at":"2024-11-29 16:14:35","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":567128,"visible":true,"origin":"","legend":"\u003cp\u003eSpherical powder, obtained by PREP method (a) and the form of particles after deformation (b)\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/692c20faf813d8a7bc17cf45.png"},{"id":70219167,"identity":"c6fceea5-d24d-4b2a-abba-4da732159c05","added_by":"auto","created_at":"2024-11-29 16:22:35","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":104230,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic of a machine for producing titanium cored wires: 1 — cassette; 2, 3 — roller stands; 4 — dosing unit; 5 — U-shaped strap; 6 — reel; 7 — frame\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/053dd27ff90f804707add843.png"},{"id":70216729,"identity":"c1a1ef91-6213-4761-b325-465f93289e5a","added_by":"auto","created_at":"2024-11-29 15:50:35","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":62673,"visible":true,"origin":"","legend":"\u003cp\u003eScheme of metal cored wire\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/49e6e482d43d5b7af3dad442.png"},{"id":70217521,"identity":"bb1d7d1e-745c-4a79-bcb7-71dd61b058fe","added_by":"auto","created_at":"2024-11-29 15:58:35","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":110853,"visible":true,"origin":"","legend":"\u003cp\u003eInstallation scheme for layer-by-layer TIG surfacing\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/9ea3f1a4ddd2869134dd6098.png"},{"id":70217525,"identity":"7e335e1c-0bfc-4569-a2b4-b474a1ecd4a9","added_by":"auto","created_at":"2024-11-29 15:58:35","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":194066,"visible":true,"origin":"","legend":"\u003cp\u003e9-layer sample, obtained with filler metal cored wire based on titanium alloy of the Ti-Zr-Nb system\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/2f4f84d4f538c13e2eae3aae.png"},{"id":70217764,"identity":"ef14a658-f6d2-418c-90b8-594659770927","added_by":"auto","created_at":"2024-11-29 16:06:35","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":124457,"visible":true,"origin":"","legend":"\u003cp\u003eX-Ray analysis of the sample\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/3f4b42eb8717e0d81f692be0.png"},{"id":70217769,"identity":"067fc0fb-bdc4-4eac-9e43-1f76c0c9ff4f","added_by":"auto","created_at":"2024-11-29 16:06:35","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":290457,"visible":true,"origin":"","legend":"\u003cp\u003eMacrostructure of the sample with marked zones in which the microstructure was studied\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/a76c94b44f4b23ef7d3373ad.png"},{"id":70216725,"identity":"4593a48e-3609-44f4-af1c-aa7dfd362c28","added_by":"auto","created_at":"2024-11-29 15:50:35","extension":"png","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":704398,"visible":true,"origin":"","legend":"\u003cp\u003eMicrostructure of fusion zone: a – zone 1, b – zone 2\u003c/p\u003e","description":"","filename":"13.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/cba41bb0a926f196770f3ccc.png"},{"id":70217530,"identity":"a62bb079-2c17-4481-99d1-6a3efc806a09","added_by":"auto","created_at":"2024-11-29 15:58:35","extension":"png","order_by":14,"title":"Figure 14","display":"","copyAsset":false,"role":"figure","size":675996,"visible":true,"origin":"","legend":"\u003cp\u003eMicrostructure of the center area: a – zone 3, b – zone 6\u003c/p\u003e","description":"","filename":"14.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/bb08f4ea51c46ba1b7c72d0b.png"},{"id":70216727,"identity":"c9298702-a3d3-42cd-b227-c314d89ba474","added_by":"auto","created_at":"2024-11-29 15:50:35","extension":"png","order_by":15,"title":"Figure 15","display":"","copyAsset":false,"role":"figure","size":1072488,"visible":true,"origin":"","legend":"\u003cp\u003eMicrostructure of the upper part of the sample (a) – zone 5 та side part of the sample (b) – zone 7\u003c/p\u003e","description":"","filename":"15.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/8c61c717192e52cb9bf3deb0.png"},{"id":70218609,"identity":"0b7fee02-508d-4d13-a358-cb2e5a36b162","added_by":"auto","created_at":"2024-11-29 16:14:35","extension":"png","order_by":16,"title":"Figure 16","display":"","copyAsset":false,"role":"figure","size":1747497,"visible":true,"origin":"","legend":"\u003cp\u003eDistribution of the chemical elements in the middle part if the detail (zone 3)\u003c/p\u003e","description":"","filename":"16.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/c52140818a534840ba2b5b0d.png"},{"id":70217523,"identity":"d66ed9b1-b797-4a9e-bf93-910ef1f21f86","added_by":"auto","created_at":"2024-11-29 15:58:35","extension":"png","order_by":17,"title":"Figure 17","display":"","copyAsset":false,"role":"figure","size":122898,"visible":true,"origin":"","legend":"\u003cp\u003eMicrohardness of the deposited sample\u003c/p\u003e","description":"","filename":"17.png","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/b75ac9279e9bd759028ce9f2.png"},{"id":70219170,"identity":"57b8283e-f2e0-423c-8572-31d88778c8a8","added_by":"auto","created_at":"2024-11-29 16:22:47","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":8663971,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5043610/v1/b5937f80-30b3-41f1-b830-63852e9b28a4.pdf"}],"financialInterests":"","formattedTitle":"Production of the Ti-Zr-Nb biomedical alloy powder and its application in the metal cored wire for DED-Arc-M process","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe use of titanium alloys in endoprosthetics has been intensively developing during the last thirty years due to its unique biocompatibility and the combination of mechanical and biomechanical properties [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]-[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. The study of titanium and its alloys as materials for endoprosthetics has achieved excellent results, which is proven by many years of positive experience in their use. At the same time, new alloys are constantly being developed, which are getting better and better in terms of their operational properties than the existing ones.