Advanced Melting Techniques for Titanium and Zirconium Alloys and Tribological Studies in Medical Implant Manufacturing

Advanced Melting Techniques for Titanium and Zirconium Alloys and Tribological Studies in Medical Implant Manufacturing | 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 Advanced Melting Techniques for Titanium and Zirconium Alloys and Tribological Studies in Medical Implant Manufacturing Nimu Chand Reger, Bavya Devi Karuppasamy This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6368274/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The melting and casting of titanium (Ti) and zirconium (Zr) are crucial in foundries producing high-performance medical implants for orthopedic and dental applications. These reactive metals exhibit high melting points, exceptional corrosion resistance, biocompatibility, and thermal stability, making them ideal for medical devices. This study provides a comprehensive overview of advanced melting techniques such as Plasma Arc Melting, Electron Beam Melting (EBM), and Vacuum Arc Remelting (VAR), which ensure high purity and uniform composition. Foundry casting methods, including investment casting, centrifugal casting, and continuous casting, facilitate the fabrication of complex implant geometries. Additionally, additive manufacturing, specifically Laser Engineering Net Shape (LENSTM), enhances implant longevity, wear resistance, and corrosion performance. The production of pure Zr and Zr-50Ti alloy was conducted via laser-based melting and casting, followed by surface oxidation treatments. Oxide layers were successfully grown on Zr and Zr-50Ti surfaces, and detailed assessments of coating morphology, oxide phases, wear resistance, and corrosion behavior were performed. X-ray diffraction confirmed the formation of Zr and Ti oxides. Oxidation at 600°C for 6 hours yielded the lowest in-vitro wear rate (2.12 ± 0.36 × 10⁻⁶ mm³/N·m), attributed to the increased ceramic layer thickness. Furthermore, compared to untreated samples, oxidized surfaces exhibited significantly enhanced in-vitro corrosion resistance in Hanks' Balanced Salt Solution (HBSS). These findings demonstrate that controlled oxidation improves the functional performance of Ti- and Zr-based implants, making them more suitable for biomedical applications. Zr-50Ti alloy Thermal oxidation Wear and Electrochemical resistance Medical implant Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction It has been reported that by 2030 around 80 million people belongs 38–42 years of age, required total joint replacements (TJR) globally [ 1 ]. The average service life of hip replacements implant lies between 10 and 15 years maximum. Presently metallic materials (Co base alloys, Ti alloys, 316L stainless steel) and ceramic materials such as (Al 2 O 3 , zirconia-toughened alumina, hydroxyapatite) are frequently used in TJR. Further among the polymer materials ultra-high molecular weight polyethylene (UHMWPE) used as liner in articulating components of TJR [ 1 ]. The excellent corrosion resistance and biocompatibility of zirconium and its alloys have made them one of the most demanded implants [ 2 ]. The complete solid solubility of Zr in Ti makes this binary alloy most corrosive resistant implant material. Generally surfaces of Zr and Ti are passivated by tiny oxide layers formed naturally in air or electrolytes [ 3 ]. In the 21st century among all the prime materials used in dentistry or orthopaedic prostheses is Ti–Zr alloy [ 4 ]. Among the advance melting and casting techniques Vacuum Arc Remelting (VAR) is widely for melting reactive metals like Ti and Zr. It involves the use of a vacuum to prevent contamination and a consumable electrode made of the metal to be melted. The metal electrode is struck by an arc in a vacuum chamber, causing it to melt and drip into a water-cooled copper crucible below. The vacuum environment minimizes the introduction of impurities. Produces high-purity ingots with a uniform composition and reduces the inclusion of gases like oxygen and nitrogen, which are detrimental to the metal's properties. Better control of melting rate is the main benefit of the vacuum arc remelting process against vacuum induction melting technique. This results in an overall directional solidification front which provides equiaxed cast structure for better microstructure and mechanical properties. The schematic representations of advanced production techniques shown in Fig. 1 a-d. A cross section of a distinctive VAR furnace working co-axially was displayed in Fig. 1 a [ 9 ]. At high temperature a metal vapour plasma arc that strikes from the electrode to the forming ingot melts the input material, generally referred as the electrode. The furnace is known as coaxial when the return feed from the power source is coupled around the crucible flange [ 10 ], [ 11 ]. The details of process parameters and operation of VAR is given elsewhere [ 12 ] as shown in Fig. 1 d. Electron Beam Melting (EBM) melts metal in a vacuum by using an electron beam as the heat source. An electron gun generates a focused beam that melts the metal feedstock. The melted metal pools in a water-cooled copper crucible, and the process is controlled to ensure a uniform composition. EBM is highly effective at producing extremely pure metals and allows precise control over the melting process [ 13 ]. Ti-6Al-4V has been the subject of a large number of research studies, reporting on surface treatments aimed at enhancing biocompatibility and osseointegration with tissues [ 14 ]. In a study on Ti–6Al–4V melted and casted by SLM and EBM techniques, Wang et al. [ 16 ] assessed the biocompatibility of products in both in-vitro and in-vivo procedures. Araújo et al. [ 12 ] used the plasma arc melting method (schematic in Fig. 1 c) to produce Cu-based alloys and Ni–Ti alloys for biomaterials applications [ 17 ]. In addition to plasma arc melting one of the popular and latest advance melting and casting technique that is Laser Engineering Net Shape (LENS) (shown in Fig. 1 b) technique widely used for aerospace, automobile and biomaterials component production. Directional solidification/cooling rates are possible with LENS machines because they produce smaller melt-pools than with traditional manufacturing techniques like die, sand and investment castings [ 18 ], [ 19 ]. Though, the ability to cast with different precursors and develop functionally graded objects, owing to numerous powder feed lines is a uniqueness of the LENS technique [ 20 ]. Furthermore, it is reported that LENS manufactured components are found to be more strong and ductile without any crack or damage under static loads suitable for key industries such as medical and aerospace [ 21 ]–[ 23 ]. The numerous distinct