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    • 专利摘要:
    The present invention describes a method of manufacturing a titanium-zirconia composite material and its embodiment by additive manufacturing, which material is characterized by a titanium metal matrix composite (CMM) alloy with a proportion of pure Ti titanium or a titanium alloy Ti6AIV4 greater than 60% by volume and a proportion of zirconia or zirconium dioxide ZrO2 less than 30% by volume but greater than 0.5% by volume. The titanium metal matrix composite (CMM) alloy with a proportion of pure titanium Ti or titanium alloy Ti6AIV4 greater than 99% by volume and a proportion of zirconia or zirconium dioxide ZrO2 at 1% by volume but higher or equal to 0.04% by volume, said material contains 0.1 to 0.3% by volume of oxygen. The mixing of the two components (metal / ceramic) is carried out in an advantageous manner in which the zirconia nanoparticles envelop the titanium particles, thus forming a zirconia layer advantageously distributed over the surface of the titanium particles. In this embodiment and according to the invention, the low-melting point metal component causes the zirconia nanoparticles to melt. The alloy is characterized in that the particle size of the titanium metal matrix is at a micrometric scale and the particle size of the zirconia is at a nanoscale. The embodiment of said interactive mixture Ti / ZrO2 is implemented by additive manufacturing and more particularly selective laser melting (SLM).
    公开号:FR3037945A1
    申请号:FR1501303
    申请日:2015-06-24
    公开日:2016-12-30
    发明作者:Abdelmadjid Djemai；Jean Jacques Fouchet
    申请人:Abdelmadjid Djemai；Jean Jacques Fouchet；
    IPC主号:
    专利说明:

    [0001] 1 Process for manufacturing a titanium zirconium alloy and its embodiment by additive manufacturing Description Pure titanium and its alloys have received considerable attention in many applications, including the medical industry, because of their increased strength, resistance to corrosion, and, above all, their biocompatibility and daring integration. As a Ti6AI4V duplex alloy consists of alpha and beta phases, consisting of 6 percent aluminum and 4 percent vanadium (Ti-64). This material has been considered the most appropriate because it has reinforced mechanical properties compared to pure titanium. However, the titanium alloy has a low hardness value and poor resistance to wear and oxidation. In particular, where tribological behavior is known, such as in valves and pin connections. When placed in an oxygen-depleted environment, typically in dental or bone implants, it is likely to release aluminum and vanadium ions, which are considered to be harmful to body fluids.
    [0002] To overcome the problems of diffusion of aluminum ions and vanadium, current techniques work on changing the surface nature of this titanium alloy using different surface engineering techniques, for example the deposition of a ceramic layer of zirconium type. These are generally polycrystalline inorganic silicates, oxides and carbides. they are refractory in nature and have a high compressive strength. Bioceramics can be subdivided as bio-inert, bioactive, and biodegradable materials. Zirconia, which behaves like ceramics, comes in three phases, monoclinic, cubic and tetragon, which can improve the final properties of the coatings produced. Bioinert ceramics such as zirconia maintain their physical and mechanical properties, even in biological media and highly corrosive media. Zirconia is very resistant to wear and tolerates the stress induced by hardening by transformation. The main application of zirconia ceramics in the medical field is total hip arthroplasty (THA), where it is used as a duplex coat alloy of the titanium alloy Ti6AI4V type implant head. Another application of zirconia ceramics is in the space field, as a thermal shield in aircraft and satellite reactors. Numerous studies have been made on the surface modification of titanium or a titanium alloy to improve their properties. surface or to make a mixture Titanium Zirconia pressed at high temperature, we quote the following publications: Y.Zhong and Al. "Characterization and thermal shock behavior of composite ceramic coating doped with ZrO2 particles on TC4 by micro arc oxidation", Applied Surface Science , 311, 158-163 (2014), Deposition of ZrO2 layer by micro-arc on titanium parts (TA6V), the objective was to increase the hardness of titanium.
    [0003] Patrik Stenlund et al., "Osseointegration Enhancement by Zr doping of Co-Cr-Mo Implants Fabricated by Electron Beam Melting" Hiroaki al, Science Direct (2015); the addition of 0.04% of zirconia increases osteointegration. Y. Zhong et al., "Characterization and thermal shock behavior of composite ceramic coating doped with ZrO 2 particles on TC4 by micro-arc oxidation", Applied Surface Science, 311, 158-163 (2014).
