Medical device or medical device component and process for preparing it

Abstract

The present invention relates to a medical device or medical device component comprising a core body made of an amorphous alloy, wherein the main alloy component of the amorphous alloy is selected from the group consisting of titanium copper (TiCu) and zirconium copper (ZrCu). The device of the invention is characterized in that it further comprises a coating formed on at least a part of a surface of the core body, the coating containing a diamond-like carbon (DLC) layer.

Description

[0001]Medical device or medical device component and process for preparing it The present invention relates to a medical device or medical device component according to the preamble of claim 1 as well as to a process for preparing the medical device or medical device component. Medical devices, such as surgical devices or dental implants or even instruments, are typically made of a material, which is biocompatible and exhibits mechanical properties meeting the respective requirements of the device. Dental implants, for example, are typically made of titanium or of a ceramic material, in particular a zirconia-based ceramic. In addition, dental implants made of a titanium alloy have been successfully introduced to the market owed to the material’s excellent combination of high strength, high corrosion resistance and sufficient biocompatibility. Despite the excellent mechanical properties of titanium alloys currently in use, further downsizing of dental implants as well as other medical devices is limited. To meet the need in modern surgery for further downsizing medical devices without compromising the mechanical properties to an unacceptable extent, amorphous metals, and in particular Bulk Metallic Glasses, have recently gained increasing attention. For example, CN110464497A relates to a dental implant made of a titanium-based amorphous metal, which is characterized by A23615WO / 30.12.2024 / including: 30-75 parts of titanium, 0-25 parts of zirconium, 0-45 parts of copper, 0-20 parts of silicon, 0-10 parts of iron, 0-10 parts of zinc, 0-5 parts of silver, and 0-15 parts of palladium. Similarly, CN110464498A relates to a zirconium-based amorphous metal dental implant, which is characterized by including: 30- 65 parts of zirconium, 0-25 parts of titanium, 0-45 parts of copper, 0-20 parts of aluminum, 0-20 parts of silicon, 0-10 parts of iron, 0-10 parts of zinc, and 0-5 parts of palladium. Amorphous metals of the composition disclosed in CN110464497A have been found to have the potential of exhibiting a compressive yield strength and a fatigue resistance much higher than that of Ti-6Al-4V. In addition, this material has been found to present a high biocompatibility. Thus, the material represents an interesting candidate for applications where a downsizing of an item is aimed at but where a decrease in the mechanical properties must be avoided or at least kept low. H.F. Li et al., “Recent advances in bulk metallic glasses for biomedical applications”, Acta Biomaterialia 2016, 36, p. 1- 20, report on a variety of different biomedical BMGs, including Ti-based, Zr-based, Fe-based, Mg-based, Zn-based, Ca-based and Sr-based BMG alloying systems, and on the developments and advances of these materials. The article in particular discusses Zr-based and Fe-based bulk metallic glasses for biomedical implants and devices. As regards BMGs containing nickel or beryllium, which are reported to have adverse side effects on human health, the article mentions the possibility of applying a coating for preventing the release of toxic ions.A23615WO / 30.12.2024 Further, A. Liens et al., “On the Potential of Bulk Metallic Glasses for Dental Implantology: Case Study on Ti40Zr10Cu36Pd14”, Materials 2018, 11, 249) report on Ti40Zr10Cu36Pd14Bulk Metallic Glass (BMG) to be attractive for future biomedical applications thanks to its high glass forming ability, the absence of toxic elements and its good mechanical properties. This article also reports on the higher corrosion potential of the BMG compared to Ti-6Al-4V alloy, indicating that more energy is required to initiate the corrosion reaction for the BMG. However, the article also reports on the Ti-based glassy (amorphous) alloy to suffer from pitting corrosion. This unwanted effect is explained in the article referenced above by the presence of copper oxide in the passive layer surface of the BMG and the finding that copper drastically decreases the corrosion resistance of metallic alloys and metallic glasses. Many works have been devoted to developing coatings to improve the surface properties of metals such as titanium alloys, steel, carbide and aluminum components. One of the most commercially used coatings are titanium carbon nitride (TiCN), titanium aluminum nitride (TiAlN), titanium nitride (TiN) and titanium aluminum carbon nitride (TiAlCN). Unfortunately, as shown by the investigation of F. X. Qin et al. (“Microstructure and Electrochemical Properties of PVD TiN, (Ti, Al) N-coated Ti-Based Bulk Metallic Glasses”, Materials Transactions, vol 50, no 6, 1 January 2009, p. 1313-1317) reducing the pitting corrosion of BMGs is not an easy task and requires further investigations. Effectively, this article reports that the resistance to pitting corrosion of an uncoated BMG and a PVD-A23615WO / 30.12.2024 TiN-coated BMG in Hanks’ solution is