• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a component (1) comprising a titanium-molybdenum substrate, said component (1) being treated using a plasma micro-arc oxidation process to obtain a ceramic coating on the surface. of the substrate. The invention also relates to a ceramizing process for growing a ceramic coating on the surface of the component (1).
    公开号:CH710708A2
    申请号:CH00176/15
    申请日:2015-02-11
    公开日:2016-08-15
    发明作者:Dreyer-Gonzales Frédéric；Houriet André
    申请人:Officine Panerai Ag；
    IPC主号:
    专利说明:

    Technical area
    The present invention relates to a component made of titanium-molybdenum alloy. It also relates to a ceramization process making it possible to improve the mechanical properties, in particular tribological, of this component.
    State of the art
    [0002] Molybdenum provides valuable properties when used as an alloying element of titanium. Thus, titanium-molybdenum alloys are highly resistant. For example, they do not corrode at high temperatures and have the advantage of being extremely cold malleable.
    [0003] Molybdenum associated with titanium can advantageously replace graphite elements in high temperature applications. In addition, molybdenum disulphide constitutes a good lubricant, especially at high temperature.
    [0004] Molybdenum is thus used in many fields thanks to its chemical and mechanical properties. It is, for example, used in the medical field for the manufacture of plates used in surgery, or for the design of dental implants.
    [0005] Molybdenum is also used in aeronautics and in the petroleum industry as a catalyst. Parts of planes and missiles are made of molybdenum. Molybdenum is also included in the composition of stainless steel used in the marine environment for its high resistance to corrosion.
    [0006] Alloys of the titanium-molybdenum type are also intended for the jewelry industry, in particular for the design of high-end watch casing components and watch movement components.
    [0007] Application EP 1 231 299 describes a multifunctional protective coating for non-ferrous alloys. This coating is a solid, hard, and porous layer. It is composed of oxidized ceramic taking the form of a matrix. A functional compound is then introduced into the pores of this matrix. The functional compounds are chosen from a series of metals and / or refractory compounds. The oxidized ceramic matrix layer is applied by an electrolytic oxidation method. This layer has high adhesion to the base. The desired porosity of the oxide layer is achieved by adjusting the parameters of the oxidation process. The functional compounds are then introduced into the porous structure of the ceramic matrix. Following the introduction of the functional compounds, the composite coating is subjected to a finishing treatment. The developed surface of the porous structure of the matrix layer creates a new coating with high cohesive strength. This surface exhibits increased hardness and mechanical strength, some plasticity, as well as resistance to contact with dynamic loads and vibrations.
    [0008] US 2010 0 252 241 describes a ceramic coated heat exchange component. The manufacturing process of the ceramic element is achieved by creating a porous metal oxide coating on an aluminum surface of the heat exchange component. This coating is obtained by electrochemical deposition of a metal oxide on the aluminum surface and by the superposition of a neutralizing agent on the metal oxides of ceramic coatings.
    [0009] The application US 2007 0 068 647 relates to a method of producing a medical implant based on a titanium alloy. The manufacture is carried out by casting the alloy in a mold whose shape corresponds to the implant to be produced. The invention provides for the use of titanium which is placed under isostatic pressure and then quenched. This invention relates to a medical implant made of a titanium-based alloy. It combines the advantages of titanium, in particular its strong mechanical properties, as well as the ease of use in a molding process. The invention also makes it possible to produce complex implants, such as, for example, femoral parts or hip prostheses which are economically impossible to obtain by conventional forging methods.
    [0010] Application EP 1 695 676 describes a method for pouring a titanium-molybdenum alloy into a mold in order to obtain an implant whose shape corresponds to the mold used. The mold is subjected to hot isostatic pressure, and is then subjected to a cooling process. The molybdenum titanium alloy contains 7.5 to 25% molybdenum and an average grain size of three millimeters.
    [0011] The titanium-molybdenum alloys have interesting mechanical and chemical qualities. However, these alloys exhibit a certain brittleness, especially in the face of wear and impact. Indeed, the mechanical and environmental stresses opposable to titanium-molybdenum components, such as friction, influence the speed of wear to which these components are subjected.