features of LENS in contrast to existing conventional casting methods, provide a variety of intriguing prospects for component manufacture that have been utilized for orthopaedic implant applications. In order to facilitate the process of bone osseointegration, different LENS manufactured hip stem implants are shown in Fig. 2 (e) with different level of porosity as per casting parameters. Another significant benefit of the LENS method is that manufacturing may be done on items with uneven surfaces and without the requirement for a powder bed after the material is delivered to a build area [ 24 ]. In concern with present investigation Reger et al [ 1 ] mentioned about the wear of UHMWPE is a major challenge of TJR that leads to implant failure and revision of the surgery. Wear-induced osteolysis in TJR has been addressed by the development of several ceramic coatings on additively manufactured metallic implants such as Zr, Ti-Zr alloy, Mg, Co-Cr-Mo alloys, 316L SS [ 25 ]. It was observed that these ceramic coatings provide excellent biocompatibility and mechanical stability. In this study, Pure Zr and Zr-50Ti alloy was melted and casted by advance LENS method successfully. The oxidation treatment on the surface of Ti–50Zr alloy was carried out at 600 ◦C for duration of 2 and 6 h. In contrast to other surface treatment methods, the current study’s strength is the use of inexpensive and effective thermal oxidation (TO) treatment for the development of in-situ developed ceramic layers on Zr and Ti-50Zr metallic substrates. Furthermore, a thorough investigation was carried out to evaluate the corrosion and wear characteristics of developed oxide coatings in simulated body fluid (SBF) and Hank’s Balanced Salt Solution (HBSS) respectively. The sequence of experimental and testing scheme are shown in Fig. 2 . As far as we are aware, there aren't many studies on the wear and corrosion resistance of pure Zr and Zr-50Ti binary alloys made with the LENS process for use in total joint replacements (TJR). 2. Materials and Method 2.1. Advance melting and casting of Zr and Zr-50Ti samples by using LENS™ Highly pure (99.9%) metal powders of Zirconium and Titanium, provided by TLS Technik GmbH & Co., Germany, particle sizes in the range of 50 µm–150 µm, used as precursor materials for the melting and casting of Zr and Zr-50Ti alloy (by wt %) in compact form by the LENS method process parameters for the alloy casting shown in Fig. 2 b. Thermal oxidation (TO) procedures were subjected to all the samples (pure Zr and Zr-50Ti alloy) at similar parameters in a standard tubular heat treatment furnace under flowing 99.98% pure O 2 at 600 ◦ C for 2 and 6 h. To avoid contamination, acetone and an ultrasonic cleaner are used to clean all the samples. 2.2. Coating thickness, phase identifications Scanning electron microscopy (SEM, Phenom ProX, Netherlands) cross-sectional micrographs were utilised to measure the oxide layer thickness grown after TO treatments. During tribological testing, further SEM was used to evaluate wear damage on the surface of the pure Zr, Zr-50Ti alloy and oxidised specimens. The phases were identified by X-ray diffraction (XRD) analysis using Siemens’ D500 Kristalloflex diffractometer. 2.3. In-Vitro tribological testing As per ASTM G 99 − 5, a ball-on-disk tribometer (NANOVEA Microphotonics Inc., CA, USA, was utilised for all sliding wear tests in the freshly make simulated physiological fluid, with a constant temperature of 37 ± 1 ◦C. Prior research has conducted and detailed the preparation procedure for the simulated bodily fluid (SBF) utilised in the wear test [ 25 ]. Using a non-contact type surface profilometer, the recorded wear track depth and width were used to calculate the sample's average wear rate (mm 3 /Nm). 2.4. In-vitro corrosion testing Following the published technique, the electrochemical experiments were carried out in the chemically synthesised HBSS using a multichannel potentiostat/galvanostat (SP300, Bio-Logic SAS, France) [ 25 ]. Before the polarisation investigation, pure Zr, Zr-50Ti, and TO-subjected specimens were allowed to stabilise in HBSS for one hour in order to obtain a stable open circuit potential (OCP). The corrosion studies were performed at a scanning rate of 10 mV/min from 0.25 V to + 1.6 V against OCP. The corrosion potential (Ecorr) and corrosion current density (Icorr), which are important parameters for corrosion study, were computed using Tafel extrapolation. 3. Result and discussions When developing Ti base metallic load bearing femoral stems via advance melting and casting route, the alloying addition of Zr to Ti offers various benefits from a metallurgical perspective. First, it is noted that at 20°C, Zr has a density of 6.50 g/cc. This low density makes it possible to create light weight Zr-Ti binary alloys for TJR applications. This binary alloy will be capable to solve the problem of stress shielding effect and minimize the revision of surgery. Second, over the full composition range, the Zr-Ti binary system produces a continuous solid solution for both the low temperature α-phase with the hexagonal close packed (HCP) structure and the high temperature β-phase with the body-cantered cubic (BCC) structure. This is because of Zr and Ti mix well together the microstructure of pure Zr and Zr-50Ti alloy displayed in Fig. 2 c. In contrast to multi-phase alloys, this capacity to produce a single-phase structure at any composition is desirable from the perspective of chemical stability since it prevents implants from galvanic corrosion in bodily fluids. Addition of Ti to Zr effectively decreases liquidus temperatures, and at about Ti-38 at% Zr composition, the congruent temperature of 1540°C is reached (Fig. 2 c). By reducing liquidus temperatures, Zr addition has a beneficial influence on the solidification process used to produce industrial and biomedical gadgets. Because load-bearing metallic biomaterials are employed in live bodies under loading conditions that are within their elastic limits, it is preferable that their elastic characteristics be as near to those of human cortical bone. Table 1 Film thickness and Electrochemical properties of oxidized and unoxidized Zr and Zr-50Ti samples Sample ID Film thickness (µm) E corr (mV) I corr (µA/mm 2 ) Passive range (mV) Pure Zr NA -228 0.018 1372 Zr-6O2h 5 ± 0.2 -276 0.023 1324 Zr-6O6h 7 ± 0.8 -186 0.006 1414 Zr-8O2h 20 ± 3 -347 0.017 1253 Zr-50Ti NA -478 -1.16 858 Zr-50Ti 6O2h 20.25 ± 4.67 -109 0.11 1207 Zr-50Ti 6O6h 38.21 ± 7.26 -202 0.36 1136 Figure 3 depicts the surface morphology and coating thicknesses of oxidized Zr and Zr-50Ti samples. It can be noticed from Fig. 3 and Table 1 that the thicknesses of the in-situ grown oxide coatings enhanced as the oxidation treatment