\u003c/p\u003e \u003cp\u003eSolving the problem of finding the optimal compositions of titanium alloys for endoprostheses allows to significantly improve most types of endoprostheses - reduce the risk of rejection reaction, reduce toxicity, increase service life, adjust mechanical properties, etc. Biocompatibility is considered the most important among all parameters of medical alloys. From this point of view, the presence of a number of alloying elements in titanium alloys is undesirable. Vanadium in the Ti6Al4V alloy, for example, which, although it was recognized as non-toxic as early as 1986, is still being avoided in use due to the possibility of its penetration into the body through friction products of pairs of endoprostheses (friction pair \"femur - hip joint\"), when the integrity of the TiO2 oxide film is broken.\u003c/p\u003e \u003cp\u003eAccording to [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e], vanadium, entering the body, damages the reproductive system, causes kidney diseases and causes a general toxic reaction of cells upon contact. For this reason, in many countries, as early as the 80s, researches were conducted on the possibility of creating and using vanadium-free compositions [\u003cspan additionalcitationids=\"CR4\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]-[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e], which led to the development of alloys known today as Ti-6Al-7Nb, Ti-5Al-2 ,5Fe, Ti-12Mo-6Zr-2Fe, Ti-15Mo-2.8Nb-0.2Si, Ti-11Mo-11Nb, Ti-35Nb-2Ta-3Zr, etc.\u003c/p\u003e \u003cp\u003eThe problems of ensuring full biocompatibility of alloys for endoprosthetics and their solution are the main driving force of research in the development of new titanium alloys. As a result of these studies around the world, many experts have come to the conclusion that the most effective alloying elements are the ones that do not reduce the biocompatibility of titanium and are safe for the human body. Among them are Nb, Ta, Zr, Sn and to some extent - Mo [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e], [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]-[\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eTitanium-zirconium alloys and Ti-Zr-Nb alloys have the most promising combination of strength and modulus. Double Ti-Zr alloys are characterized by strength in the range of 600...1450 MPa and modulus of elasticity of 72...110 GPa, while Ti-Zr-Nb compositions have strength in the range of 600...1000 MPa and modulus of elasticity in the range of 58...80 GPa, which is much better than the combination of the same parameters in the Ti6Al4V alloy [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eHaving analyzed the relevance of using low-modulus titanium alloys for endoprosthetics and the technology of manufacturing finished products from them, which involve the presence of rods for fixation, or other loaded and massive elements, it was concluded that the DED-Arc (Direct Energy Deposition-Arc) Additive Manufacturing (AM) technique, which is also known as Wire and Arc AM (WAAM), method is appropriate as an alternative to existing additive manufacturing methods.\u003c/p\u003e \u003cp\u003eDespite the large number of studies on the production of parts by the DED-Arc-M, the majority of research is confined only to the production of parts using solid wires. There are practically no studies on the use of flux-cored wire for obtaining parts from titanium alloys by this method. The use of flux-cored wire in the production of parts by the DED-Arc-M makes it possible to produce parts from titanium alloys of various compositions and significantly increase the range of titanium alloys that can be used to produce parts by this method.\u003c/p\u003e \u003cp\u003eBased on above mentioned, the following tasks were set: obtaining an alloy based on the Ti-Zr-Nb system, manufacturing a powder from obtained alloy, developing a metal powder wire based on this alloy, using it in multilayer surfacing, and studying the structure and properties of the obtained samples.\u003c/p\u003e"},{"header":"2. Materials and methods","content":"\u003ch2\u003e2.1.\u0026nbsp; \u0026nbsp; \u0026nbsp;Obtaining the Ti-Zr-Nb system alloy\u003c/h2\u003e\n\u003cp\u003eObtaining finished products from the Ti-Zr-Nb system alloy remains a multi-stage, complex and very expensive process. According to the conventional technological cycle, such production involves multiple (at least two times) vacuum-arc remelting, deformation of the ingot, and its subsequent mechanical and thermal treatment [8]. As an alternative, you can consider atomizing the ingot to obtain powder and subsequent 3D printing from it, but the most profitable way from an economic point of view is obtain products using casting technologies.\u003c/p\u003e\n\u003cp\u003eThe most versatile and multifunctional casting method for obtaining castings from titanium and its alloys is the electron-beam casting technology (electron-beam garnish melting), developed at the Physical and Technological Institute of Metals and Alloys of the NAS of Ukraine, [9]-[10]. This method allows for the preparation of the wide range of alloy melts based on refractory and highly reactive metals, alloys based on intermetallics, special and complex titanium alloys, which include the biomedical alloy of Ti-Zr-Nb systems.