    The first documents referred to refer to the conventional method of ceramization by oxidation, making it possible to solidify non-ferrous metal alloys. However, the ceramization process mentioned in these documents is carried out on a non-ferrous alloy other than titanium-molybdenum. In addition, the mentioned ceramic coating is formed on a component for the sole purpose of promoting a heat exchange process. The other documents referred to refer to components made of titanium, or even of a titanium-molybdenum alloy, and demonstrate the qualities revealed by such an alloy, such as its malleability during a molding process, for example. Despite the mechanical and chemical qualities imparted to the titanium-molybdenum alloy, it exhibits improved corrosion and wear resistance, none of the documents mentioned describes means for resolving this problem.
    To overcome these various drawbacks, the invention provides various technical means.
    Brief summary of the invention
    [0014] First of all, a first object of the invention is to provide a component having high resistance to a corrosive environment.
    [0015] Another object of the invention is to provide a component showing high resistance to wear.
    [0016] Finally, another object of the invention is to provide a component having advantageous mechanical and chemical properties for applications in a wide variety of fields, and in particular in watchmaking.
    [0017] To do this, the invention provides a component comprising a titanium-molybdenum substrate treated with a plasma micro-arc oxidation process making it possible to obtain a ceramic coating on the surface of said substrate.
    [0018] Such a composition allows the titanium-molybdenum component to be endowed with exceptional properties. The ceramized layer indeed has a high resistance to corrosion as well as very good mechanical properties. In addition, in the event of violent impacts on the ceramic layer, the exposed titanium will exhibit good resistance to wear and corrosion for a metal.
    [0019] According to such a configuration, the ceramic coating located on the surface of the substrate has a thickness of between 20 and 150 microns.
    [0020] According to a first variant, the substrate comprises holes and / or threads and / or threads. The interior of the component's holes and / or threads and / or threads is also ceramic with reduced thickness.
    [0021] According to another variant, the ceramic layer consists of alumina oxide Al2O3 or magnesium oxide MgO.
    According to yet another variant, the ceramic coating has a hardness of between 1500 Hv and 3000 Hv, depending on the ceramization parameter and on the density of the ceramized layer.
    [0023] Advantageously, the titanium-molybdenum substrate has an average hardness of 400 Hv.
    [0024] According to an advantageous embodiment, the ceramic coating withstands a test of ten drops on a gravel bed at a height of 40 centimeters of the component, according to ISO 23160 standards.
    [0025] According to another advantageous embodiment, the ceramic coating shows a surface condition comprising slight alterations after 36 hours of a test in accordance with ISO 23160.
    [0026] Advantageously, the titanium-molybdenum alloy is suitable for the manufacture of small plates subjected to environmental or mechanical constraints.
    [0027] Also advantageously, the component constitutes a component for watchmaking or watch movement, or of a dental implant, or of eyewear, or even of a writing instrument.
    [0028] The invention also provides a ceramization process for growing a ceramic coating on the surface of a component comprising a titanium-molybdenum substrate. The process is a plasma micro-arc oxidation process comprising the following steps:immersing the component to be coated in an electrolytic bath composed of an aqueous solution of alkali metal hydroxide, the component forming one of the electrodes; andthe application of a current comprising positive and negative current pulses alternating with a frequency between 10 Hz and 10,000 Hz.
    According to a first embodiment, the amplitude of the current pulses is between 2 and 200 A / dm <2> so as to apply a voltage between the component and the cathode, of the order of 100 volts at 1000 volts.
    [0030] A voltage between 100 volts and 1000 volts has the advantage of creating an electrolytic plasma necessary for the formation of the coating on the component.
    [0031] According to another embodiment, the current pulses are separated by a dead time where no current is applied.
    [0032] According to yet another embodiment, the duration of the dead time is preferably about 10% of the total duration of the current draw.
    [0033] Thus the duration of the dead time is such that the voltage drops to zero. For example, each of the positive and negative current pulses may have a maximum amplitude followed by a decrease in current to zero.
    [0034] Advantageously, the minimum average voltage is adjusted so as to be between 0 and 99.9% of the maximum voltage.
    According to an alternative embodiment, a surface preparation comprising a cleaning and degreasing step is carried out.
    [0036] According to yet another variant embodiment, a micro-sandblasting step is carried out following the growth of the layer in order to partially remove the porous surface part.
    [0037] Advantageously, the components comprising areas of holes and / or threads and / or internal threads are the subject of a first phase of fine ceramization.