identical (0.3E / V), with a slight improvement when using PVD-TiAlN coatings (as seen in Figure 5 of the article). Although the detrimental effects of the material suffering from pitting corrosion are not fully understood yet, it would in view of the material’s use for a medical device be desirable to further reduce or even eliminate this effect while maintaining the desirable properties in terms of mechanical stability and biocompatibility. In particular, it would be desirable to reduce or eliminate pitting corrosion also under harsh conditions, e.g. in an acidic environment. In view of the drawbacks mentioned above, the object of the present invention is thus to provide a medical device or medical device component, which in terms of mechanical properties and biocompatibility has the favorable properties of an amorphous alloy, in particular a Ti-based BMG such as Ti40Zr10Cu36Pd14, but which simultaneously exhibits a reduced tendency to suffer from pitting corrosion also under harsh conditions. This object is solved by the subject matter of claim 1. Preferred embodiments of the present invention are defined in the dependent claims. According to claim 1, the present invention thus relates to a medical device or medical device component comprising a core body made of an amorphous alloy, wherein the main alloy component of the amorphous alloy is selected from the group consisting of titanium copper (TiCu) and zirconium copperA23615WO / 30.12.2024 (ZrCu). In particular, the amorphous alloy is in the form of a Bulk Metallic Glass, i.e. an amorphous alloy in bulk form. The medical device or medical device component of the present invention further comprises a coating formed on at least a part of a surface of the core body, the coating containing a diamond-like carbon (DLC) layer. In the course of the present invention, it has been found that by the formation of a coating containing a DLC-layer on the surface of the core body, the material’s tendency to suffer from pitting corrosion can be reduced substantially. Ultimately, this allows to obtain a medical device which exhibits exceptional mechanical properties and which remains stable even if kept in a corrosive environment. As regards the reduced pitting corrosion tendency, it has further been found that the effect is also achieved in relatively harsh conditions, in particular in acidic conditions such as a pH of about 2. In addition, the effect has been found to be more pronounced than for a TiN coating or a TiAlN coating as disclosed in the article of F.X. Qin et al. referenced above. This in turn makes it possible to further downsize existing medical devices, which despite their reduced dimensions exhibit sufficient mechanical properties and which remain stable over time. The term “Bulk Metallic Glass” or “BMG” as used in the context of the present invention relates to an amorphous alloy (synonymous to a metallic glass) in bulk form. Specifically,A23615WO / 30.12.2024 the term “in bulk form” has in this regard the meaning that the amorphous alloy can be produced in a fully dense and amorphous rod having a diameter of at least 1 mm. In relating to a core body made of an amorphous alloy, specifically BMG, the present invention is different from technologies relating to conventional metallic substrates, such as stainless steel, and hence also from the technology described in US 2009 / 0246243. The term “diamond-like carbon” or “DLC” as used in the context of the present invention relates to a metastable form of amorphous carbon containing a significant fraction of sp3 bonds (as for example described by J. Robertson, “Diamond-like amorphous carbon, Materials Science and Engineering R 37 (2002) 129-281). More specifically, the “DLC” as used in the context of the present invention relates to an amorphous, partially hydrogenated carbon (in general referred to as a -C:H), in which some of the valence electrons of the carbon atoms are in sp3 configuration and some are in sp2 configuration. For a detailed specification of this DLC film, it is referred to VDI-Richtlinien VDI 2840, Kohlenstoffschichten; Grundlagen, Schichttypen und Eigenschaften / Carbon films; Basic knowledge, film types and properties, Verein Deutscher Ingenieure, June 2021, in particular to chapter 5.2.4 (page 18, first bulletpoint). For the purpose of the present invention, a titanium-based amorphous alloy or BMG (i.e. an amorphous alloy or BMG containing titanium and copper as main alloy components) is preferred, since it offers an exceptional specific strength, a high corrosion resistance, a high hardness, a low Young’sA23615WO / 30.12.2024 modulus, as well as a ductility and processing capabilities, which are particularly advantageous for medical devices. Among the titanium-based amorphous alloys or BMGs, a BMG of the Ti-Zr-Cu-Pd system is particularly preferred for biomedical applications, primarily owed to the absence of toxic elements, such as nickel (Ni) or beryllium (Be). In addition, amorphous alloys or BMGs of this system have been found to exhibit a glass forming ability large enough to machine dental implants and dental instruments used in oral implantology without compromising their outstanding mechanical properties. According to a specific embodiment of the present invention, the amorphous alloy contains titanium and copper as the main alloy components and further contains at least one secondary alloy component