![]() Additive refractory metal component, additive manufacturing process and powder
专利摘要:
Component having a matrix phase of at least one material selected from a group comprising molybdenum, a molybdenum-based alloy, tungsten, a tungsten-based alloy, and a molybdenum-tungsten-based alloy made by laser or electron beam in an additive manufacturing process, wherein the molybdenum content, the tungsten content or the sum amount of molybdenum and tungsten is greater than 85 at% and wherein the component contains particles whose melting point is above the melting point of the matrix phase. 公开号:AT16308U2 申请号:TGM50191/2018U 申请日:2018-11-19 公开日:2019-06-15 发明作者:Leitz Karl-Heinz;Kestler Heinrich;Singer Peter;Leichtfried Gerhard;Braun Jakob;Kaserer Lukas;Stajkovic Janko 申请人:Plansee Se; IPC主号:
专利说明:
The invention relates to a component with the features of the preamble of claim 1, an additive manufacturing method for producing a component with the features of the preamble of claim 9 and a use of a powder for an additive manufacturing method. Tungsten, molybdenum and their alloys are due to the high melting point, the low thermal expansion coefficient and the high thermal conductivity for different high-performance applications, such as for X-ray anodes, heat sinks, high-temperature heating zones, thrusters, extrusion matrices, molded parts for injection molding, hot runner nozzles , Resistance welding electrodes or components used for ion implantation systems. In addition, these elements have a high density, which ensures good shielding behavior against electromagnetic and particle radiation. Due to the comparatively low ductility at room temperature and the high DBTT (Ductile Brittle Transition Temperature), the processing properties are unfavorable for both cutting and non-cutting processes. In addition, with the exception of molybdenum rhenium and tungsten rhenium, the weldability of these materials is poor. A large-scale process for the production of components from these materials is the powder metallurgical production route, in which the corresponding starting powders are pressed and sintered and are usually subsequently shaped at a high temperature (temperature greater than DBTT). The achievable with additive manufacturing methods for geometrical component design far exceed those of conventional methods. In the case of materials such as molybdenum, tungsten and their alloys in particular, the additive manufacturing process is particularly advantageous since, compared to other metallic materials, these materials are much more difficult to machine with conventional manufacturing methods. In the additive manufacturing of metallic materials, mostly powder, less often wires, are used as the starting material. For metallic materials, several processes have been established, such as selective laser sintering (SLS), in which layered powder is sintered locally using a laser beam, selective laser beam melting (SLM) and selective electron beam melting (SEBM), in which layered powder is locally melted, and laser Metal deposition (LMD), in which a powder fed through a nozzle is melted. Additive manufacturing processes do not require any cutting or forming tools, which enables inexpensive production of components with a small number of pieces. In addition, high resource efficiency is achieved, since powder particles that have not melted or sintered together can be reused. A disadvantage of these processes is currently the very low build-up rate. In addition, it must be taken into account in the case of beam-based additive manufacturing processes that other metal-physical mechanisms are effective in comparison to conventional consolidation processes, such as casting or sintering. While surface and grain boundary diffusion determine the compaction during sintering, processes that involve local melting and solidification with a high cooling rate, such as SLM, SEBM and LMD, have different mechanisms of action, which are significantly more complex and not yet fully understood. Wetting behavior, Marangoni convection, recoil effects due to evaporation, segregation, epitaxial grain growth, solidification time, heat flow, heat flow direction and internal stresses as a result of solidification loss should be mentioned. Material concepts that are successful with conventional processes usually do not lead to error-free components in beam-based additive processes. The production of pure tungsten via selective laser beam melting is described in a technical article by Dianzheng Wang et al. (Appl. Sci. 2007, 7, 430), the production of molybdenum via selective laser beam melting in a technical article by D. Faidel et al. (additives 1/11 AT 16 308 U2 2019-06-15 Austrian patent office Manufacturing 8 (2015) 88-94). WO 2012/055398 discloses a selective laser beam melting process for refractory metals, the composition of the material being able to be changed by reaction with a reactive gas contained in the atmosphere during the construction of the component. In the publication CN 103074532 A and the associated article “Selective Laser Melting Additive Manufacturing of Hard-to-Process Tungsten-Based Alloy Parts With Novel Crystalline Growth Morphology and Enhanced Performance”, Journal of Manufacturing Science and Engineering, August 2016, Vol. 138 , 081003, by Dongdong Gu et al., Describes the laser melting of mechanically alloyed tungsten-TiC powder. S.K. Makineni et al. describe in "Synthesis and stabilization of a new phase regime in a Mo-Si-B based alloy by laser-based additive manufacturing", Acta Materialia 151 (2018), 31 40 the production of a molybdenum-based alloy using grain-refining lanthanum nanoparticles , US 2018/0214949 A1 and WO 2018/144323 show the use of grain-refining nanoparticles for the production of powders for additive manufacturing, which contain particles made of an aluminum alloy. The most widely used additive manufacturing process is the selective laser beam melting process (SLM). Here, a powder layer is applied to a substrate using a doctor blade. A laser beam is then passed over this layer of powder. This melts the powder particles locally, as a result of which the individual powder particles melt together and with the previously applied layer. A layer of the component to be manufactured is thus created by successive local melting of powder particles and subsequent solidification. Another layer of powder is then applied to the already processed layer of powder and the process begins again. The component is thus built up with each new powder layer, the direction of construction being arranged normal to the respective levels of the powder