    [0038] Also advantageously, the components are then subjected to strong ceramization.
    Brief description of the figures
    All the implementation details are given in the following description, supplemented by FIGS. 1 to 5b, presented only for the purposes of non-limiting examples, and in which: FIG. 1 is a schematic view of an electrolysis plant; fig. 2 is a sectional view of the component having a ceramic coating formed by the plasma micro-arc oxidation process; figs. 3a, 3b and 3c show different views of a coating formed by the oxidation process according to the invention; fig. 4 illustrates a watch case; and fig. 5a and 5b represent the layer obtained on the titanium-molybdenum component by the plasma micro-arc oxidation process.
    Example (s) of embodiment of the invention
    The invention provides a component 1 comprising a substrate 7 made of a titanium-molybdenum alloy (for example of the TiMo15 type). Component 1 is treated using a plasma micro-arc oxidation process to obtain a ceramic coating 2 on the surface of the titanium-molybdenum substrate 7.
    Table 1 compares the mechanical properties of the titanium-molybdenum alloy TiMo15 with those of a conventional titanium alloy and type 316 L stainless steel.
    [0042] Table 2 demonstrates the excellent corrosion resistance of titanium-molybdenum. The comparative tests concern the corrosion rate in mm / year of a Grade 2 titanium and a titanium type TiMo15 immersed in different acid and basic solutions.
    [0043] Table 3 shows the chemical composition of a typical TiMo15 alloy (eg Erigan alloy, Zapp).
    [0044] FIG. 2 is a sectional illustration of component 1 according to the invention. This component 1 has a coating 2 formed by the plasma micro-arc oxidation process. The coating 2 comprises a hard layer 21 of thick ceramic obtained by processing the substrate and forming approximately two thirds of the total thickness of the coating 2. A porous outer layer 22 growing on the substrate constitutes approximately one third of the total thickness of the coating. coating 2. For example, for 30 micron thickened growth, about 66 microns of base substrate is processed.
    [0045] The coating 2 is formed by the substrate material 7 transformed during the oxidation process. Coating 2 grows beyond the initial surface 8 of component 1. An extra thickness is created relative to the initial surface 8 of component 1 by growing coating 2.
    The ceramized layer has excellent properties against corrosion as well as against wear. The good mechanical properties also promote the resistance of the layer, in particular during impacts or stresses with high mechanical stresses.
    The thickness of the coating 2 ranges from one to several tens of microns in the holes and threads and a few hundred microns on substantially smooth and homogeneous surfaces. The importance of the thickness of the coating layer 2 affects the thickness of the functional layer A 1/3 - 2/3 ratio is observed between the porous layer 22 (1/3) and the dense layer 21 (2/3). The greater the thickness of the coating layer 2, the greater the thickness of the dense layer 21. Most of the porous layer is also removed during the micro-sandblasting step.
    The coating 2 thus obtained has a hardness of up to 3000 Hv. This coating 2 therefore has excellent resistance to wear, impact and corrosion. Coating 2 also has a coloring corresponding to the natural coloring of titanium oxide (pigeon gray).
    [0049] FIG. 2 shows a sectional view of component 1 with the coating 2 formed by the ceramization process.
    The components 1 treated by the plasma micro-arc oxidation process can be mechanical watch movement components subjected to mechanical stresses, or watch trim components subjected to aggressive environmental stresses, such as wear, humidity, etc. These components 1 can also belong to eyewear or even writing objects.
    The ceramization process or micro-arc oxidation process is carried out by electrolytic treatment. Fig. 1 shows an exemplary embodiment of an installation for electrolytic treatment.
    [0052] According to FIG. 1, the installation comprises a tank 3 containing an electrolytic bath 4. A cathode 5, as well as an anode corresponding to component 1 to be coated are immersed in an electrolyte 4. This installation also includes a current supply unit 6 capable of generating an alternating current 31.
    The ceramization process or oxidation process by plasma microarcs comprises various steps. The first step is, according to one embodiment, to immerse the component 1 to be coated in the electrolyte 4. Then the alternating current 31 is generated in order to apply a voltage between the component 1 and the cathode 5.