selected from the group consisting of zirconium (Zr), palladium (Pd), and mixtures thereof. In this regard, it is further preferred that the amorphous alloy, and in particular the Bulk Metallic Glass, further contains at least one tertiary alloy component selected from the group consisting of iron (Fe), gallium (Ga), tin (Sn), silicon (Si), yttrium (Y), silver (Ag), scandium (Sc), sulfur (S), niobium (Nb), hafnium (Hf), zinc (Zn), tantalum (Ta), and mixtures thereof. More specifically, the amorphous alloy contains 15-55 weight- % of titanium, 1-45 weight-% of copper, 0-30 weight-% of zirconium, 0-30 weight-% of palladium, 0-10 weight-% of silicon, 0-20 weight-% of iron, 0-10 weight-% of zinc, and 0- 20 weight-% of silver, based on the total weight of the amorphous alloy. In this regard, it is further preferred that the amorphousA23615WO / 30.12.2024 alloy, and in particular the Bulk Metallic Glass, contains 20-45 weight-%, preferably 25-35 weight-%, of titanium, 15-45 weight-%, preferably 30-40 weight-%, of copper, 5-30 weight-%, preferably 10-20 weight-% of zirconium, 0-30 weight-%, preferably 0-25 weight-% of palladium, 0-15 weight-%, preferably 0-10 weight-% of tin, 0-2 weight-%, preferably 0-1 weight-% of silicon, 0-10 weight-%, preferably 0-5 weight-% of iron, and 0-15 weight-%, preferably 0-10 weight-% of silver, based on the total weight of the amorphous alloy. Most preferably, the amorphous alloy, and in particular the Bulk Metallic Glass, is of the composition Ti40Zr10Cu36Pd14, whereby the suffixes relate to the atomic percentages of the respective components. This material has been found to exhibit particularly good mechanical properties, in particular a much higher strength and a much lower Young’s modulus compared to a Ti-6Al-4V alloy currently in use. Surprisingly, the coating according to the present invention has been found to exhibit a high scratch resistance and hence a very good adhesion when formed on an amorphous alloy. In particular, the scratch resistance and the adhesion to the substrate has been found to be improved compared to the coating being formed onto a crystalline alloy, such as Ti-6Al-4V. In addition, it has been found that the coating shows particularly good adhesion on the surface of the amorphous alloy, if formed directly on the surface of the core body. In other words, no additional silicon or titanium layer mediating bonding between the materials is required. This embodiment ofA23615WO / 30.12.2024 the present invention, in which no silicon or titanium layer is present between the amorphous alloy and the coating, is in further distinction to the technology disclosed in US 2009 / 0246243 A1, which teaches an intermediate layer comprising a silicon or a titanium material to be essential. According to a particularly preferred embodiment, the coating further contains an intermediate layer formed between the DLC layer and the surface of the core body. Said intermediate layer optionally may comprise chromium. The intermediate layer according to this embodiment has been found to function as an adhesive layer, providing particularly good adhesion and, thus, a particularly high scratch resistance of the coating. Specifically, the intermediate layer is formed directly adjacent to the surface of the core body and the DLC layer, and thus without any further intermediate layers. Typically, the coating has a thickness in the range of from 1 to 5 µm, preferably of from 2 to 4 µm, and most preferably of about 3 µm. If an intermediate layer is present, the intermediate layer typically has a thickness in the range from 250 to 750 nm, preferably of about 500 nm, with the DLC layer having a thickness in the range of from 1.25 to 3.75 µm, preferably of about 2.5 µm. In the context of the present invention, the term “thickness” relates to an average thickness of the coating or of the respective layer, taking into account that, typically, the thickness is not perfectly uniform and that the methods for determining the thickness of the coating or layer may for one surface area lead to a value slightly deviating from the oneA23615WO / 30.12.2024 determined for another area. The term “about” as used in the context of the present invention thus relates to a possible deviation from the average of the indicated thickness by up to + / - 5%. According to a preferred embodiment, the DLC layer contains a silicon-based inner layer region which is an inner DLC layer region containing silicon as a main component. The DLC layer also comprises an outer DLC layer region containing a carbon- based outer layer region which is an outer layer region containing carbon as a main component. More preferably, the proportion of silicon contained in the inner DLC layer region decreases gradually in the direction of the outer DLC layer region and the proportion of carbon contained in the outer DLC layer region decreases gradually in the direction of the inner DLC layer region. Thus, a particularly good adhesion can be established, owed to the silicon-based inner region showing improved adhesion properties compared to the carbon-based outer region. Preferably, the inner DLC layer region has in this embodiment a thickness in the range of from 250 nm to 750 nm, preferably of from 400 nm to 600 nm, and more preferably of about 500 nm. The outer DLC layer region has in this embodiment preferably a thickness in the range of from 1 µm to 3 µm, and