temperature and soaking period increased. No cracks, flaws, pores and delamination were visible because of strong adhesion of ceramic layers to both substrates. In comparison to Zr-50Ti ceramic layer thicknesses, the total oxide layer thicknesses on Zr were lower. This can be explained thermodynamically by the fact that O 2 has a greater affinity for Ti (ΔG = − 218 Kcal/mol for TiO 2) than for Zr (ΔG = − 118 Kcal/ mol for ZrO 2 ). The highest oxide thickness measured in particularly Zr-50Ti samples those oxidized at 600°C for 6h duration in presence of pure oxygen. The XRD patterns of the Zr, Zr-50Ti alloy, and oxidized specimens are displayed in Fig. 4(a–b) , respectively. It can observed from Fig. 2 a &b , Zr and Zr-50Ti alloy were found to have pure Zr and a solid solution phase made up of Zr-50Ti binary alloy, respectively, in their XRD patterns. Moreover, this validates that the LENS method can produce superior quality metals and alloys free of contaminants and impurities for use in implants. The XRD plots of the oxidized pure Zr samples for the 6O2h and 6O6h samples, respectively, are shown in Fig. 2 (b and c) . XRD peaks suggested that resultant phases mainly composed of in-situ developed oxide coatings of ZrO 2 and Zr 2 O Fig. 2 (b,c and d) after TO treatment on Zr samples. The (Ti–Zr)O 4 diffraction peaks were found for the two oxidised Zr–50Ti specimens. The primary oxide phase of grown ceramic layer was (Ti–Zr)O 4 identified shown in Fig. 4b . Ti and Zr exhibit considerable affinity for oxygen at high temperatures, as is thermodynamically reported. Both elements participated equally in the oxidation process at 600°C for 2 and 6h, respectively, under the conventional surface treatment conditions [ 26 ]. Further, Fig. 5A and Fig. 5B shows the wear rate of bare Zr, Zr-50Ti alloy and their oxidized samples. In comparison to Zr and Zr-50Ti samples that were not treated, their respective oxidized samples showed lower wear rates in SBF at 37 ± 1°C. Furthermore, when TO-treated samples were compared to bare Zr and Zr-50Ti samples, the wear rate of the 6O2h and 6O6h samples decreased dramatically ( Fig. 5 ). The wear rate of samples oxidized at 600°C for 6 h was 2.87 ×10 − 6 mm 3 /N m, which is two times lesser than that of untreated Zr, which was 4.99 ×10 − 4 mm 3 /N m. The formation of hard, well adhere and tough in-situ oxide layers on the Zr and its alloy surface results in decreased wear rates shown in worn morphologies of untreated and oxidized samples depicted in Fig. 6 (a-f) . The grooves are abrasive in nature in case of worn morphology of both the untreated samples. The micro cutting, shallow and smooth grooves formed when pure Zr oxidized samples undergone wear test. Whereas deep, wide and micro grooves observed when Zr-50Ti after oxidation treatment went through wear test. In the freshly prepared HBSS solution, the in-situ produced ceramic layers and untreated Zr and Zr-50Ti were tested for their in-vitro electrochemical properties. The results of these tests are displayed as potentiodynamic polarisation curves (PPC), as shown in Fig. 7A&B . The passivity range for the samples was determined by the difference between the breakdown potential (Eb) and zero current potential (Zcp), as shown in Table 1 . Table 1 lists the passive range of the untreated alloy Zr-50Ti, which is 858 mV. In contrast, the passivity range after oxidation declined to 1136 mV and then slightly increased upto 1207 mV of Zr-50Ti6O2h and Zr-50Ti6O6h samples respectively. Passivity ranges were greater in both situations than in samples found of Zr-50Ti alloy. Further the range of passivity of untreated Zr samples is observed as 1372 mV although post oxidation of these samples at 600 for 2 and 6h the passive ranges were 1324 and 1414 mV recorded respectively. However, the passivity range decreased owing to the multi-break-down potentials observed in samples. It is expected that oxide coating will dissolve in the HBSS solution, but still, it shows resistance to corrosion of the pure Zr and Zr-50Ti samples. Among all the samples the lowest current density of 0.006 µA/mm 2 and highest passive ranges of 1414 was found for Zr6O6h samples. In contrast, all other oxidised samples of Zr and Zr-50Ti alloys showed good corrosion current density and optimal corrosion potential. Oxidized specimens showed better corrosion resistance because of their outstanding stability. 4. Conclusions The surface oxidation method effectively developed well-adherent, in-situ grown ceramic coatings on Zr and Zr-50Ti alloy produced by LENS™. Thermal oxidation treatments led to the formation of oxide layers specifically ZrO 2 and (Zr-Ti)O 4 as confirmed by XRD analysis. The oxidised Zr samples demonstrated significantly enhanced chemical stability in HBSS (pH = 7.4), evidenced by a positive shift in corrosion potential and a substantial reduction in corrosion current density compared to Zr-50Ti alloy samples. Additionally, the robust and hard oxide coatings greatly improved the wear resistance of the oxidized samples compared to their bare counterparts. Among all the samples, Zr6O6h exhibited the best corrosion resistance, superior wear resistance, and optimal layer thickness. Based on these findings, oxidized samples are recommended for further advanced clinical-level in-vitro and in-vivo biological testing for potential use in load-bearing implants and orthopaedic applications. Credit authorship contribution statement Nimu Chand Reger : Writing-review & editing, writing-original draft, validation, supervision, project administration, methodology, investigation, formal analysis, data curation, conceptualization. Bavya Devi Karuppasamy : Writing-review & editing. Declarations Funding: This research did not receive any funding Data availability : All data generated or analysed during this study are included in the published article. Declaration of competing interest : The authors declare that they have no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Conflicts of Interest : Authors declare no conflict of interest. Ethics approval and consent to participate : Not applicable Consent for publication : Not applicable Author Contribution Credit authorship contribution statementNimu Chand Reger: Writing-review & editing, writing-original draft, validation, supervision, project administration, methodology, investigation, formal analysis, data curation, conceptualization. Bavya Devi Karuppasamy: Writing-review & editing. 