    [0054] According to this embodiment, the electrolyte 4 can comprise an aqueous solution composed of alkali metal hydroxide such as potassium or sodium, and an oxyacid salt of an alkali metal. Electrolyte 4 is typically maintained at a temperature between 10 ° C and 55 ° C
    The applied current comprises positive and negative current pulses, alternating between a frequency between 10 and 10,000 Hertz. The amplitude of the current pulses is between 2 and 200 A / dm <2> in order to apply a voltage between component 1 and cathode 5 of the order of 100 to 1000 volts. A voltage of this order makes it possible to create an electrolytic plasma which is necessary for the formation of the coating 2 on the component 1.
    [0056] According to another variant embodiment, the current pulses can also be separated by a dead time, during which no current is applied. The duration of the dead time is approximately 10% of the total duration of the current draw, so that the voltage drops to zero. For example, each of the positive and negative current pulses may have a maximum amplitude, followed by a current decrease to zero. Consequently, the voltage to be emitted is cycled between a minimum voltage (“baseline”) and a maximum voltage (“ceiling line”). The minimum voltage is preferably adjusted between a voltage between 0 and 99.9% of the maximum peak of the ceiling voltage. The base voltage (for example 30% of the ceiling voltage) will promote the formation of electric micro-arcs visible to the naked eye, while a more substantial base voltage (for example 60% of the ceiling voltage) , will promote the creation of a continuous plasma, also visible to the naked eye (relative to retinal perception from 0.1 to 0.2 seconds). The influence of the choice of the basic minimum average tensions compared to the maximum tension and therefore of the type of micro-arcs obtained makes it possible to control a more or less dense and homogeneous layer. The densification of the layer is also a function of the frequency of alternation between the anode and cathode currents. Indeed, the growth of the nanoporous layer takes place under an anode current while under a cathode current the densification of the nanoporosities is observed.
    [0057] Consequently, the choice to favor a minimum voltage intensity over a maximum voltage makes it possible to control the result, ie the density and the more or less pronounced homogeneity of the layer of the ceramic coating 2. The densification of the layer is in fact consecutive to the frequency of alternation between the anode and cathode currents.
    The growth rate of the coating 2 therefore depends on the type of frequency and the nature of the pulse emitted. In particular, the rate of growth depends on the passage between cathode and anode current and the magnitude of the current. For example, the growth rate of coating 2 may be 1 micron per minute, for an applied voltage of 100 to 400 volts and a frequency of the order of 1000 hertz. The thickness of the coating 2 thus obtained can vary between a thickness of tens of microns in a homogeneous manner on the part, provided that the positioning used to hold the component is suitable and does not modify the formation of micro-arcs, and a thickness of a hundred microns. The plasma microarcs oxidation process is described for example in document WO 03 083 181.
    The intensity of the ceramization process varies depending on the component 1 to be coated. Thus, the ceramization of a component 1 comprising areas of threading, tapping and holes, is said to be fine. This type of ceramization generates a coating 2 with a thickness of a few microns (for example a thickness between 1 and 100 microns or between 10 and 50 microns) making it possible to densify and harden the heterogeneous areas. In fact, it is advantageous for the areas comprising a particularly fine structure to be coated with a coating 2 that is less thick than on the rest of the surface of component 1.
    [0060] Thus, according to a variant of the oxidation process by plasma microarcs, it firstly makes it possible to obtain a coating 2 on the areas with fine structuring.
    Then, the ceramization is advantageously continued by a so-called strong ceramization. In the latter case, the coating layer 2 extends from several tens to hundreds of microns. The finely structured areas are protected by gaskets in order to form the coating 2 on the rest of the component 1. The gaskets used to mask the finely structured areas can be made of silicone or any other means of protection resistant to the oxidation treatment. by plasma micro-arcs and can be eliminated at the end of the process. This seal has the effect of creating a selective effect and preventing any growth of oxidation by micro-arcs on the areas protected by the silicone seal. Indeed, too strong ceramization on threaded areas for example, could erode the thread.
    A surface preparation is necessary before the implementation of the ceramization process. Components 1 should be cleaned and degreased with boiling water, or prepared by the use of an alkaline cleaner such as PARCO cleaner solution (product of Henkel Surface Technologies, a division of Henkel Corporation, Madison Heigts, Michigan) . After cleaning, the part is rinsed with distilled water.