    [0004] Keiichiro Tohgo et al., Shizuoka Univerdsity (Japan), "Manufacturing of PSZ-Ti composites by spark plasma sintering and their mechanical properties", Materials Science & Engineering, A621, 166-172 (2015). T. Fujii, K.Tohgo, H.Araki, K.Wakazono, M.Ishikura, Y.Shimamura, J.SolidMech.Mater.Eng.41699-1710 (2010). N-R Park et al., "Fast low-temperature consolidation of a nanostructured 2Ti-Zr02 composite for biomedical applications", Ceramics International, 40, 6311-6317 (2014).
    [0005] 3037945 2 5 Proceedings: Tohgo et al., "Progress of Composites" 2008 in Asia and Australasia - The 6th Asian- Australasian Conference on Composite Materials, ACCM (2008). Chien-Cheng Lin et al., "Effect of Yttria on Interfacial Reactions Between Titanium Melt and Hot-Pressed Yttria / Zirconia Composites at 1700 ° C", Chiao Tung University (Taiwan), J.Am.Ceram.Soc., 91, 2321-2327 (2008).
    [0006] J. Cao et al., "Brazing ZrO2 ceramic to Ti-6AI-4V alloy using NiCrSiB amorphous filler foil": Interfacial microstructure and joint properties, Materials characterization 81, 85-91 (2013). The state of the art can be defined by patents; "Titanium-zirconium binary alloy for surgical implants and corresponding production method" filed June 10, 1997 by Straumann AG under number W01997029624A2, in this embodiment the Titanium Zirconia mixture is made by hot forging. "Titanium Based Alloy" filed May 6, 2006 by Igor Vasilievich Al under the number W02006123968A2 20 "Mixed titanium oxide powder and zirconium" filed on December 20, 2005 by Degussa, Kai Schumacher, Oswin Klotz, Uwe Diener under No. W02006067129A2 "Basic Products for the Manufacture of Ceramic Materials" filed on 28 January 1987 by Degussa Aktiengesellschaft under the number EP0241647A2 "Dioxide of doped titanium" deposited on 29 March 2000 by DEGUSSA AG under number 25 EP1138632A1 "Titanium coprecipitated of dioxide / silicon dioxide and titanium dioxide / zirconium dioxide-coprecipitated as polycondensation catalysts for polyesters and copolyesters "deposited on January 2, 1995 by AkzoNOBEL NV under the number US5684116 None of these embodiments discloses a process for the production of zirconium titanium alloy with its embodiment by additive manufacturing Additive manufacturing and for some Specific additive technologies (SLM, EBM, SLA) have several possibilities for controlling geometry, porosity, inter connectivity and 3D architecture through changes in manufacturing parameters, let's mention the main parameters for the technology selective laser melting: - the power of the lasers - the scanning speed 40 - the spot diameter - the laser scanning strategy - the overlap between two melting points - the thickness of the layers of the powder 45 The melting process Selective Laser Melting (SLM) Selective Laser Melting (SLM) is a process used to manufacture complex three-dimensional components from metal powders, ceramic or polymer powders. The technology is mature and already used in the aeronautics and medical industries to manufacture complex components with high densities and homogeneity. We cite one of the first patents of the Fraunhofer Institute in Germany, filed Oct. 27, 1997 under the number W01998024574A1, which describes the SLM process in a more precise way. The name SLM will be maintained throughout the text of the patent. The present invention describes a method of manufacturing a titanium zirconium alloy and its embodiment by additive manufacturing. The titanium zirconium alloy is composed of a pure titanium or titanium alloy of Ti6AI4V type consisting of alpha and beta phases, consisting of 6% aluminum and 4% vanadium. Zirconia exists in one of three crystalline forms (allotropic forms), monoclinic, quadratic, cubic with respective melting temperatures of 1100 ° C, 2300 ° C, 2700 ° C. These transformations are accompanied by variations in volume (dilatation of 3 to 5% during the quadratic-monoclinic transformation). Since the sintering temperature is around 1450 ° C, it is necessary to stabilize the zirconia in one of the high temperature structures in order to avoid fragmentation during cooling. The addition of some% MgO, CaO, Y203 or CeO2 leads to this result. In the present invention Y203 is used to stabilize zirconia, Y-TZP: (zirconia stabilized in quadratic form with yttrium oxide (Y 2 O 3).