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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-6368274","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":453837331,"identity":"3986efeb-7f5b-4dc8-92e6-e9baf8ad7d88","order_by":0,"name":"Nimu Chand Reger","email":"","orcid":"","institution":"NIT Trichy","correspondingAuthor":false,"prefix":"","firstName":"Nimu","middleName":"Chand","lastName":"Reger","suffix":""},{"id":453837332,"identity":"074c3936-58f0-4b50-9ca0-1a0476cd3111","order_by":1,"name":"Bavya Devi Karuppasamy","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA3klEQVRIiWNgGAWjYDCCAzxgioexvQFIGVgQr0WGuecASIsE8Vps2GckgGgitPDdPnvwM2+bHQ/vzOdXN/wokGDgb+9OwKtF8lxesjRvWzKP5Oycsps9QIdJnDm7Aa8WgzM8BpIz25h5DGfnpN3gAWoxkMglqMX458y2eh77m2fSbv4hUouZxMe2wzyMM9iP3SbKFskzfGkWH84d52HsyWG7LWMgwUPQL3xneA/fSCirtmdsP/7s5ps/NnL87b34tYABIxuI5DEAk4SVg8EfEMH+gEjVo2AUjIJRMNIAAHPWR9wt+QDXAAAAAElFTkSuQmCC","orcid":"","institution":"KPR Institute of Engineering and Technology","correspondingAuthor":true,"prefix":"","firstName":"Bavya","middleName":"Devi","lastName":"Karuppasamy","suffix":""}],"badges":[],"createdAt":"2025-04-03 10:08:20","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6368274/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6368274/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":82332518,"identity":"489a7672-bf81-4f39-985a-dc0e819ac74f","added_by":"auto","created_at":"2025-05-09 07:34:59","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":151380,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representations of advanced production techniques (a) Vacuum Arc Melting [5](b) Laser Engineering Net shape [6] (c) Plasma Arc Melting [7] (d) Electron Beam melting [8] for Ti and its alloys manufacturing\u003c/p\u003e","description":"","filename":"1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/49b8d48c1f3593b471856dd4.jpg"},{"id":82332144,"identity":"53fd04f9-4be4-43eb-a6db-c3119f6bf7e0","added_by":"auto","created_at":"2025-05-09 07:26:59","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":201939,"visible":true,"origin":"","legend":"\u003cp\u003eExperimental and testing scheme (a) Pictorial view of LENS @CGCRI Kolkata [6](b) Process Parameters of LENS [6](c) Binary Phase diagram of Ti-Zr alloy [15] (d) LENS and Surface Treatment cycle (e) Typical prototype of dense HIP implant [6](f) Worn Morphology of Zr and Zr-Ti alloy samples\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/e33348f9473b09cff8ea24a3.jpg"},{"id":82332148,"identity":"48d553ca-5dab-48f9-b624-443d9212c48c","added_by":"auto","created_at":"2025-05-09 07:26:59","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":754360,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCoating thickness and Surface morphology of untreated and TO-treated Zr and Zr-50Ti samples\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/bb1d3252374181234dd8e9c5.png"},{"id":82332176,"identity":"3a0125fd-d7fd-4393-a979-b4a1e806707c","added_by":"auto","created_at":"2025-05-09 07:27:00","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":603531,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of untreated and TO-treated Zr and Zr-50Ti A (a) Pure Zr (b) Zr6O2h (c) Zr6O6h (d)Zr8O2h and B (a) Zr-50Ti (b) Zr-50Ti6O2h (c) Zr-50Ti6O6h samples\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/2721ad83e379c878bfa662ba.png"},{"id":82332146,"identity":"b8c9a87c-46d8-478c-80cf-e15d2fd16916","added_by":"auto","created_at":"2025-05-09 07:26:59","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":335822,"visible":true,"origin":"","legend":"\u003cp\u003eWear rate of (A) untreated and TO-treated Zr and (B) untreated and TO-treated Zr-50Ti samples\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/b11b82ea90e1f128710259ab.png"},{"id":82332149,"identity":"ef1121d9-4c05-42d0-a5de-b55ded7cf2a5","added_by":"auto","created_at":"2025-05-09 07:26:59","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":835585,"visible":true,"origin":"","legend":"\u003cp\u003eWorn morphology (a) Zr (b) Zr6O2h (c) Zr6O6h (d) Zr-50Ti (e) Zr-50Ti6O2h Zr-50Ti6O6h samples\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/719783d585436d65997530d2.png"},{"id":82332528,"identity":"acc33398-a2d3-4ff3-b507-ec06c86f514b","added_by":"auto","created_at":"2025-05-09 07:34:59","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":330540,"visible":true,"origin":"","legend":"\u003cp\u003ePotentiodynamic polarization curves A (a) Pure Zr (b) Zr6O2h (c) Zr6O6h (d)Zr8O2h and B (a) Zr-50Ti (b) Zr-50Ti6O2h (c) Zr-50Ti6O6h\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/2dac5a0eeda93723571e9914.png"},{"id":85378986,"identity":"54cc97e4-8cf5-4fdf-8c57-eb2dbb69cfae","added_by":"auto","created_at":"2025-06-25 08:54:14","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4439099,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6368274/v1/4d4ba8cc-b7e1-4c61-9e39-30898adf7383.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Advanced Melting Techniques for Titanium and Zirconium Alloys and Tribological Studies in Medical Implant Manufacturing","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eIt has been reported that by 2030 around 80\u0026nbsp;million people belongs 38\u0026ndash;42 years of age, required total joint replacements (TJR) globally [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. The average service life of hip replacements implant lies between 10 and 15 years maximum. Presently metallic materials (Co base alloys, Ti alloys, 316L stainless steel) and ceramic materials such as (Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, zirconia-toughened alumina, hydroxyapatite) are frequently used in TJR. Further among the polymer materials ultra-high molecular weight polyethylene (UHMWPE) used as liner in articulating components of TJR [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. The excellent corrosion resistance and biocompatibility of zirconium and its alloys have made them one of the most demanded implants [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. The complete solid solubility of Zr in Ti makes this binary alloy most corrosive resistant implant material. Generally surfaces of Zr and Ti are passivated by tiny oxide layers formed naturally in air or electrolytes [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn the 21st century among all the prime materials used in dentistry or orthopaedic prostheses is Ti\u0026ndash;Zr alloy [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Among the advance melting and casting techniques Vacuum Arc Remelting (VAR) is widely for melting reactive metals like Ti and Zr. It involves the use of a vacuum to prevent contamination and a consumable electrode made of the metal to be melted. The metal electrode is struck by an arc in a vacuum chamber, causing it to melt and drip into a water-cooled copper crucible below. The vacuum environment minimizes the introduction of impurities. Produces high-purity ingots with a uniform composition and reduces the inclusion of gases like oxygen and nitrogen, which are detrimental to the metal's properties. Better control of melting rate is the main benefit of the vacuum arc remelting process against vacuum induction melting technique. This results in an overall directional solidification front which provides equiaxed cast structure for better microstructure and mechanical properties.