more preferably of about 2 µm. In the context of the present invention, it has further been found that the lowering of the material’s susceptibility to pitting corrosion may to a certain degree also be governed by the surface topography of the core body. Preferably, theA23615WO / 30.12.2024 surface of the core body on which the coating is formed has an arithmetical mean roughness Sa of less than 1 µm, preferably less than 0.5 µm, more preferably less than 0.3 µm, and even more preferably less than 0.2 µm. The present invention encompasses any medical devices, and in particular any surgical and dental devices, and components thereof. In consideration of the advantages pointed out above, the medical device or medical device component is preferably a surgical device or a dental implant, prosthesis or abutment, preferably a dental implant supported prosthesis or abutment, more preferably a screw for use in a dental implant supported prosthesis or abutment, or a surgical or a dental instrument, preferably a dental instrument, more preferably a dental driving tool, or a handpiece for use in surgical or dental procedures, in particular a handpiece for dental procedures, or a motor for use in surgical or dental procedures, in particular a motor for use in dental procedures. The present invention is particularly suitable for dental instruments, since for these instruments a relative smooth core body can be used, as opposed to a dental implant, which in general requires a surface topography of a certain roughness for obtaining a high osseointegration (i.e. a fast, strong and stable interaction of the implant with the surrounding bone tissue). Since the corrosion resistance is particularly pronounced for a medical device comprising a relatively smooth core body, the medical devices or medical device components prepared according to the present invention, in particular the dental instruments obtained, have the advantage to remainA23615WO / 30.12.2024 corrosion resistant even after a long-term exposure to a humid and warm environment. According to a particularly preferred embodiment, the medical device is a dental driving tool. Nonetheless, the medical device can also be a dental implant, which can in particular be preferred in cases where a smaller implant size is aimed at, as discussed above. According to a further aspect, the present invention further relates to a process for preparing the medical device or medical device component as described above, wherein the process comprises the steps of a) providing a core body made of an amorphous alloy wherein the main alloy component of the amorphous alloy is selected from the group consisting of titanium copper (TiCu) and zirconium copper (ZrCu), and b) applying on the surface of the core body a coating containing a diamond-like carbon (DLC) layer. In a preferred embodiment of the invention, the diamond-like carbon (DLC) layer can be applied onto the surface of the core body using a vapor deposition method, in particular using Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), Plasma-Enhanced Vapor Deposition (PECVD) or combinations of these methods. According to particularly preferred embodiment, the DLC layer is applied onto the surface of the core body by Plasma-Enhanced Vapor Deposition (PECVD; also referred to as Plasma-ActivatedA23615WO / 30.12.2024 Chemical Vapor Deposition or “PACVD”), which is a combination of CVD and PVD. The preference for PECVD is owed to the relatively low process temperatures of this method, which can e.g. be lower than 250°C and thus well below the glass temperature of the amorphous alloy, in particular the Ti40Zr10Cu36Pd14, which is a preferred material of the present invention, as discussed above. Hence, the DLC layer is, according to a further preferred embodiment, applied onto the surface of the core body using a vapor deposition method at a temperature of below 300°C, preferably of below 250°C. In line with the description of a preferred embodiment of the medical device or medical device component referred to above, it is further preferred that step b) comprises the sub-steps of b.1. applying on the surface of the core body an intermediate layer, said first layer containing chromium as a main component. In this regard, it is further preferred that step b) comprises in addition the sub-steps of b.2. applying on the intermediate layer an inner DLC layer region, said inner DLC layer region containing silicon as a main component, and b.3. applying on the inner DLC layer region an outer DLC layer region, said outer DLC layer region containing carbon as a main component. As discussed above, both the inner DLC layer region and the outer DLC layer region are preferably applied by using PECVD.A23615WO / 30.12.2024 In particular in the case, in which a machined core body is provided in step a), it is preferred that the method further comprises the step of polishing the core body prior to step b). By this polishing, debris and / or burrs clinging onto the surface are efficiently removed. Ultimately, uncovered areas, which may result from debris and / or detaching from the surface after step b), can be efficiently avoided or at least decreased. As will be discussed in further detail in the context of the working examples below, a specific method of the present invention comprises the steps of - cleaning the surface of the core body to be treated by ion bombardment, e.g. using