    [0007] The additive manufacture of bi-component metal / ceramic parts by SLM involves significant thermal stresses due to localized laser heating and phase changes generating heterogeneous microstructures. Ductile materials with high thermal conductivity and high tenacity behave much better with the SLM process, ceramic materials will tend to crack if the cooling is not mastered. melting as binder can be used for the additive manufacture of ceramics, in this case only the metal component melt constituting the dense network of the workpiece, the ceramic remains porous. To overcome the porosity problem and according to the invention, the low melting point metal material is at a micrometric scale and the ceramic is at a nanoscale. In order to obtain a functional and dense part, it is necessary to have the total melting of the metallic elements and the ceramic elements and to do this, the mixture of the two components (metal / ceramic) is produced in an advantageous mode where the nanoparticles of zirconia wrap the titanium particles, thus forming a zirconia layer advantageously distributed on the titanium particles. In this embodiment and according to the invention, the low melting metal component results in the melting of the zirconia nanoparticles. According to the invention, and to achieve a total melting of a mixture of metal powders and YTtriated zirconia ceramic powders (YSZ), the mixture is fused by a concentration of a source of energy.
    [0008] The metal powders are pure titanium or an alloy of Ti6AIV4 type, the ceramic powders are of zirconia type Zr / stabilized zirconia / zirconia yttrie Zr02 / Y203 with a concentration of yttrium oxide 11.8c1 / 05Y203 <30% ; It is important that the mixture of the metal powders and the ceramic powders according to the invention are melted. Indeed, the use of sintered grains, co-precipitated grains or fused grains determines the properties of the final material. The mixtures according to the invention may also comprise one or more of the following optional characteristics: preferably, the content of titanium Ti or of a Ti6AIV4 alloy is greater than 40%, preferably greater than 60% and / or preferably less than 99.50%, preferably less than 95.5%. A pure titanium powder or a Ti6AIV4 alloy according to the invention may also comprise one or more of the following optional characteristics: A particle size of less than 70 μm, preferably less than 45 μm; preferably less than 30 μm, preferably less than 10 μm, preferably greater than 5 μm.
    [0009] In a first particular embodiment, the yttria-containing zirconia powder has a particle size of less than 250 nm, preferably less than 130 nm, and / or a median size of between 65 nm and 85 nm, and / or an upper minimum size. at 30 nm; in a second particular embodiment, the yttria-containing zirconia powder has a particle size of less than 75 nm, preferably less than 70 nm, and / or a median size of between 35 nm and 50 nm, and / or a minimum size greater than 15 nm, preferably greater than 20 nm; in a third particular embodiment, the yttria-containing zirconia powder has a particle size of less than 40 nm, preferably less than 35 nm, and / or a median size of between 10 nm and 25 nm, and / or an upper minimum size. at 3 nm, preferably greater than 5 nm. - In a fourth particular embodiment, the yttria Zirconia powder has a particle size less than 15 nm, preferably less than 10 nm, and / or a median size less than 5 nm. preferably, the content of ZrO 2 / Y 2 O 3 is greater than 0.4%, preferably greater than 13.5% and / or, preferably, less than 30.0%, preferably less than 60%; preferably, the content of Y 2 O 3 is less than 1.7%, preferably less than 1.6%, less than 1.5%, preferably less than 1.4%, preferably less than 1.3%. preferably less than 1.2%, preferably less than 1.1%, preferably less than 1.0%, preferably less than 0.9%, preferably less than 0.8%, preferably less than 0.5%, or even less than 0.4% and / or preferably greater than 0.1%; The TiO 2 titanium dioxide content resulting from the reaction of titanium with the oxygen provided by Yttrium Y 2 O 3 is preferably less than 0.4%, preferably less than 0.3%, more preferably less than 0, 2%, and / or preferably greater than 0.01%, preferably greater than 0.1%; preferably, the content of Y 2 O 3 is between 0.1% and 0.5% and the content of TiO 2 is between 0.1% and 0.2%, preferably the content of "other oxides" is less than 1.5%, preferably less than 1%, preferably less than 0.7%, preferably less than 0.5%, preferably less than 0.3%, preferably less than 0.2%. or even less than 0.1%, the oxidation properties are advantageously improved; preferably, the "other oxides" are impurities; Preferably, the HfO 2 content is less than 2.0%, less than 1.8%, less than 1.6%, or even less than 1.4%; In another embodiment, the Y203 content is greater than 0.1%, greater than 0.2%, greater than 0.3%, greater than 0.4%, or greater than 0.5%, greater than 0.6%, or greater than 0.7%.