\u003c/p\u003e\n\u003cp\u003eUnder the conditions of electron-beam garnish melting, melts are prepared in a vacuum inside a copper water-cooled crucible and the skull is frozen on its inner walls. In the process of melting, the charge is placed inside the skull, melted to form a liquid metal surface and exposed to electromagnetic stirring (EMS). The power of electron beam heating (EBH) should increase gradually in the process of melting and electromagnetic stirring. In this way, an increase in the volume of liquid metal is achieved, which is controlled by measuring the temperature of the water that cools the crucible. When the temperature stops rising, the corresponding increase in the volume of the liquid metal also stops.\u003c/p\u003e\n\u003cp\u003eAll experimental melting was carried out in a mode that provided for gradual melting of the charge for 30-40 minutes at an electron-beam heating power of 12-24 kW. Then, for 20-30 minutes under the action of EMS, the EBH gradually increased to 60 kW until the cooling water temperature growth stopped. After that, for 5-10 minutes, the final stage of preparing the melt was carried out at the EBH power around 70 kW and the melt was poured into the mold.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eNext, the chemical composition of the resulting castings was investigated. Dual alloys of the Ti-Zr and Ti-Nb systems had relatively minor deviations from the expected chemical composition.\u003c/p\u003e\n\u003cp\u003eThe results of experimental melts showed that zirconium in titanium is absorbed completely, and small deviations from the exact chemical composition are mostly associated with the dissolution of the skull metal. Niobium, due to its greater density, is absorbed worse and settles to a greater extent on the walls and bottom of the garnish.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe simultaneous fusion of titanium, zirconium and niobium in almost equal proportions showed the predominant role of niobium in the process of preparing the melt. All three metals are infinitely soluble in each other. At the same time, niobium has the highest density, heat capacity and melting point. These factors most likely contribute to the formation of the melt volume precisely on the basis of niobium. In the process of melting this alloy, there was an active growth of the \u0026quot;garnishment collar\u0026quot; - a metal ring above the level of the liquid metal bath. The chemical composition of this formation contained mainly titanium and zirconium.\u003c/p\u003e\n\u003cp\u003eDifferences in the chemical composition in the different parts of each of the castings were less than 1%. For a preliminary assessment of their quality, a visual inspection and mechanical processing were carried out (Fig. 1).\u003c/p\u003e\n\u003cp\u003eThe microstructure study of the alloys was carried out simultaneously with the analysis of the distribution of chemical elements (Fig. 2). The presented structures are homogeneous and clearly reflect the dependence of the structural phase state of titanium alloys on their chemical composition. Thus, in the cast state, the Ti-13Zr-13Nb alloy has the smallest amount of \u0026beta;-phase. The conditions of crystallization of the casting and its chemistry do not allow recording the \u0026beta;-structure. Instead, there are hardening type structures. EDX analysis of the sample shows a uniform distribution of elements.\u003c/p\u003e\n\u003cp\u003eThus, it can be stated that in the EBM conditions, the production of titanium alloys castings with a high content of zirconium and niobium in wide concentration ranges allows to achieve high quality alloys, their uniform structure and chemical composition.\u003c/p\u003e\n\u003ch1\u003e2.2.\u0026nbsp;\u0026nbsp;Production of Ti-13Zr-13Nb alloy powders\u003c/h1\u003e\n\u003cp\u003eThe creation of metal powder wires based on titanium alloys for various purposes solves an urgent problem in the field of modern additive technologies, namely, their use allows obtaining high-quality multilayer samples [11]. One of the important and complex technological processes in the production of metal powder wires is the preparation of their core - the metal component, that is, the powder itself. Today, we have the opportunity to use two methods of producing titanium-based powders: Hydrogenation-DeHydrogenation (HDH) and Plasma Rotating Electrode Process (PREP).\u003c/p\u003e\n\u003ch3\u003e2.2.1.\u0026nbsp; Production of Ti-13Zr-13Nb alloy powder by HDH method\u003c/h3\u003e\n\u003cp\u003eHDH technology (Fig. 3) is based on the property of hydrogen to reduce the strength of metallic titanium (brittleness). The essence of the process is described by the reverse reaction of hydrogenation-dehydrogenation Ti + H2 \u0026harr; TiH2 [12]-[13].\u003c/p\u003e\n\u003cp\u003eUnder certain conditions (temperature, pressure), titanium and its alloys are saturated with hydrogen. The obtained titanium hydride is easily crushed into fractions in the range of 5...250 \u0026mu;m. Next, the resulting powder is subjected to high-temperature processing in a vacuum to remove hydrogen. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThis technology for the production of titanium powders by the HDH method includes the following main technological operations:\u003c/p\u003e\n\u003cp\u003e- preparation and loading of primary charge materials (sponge titanium, ingots, blanks, scrap, etc.);\u003c/p\u003e\n\u003cp\u003e- hydrogenation of titanium material;\u003c/p\u003e\n\u003cp\u003e- grinding of titanium hydride;\u003c/p\u003e\n\u003cp\u003e- screening of hydride titanium powder;\u003c/p\u003e\n\u003cp\u003e- degassing of titanium powder\u003c/p\u003e\n\u003cp\u003eThe main advantages of the technology for the production of titanium powders by the HDH method:\u003c/p\u003e\n\u003cp\u003e- the use of hydrogen technology allows obtaining titanium powders with a low content of impurities;\u003c/p\u003e\n\u003cp\u003e- obtaining a wide range of powder particle sizes from 250 to 5 \u0026mu;m;\u003c/p\u003e\n\u003cp\u003e- a closed cycle for the use of water and gases allows to organize ecologically clean production;\u003c/p\u003e\n\u003cp\u003e- HDH technology allows processing a wide range of materials containing titanium (sponge titanium, titanium scrap, shavings, waste, etc.) into powders.