nitrogen (N); - carrying out a PVD step to deposit by ion bombardment an intermediate layer comprising chromium, whereby a bias current is applied on the target; - carrying out a PECVD step, involving plasma activation of silicone-based precursor gases promoting the precipitation of the inner DLC layer region on the surface, followed by injection of a carbon-based gas (e.g. C2H2) in the vacuum chamber to deposit the outer DLC layer region More specifically, the whole process is conducted at a temperature of below 300°C, preferably of below 250°C.A23615WO / 30.12.2024 EXAMPLES The disclosure is further illustrated by the following examples, which are not to be construed as limiting this disclosure in scope or spirit, it is to be understood that the examples are provided to illustrate certain embodiments. Unless otherwise noted, reagents and solvents were used as received from commercial suppliers. The present invention is further illustrated by way of the following working examples along with the corresponding figures, of which Fig. 1 shows the anodic potentiodynamic polarization curves of a body containing a core body made of a Ti-based BMG and a coating according to the present invention in a chlorine containing environment compared to a body solely consisting of the Ti-based BMG core body (without a coating); Fig. 2 shows the anodic potentiodynamic polarization curves of the bodies referred to in the context of Fig. 1 in both a chlorine-containing and an acidic- containing environment; Fig. 3 shows the surface defects of a body containing a coating according to the present invention (reflected by the proportion of uncoated areas in relation to the total area), a first pair of samples comprising a core body having an arithmetical meanA23615WO / 30.12.2024 roughness Sa of about 0.8 µm and a second pair of samples comprising a core body having a Sa of lower than 0.2 µm; Fig. 4 shows the anodic potentiodynamic polarization curves of the samples referred to in the context of Fig. 3 as well as of an uncoated body in a chlorine- containing and acidic-containing environment; Fig. 5 shows for three bodies according to the present invention the friction coefficient determined in relation to the load applied to the respective body in comparison to comparative samples containing a core body of a crystalline alloy (Ti-6Al-4V) coated with a DLC coating; and Fig. 6 shows for three bodies according to the present invention the friction coefficient determined in relation to the load applied to the respective body in comparison to comparative samples containing a core body of a crystalline alloy (Ti-6Al-4V) coated with a DLC coating and a core body according to the present invention but coated with a TiN coating. Analytical details PVD & PECVD a) DLC The DLC coating of the samples was carried out by a method as outlined above comprising the following steps:A23615WO / 30.12.2024 1) Cleaning of the sample surface by ion bombardment using an inert gas, for example, nitrogen (N). 2) Physical Vapor Deposition (PVD) step to deposit by ion bombardment the Cr interlayer. A bias current is applied on the target (like a polarization anode-cathode). 3) An alternative to Physical Vapor Deposition (PVD) is the Plasma-Enhanced Chemical Vapor Deposition (PECVD) which consists of the plasma activation of precursor gases promoting the precipitation of dense thin film on the sample, for example, a silicon-based one. Then, a carbon-based gas (e.g. C2H2) is injected in the vacuum chamber to deposit the carbon- based thin film. The whole process is conducted at a temperature below 250°C. b) TiN The TiN (titanium nitride) coating of the samples was carried out by a method comprising the following steps: 1) Cleaning of the sample surface by ion bombardment using an inert gas, for example, nitrogen (N). 2) Arc-assisted Physical Vapor Deposition (PVD) step to deposit titanium ejected from a metallic target by the electric arc and nitrogen introduced in a gaseous form so as to form TiN. The whole process is conducted at a temperature between 250°C and 450°C.A23615WO / 30.12.2024 Scanning electron microscope (SEM) The surface of the sample bodies was observed using a SEM TESCAN VEGA 3 at an acceleration voltage of 10 keV and a working distance of 10 mm in secondary electron (SE) mode. In backscattered electron (BSE) mode the acceleration voltage was increased to 15 keV. Energy dispersive X-ray spectroscopy (EDXS) The chemical compositions of the samples and the DLC coating were assessed by EDXS using an Oxford Instruments X-act Penta FET detector equipped on a Scanning Electron Microscope (SEM, TESCAN VEGA 3, TESCAN) at an acceleration voltage of 15 or 20 keV and at a working distance of 15 mm. The data was acquired and analyzed using the software Aztec One (Oxford Instruments). Measurement of surface defects area Surface defects (which in this context refer to surface areas of the body sample that are not covered by the DLC coating) appear in a light colour (near white) on the SEM images in backscattered electron (BSE) mode, in contrast to the covered areas which appear in dark colour (near black).The per mille (‰) of uncovered area in relation to the total usable area of the body sample was estimated by post-treating SEM images in BSE mode on the free-access image processing program ImageJ. Sa (arithmetical mean height) The surface roughness parameter Sa, defined