    [0010] The mixing of pure Ti titanium powders or Ti6Al4V alloys with ZrO 2 / Y 2 O 3 nanometer powders is carried out according to a particularly advantageous mixing mode, under argon-type inert gas or under vacuum until a mixture is obtained. homogeneous with formation of films coating the titanium particles with ZrO 2 / Y 2 O 3.
    [0011] The addition of the zirconia in the titanium makes it possible to increase the hardness of the material and the resistance to wear. To achieve the fusion, it is important to understand the interaction between a titanium alloy and a refractory material of the ceramic type. (Zirconia). The interaction of the Ti / ZrO2 pair is a multivariate, tightly coupled, unstable, nonlinear and unbalanced process. The following table describes all 40 thermo-physical parameters of titanium and zirconia. Ti Zr02 Density (g / cm3) 4.13 5.77 Specific heat (J / (g. ° C) 0.5275 1.5 Thermal conductivity (w / (cm.C °)) 0.1704 6.8 x 10-5 Crystallization temperature (J / g) 435.4 - Reaction to heat (J / g) 1.023 - Oxygen diffusion coefficient (cm2 / s) 0.14 x 10-4x exp [-138000 / RT1 In molten titanium 0.33 x exp [-126000 / RT] In molten titanium in its beta 13-Ti phase Young's modulus 110-140 Gpa 200 Gpa Breaking strength 850-900 Mpa 600Mpa Toughness 33- 110 Mpa.m1 / 2 7-13 Mpa.m1 / 2 Elongation at break (%) 13-16% - Hardness Vickers (HV) 290-350 1200 Melting temperature 1668 ° C 2700 ° C CTE (20-200 ° C) C) 8.5 .10-6 / K 10.5 .10-6 / K Thermo-physical parameters of titanium and zirconia 3037945 5 In such a process, the transfer of energy quantity, the transfer of heat, the mass transfer and the chemical reaction interact intensively with one another, therefore, it is necessary to understand the reaction of the interacting mixture. if Ti / Zr02 for the implementation of such a method. This results in the control of the melting temperature of the Ti / ZrO2 interactive mixture, the transfer of heat and mass between the molten titanium and the molten zirconia. Such a reaction is reactive, unstable and varying with the time of exposure to the fusion. In addition, the chemical reaction of the interactive Ti / ZrO 2 mixture affects the temperature of the mixture and the oxygen concentration. As the concentration of zirconia Zr increases, titanium Ti reacts with oxygen O and zirconia becomes oxygen deficient. The heat of the reaction raises the temperature of the mixture and accelerates the diffusion of Ti, O, Zr, which increases the concentration of Ti, O, Zr and accelerates the reaction of the interactive Ti / ZrO 2 mixture again, thus forming a intense interaction between heat transfer, mass transfer and chemical reaction. The chemical reactions between Ti and ZrO 2 are not thermodynamically favorable, because the Gibbs G free enthalpy functions of the following equations are positive or slightly negative at the melting temperature of 1700 ° C. Ti + ZrO 2> TiO + Zr + 1/2 O 2 G1 = 157.15 kcal / mol Ti + ZrO 2> TiO + Zr A G2 = 33.14 kcal / mol 2 Ti + 3/2 ZrO 2> Ti 2 O 3 + 3/2 A G3 = 0.42 kcal / mol 3 Ti + 5/2 ZrO2> Ti305 + 5/2 Zr A G4 = 26.82 kcal / mol According to the following chemical reactions, titanium can not be a reducing agent for the oxide of zirconium. On the other hand, titanium can reduce zirconium oxide at high temperatures. The existence of the titanium sub-oxides (Ti 2 O, Ti 3 O) and the oxygen deficiency of the zirconia (ZrO 2) lead to the total reduction of the zirconia by the titanium during the solidification.