\u003c/p\u003e\n\u003cp\u003eTo obtain Ti-13Zr-13Nb alloy powder, the method of hydrogenation of the cast alloy was used. In the process of hydrogenation, the workpiece was heated to a temperature of about 900 \u0026ordm;С, followed by hydrogen treatment. In the process of hydrogen saturation, deformation of crystal lattices took place, which led to embrittlement of the material. Due to this, it was possible to grind the alloy into powder. After grinding the alloy, the powder was classified into fractions. The fraction (5...50 \u0026mu;m) required for the research was subjected to thermal vacuum treatment to remove hydrogen from the powder (Fig. 4).\u003c/p\u003e\n\u003ch2\u003e2.2.2.\u0026nbsp; Obtaining of Ti-13Zr-13Nb alloy powder by the PREP method\u003c/h2\u003e\n\u003cp\u003eThe PREP method [14] is as follows: the sputtering alloy electrode rotates around a horizontal axis, and its free end is melted using a plasma torch. Drops of molten metal break off from the rotating electrode and crystallize in free flight before hitting the walls of the spray chamber. In the chamber where the electrode rotates and spraying takes place, there must be an environment protecting against oxidation. This makes it possible to obtain powders with high surface purity (Fig. 5).\u003c/p\u003e\n\u003cp\u003eThe powder particles are smooth, spherical in shape, the average particle size is 200 \u0026mu;m, the yield of particles with sizes from 50 to 500 \u0026mu;m is 75%. One of the advantages of powders obtained by this method is their high fluidity and purity (low oxygen content). The disadvantage of this material when used as a core is the spherical shape of the granules - during welding, they are not tightly held in the formed tube and fly apart under the pressure of the welding arc. In order to avoid such problems, it is necessary to carry out preliminary work on changing the shape of particles, namely their deformation, which is a rather long process and requires special equipment (Fig. 6).\u003c/p\u003e\n\u003cp\u003eFor the above reasons, it is of interest to use the metal component of the core of metal powder wires obtained by another method. That is why further experiments on obtaining a wire were carried out with powder obtained by the HDH method, with a size of 5...50 \u0026mu;m.\u003c/p\u003e\n\u003ch1\u003e2.3.\u0026nbsp;\u0026nbsp;Production of metal cored wire based on Ti-13Zr-13Nb alloy\u003c/h1\u003e\n\u003cp\u003eThe development and production of metal cored wire based on Ti-13Zr-13Nb titanium alloy was carried out by the metal dragging method on the installation (Fig. 7), which is designed for the production of titanium cored wires [15]. VT1-00 titanium foil with a thickness of 0.2 mm was used as the shell. It was established that the optimal linear speed during dragging after forming is a speed of 0.4 m/min, which ensures optimal pouring of the charge into the formed chute, and also eliminates the curvature of the output tube. Pulling was carried out using a set of dies with a step of 0.1 mm. The wire was fed into the spinneret in such a way that it is placed on the reel with the seam outward, since the stretching of the outer fibers leads to additional closure of the seam, and also eliminates distortion (corrugation).\u003c/p\u003e\n\u003cp\u003eAs the result, the wire with 3.0 mm diameter was obtained, with a filling factor of 65% (Fig.8).\u003c/p\u003e\n\u003ch1\u003e2.4.\u0026nbsp;\u0026nbsp;Multi-layer deposition process with filler metal cored wire (DED-Arc-M)\u003c/h1\u003e\n\u003cp\u003eMultilayer TIG surfacing with the obtained metal cored wire based on medical titanium alloy was carried out on the equipment designed for TIG welding and surfacing of titanium-based alloys (Fig. 9). The process was carried out on a pre-determined mode: I\u003csub\u003eW\u003c/sub\u003e, = 210 A, Uarc = 12,7 V, Vweld = 8 m/h, Vwire = 34 m/h, Larc = 3,5 mm.\u003c/p\u003e\n\u003ch1\u003e2.5.\u0026nbsp;\u0026nbsp;Methods used in research\u003c/h1\u003e\n\u003cp\u003eFlaw detection was carried out on the X-ray machine RAP 150/300 (of constant action) in transmission mode: I = 10 mA, F = 1000 mm, U = 110 kV, t = 2 min, control sensitivity: 0,16 mm, the image quality indicator is wired 10TIEN, film is FujiFilm IX800.\u003c/p\u003e\n\u003cp\u003eThe content of oxygen, nitrogen and hydrogen was determined by the method of reduction melting in the flow of the carrier gas. The oxygen content was determined on LECO RO-316 determinator, measurement sensitivity - 10\u0026ndash;5 wt%; nitrogen content was determined on LECO TN-114 determinator, measurement sensitivity - 10\u0026ndash;5 wt%; hydrogen content was determined on LECO RH-2 determinator, measurement sensitivity - 10-5\u0026ndash;5 wt%.\u003c/p\u003e\n\u003cp\u003eMicrostructure studies were performed by electron microscopy on Tescan Vega 3 scanning electron microscope. It allows to obtain a topographic image in the mode of detection of secondary electrons (SE - secondary electrons) and an image by contrast according to the atomic weight of the components in the mode of detection of reflected electrons (BSE - backscattered electrons). Preference was given to the second mode. During microscopic studies, local chemical analysis of phases and EDX-mapping (color elemental distribution by their atomic weight) were determined by Bruker detector, installed on microscope.\u003c/p\u003e\n\u003cp\u003eStudies of microhardness were carried out on a microhardness tester PMT-3 with a load on the indenter of 100 g.