    [0063] The components 1 which have been subjected to the oxidation process by plasma micro-arcs comprise an oxidized ceramic layer making it possible to obtain various advantages. These advantages are a high hardness of between 1500 and 3000 Hv (Vickers hardness), a strong resistance to wear, impact and corrosion, as well as a natural coloration of the oxide of the substrate 7 in titanium-molybdenum. Such a method also makes it possible to obtain perfect adhesion between the ceramic coating 2 and the substrate 7. In fact, the ceramic layer is not projected onto the substrate 7 but is partly obtained by extension of the substrate 7. Finally, such a method makes it possible to coat the internal parts of the components 1 with a ceramic coating 2. This process finally generates a low coefficient of friction between the parts respectively treated, which makes it possible to envisage pivoting without lubricant.
    [0064] Figs. 3a to 3c make it possible to observe the surface condition of the coating following the ceramization process, in this case on a watch component. Fig. 3a shows a rough surface finish. Fig. 3b is a cross section of the coating layer 2 obtained by growth. Fig. 3c represents the surface of the coating after micro-sandblasting type tribofinishing.
    [0065] FIG. 4 shows, by way of example, a watch case on which the micro-arc oxidation process has been carried out. The coating 2 has been formed on different parts of the watch case, such as the middle part 91, the lugs 92, the lever 93, and the crown cover 94, as well as on the bezel 95, and the crown 96.
    [0066] Figs. 5a and 5b represent the coating 2 obtained on a substrate 7 of titanium-molybdenum. The coating layer 2 has not been subjected to a tribofinishing here and therefore has a higher surface roughness than on a part which has undergone micro-sandblasting.
    A micro-sandblasting type tribofinishing step is preferably carried out following the ceramization process. This step allows, as illustrated in fig. 3a to 3c, to obtain an optimum surface condition and free of the last microns of the porous ceramic layer 22.
    The ceramic coating 2 obtained by such a process comprises a dense and uniform layer, with a thickness of between 20 and 50 microns.
    The ceramic coating 2 on the surface of the substrate 7 has a layer of hardness amounting to an average of 2800 to 3000 Hv. The hardness and strength of the ceramic coating 2 are reported by a series of tests.
    [0070] The purpose of the wear test is first of all to assess the resistance of a component 1 comprising a ceramic coating 2 against ceramic balls. To do this, the sample is mixed with 2 kilos of ceramic balls with a diameter of 3 millimeters, half a liter of water and 10 cubic centimeters of wetting agent, for 36 hours. The speed of rotation is 46 revolutions per minute.
    [0071] After 6 hours of testing, the sample exhibits shiny surfaces. No change was observed after 36 hours of testing. The sample is therefore highly resistant to wear.
    The second test is called "fine stripes". It consists of placing the sample together with 5 to 15 markers and 10 grams of "Bremor BR650" glass powder in a chamber with a diameter of 80 millimeters and 60 millimeters in height comprising blotter walls. This is rotated for 24 hours at a speed of 90 rpm. The fine scratch test demonstrates excellent resistance of the ceramic coating 2 to scratches.
    [0073] The ceramic coating 2 is also the subject of a drop test on a gravel bed. This test, carried out in accordance with ISO 23160, consists of dropping the sample on a bed of 8 centimeters by 500 square centimeters of ceramic chips 3 millimeters in diameter, 12 millimeters in length and with a hardness of 800 to 1000 Hv. . The fall is carried out from a height of 40 centimeters. The watch case to be tested is loaded with a weight representing the weight of the mechanical movement normally integrated in the watch head. Following a dozen falls on a bed of gravel and ceramics, very low impacts are observed at the edges of the components. The middle part therefore has excellent resistance to shocks and impacts on a gravel bed.
    Finally, the ceramic coating 2 is subjected to the synthetic sweat test in accordance with NIHS 96-50 and ISO 3160-2 standards. The parts tested are placed on a support soaked in sweat in an environment of 40 degrees and a relative humidity of 95 to 100%, for a period of 6 days. After 6 days of testing, corrosion pitting is visible on the tested areas of titanium devoid of ceramic coating. Therefore, the ceramic coating 2 makes it possible to create a protective layer of the titanium-molybdenum substrate 7. No corrosion is visible on the areas of the caseband coated with a ceramic layer.