    [0012] According to the invention, the titanium zirconium composite mixture is fused by a concentration of a ytterbium, CO2 or plasma fiber laser energy source. In an advantageous embodiment, the oxygen content during the melting of the Ti / ZrO 2 interactive mixture is substantially zero during the first second of the laser melting. After 5 seconds, there is a rapid increase in oxygen content, thereby forming TiO 2 titanium dioxide by reacting with titanium. Indeed, the melting temperature of the interactive Ti / ZrO 2 (liquid titanium) mixture increases as the laser exposure time is maintained, leading to the activation of Zr and O and the increase in concentration gradient. During this time, by increasing the temperature, the Zr and O levels increase, which induces the diffusion of Ti, Zr and titanium oxides (Ti20, Ti30). Therefore, due to the presence of additional oxygen and Zr available for reaction with titanium, the reaction of the interactive mixture Ti / ZrO 2 becomes more intensive, remember that the reaction of the interactive mixture Ti / ZrO 2 is not isolated. thermal. The heat released by the reaction also increases the temperature locally and accelerates the diffusion of oxygen. On the other hand, the diffusion of oxygen is accelerated because of its smaller atomic radius. The melting temperature is an important parameter that influences the diffusion of oxygen. In order to improve the fluidity of the titanium during the reaction, it is necessary to preheat the reaction chamber before melting.
    [0013] During the manufacturing process, a portion of the oxygen atoms react with the titanium Ti to form titanium oxide (TiO 2), advantageously contributing to the improvement of the hardness of the Ti phase and consequently to the improvement of the mechanical properties of the composites. The mechanical properties of the Ti / ZrO2 composite material are greatly affected by the formation of titanium oxide in the titanium matrix.
    [0014] The hardness increases considerably with the increase of the D'Oz content up to 1 vol. Overall, the compressive strength of the Ti / ZrO 2 composite increases in a manner similar to the hardness. Even a very small amount of ZrO 2 contributes to the formation of titanium oxide, which leads to an improvement in the hardness as well as the brittleness of the Ti / ZrO 2 composite material beyond a certain amount.
    [0015] The invention also relates to a method for manufacturing a powder according to the invention comprising the following successive steps: A) preparation of a digital file of a geometrical shape to be produced, said digital file is virtually cut off from ( 1) to (n) in appropriate thicknesses with respect to the axis of construction Z. B) preparation of a mixture of pure titanium or a titanium alloy, zirconia, yttrium oxide (Ti / ZrO 2 / Y 2 O 3 ) C) argon of a laser melting chamber D) heating a substrate or titanium plate minimum temperature 200 ° C maximum temperature 1500 ° CE) deposition of a first layer of the mixture Ti / Zr02 / Y203 on a substrate or a titanium plate according to step C), the thickness of the powder bed is less than 50 μm and greater than 5 μm F) A focused energy source selectively fuse a part of the powder bed according to Slicing described in step A) G) Steps E) and F) are executed "n" times where (n) represents the number of layers of the shape to be realized. Definitions Classically referred to as "composite", a material containing both a ceramic phase and a metal phase with a base matrix, said matrix is either metallic and there is referred to as CMM (Metal Matrix Composite), or ceramic and here we are talking about CMC (Ceramic Matrix Composite).
    [0016] A product is conventionally called "molten" when it is obtained by a process using a raw material melting phase and a cooling solidification phase. A precursor of ZrO 2, Al 2 O 3, TiO 2 or Y 2 O 3 is a compound capable of leading to the formation of these oxides by a process comprising a melting and then a solidification by cooling. "Zr02", "zirconium oxide" and "zirconia" are synonyms. When reference is made to "ZrO 2", zirconium oxide or zirconia, it should be understood (ZrO 2 + HfO 2). Indeed, a little HfO2, chemically indissociable from ZrO2 and having similar properties, is still naturally present in zirconia sources at levels generally less than 2%. In other words, "ZrO 2 + HfO 2" means ZrO 2 and the traces of HfO 2 naturally present in the zirconia sources. The "melting point" indicates a zone or basin on the bed of powder where the laser melts the matter, 45 we speak of "melting pool" in the English literature. Unless otherwise indicated and without limitations, all the zirconium oxide contents according to the invention are volume percentages expressed on the basis of the oxides.
    [0017] Other features and advantages of the invention will become apparent on reading the following description and on examining the appended drawings in which FIG. 1 schematically represents the passage of the energy of the laser melting. a thickness of 10 μm on the powder bed according to the invention.