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe schematic representations of advanced production techniques shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea-d. A cross section of a distinctive VAR furnace working co-axially was displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. At high temperature a metal vapour plasma arc that strikes from the electrode to the forming ingot melts the input material, generally referred as the electrode. The furnace is known as coaxial when the return feed from the power source is coupled around the crucible flange [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. The details of process parameters and operation of VAR is given elsewhere [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e] as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed. Electron Beam Melting (EBM) melts metal in a vacuum by using an electron beam as the heat source. An electron gun generates a focused beam that melts the metal feedstock. The melted metal pools in a water-cooled copper crucible, and the process is controlled to ensure a uniform composition. EBM is highly effective at producing extremely pure metals and allows precise control over the melting process [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Ti-6Al-4V has been the subject of a large number of research studies, reporting on surface treatments aimed at enhancing biocompatibility and osseointegration with tissues [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn a study on Ti\u0026ndash;6Al\u0026ndash;4V melted and casted by SLM and EBM techniques, Wang et al. [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e] assessed the biocompatibility of products in both \u003cem\u003ein-vitro\u003c/em\u003e and \u003cem\u003ein-vivo\u003c/em\u003e procedures. Ara\u0026uacute;jo et al. [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e] used the plasma arc melting method (schematic in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec) to produce Cu-based alloys and Ni\u0026ndash;Ti alloys for biomaterials applications [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. In addition to plasma arc melting one of the popular and latest advance melting and casting technique that is Laser Engineering Net Shape (LENS) (shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb) technique widely used for aerospace, automobile and biomaterials component production. Directional solidification/cooling rates are possible with LENS machines because they produce smaller melt-pools than with traditional manufacturing techniques like die, sand and investment castings [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e], [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Though, the ability to cast with different precursors and develop functionally graded objects, owing to numerous powder feed lines is a uniqueness of the LENS technique [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Furthermore, it is reported that LENS manufactured components are found to be more strong and ductile without any crack or damage under static loads suitable for key industries such as medical and aerospace [\u003cspan additionalcitationids=\"CR22\" citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u0026ndash;[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. The numerous distinct features of LENS in contrast to existing conventional casting methods, provide a variety of intriguing prospects for component manufacture that have been utilized for orthopaedic implant applications. In order to facilitate the process of bone osseointegration, different LENS manufactured hip stem implants are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e\u003cb\u003e(e)\u003c/b\u003e with different level of porosity as per casting parameters. Another significant benefit of the LENS method is that manufacturing may be done on items with uneven surfaces and without the requirement for a powder bed after the material is delivered to a build area [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. In concern with present investigation Reger et al [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e] mentioned about the wear of UHMWPE is a major challenge of TJR that leads to implant failure and revision of the surgery.\u003c/p\u003e \u003cp\u003eWear-induced osteolysis in TJR has been addressed by the development of several ceramic coatings on additively manufactured metallic implants such as Zr, Ti-Zr alloy, Mg, Co-Cr-Mo alloys, 316L SS [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. It was observed that these ceramic coatings provide excellent biocompatibility and mechanical stability. In this study, Pure Zr and Zr-50Ti alloy was melted and casted by advance LENS method successfully. The oxidation treatment on the surface of Ti\u0026ndash;50Zr alloy was carried out at 600 ◦C for duration of 2 and 6 h. In contrast to other surface treatment methods, the current study\u0026rsquo;s strength is the use of inexpensive and effective thermal oxidation (TO) treatment for the development of in-situ developed ceramic layers on Zr and Ti-50Zr metallic substrates. Furthermore, a thorough investigation was carried out to evaluate the corrosion and wear characteristics of developed oxide coatings in simulated body fluid (SBF) and Hank\u0026rsquo;s Balanced Salt Solution (HBSS) respectively. The sequence of experimental and testing scheme are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. As far as we are aware, there aren't many studies on the wear and corrosion resistance of pure Zr and Zr-50Ti binary alloys made with the LENS process for use in total joint replacements (TJR).\u003c/p\u003e"},{"header":"2. Materials and Method","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Advance melting and casting of Zr and Zr-50Ti samples by using LENS\u0026trade;\u003c/h2\u003e \u003cp\u003eHighly pure (99.9%) metal powders of Zirconium and Titanium, provided by TLS Technik GmbH \u0026amp; Co., Germany, particle sizes in the range of 50 \u0026micro;m\u0026ndash;150 \u0026micro;m, used as precursor materials for the melting and casting of Zr and Zr-50Ti alloy (by wt %) in compact form by the LENS method process parameters for the alloy casting shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb. Thermal oxidation (TO) procedures were subjected to all the samples (pure Zr and Zr-50Ti alloy) at similar parameters in a standard tubular heat treatment furnace under flowing 99.98% pure O\u003csub\u003e2\u003c/sub\u003e at 600\u003csup\u003e◦\u003c/sup\u003eC for 2 and 6 h. To avoid contamination, acetone and an ultrasonic cleaner are used to clean all the samples.