as the arithmetical mean height to a surface, was measured using a 3D non-contactA23615WO / 30.12.2024 optical profiler Sensofar Neox machine (SENSOFAR). The measurement was completed on an acquisition area of 870 x 650 μm2with an objective x20 using Vertical Scanning Interferometry (VSI) technique. The acquired data was post- treated on the SensoMAP software (SENSOFAR) to extract the Sa parameter. Measurement of corrosion resistance The corrosion performances of the sample bodies were investigated by electrochemical measurements in a three- electrode glass cell using a Gamry instrument 600+ potentiostat (GAMRY Instruments) with a graphite rod as counter electrode and a saturated calomel electrode (SCE) as reference electrode (potential ESCE= 268 mV vs Standard Hydrogen Electrode potential at 25 °C). The working electrode consisted of a sample body connected to a copper wire on its uncoated circular face. Only the coated circular face of the sample body was in contact with the electrolyte solution, the other parts of the sample body being insulated by waterproof sheath. The electrochemical tests were performed in two different electrolyte solutions maintained at 37°C by a water circulating temperature control unit: 1) in an aerated and neutral saline solution (pH = 7.4) composed of 0.9 weight / volume percentage concentration (w / v%) of sodium chloride (NaCl) as recommended in the ISO 10271 standard and 2) in an aerated acidic saline solution (pH = 2.3) composed of 0.9 w / v% NaCl + 1 w / v% lactic acid. The electrochemical tests consisted of open circuit potential (OCP) measurements during 6H to reach a steady state and wereA23615WO / 30.12.2024 followed by linear polarization measurements. The polarization curves parameters were set to a scan rate of 0.17 mV / s (millivolt per seconds), from −0.2 V vs SCE to +1 V vs SCE. To compare the corrosion performances between the samples, the electrochemical metrics Ecorr (corrosion potential), Epit (pitting potential) and Icorr(corrosion current density) were estimated from the anodic polarization curves. In particular, Ecorrand Icorrwere estimated by Tafel’s extrapolation method. Measurement of scratch resistance The adhesion of the DLC coating on the sample bodies was estimated through scratch tests. Scratches were achieved using a Bruker UMT Tribolab equipped with a Rockwell diamond indenter (curvature radius 200 μm) in a ramp loading mode starting from 0.5 to 15 Newton for a total scratch length of 1.5 mm. Scratch tests were performed 3 times per body sample at room temperature. Similar tests were performed to measure the adhesion of the TiN coating on the sample bodies. Preparation of samples Ingots with a targeted composition of Ti40Zr10Cu36Pd14 (in atomic%), or Ti29Zr13.8Cu34.6Pd22.6 (in mass %), were prepared by arc melting highly pure elements (purities above 99.9%) in an argon atmosphere. Rods of 3.4 mm in diameter and 40 mm in length were rapidly solidified into a cylindrical water-cooled copper mold by injection casting. The composition of all the rods was controlled by Energy-Dispersive X-ray spectroscopy (EDX) on a Scanning Electron Microscope (TESCAN VEGA 3).A23615WO / 30.12.2024 From the rods obtained, smaller cylinders of 3.4 mm in diameter and 3 mm in length were cut. In the middle of each cylinder, a groove was machined on its entire circumference so that the cylinders can later be held in place by a wire during the DLC or TiN process. The groove was 0.5 μm deep with a diameter of 1 μm. For a first set of cylinder samples, core body (CBIA) was grounded and polished using silicon carbide (SiC) papers with grains of #1200 and #2500 grits to obtain a surface having an average mean roughness Sa of less than 0.2 µm. Surface polishing was conducted on a MetaServ 250 Grinder-Polisher (BUEHLER) at a rotation speed of 150 rounds per min (rpm) for 5 minutes for each SiC paper grit on both circular faces of CBI1and CBI2. For a second set of samples, core body (CBIB) having an average mean roughness Sa of about 0.8 µm was prepared. Prior to the DLC deposition, all the core bodies CBIA and CBIB were cleaned successively in an acetone bath followed by an ethanol bath (5 min per ultrasonic bath). Then, all of the core bodies were subjected to PECVD treatment, by which in a first step an intermediate layer containing chromium as a main component was deposited on the surface of the core body by PVD. On the intermediate layer, an inner silicon-based DLC layer region, which contains silicon as a main component, was applied by PECVD, followed by the application of an outer DLC layer onto the inner DLC layer deposited by PECVD, said outer DLC layer being a carbon-based DLC layer which contains carbon as a main component (regarding the details of the method, see description under “PVC & PECVD” above). Lastly, sample bodiesA23615WO / 30.12.2024 CBIAand CBIBwere cut in half at their groove using a micro- cutting machine and without damaging the circular faces coated by DLC. Cutting CBIAand CBIBresulted in 4 disks having a diameter of 3.4 mm and a length of 1 mm. Thus, sample bodies BinvA1and BinvA2(based on “smooth” core body CBIA) and sample bodies BinvB1 and BinvB2(based on “rough” core bodies CBIB) according to the present invention were achieved. For reasons of comparison, uncoated sample BcompAwas prepared in a similar way than BinvA1and BinvA2 and another uncoated sample BcompBwas