    [0018] FIG. 2 diagrammatically shows in section the laser melting points and their overlap according to the invention. Figure 3 shows the concentration curve of oxygen in the Ti / ZrO 2 alloy at different temperatures. FIG. 4 represents the time diffusion of oxygen in the Ti / ZrO2 alloy according to the invention.
    [0019] FIG. 5 shows the correlation between the volume fraction of ZrO 2 and the hardness of the Ti / ZrO 2 alloy according to the invention. DETAILED DESCRIPTION OF ONE EMBODIMENT OF THE INVENTION During the melting process, a part of the atoms Oxygen reacts with titanium to form titanium oxide TiO 2, which can contribute to the improvement of the hardness of the titanium phase as shown in the curve in (Figure 5). Indeed, the hardness increases considerably with the increase of the ZrO2 content up to 1 vol. %. The compressive strength of composites can increase in a manner similar to hardness. Even a very small amount of ZrO 2 contributes to the formation of titanium oxide, which leads to an improvement in the hardness of the interactive Ti / ZrO 2 alloy. In order to limit the oxygen concentration during melting, the exposure time of the laser spot in the melting zone (titanium in the liquid phase) does not exceed 5 seconds, advantageously the exposure time is less than 1 second as shown in the curve in (fig-4). The oxygen concentration remains low up to 9.5 pm of the depth of the laser spot as indicated in the curve in (fig-3), the point of inflection is at 10 pm of the laser spot, beyond this thickness of the powder bed the increase of the oxygen level is exponential. The depth of the laser spot (1-1) corresponds to the thickness of the powder bed (1-4) where the melting of the materials reacted is complete. The radiation of the focused energy (1-2) on a melting point is absorbed largely by the reaction materials (titanium, zirconia) (1-3). Because the titanium powder is on a micrometric scale coated with nanoscale zirconia powder, the passage of the titanium grain from the solid phase to the liquid phase causes the zirconia grains to melt on its surface. (1-3). The fusion and cohesion between the melting points (2-3) depends on the spot and the power of the laser, 40 in an advantageous embodiment the spot of the laser (2-1) is between 0.1mm and 0.2 mm and a laser power of 400 W and still advantageously 1000W. The cohesion of the melting points (2-3) largely depends on the state (liquid, solid or semi-solid) in which the melting point is at the pass of the laser in direct mode or in cross mode. The modes of passage of the laser depend on the strategy of the pathway used to scan the surfaces.
    [0020] The titanium-zirconia melting is advantageously carried out with an exposure time of the unit melting point of less than 1 second as indicated in the curve in (FIG. 4) and on a layer thickness of the powder bed of less than 10 μm as indicated. The mechanical properties of the Ti / ZrO 2 composite materials are very much affected by the formation of titanium oxide in the titanium matrix.
    [0021] The powder bed is maintained at a temperature of 200 ° C (2-6) in this embodiment or advantageously 400 ° C, preheating is provided by an electrical resistance placed at the lower level of the substrate (2-4) of the production tray, with a holding time of 50 seconds or preferably 100 seconds, and the selected melting temperature is 1700 ° C, or preferably 1750 ° C, or preferably 1800 ° C. The variation of the oxygen content in the interactive mixture Ti / ZrO 2 and the thickness of the reactive layer are two closely related parameters.
    [0022] The thicknesses of reactive layers vary with the hold time at different melting temperatures of 1700 ° C, 1750 ° C or 1800 ° C, the preheating temperature being set at 200 ° C. As the melting time increases, oxygen diffuses into the molten material and reacts with the titanium, so that the thickness of the reactive layer on the Ti face gradually increases. The variation of the thickness of the reactive layer can be divided into three stages: inoculation (0-1 s), linear increase (1-5 s) and parabolic increase (after 5 s) (fig-3). This is because the chemical reaction between Ti in the liquid phase and ZrO2 takes place under the global action of temperature and concentration. The higher melting temperature results in a higher oxygen content and a greater thickness of the reactive layer. The O content increases with the increase of the holding time of the laser spot on a reaction zone. The evolution of the thickness of the reactive layer can be divided into three stages: inoculation (0-1 s), linear increase (1-5 s) and parabolic increase (after 5 s).