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Coating thickness, phase identifications\u003c/h2\u003e \u003cp\u003eScanning electron microscopy (SEM, Phenom ProX, Netherlands) cross-sectional micrographs were utilised to measure the oxide layer thickness grown after TO treatments. During tribological testing, further SEM was used to evaluate wear damage on the surface of the pure Zr, Zr-50Ti alloy and oxidised specimens. The phases were identified by X-ray diffraction (XRD) analysis using Siemens\u0026rsquo; D500 Kristalloflex diffractometer.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. In-Vitro tribological testing\u003c/h2\u003e \u003cp\u003eAs per ASTM G 99\u0026thinsp;\u0026minus;\u0026thinsp;5, a ball-on-disk tribometer (NANOVEA Microphotonics Inc., CA, USA, was utilised for all sliding wear tests in the freshly make simulated physiological fluid, with a constant temperature of 37\u0026thinsp;\u0026plusmn;\u0026thinsp;1 ◦C. Prior research has conducted and detailed the preparation procedure for the simulated bodily fluid (SBF) utilised in the wear test [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Using a non-contact type surface profilometer, the recorded wear track depth and width were used to calculate the sample's average wear rate (mm\u003csup\u003e3\u003c/sup\u003e/Nm).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. In-vitro corrosion testing\u003c/h2\u003e \u003cp\u003eFollowing the published technique, the electrochemical experiments were carried out in the chemically synthesised HBSS using a multichannel potentiostat/galvanostat (SP300, Bio-Logic SAS, France) [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Before the polarisation investigation, pure Zr, Zr-50Ti, and TO-subjected specimens were allowed to stabilise in HBSS for one hour in order to obtain a stable open circuit potential (OCP). The corrosion studies were performed at a scanning rate of 10 mV/min from 0.25 V to +\u0026thinsp;1.6 V against OCP. The corrosion potential (Ecorr) and corrosion current density (Icorr), which are important parameters for corrosion study, were computed using Tafel extrapolation.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Result and discussions","content":"\u003cp\u003eWhen developing Ti base metallic load bearing femoral stems via advance melting and casting route, the alloying addition of Zr to Ti offers various benefits from a metallurgical perspective. First, it is noted that at 20\u0026deg;C, Zr has a density of 6.50 g/cc. This low density makes it possible to create light weight Zr-Ti binary alloys for TJR applications. This binary alloy will be capable to solve the problem of stress shielding effect and minimize the revision of surgery. Second, over the full composition range, the Zr-Ti binary system produces a continuous solid solution for both the low temperature \u0026alpha;-phase with the hexagonal close packed (HCP) structure and the high temperature \u0026beta;-phase with the body-cantered cubic (BCC) structure. This is because of Zr and Ti mix well together the microstructure of pure Zr and Zr-50Ti alloy displayed in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec.\u003c/p\u003e\n\u003cp\u003eIn contrast to multi-phase alloys, this capacity to produce a single-phase structure at any composition is desirable from the perspective of chemical stability since it prevents implants from galvanic corrosion in bodily fluids. Addition of Ti to Zr effectively decreases liquidus temperatures, and at about Ti-38 at% Zr composition, the congruent temperature of 1540\u0026deg;C is reached (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec). By reducing liquidus temperatures, Zr addition has a beneficial influence on the solidification process used to produce industrial and biomedical gadgets. Because load-bearing metallic biomaterials are employed in live bodies under loading conditions that are within their elastic limits, it is preferable that their elastic characteristics be as near to those of human cortical bone.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\n \u003ctable id=\"Tab1\" border=\"1\"\u003e\n \u003ccaption\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eFilm thickness and Electrochemical properties of oxidized and unoxidized Zr and Zr-50Ti samples\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample ID\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eFilm thickness (\u0026micro;m)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eE\u003csub\u003ecorr\u003c/sub\u003e (mV)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eI\u003csub\u003ecorr\u003c/sub\u003e (\u0026micro;A/mm\u003csup\u003e2\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003ePassive range (mV)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ePure Zr\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eNA\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-228\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.018\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1372\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eZr-6O2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-276\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.023\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1324\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eZr-6O6h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e7\u0026thinsp;\u0026plusmn;\u0026thinsp;0.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-186\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.006\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1414\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eZr-8O2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e20\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-347\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.017\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1253\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eZr-50Ti\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eNA\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-478\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e-1.16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e858\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eZr-50Ti 6O2h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e20.25\u0026thinsp;\u0026plusmn;\u0026thinsp;4.67\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-109\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1207\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eZr-50Ti 