\u003c/p\u003e\n\u003cp\u003eTo study micromechanical properties of the obtained sample, microindentation testing was used on the \u0026ldquo;Micron-Gamma\u0026rdquo; device [16]-[18], which works according to the Oliver and Farr method of \u0026quot;An Improved technique for determining the hardness (H) and elastic modulus (E) using load displacement sensing indentation experiments\u0026quot; to determine microhardness, Young\u0026apos;s modulus and plasticity coefficient by indentation diagrams, which are automatically recorded and processed during continuous loading/unloading of a diamond trihedral pyramidal Berkovich indenter according to ISO/FDIS 14577-1: 2015; Metallic materials - Instrumented indentation test for hardness and material parameters - Part 1: Test method (ISO Central Secretariat, Geneva, Switzerland). Testing was carried out with a 100 g load on the indenter which is a good general-purpose value for titanium alloys [16] and allows to eliminate possible size effect of such measurements and to obtain values which are more of an integral characteristic of a whole material and not of a particular structural element [17]-[18]. The step between each indentation is determined by the load value to eliminate the influence of adjacent measurements and was 100 \u0026mu;m. The sample was studied along all of the layers by its entire height and layer by layer for more detail and statistics. The step between measurements of each of the deposited layers was 1000 \u0026mu;m and they were done in their middle parts to eliminate the effect of interlayer boundaries. Typical diagrams of indentation show that curves for each measurement are similarly shaped and fall into a narrow value range which indicates that obtained layers have high uniformity and defects if any are negligible.\u003c/p\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003eAs a result of the experiments a 9-layer sample was obtained with metal cores wire based on the powder of the Ti-13Zr-13Nb alloy (Fig. 10). The wire melting process for this case was stable, the layers were deposited with a constant height (on average, the height of each layer is 1.6-1.8 mm), the width of the sample is about 11 mm and 15.2 mm high. The base is 6 mm thick pure titanium.\u003c/p\u003e\n\u003cp\u003eThe X-ray analysis did not reveal any significant defects, except for a small sized pores (up to 50 \u0026mu;m), which is allowed in welded titanium alloys. They are mostly located in the middle part of each layer (Fig. 11).\u003c/p\u003e\n\u003cp\u003eGas analysis was carried out for the ingot itself, for the powder and for the surfaced metal (Table 1).\u003c/p\u003e\n\u003cp\u003eTable 1. Results of gas analysis of samples\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\" width=\"472\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 255px;\"\u003e\n \u003cp\u003e\u003cem\u003eResearch area\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003e\u003cem\u003e[O], wt%\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e\u003cem\u003e[N] , wt%\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e\u003cem\u003e[H] , wt%\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 255px;\"\u003e\n \u003cp\u003eCasting of the Ti-13Zr-13Nb\u0026nbsp;alloy\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003e0,82\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e0,034\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e0,026\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 255px;\"\u003e\n \u003cp\u003eHDH powder of Ti-13Zr-13Nb alloy\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003e2,76\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e0,61\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e0,0157\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 255px;\"\u003e\n \u003cp\u003eThe metal of the surfaced sample\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 66px;\"\u003e\n \u003cp\u003e1,35\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e0,072\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 76px;\"\u003e\n \u003cp\u003e0,0063\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003eA significant increase in oxygen in the material is undoubtedly associated with a significant increase in the specific area of the material. Each particle of the alloy powder was covered with an oxide layer since titanium and zirconium are very prone to oxidation. It is possible that during the hydrogenation process, local overheating occurred during the exothermic hydrogenation reactions of titanium and zirconium. Some recrystallization of the alloy may have also occurred during grinding. This could\u0026apos;ve lead to local phase transitions with the formation of structures based on the Ti-Zr-Nb system, which have an increased affinity for oxygen.\u003c/p\u003e\n\u003cp\u003eThe decrease in oxygen content after the surfacing process is due to the fact that pure titanium foil was added to the content of the composite wire. A significant decrease in the specific surface area of the material also have occurred during the surfacing process. Presumably, this led to the migration of metal oxides to the surface, which led to reduced amount of total oxygen in the center of the detail.\u003c/p\u003e\n\u003cp\u003eOxygen alloying technologies of titanium alloys belong to the topic of economical alloying. Thanks to dosed alloying with elements such as oxygen, nitrogen and carbon, it is possible to increase the strength of alloys without the use of expensive alloying elements. The relatively low modulus of elasticity of the Ti-13Zr-13Nb alloy is accompanied by a decrease in strength. The technology of economical alloying with oxygen is proposed to eliminate this shortcoming [19-20]. This technology can be implemented by the method of passivation of the powder material after degassing. In the research process it was quite difficult to control the degree and speed of material passivation.