    [0023] Titanium-zirconia composite materials containing the two components titanium and zirconia, characterized in that this alloy (i) is a titanium metal matrix composite (CMM) alloy with a proportion greater than 60% by volume and a proportion of zirconia smaller than 30% by volume but greater than 0.5% by volume, (ii) is a titanium metal matrix composite (CMM) alloy with a proportion greater than 99% by volume and a zirconia proportion of less than 1% by volume but greater than or equal to equal to 0.04% by volume, (iii) Contains 0.1 to 0.3% by volume of oxygen Process for making the titanium-zirconia composite alloy according to claim 6, characterized in that the manufacturing operation is carried out at higher temperatures at 1650 ° C. A method for manufacturing the titanium-zirconia composite alloy, characterized in that the manufacturing operation is performed by a focused energy source which selectively fuses a portion of the powder bed. 35 40 45
    权利要求:
    Claims (10)
    [0001]
    1. Titanium-zirconia composite materials containing the two components titanium and zirconia, characterized in that this alloy (i) is a composite metal matrix composite (CMM) titanium with a proportion greater than 60% by volume and a proportion of zirconia less than 30% by volume but greater than 0.5% by volume, is a titanium metal matrix (CMM) composite alloy with a proportion greater than 99% by volume and a zirconia proportion of less than 1% by volume but greater than or equal to equal to 0.04% by volume, Contains 0.1 to 0.3% by volume of oxygen 15
    [0002]
    2- titanium-zirconia composite materials according to claim 1, characterized in that the particle size of the titanium metal matrix is between 5 pm and 50 pm and the particle size of the zirconia is between 5 nm and 250 nm.
    [0003]
    3- titanium-zirconia composite materials according to claim 1 or 2, characterized in that the particle size of the titanium metal matrix is at a micrometric scale and the particle size of the zirconia is at a nanoscale.
    [0004]
    4- titanium-zirconia composite materials according to one of claims 1 to 3, characterized in that the laser spot exposure time is between 1 and 5 seconds.
    [0005]
    5- titanium-zirconia composite materials according to one of claims 1 to 4, characterized in that the thickness of the powder bed is between 5 and 50 microns. 25
    [0006]
    6. Process for manufacturing the titanium-zirconia composite alloy, characterized in that the manufacturing operation is performed by a focused energy source which selectively fuse a portion of the powder bed.
    [0007]
    7. A process for producing the titanium-zirconia composite alloy according to claim 6, characterized in that the manufacturing operation is carried out at temperatures above 1650 ° C. 30
    [0008]
    8- A method for manufacturing the titanium-zirconia composite alloy according to claim 6 or 7, characterized in that the manufacturing operation is performed with a laser spot exposure time less than 5 seconds per melting zone.
    [0009]
    9- titanium-zirconia composite materials according to one of claims 1 to 8, for dental and surgical implant manufacturing application 35
    [0010]
    10- titanium-zirconia composite materials according to one of claims 1 to 8, for the industrial application of heat shield application
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    Bandyopadhyay et al.2022|Additive Manufacturing of Metal Matrix Composites for Structural and Biomedical Applications
    同族专利:
    公开号 | 公开日
    FR3037945B1|2019-08-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20040243241A1|2003-05-30|2004-12-02|Naim Istephanous|Implants based on engineered metal matrix composite materials having enhanced imaging and wear resistance|WO2018100251A1|2016-11-30|2018-06-07|Abdelmadjid Djemai|Titanium-zirconium alloy and method for the production thereof by means of additive manufacturing|
    EP3489375A1|2017-11-22|2019-05-29|Paris Sciences et Lettres - Quartier Latin|Ternary ti-zr-o alloys, methods for producing same and associated utilizations thereof|
    WO2019213354A1|2018-05-03|2019-11-07|The United States Of America As Represented By The Secretary Of The Navy|Dental ridge augmentation matrix with integrated dental implant surgical drill guide system|
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    优先权:
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    FR1501303A|FR3037945B1|2015-06-24|2015-06-24|PROCESS FOR PRODUCING A TITANIUM ZIRCONIUM ALLOY AND ITS ADDITIVE MANUFACTURING METHOD|
    FR1501303|2015-06-24|FR1501303A| FR3037945B1|2015-06-24|2015-06-24|PROCESS FOR PRODUCING A TITANIUM ZIRCONIUM ALLOY AND ITS ADDITIVE MANUFACTURING METHOD|
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