6O6h\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e38.21\u0026thinsp;\u0026plusmn;\u0026thinsp;7.26\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-202\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.36\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1136\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e depicts the surface morphology and coating thicknesses of oxidized Zr and Zr-50Ti samples. It can be noticed from Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e \u003cstrong\u003eand\u003c/strong\u003e Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e that the thicknesses of the in-situ grown oxide coatings enhanced as the oxidation treatment temperature and soaking period increased. No cracks, flaws, pores and delamination were visible because of strong adhesion of ceramic layers to both substrates. In comparison to Zr-50Ti ceramic layer thicknesses, the total oxide layer thicknesses on Zr were lower. This can be explained thermodynamically by the fact that O\u003csub\u003e2\u003c/sub\u003e has a greater affinity for Ti (\u0026Delta;G\u0026thinsp;=\u0026thinsp;\u0026minus;\u0026thinsp;218 Kcal/mol for TiO\u003csub\u003e2)\u003c/sub\u003e than for Zr (\u0026Delta;G\u0026thinsp;=\u0026thinsp;\u0026minus;\u0026thinsp;118 Kcal/ mol for ZrO\u003csub\u003e2\u003c/sub\u003e). The highest oxide thickness measured in particularly Zr-50Ti samples those oxidized at 600\u0026deg;C for 6h duration in presence of pure oxygen.\u003c/p\u003e\n\u003cp\u003eThe XRD patterns of the Zr, Zr-50Ti alloy, and oxidized specimens are displayed in \u003cstrong\u003eFig.\u0026nbsp;4(a\u0026ndash;b)\u003c/strong\u003e, respectively. It can observed from Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea \u003cstrong\u003e\u0026amp;b\u003c/strong\u003e, Zr and Zr-50Ti alloy were found to have pure Zr and a solid solution phase made up of Zr-50Ti binary alloy, respectively, in their XRD patterns. Moreover, this validates that the LENS method can produce superior quality metals and alloys free of contaminants and impurities for use in implants. The XRD plots of the oxidized pure Zr samples for the 6O2h and 6O6h samples, respectively, are shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e\u003cstrong\u003e(b and c)\u003c/strong\u003e. XRD peaks suggested that resultant phases mainly composed of in-situ developed oxide coatings of ZrO\u003csub\u003e2\u003c/sub\u003e and Zr\u003csub\u003e2\u003c/sub\u003eO Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e \u003cstrong\u003e(b,c and d)\u003c/strong\u003e after TO treatment on Zr samples.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\n \u003cdiv class=\"colspec\" align=\"left\"\u003e\u0026nbsp;\u003c/div\u003e\n \u003cdiv class=\"colspec\" align=\"left\"\u003e\u0026nbsp;\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eThe (Ti\u0026ndash;Zr)O\u003csub\u003e4\u003c/sub\u003e diffraction peaks were found for the two oxidised Zr\u0026ndash;50Ti specimens. The primary oxide phase of grown ceramic layer was (Ti\u0026ndash;Zr)O\u003csub\u003e4\u003c/sub\u003e identified shown in \u003cstrong\u003eFig.\u0026nbsp;4b\u003c/strong\u003e. Ti and Zr exhibit considerable affinity for oxygen at high temperatures, as is thermodynamically reported. Both elements participated equally in the oxidation process at 600\u0026deg;C for 2 and 6h, respectively, under the conventional surface treatment conditions [\u003cspan class=\"CitationRef\"\u003e26\u003c/span\u003e]. Further, \u003cstrong\u003eFig.\u0026nbsp;5A and Fig.\u0026nbsp;5B\u003c/strong\u003e shows the wear rate of bare Zr, Zr-50Ti alloy and their oxidized samples. In comparison to Zr and Zr-50Ti samples that were not treated, their respective oxidized samples showed lower wear rates in SBF at 37\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u0026deg;C. Furthermore, when TO-treated samples were compared to bare Zr and Zr-50Ti samples, the wear rate of the 6O2h and 6O6h samples decreased dramatically (\u003cstrong\u003eFig.\u0026nbsp;5\u003c/strong\u003e). The wear rate of samples oxidized at 600\u0026deg;C for 6 h was 2.87 \u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e mm\u003csup\u003e3\u003c/sup\u003e/N m, which is two times lesser than that of untreated Zr, which was 4.99 \u0026times;10 \u003csup\u003e\u0026minus;\u0026thinsp;4\u003c/sup\u003e mm\u003csup\u003e3\u003c/sup\u003e/N m.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\n \u003cdiv class=\"colspec\" align=\"left\"\u003eThe formation of hard, well adhere and tough \u003cem\u003ein-situ\u003c/em\u003e oxide layers on the Zr and its alloy surface results in decreased wear rates shown in worn morphologies of untreated and oxidized samples depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e \u003cstrong\u003e(a-f)\u003c/strong\u003e. The grooves are abrasive in nature in case of worn morphology of both the untreated samples. The micro cutting, shallow and smooth grooves formed when pure Zr oxidized samples undergone wear test. Whereas deep, wide and micro grooves observed when Zr-50Ti after oxidation treatment went through wear test.\u0026nbsp;\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eIn the freshly prepared HBSS solution, the in-situ produced ceramic layers and untreated Zr and Zr-50Ti were tested for their in-vitro electrochemical properties. The results of these tests are displayed as potentiodynamic polarisation curves (PPC), as shown in \u003cstrong\u003eFig.\u0026nbsp;7A\u0026amp;B\u003c/strong\u003e. The passivity range for the samples was determined by the difference between the breakdown potential (Eb) and zero current potential (Zcp), as shown in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\n \u003cdiv class=\"colspec\" align=\"left\"\u003eTable\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e lists the passive range of the untreated alloy Zr-50Ti, which is 858 mV. In contrast, the passivity range after oxidation declined to 1136 mV and then slightly increased upto 1207 mV of Zr-50Ti6O2h and Zr-50Ti6O6h samples respectively. Passivity ranges were greater in both situations than in samples found of Zr-50Ti alloy. Further the range of passivity of untreated Zr samples is observed as 1372 mV although post oxidation of these samples at 600 for 2 and 6h the passive ranges were 1324 and 1414 mV recorded respectively. However, the passivity range decreased owing to the multi-break-down potentials observed in samples. It is expected that oxide coating will dissolve in the HBSS solution, but still, it shows resistance to corrosion of the pure Zr and Zr-50Ti samples. Among all the samples the lowest current density of 0.006 \u0026micro;A/mm\u003csup\u003e2\u003c/sup\u003e and highest passive ranges of 1414 was found for Zr6O6h samples. In contrast, all other oxidised samples of Zr and Zr-50Ti alloys showed good corrosion current density and optimal corrosion potential. Oxidized specimens showed better corrosion resistance because of their outstanding stability.