\u003c/p\u003e\n\u003cp\u003eStudies of the structural and phase characteristics and distribution of components of the surfanced metal were conducted. The macrostructure of the sample is represented by columnar grains that were formed during crystallization in the direction of the heat dissipation (Fig. 12).\u003c/p\u003e\n\u003cp\u003eThe fusion zone (zones 1 and 2) can be considered potentially the most problematic because of the longest path that the molten metal takes having time to cool down. This can lead to a poor connection between the volumes of solid and surfaced metal and cause the appearance of microdefects. The microstructure of this zone (Fig. 13) shows a high-quality continuous connection without cracks in the surfacing zone. On the lateral side, at a distance of 500-800 \u0026mu;m from the surfacing zone, the presence of small (up to 100 \u0026mu;m) surface defects is observed.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe formation of a high-quality continuous connection with a diffusion zone of about 15-20 \u0026mu;m is observed closer to the edge, in which there is no clear structural gradient (Fig. 13 a).\u003c/p\u003e\n\u003cp\u003eCloser to the center, there are inflows of deposited metal with twice as large diffusion zone approximately 20-40 \u0026mu;m. The first row of grains of the deposited metal is equiaxed, which is related to the conditions of heat removal. All subsequent rows of grains have a characteristic columnar structure. The central part of the fusion zone (region 2) is characterized by the largest diffusion zone with a width of 50-100 \u0026mu;m. The transition zone and the base metal above it have favorable characteristics \u0026ndash; it is uniformed, fine-grained, with an absence of defective areas (Fig. 13 b).\u003c/p\u003e\n\u003cp\u003eIf the columnar grains in the structure of the previous zone had dimensions of about (80-120)x(200-300) \u0026mu;m, then the grains in the zone 3, that is closer to the center (Figure 14 a) are about 2-3 times larger, and the structure itself is less homogeneous It also has inclusions of equiaxed configuration, which are horizontally formed columnar crystals. The growth of such grains occurs due to the movement of the crystallization front along the axis of the deposited layer formation. Such structures are observed closer to the existing solid phase of previously deposited layers.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe microstructure of zone 4 is characterized by the relatively small sizes of primary \u0026beta;-grains and the simultaneous presence of rather large needles of the \u0026alpha;\u0026acute;-phase. The microstructure of zone 6 shows fairly large grains, similar to zone 4, but without the presence of horizontally formed grains, which is associated with proximity to the side of the surfacing and more intense cooling (Figure 14 b).\u003c/p\u003e\n\u003cp\u003eThe structure of the upper part of the surfacing (zone 5) shows the same grain size and shape as the previous zones, as well as the presence of pores at a depth of up to 1 mm from the surface (Fig. 15 a).\u003c/p\u003e\n\u003cp\u003ePart of the surfacing from Fig.15 b (zone 7) shows the presence of both large and small grains, the width of which varies from 40 to 180 \u0026mu;m. Also, the presence of pores up to 5 \u0026mu;m deep from the edge up to 200 \u0026mu;m is noted.\u003c/p\u003e\n\u003cp\u003eIn all the figures given, you can see evenly distributed acicular structures inside the primary grain. The dimensions of needle-like structures can be visibly different within the same field of research. Taking into account the chemical composition of the surfacing, the question of the presence of separated \u0026alpha;- and \u0026beta;-phases arises.\u003c/p\u003e\n\u003cp\u003eStudies of the distribution of chemical elements by the EDX-mapping method showed high uniformity of the deposited metal (Fig. 16). Analysis of the chemical composition of the middle part of the sample (zone 3) shows the zirconium and niobium content of 6.53 and 6.67% by weight accordingly. The decrease in the number of these elements is due to the additional alloying with the pure titanium shell of the wire.\u003c/p\u003e\n\u003cp\u003eDue to the high content of oxygen in the deposited metal, it is impossible to produce cylindrical samples for strength testing, since the deposited metal is very brittle and not amenable to lathe processing. It was also impossible to test flat samples made by the electrospark method. The fragility of the metal is also confirmed by the high values of microhardness - 4200-5000 MPa (Fig. 17).\u003c/p\u003e\n\u003cp\u003eSummarizing the data that we observed from all the layers we can conclude that the higher values of microhardness and Young\u0026rsquo;s modulus are observed in the middle layers of the sample with layer #5 in particular having the highest H = 10,39 GPa and E = 133 GPa but with a plasticity coefficient k = 0,59 among the lowest (Table 2).