prepared in a similar way than BinvB1and BinvB2. Specifically, BcompAand BcompB differ from BinvA1and BinvA2 and from BinvB1and BinvB2,respectively, in that the DLC coating step was not applied. An additional comparative sample BcompC made of Ti-6Al-4V was prepared in a similar way than BinvA1and BinvA2.Lastly, a further additional comparative sample BcompD comprising a Ti40Zr10Cu36Pd14body coated with TiN was prepared in a similar way than BinvA1and BinvA2. A list of the samples referred to above, in which the material used, the surface finish and the (non-)presence of the DLC coating is summarized, is given in Table 1 and Table 2 below, in which also the reference to the respective figure is indicated.A23615WO / 30.12.2024 Table 1 Samples ID Material Surface finish DLC (Y / N) Fig. e B No As-machined 1 B Yes B No Polished 2 B Yes B BMG Polished Yes 3 B Ti Zr Cu Pd As-machined B Polished No B Polished 4 Yes B As-machined B Polished Yes 5 B Ti-6Al-4V ELIA23615WO / 30.12.2024 Table 2 Samples Material Surface Type of Fig. ID finish Coating B BMG Ti Zr Cu Pd DLC B Ti-6Al-4V ELI Polished 6 B BMG Ti Zr Cu Pd TiN As shown in Fig. 1 (relating to the corrosion resistance measurement at physiological pH), the sample of the present invention BinvB1 showed a corrosion current density (Icorr) far lower than the one determined for the uncoated comparative sample BcompB. In addition, an ∆E (corresponding to Epit – Ecorr) was determined for the sample of the present invention, which is far higher (by a factor of about 2) than the one determined for the uncoated comparative sample. Both these results are indicative of a higher corrosion resistance and a reduced susceptibility to pitting corrosion of the sample according to the present invention over the comparative sample. A similar result in terms of a higher corrosion resistance and a reduced pitting corrosion susceptibility of the sample of the present invention BinvA1 is shown in Fig. 2 (relating to the corrosion resistance measurement in an acidic environment). According to Fig. 2, no pitting corrosion for the sample ofA23615WO / 30.12.2024 the present invention BinvA1was determined at all, showing that the coating according to the present invention is also protective in an environment which is both chlorine-containing and acidic-containing. As discussed above, it was found in the context of the present invention that the lowering of the material’s susceptibility to pitting corrosion is to a certain degree also governed by the surface topography of the core body. This is illustrated by Fig. 4, showing for sample BinvA1(based on core body CBIAhaving a relatively smooth surface) a lower sensitivity to pitting corrosion as compared to samples BinvB2(based on core body CBIB having a relatively rough surface). The surface defects of samples BinvA1and BinvB2are given in Fig. 3, showing for sample BinvB2substantially higher surface defects than for BinvA1. Although for sample BinvB2(exhibiting a relative high degree of surface defects) a slightly higher Icorr and a higher ∆E were determined than for sample BinvA1, also sample BinvB2showed a higher corrosion resistance and a further reduced pitting corrosion susceptibility over the (uncoated) comparative sample BcompA, as shown in Fig. 4. Measurement of scratch resistance For determining the scratch resistance, sample body BinvA2 according to the present invention and of comparative samples BcompC and BcompD were subjected to a scratch resistance test using a Rockwell indent and applying a ramp load from 0.5 to 15 N for a scratch length of 1.5 mm.A23615WO / 30.12.2024 The results are presented in Fig. 5, showing for the body BinvA2,according to the present invention, a friction coefficient lower than the one of the comparative sample BcompCcontaining a core body of a crystalline alloy (Ti-6Al-4V). These results give clear evidence that an improved adhesion of the DLC layer coating is achieved when applied on a core body of an amorphous alloy (according to the present invention) than when applied on a crystalline alloy. Hence, a medical device or medical device component can be achieved, which even when subjected to high forces exhibits a high scratch resistance and, hence, a low susceptibility of the coating to be scratched or to delaminate. The results presented in Fig. 6 show the difference observed during a scratch test when using a traditional alloy coating, such as TiN, and a DLC coating. The body BinvA2, according to the present invention, has a friction coefficient lower than the one of the comparative sample BcompC containing a core body of a crystalline alloy (Ti-6Al-4V), and a friction coefficient lower than the comparative sample BcompD containing a similar core body (Ti40Zr10Cu36Pd14) but this time coated with a layer made of TiN (about 2μm thickness). These results clearly show evidence that an improved adhesion of the DLC layer coating is achieved when applied on a core body of an amorphous alloy (according to the present invention) than when applied on a crystalline alloy. But more importantly, these results show that the DLC is superior to the traditional TiN coatings. Hence, a medical device with enhanced properties can be achieved, which even when subjected to high forcesA23615WO / 30.12.2024 exhibits a high scratch resistance and, hence, a low susceptibility of the coating to be scratched or to delaminate.A23615WO / 30.12.2024