\u003c/div\u003e\n\u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eThe surface oxidation method effectively developed well-adherent, \u003cem\u003ein-situ\u003c/em\u003e grown ceramic coatings on Zr and Zr-50Ti alloy produced by LENS\u0026trade;. Thermal oxidation treatments led to the formation of oxide layers specifically ZrO\u003csub\u003e2\u003c/sub\u003e and (Zr-Ti)O\u003csub\u003e4\u003c/sub\u003e as confirmed by XRD analysis. The oxidised Zr samples demonstrated significantly enhanced chemical stability in HBSS (pH\u0026thinsp;=\u0026thinsp;7.4), evidenced by a positive shift in corrosion potential and a substantial reduction in corrosion current density compared to Zr-50Ti alloy samples. Additionally, the robust and hard oxide coatings greatly improved the wear resistance of the oxidized samples compared to their bare counterparts. Among all the samples, Zr6O6h exhibited the best corrosion resistance, superior wear resistance, and optimal layer thickness. Based on these findings, oxidized samples are recommended for further advanced clinical-level \u003cem\u003ein-vitro\u003c/em\u003e and \u003cem\u003ein-vivo\u003c/em\u003e biological testing for potential use in load-bearing implants and orthopaedic applications.\u003c/p\u003e \u003cp\u003e \u003cb\u003eCredit authorship contribution statement\u003c/b\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eNimu Chand Reger\u003c/b\u003e: Writing-review \u0026amp; editing, writing-original draft, validation, supervision, project administration, methodology, investigation, formal analysis, data curation, conceptualization. \u003cb\u003eBavya Devi Karuppasamy\u003c/b\u003e: Writing-review \u0026amp; editing.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eFunding:\u003c/h2\u003e \u003cp\u003eThis research did not receive any funding\u003c/p\u003e \u003cp\u003e \u003cb\u003eData availability\u003c/b\u003e: All data generated or analysed during this study are included in the published article.\u003c/p\u003e \u003cp\u003e \u003cb\u003eDeclaration of competing interest\u003c/b\u003e: The authors declare that they have no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003cp\u003e \u003cb\u003eConflicts of Interest\u003c/b\u003e: Authors declare no conflict of interest.\u003c/p\u003e \u003cp\u003e \u003cb\u003eEthics approval and consent to participate\u003c/b\u003e: Not applicable\u003c/p\u003e \u003cp\u003e \u003cb\u003eConsent for publication\u003c/b\u003e: Not applicable\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eCredit authorship contribution statementNimu Chand Reger: Writing-review \u0026amp; editing, writing-original draft, validation, supervision, project administration, methodology, investigation, formal analysis, data curation, conceptualization. Bavya Devi Karuppasamy: Writing-review \u0026amp; editing.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eN.C.R would like to acknowledge the support from the Director, National Institute of Technology Tiruchirappalli and B.D.K acknowledge the support of Principal, KPR Institute of Engineering and Technology, Coimbatore, Tamil Nadu to carry out this research work.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eN. C. Reger, V. K. Balla, M. Das, and A. K. Bhargava, \u0026ldquo;Wear and corrosion properties of in-situ grown zirconium nitride layers for implant applications,\u0026rdquo; \u003cem\u003eSurf. Coatings Technol.\u003c/em\u003e, vol. 334, no. 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Coatings Technol., vol. 283, pp. 101\u0026ndash;107, 2015, doi: \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1016/j.surfcoat.2015.10.051\u003c/span\u003e\u003cspan address=\"10.1016/j.surfcoat.2015.10.051\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Zr-50Ti alloy, Thermal oxidation, Wear and Electrochemical resistance, Medical implant","lastPublishedDoi":"10.21203/rs.3.rs-6368274/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6368274/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe melting and casting of titanium (Ti) and zirconium (Zr) are crucial in foundries producing high-performance medical implants for orthopedic and dental applications. These reactive metals exhibit high melting points, exceptional corrosion resistance, biocompatibility, and thermal stability, making them ideal for medical devices. This study provides a comprehensive overview of advanced melting techniques such as Plasma Arc Melting, Electron Beam Melting (EBM), and Vacuum Arc Remelting (VAR), which ensure high purity and uniform composition. Foundry casting methods, including investment casting, centrifugal casting, and continuous casting, facilitate the fabrication of complex implant geometries. Additionally, additive manufacturing, specifically Laser Engineering Net Shape (LENSTM), enhances implant longevity, wear resistance, and corrosion performance. The production of pure Zr and Zr-50Ti alloy was conducted via laser-based melting and casting, followed by surface oxidation treatments. Oxide layers were successfully grown on Zr and Zr-50Ti surfaces, and detailed assessments of coating morphology, oxide phases, wear resistance, and corrosion behavior were performed. X-ray diffraction confirmed the formation of Zr and Ti oxides. Oxidation at 600\u0026deg;C for 6 hours yielded the lowest in-vitro wear rate (2.12\u0026thinsp;\u0026plusmn;\u0026thinsp;0.36 \u0026times; 10⁻⁶ mm\u0026sup3;/N\u0026middot;m), attributed to the increased ceramic layer thickness. Furthermore, compared to untreated samples, oxidized surfaces exhibited significantly enhanced in-vitro corrosion resistance in Hanks' Balanced Salt Solution (HBSS). These findings demonstrate that controlled oxidation improves the functional performance of Ti- and Zr-based implants, making them more suitable for biomedical applications.\u003c/p\u003e","manuscriptTitle":"Advanced Melting Techniques for Titanium and Zirconium Alloys and Tribological Studies in Medical Implant Manufacturing","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-09 07:26:54","doi":"10.21203/rs.3.rs-6368274/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"3d59f871-33de-4fb7-920c-90b06b66cf5c","owner":[],"postedDate":"May 9th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-06-25T08:53:41+00:00","versionOfRecord":[],"versionCreatedAt":"2025-05-09 07:26:54","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6368274","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6368274","identity":"rs-6368274","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}