\u003c/p\u003e\n\u003cp\u003eTable 2. Properties of each layer\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eLayer\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eH, GPa\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eE, GPa\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003ek\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e9\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e8,63\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e107\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,57\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e8\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e6,5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e88\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,61\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e7\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e8,7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e112\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,59\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e6\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e7,69\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e123\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,67\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e5\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e10,39\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e133\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,59\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e4\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e8,06\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e122\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,65\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e3\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e7,65\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e124\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,67\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e2\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e6,79\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e104\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,65\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003e1\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e5,82\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,72\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003ebase metal\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e2,04\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0,89\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003eAverage values for the sample (excluding base metal and layer 1) are: microhardness H = 8,05 GPa, Young\u0026rsquo;s modulus E = 114 GPa and plasticity coefficient k = 0,63.\u003c/p\u003e"},{"header":"6. Conclusions","content":"\u003cp\u003e1. Thanks to the electron-beam casting technology, it is possible to smelt complex titanium alloys with a high content of zirconium and niobium. Using this technology, a high-quality Ti-13Zr-13Nb alloy with a uniform structure and chemical composition was obtained.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e2. Powders based on Ti-13Zr-13Nb alloy were obtained by HDH and PREP methods. The work was carried out using HDH powder with dimensions of 5...50 μm.\u003c/p\u003e\n\u003cp\u003e3. A metal cored wire with a diameter of 3.0 mm and a filling factor of 0.6 was developed based on the HDH powder of the Ti-13Zr-13Nb alloy.\u003c/p\u003e\n\u003cp\u003e4. Layer-by-layer TIG surfacing (DED-Arc-M technique) with filler metal cored wire based on Ti-13Zr-13Nb alloy was performed. As a result, a 9-layer sample with a height of 15.2 mm and a width of 11 mm was obtained.\u003c/p\u003e\n\u003cp\u003e5. There are almost no pores in the obtained sample by DED-Arc-M, the structure is homogeneous. The analysis of the chemical composition of the sample showed the homogeneity of the distribution of elements: Zr = 6.5% by weight, Nb = 6.7% by weight. The number of these elements decreased due to the presence of a pure titanium shell in the metal powder wire.\u003c/p\u003e\n\u003cp\u003e6. The amount of oxygen in the deposited sample exceeds the maximum values by several times, which is indicated by microhardness tests - 4200-5000 MPa. This, in turn, affected the fragility of the sample and made it impossible to determine its strength. Regulation of the oxygen content (reduction of its level) in the HDH powder to increase the strength of the samples is expected to be carried out in the next work, as well as the use of Ti-13Zr-13Nb alloy powders produced by the PREP method.\u003c/p\u003e\n\u003cp\u003e7. Average values for the sample (without base metal and first layer) are: Young's modulus E = 114 GPa and plasticity coefficient k = 0.63.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eConflict of Interest\u003c/h2\u003e \u003cp\u003eThe author declares that there exists no competing financial interest or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eFunding\u003c/h2\u003e \u003cp\u003eThe work was carried out within the framework of a grant received from the National Academy of Sciences of Ukraine to research laboratories/groups of young scientists of the National Academy of Sciences of Ukraine to conduct research in the priority directions of the development of science and technology on the topic: \" Investigation of the structure and quality of products made of titanium alloys for biomedical purposes, obtained by the WAAM method using a new class of metal powder wires\" (State registration number: 0122U002067)\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eVadiraj A, Kamaraj M (2010) Fretting fatigue behavior of surface modified biomedical titanium alloys. Trans Indian Inst Met 63: 217\u0026ndash;223. https://doi.org/10.1007/s12666-010-0030-0\u003c/li\u003e\n\u003cli\u003eM\u0026uuml;ller-Heupt LK, Schiegnitz E, Kaya S, Jacobi-Gresser E, Wolfgang K\u0026auml;mmerer P, Al-Nawas B (2022) Diagnostic tests for titanium hypersensitivity in implant dentistry: a systematic review of the literature. Int J Implant Dent 8: 29. https://doi.org/10.1186/s40729-022-00428-0\u003c/li\u003e\n\u003cli\u003eShunxing L (2020) Review of the design of titanium alloys with low elastic modulus as implant materials. Advanced Engineering Materials. Vol.22(11). https://doi.org/10.1002/adem.202000555\u003c/li\u003e\n\u003cli\u003eNiinomi M (2011) Low Modulus Titanium Alloys for Inhibiting Bone Atrophy. Biomaterials Science and Engineering (Book). Edited by Prof. Rosario Pignatello: 249-268. https://doi.org/10.5772/24549\u003c/li\u003e\n\u003cli\u003eSilva HM, Schnedek SG, Neto CM (2004) Study of nontoxic aluminum and vanadium-free titanium alloys for biomedical applications. Materials Science and Engeneering