Claims

Claims 1. A medical device or a medical device component comprising a core body made of an amorphous alloy, wherein the main alloy component of the amorphous alloy is selected from the group consisting of titanium copper (TiCu) and zirconium copper (ZrCu), characterized in that the device further comprises a coating formed on at least a part of a surface of the core body, the coating containing a diamond-like carbon (DLC) layer.

2. The medical device or medical device component according to claim 1, wherein the amorphous alloy is a Bulk Metallic Glass.

3. The medical device or medical device component according to any of the preceding claims, wherein the amorphous alloy contains titanium and copper as the main alloy components and further contains at least one secondary alloy component selected from the group consisting of zirconium (Zr), palladium (Pd), and mixtures thereof.

4. The medical device or medical device component according to claim 3, wherein the amorphous alloy further contains at least one tertiary alloy component selected from the group consisting of iron (Fe), gallium (Ga), tin (Sn), silicon (Si), yttrium (Y), silver (Ag), scandium (Sc), sulfur (S), niobium (Nb), hafnium (Hf), zinc (Zn), tantalum (Ta), and mixtures thereof.

5. The medical device or medical device component according to claim 4, wherein the amorphous alloy contains 15-55 weight-% of titanium, 1-45 weight-% of copper, 0-30 weight-% of zirconium, and 0-30 weight-% of palladium, 0- 10 weight-% of silicon, 0-20 weight-% of iron, 0-10A23615WO / 30.12.2024weight-% of zinc, and 0-20 weight-% of silver, based on the total weight of the amorphous alloy.

6. The medical device or medical device component according to claim 5, wherein the amorphous alloy contains 20-45 weight-%, preferably 25-35 weight-%, of titanium, 15-45 weight-%, preferably 30-40 weight-%, of copper, 5-30 weight-%, preferably 10-20 weight-% of zirconium, 0-30 weight-%, preferably 0-25 weight-% of palladium, 0-15 weight-%, preferably 0-10 weight-% of tin, 0-2 weight-%, preferably 0-1 weight-% of silicon, 0-10 weight-%, preferably 0-5 weight-% of iron, and 0-15 weight-%, preferably 0-10 weight-% of silver, based on the total weight of the amorphous alloy.

7. The medical device or medical device component according to any of claims 3 to 6, wherein the amorphous alloy is of the composition Ti40Zr10Cu36Pd14, the suffixes relating to the atomic percentages of the respective components.

8. The medical device or medical device component according to any of the preceding claims, wherein the coating is formed directly on the surface of the core body.

9. The medical device or medical device component according to any of the preceding claims, wherein the coating further contains an intermediate layer formed between the DLC layer and the surface of the core body, the intermediate layer comprising chromium.

10. The medical device or medical device component according to any of the preceding claims, wherein the DLC layer contains a silicon-based inner DLC layer region and a carbon-based outer DLC layer region.

11. The medical device or medical device component according to claim 10, wherein the proportion of silicon containedA23615WO / 30.12.2024in the inner DLC layer region decreases gradually in the direction of the outer DLC layer region and the proportion of carbon contained in the outer DLC layer region decreases gradually in the direction of the inner DLC layer region.

12. The medical device or medical device component according to any of the preceding claims, wherein the surface of the core body on which the DLC coating is formed has an arithmetical mean roughness Sa of less than 1 µm, preferably less than 0.5 µm, more preferably less than 0.3 µm, and even more preferably less than 0.2 µm.

13. The medical device or medical device component according to any of the preceding claims, wherein the medical device is a surgical device, a dental implant, a prosthesis, an abutment, a dental implant supported prosthesis or abutment, a screw for use in a dental implant supported prosthesis or abutment, a surgical instrument, a dental instrument, a dental driving tool, a handpiece for use in surgical or dental procedures, a motor for use in surgical procedures, or a motor for use in dental procedures.

14. A process for preparing a medical device or medical device component according to any of the preceding claims, wherein the process comprises the steps of a. providing a core body made of an amorphous alloy, wherein the main alloy component of the amorphous alloy is selected from the group consisting of titanium copper (TiCu) and zirconium copper (ZrCu), and b. applying onto the surface of the core body a coating containing a diamond-like carbon (DLC) layer.

15. The process according to claim 14, wherein the diamond-A23615WO / 30.12.2024like carbon (DLC) layer is applied onto the surface of the core body using a vapor deposition method at a temperature of below 300°C, preferably of below 250°C.A23615WO / 30.12.2024

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