    Reference numbers used in figures
    1 component 2 coating 21 hard layer 22 porous outer layer 3 tank 31 alternating current 4 electrolytic bath 5 cathode 6 power supply 7 titanium-molybdenum substrate 8 initial surface 9 watch case 91 middle part 92 horns 93 lever 94 crown 95 bezel 96 crown cover
    权利要求:
    Claims (18)
    [1]
    1. Component (1) comprising a substrate (7) of titanium-molybdenum,characterized in that said component (1) is treated using a plasma micro-arc oxidation process to obtain a ceramic coating (2) on the surface of the substrate (7).
    [2]
    2. Component (1) according to claim 1, on which the ceramic coating (2) located on the surface of the substrate (7) has a thickness between 20 and 150 microns.
    [3]
    3. Component (1) according to one of claims 1 or 2, wherein the substrate (7) has holes and / or threads and / or threads and wherein the coating (2) ceramic located inside the holes and / or internal threads and / or threads has a thickness between 1 and 100 microns, and preferably between 10 and 50 microns.
    [4]
    4. Component (1) according to one of claims 1 to 3, wherein the ceramic coating (2) consists of a layer of titanium oxide.
    [5]
    5. Component (1) according to one of claims 1 to 4, wherein the ceramic coating (2) has a hardness of between 1500 Hv and 3000 Hv.
    [6]
    6. Component (1) according to one of claims 1 to 5, wherein the substrate (7) of titanium-molybdenum has an average hardness of 400 Hv.
    [7]
    7. Component (1) according to one of claims 1 to 6, wherein the coating (2) ceramic withstands a ten drop test on a gravel bed at a height of 40 cm of the component (1) according to ISO standards. 23160.
    [8]
    8. Component (1) according to one of claims 1 to 7, wherein the ceramic coating (2) shows a surface condition with slight alterations after 36 hours of a test in accordance with ISO 23160.
    [9]
    9. Component (1) according to one of claims 1 to 8, constituting a component for watchmaking or watch movement, or dental implant, or eyewear, or writing instrument.
    [10]
    10. Ceramization process making it possible to grow a ceramic coating (2) on the surface of a component (1) comprising a substrate (7) of titanium-molybdenum, characterized in that the process is a micro oxidation process. -plasma arcs comprising the following steps:immersing the component (1) to be coated in an electrolytic bath (4) composed of an aqueous solution of alkali metal hydroxide, the component (1) forming one of the electrodes; andapplication of a current comprising pulses of positive and negative currents alternating with a frequency between 10 Hz and 10,000 Hz.
    [11]
    11. Ceramization method according to claim 10, wherein the amplitude of the current pulses is between 2 and 200 A / dm <2> so as to apply a voltage between the component (1) and the cathode (5), of the order of 100 V to 1000 V.
    [12]
    12. Ceramization process according to one of claims 10 or 11, wherein the current pulses are separated by a dead time where no current is applied.
    [13]
    13. A ceramization process according to claim 12, wherein the duration of the dead time is preferably about 10% of the total duration of the current draw.
    [14]
    14. Ceramization process according to one of claims 10 to 13, wherein the minimum average voltage is adjusted to be between 0 and 99.9% of the maximum voltage.
    [15]
    15. Ceramization process according to one of claims 10 to 14, wherein a surface preparation comprising a cleaning and degreasing step is carried out.
    [16]
    16. Ceramization process according to one of claims 10 to 15, wherein a micro-sandblasting step is performed.
    [17]
    17. Ceramization process according to one of claims 10 to 16, wherein the components (1) comprising areas of holes and / or threads and / or threads are the subject of a first phase of fine ceramization.
    [18]
    18. The ceramization process according to claim 17, wherein the components (1) are then subjected to a strong ceramization phase.
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    同族专利:
    公开号 | 公开日
    CH710708B1|2020-11-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2019-03-15| PK| Correction|Free format text: RECTIFICATION INVENTEUR |
    优先权:
    申请号 | 申请日 | 专利标题
    CH00176/15A|CH710708B1|2015-02-11|2015-02-11|Titanium-molybdenum component comprising a ceramized surface layer and ceramization process.|CH00176/15A| CH710708B1|2015-02-11|2015-02-11|Titanium-molybdenum component comprising a ceramized surface layer and ceramization process.|
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