C. No 24 (5): 679-682. https://doi.org/10.1016/j.msec.2004.08.051\u003c/li\u003e\n\u003cli\u003eWang K (1996) The use of titanium for medical applications in USA. Material Science and Engeneering. Vol. 213: 134-137. https://doi.org/10.1016/0921-5093(96)10243-4\u003c/li\u003e\n\u003cli\u003eBao X, Li X, Ding J, Liu X, Meng M, Zhang T (2022) Exploring the limits of mechanical properties of Ti-Zr binary alloys. Materials Letters, Vol. 318, 132091. https://doi.org/10.1016/j.matlet.2022.132091\u003c/li\u003e\n\u003cli\u003eMetthew J, Donachie Jr (2000) Titanium: a technical guide, 2nd edition. Winchester, USA\u003c/li\u003e\n\u003cli\u003eLadokhin SV, Voron MM, Drozd YO, Matviets YO, Kulak LD, Kuz\u0026apos;menko MM (2020) Features of Obtaining Titanium Alloys of Ti\u0026minus;Al\u0026minus;Si\u0026minus;Zr\u0026minus;Mo\u0026minus;Nb\u0026minus;Sn System under Conditions of Electron-Beam Foundry Technology. Casting processes. Vol. 140 (2): 8-14. https://doi.org/10.15407/plit2020.02.008\u003c/li\u003e\n\u003cli\u003eKaliuzhnyi P, Voron M, Mykhnian O, Tymoshenko A, Neima O, Iangol O (2021) Interaction of titanium with ceramic molds in the conditions of electron beam casting technology. Archives of Foundry Engineering. Vol. 21 (3): 27-32. https://doi.org/10.24425/afe.2021.136109\u003c/li\u003e\n\u003cli\u003eSchwab S, Selin R, Voron M (2023) Welding materials for TIG welding, surfacing, and WAAM technology of titanium alloys. 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The Paton Welding Journal, 2019, (6): 34-37. http://dx.doi.org/10.15407/tpwj2019.06.06\u003c/li\u003e\n\u003cli\u003eKhokhlova J, Khokhlov M, Tunik A, Ishchenko A (2014) Nanoindentation of micro weld formed through thin nanolayered filler. Solid Mechanics and its Applications, Volume 203: 251-262. https://doi.org/10.1007/978-94-007-6919-9_13\u003c/li\u003e\n\u003cli\u003eZavdoveev A, Klapatyuk A, Baudin T, MacDonald E, Mohan D, Oliveira JP, Gajvoronskiy A, Poznyakov V, Kim HS, Brisset F, Khokhlov M, Heaton M, Rogante M, Skoryk M, Vedel D, Kozin R, Klochkov I, Motrunich S (2023) Non-equimolar Cantor high entropy alloy fabrication using metal powder cored wire arc additive manufacturing. Additive Manufacturing Letters, Volume 6, 100124. https://doi.org/10.1016/j.addlet.2023.100124\u003c/li\u003e\n\u003cli\u003eKostin V, Khokhlova J, Khokhlov M, Makhnenko A, Puzrin O (2023) Formation of Nanostructures in the Weld Nugget Zone in Friction Stir Welding of Mg-Al Alloys. Proceedings of the 2023 IEEE 13th International Conference Nanomaterials: Applications and Properties, NAP 2023 \u0026ndash; Pages IMT041-IMT045. https://doi.org/10.1109/NAP59739.2023.10311017\u003c/li\u003e\n\u003cli\u003eHan C.-B., Lee D.-G. (2024) Effect of Oxygen on Static Recrystallization Behaviors of Biomedical Ti-Nb-Zr Alloys. Metals, 14, 333. https://doi.org/10.3390/met14030333\u003c/li\u003e\n\u003cli\u003ePoggie RA, Kovacs P, Davidson JA (1996) Oxygen Diffusion Hardening of Ti-Nb-Zr Alloys. Materials and Manufacturing Processes, 11(2): 185\u0026ndash;197. https://doi.org/10.1080/10426919608947472\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":true,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"welding-in-the-world","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"witw","sideBox":"Learn more about [Welding in the World](https://www.springer.com/journal/40194)","snPcode":"40194","submissionUrl":"https://www.editorialmanager.com/witw/","title":"Welding in the World","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Biomedical titanium alloy, electron-beam casting, Ti-Zr-Nb, titanium powder, HDH, cored wire, DED-Arc-M","lastPublishedDoi":"10.21203/rs.3.rs-5043610/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5043610/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe use of biomedical titanium alloys is gaining more and more interest and attention. In this work, the Ti-Zr-Nb system alloy was produced and studied, as well as its powder, that was obtained by the Hydrogenation-Dehydrogenation method. The problem of using powders obtained by this method is shown. Based on obtained powder, an experimental metal powder wire was made, which was used as filler material for TIG surfacing. As a result, a multilayer deposited detail was obtained, of which the microstructure and properties (modulus of elasticity and microhardness) were investigated.\u003c/p\u003e","manuscriptTitle":"Production of the Ti-Zr-Nb biomedical alloy powder and its application in the metal cored wire for DED-Arc-M process","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-11-29 15:50:30","doi":"10.21203/rs.3.rs-5043610/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2024-11-12T15:23:09+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-11-12T15:18:15+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Welding in the World","date":"2024-09-22T07:34:46+00:00","index":"","fulltext":""},{"type":"submitted","content":"Welding in the World","date":"2024-09-17T02:45:11+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-09-09T09:59:04+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"welding-in-the-world","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"witw","sideBox":"Learn more about [Welding in the World](https://www.springer.com/journal/40194)","snPcode":"40194","submissionUrl":"https://www.editorialmanager.com/witw/","title":"Welding in the World","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"835f66ac-a6a7-4bc5-bc38-bb280b9559fb","owner":[],"postedDate":"November 29th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2025-05-23T11:57:04+00:00","versionOfRecord":[],"versionCreatedAt":"2024-11-29 15:50:30","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5043610","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5043610","identity":"rs-5043610","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}