layers. Since the additive manufacturing process forms a characteristic microstructure, it is possible for a person skilled in the art to recognize whether a component is manufactured by a conventional process or by an additive manufacturing process. Molybdenum and tungsten have a high melting point, a high thermal conductivity in the solid phase and a high surface tension and viscosity in the liquid phase. These materials are among the most difficult to process using an additive manufacturing process. The short time in the molten phase due to the high thermal conductivity, combined with the high surface tension and the high viscosity, favor the balling effect, which in turn leads to pores and thus to crack-causing defects and a low density. The balling effect also has a negative effect on the surface quality, especially on the surface roughness. Since molybdenum and tungsten have a very low fracture toughness, local defects, combined with the inherent, thermally induced stresses inherent in the process, lead to cracks. Components made of molybdenum and tungsten produced by selective laser or electron beam melting show a stem-crystalline structure, the average grain aspect ratio (Grain Aspect Ratio - GAR value; ratio grain length to grain width) in the direction of construction typically being greater than 8. In the plane normal to the direction of construction, an intercrystalline crack network forms, which depicts the melting trace of the laser or electron beam. The cracks are predominantly intergranular hot and cold cracks. These are partially connected to each other, which means that components often have open porosity and are not sealed against gases and liquids. If the component is subjected to stress, there is generally no plastic deformation and intercrystalline fracture behavior is predominantly observed. An intergranular fracture behavior is a fracture that is mainly caused by cracks along the grain boundaries. Due to this fracture behavior, components manufactured in this way have low fracture strength, low fracture toughness and low ductility. 2/11 AT 16 308 U2 2019-06-15 Austrian Patent Office The object of the invention is to provide a generic component, wherein the molybdenum content, the tungsten content or the total content of molybdenum and tungsten is greater than 85 at%, in which the problems discussed above are avoided - a generic additive manufacturing method for the reliable production of a component with the aforementioned properties using a starting powder, the molybdenum content, the tungsten content or the total content of molybdenum and tungsten being greater than 85 at% [0014] ] - and a powder which exhibits optimized behavior for use in an additive manufacturing process, the powder particles from at least one material selected from a group comprising molybdenum, a molybdenum-based alloy, tungsten, a tungsten-based alloy and a Has molybdenum-tungsten-based alloy, wob ei the particles have a matrix phase and the molybdenum content, the tungsten content or the total content of molybdenum and tungsten is greater than 85 at%. [0015] In particular, it is the object of the invention to provide a component which has the following properties: [0016] - reduced frequency of defects, in particular cracks [0017] - improved strength [0018] - improved fracture toughness [0019] - improved ductility [0020] - improved density This object is achieved by a component with the features of claim 1, solved an additive manufacturing method with the features of claim 9 and a use of a powder with the features of claim 14. Advantageous embodiments of the invention are defined in the dependent claims. [0022] In the present disclosure, a powder is understood to mean a collection of particles. The particles can e.g. B. as a volume component of particles of the powder (in particular, for example, in the form of precipitates), as particles adhering to the surface of particles of the powder or as components of the powder which are present separately from the particles. [0023] Molybdenum-based alloy is understood to mean an alloy which contains at least 50 at% molybdenum. A molybdenum-based alloy for use in the invention has at least 85, 90, 95 or 99 at% molybdenum. A tungsten based alloy contains at least 50 at% tungsten. A tungsten-based alloy for use in the invention has at least 85, 90, 95 or 99 at% tungsten. A molybdenum-tungsten alloy is understood to mean an alloy which has at least 50 at% molybdenum and tungsten in total, in particular at least 80, 90, 95 or 99 at% molybdenum and tungsten in total. Molybdenum-tungsten alloys are a preferred embodiment in all concentration ranges. Typically, components made of molybdenum, tungsten, molybdenum and tungsten-based alloys produced using beam-based additive manufacturing processes have an oxygen content of between 0.25 and 0.6 at%. When using mechanically alloyed starting powders, significantly higher oxygen contents of 2 at% and above can also occur. The additive manufacturing process, such as selective laser or electron beam melting, does not reduce the oxygen content. When using high-resolution examination methods such as scanning or transmission electron microscopy, it can be seen that in the case of components according to the prior art, the oxygen is mainly excreted at the grain boundaries in the form of molybdenum or tungsten oxide. This 3.11 AT 16 308 U2 2019-06-15 Austrian patent office Excretions are responsible for the intergranular fracture behavior with consequently low breaking strength and toughness of additively manufactured components made of molybdenum, tungsten and their alloys. The high oxygen content can cause both hot and cold cracks. Hot cracks occur during production due to a reduced grain boundary strength. In the given case, in the heat-affected zone of the melting trace, the grain boundary strength is adversely affected by the melting of the oxides deposited on the grain boundaries. Cold cracks are due to thermally induced stresses in connection with defects (pores, micro cracks), which act as crack nuclei. If the grain boundary strength is clearly lower than the strength inside the grain, as is the case with the prior art, an intercrystalline crack pattern occurs. In addition, a high oxygen content also increases the balling effect. The oxygen is enriched in the edge area of the melting zone and reduces the surface tension there. Marangoni convection thus favors a material flow from the edge area into the center of the melting zone, which significantly increases the balling triggered by the Plateau-Rayleigh instability. The basic idea of the invention is to use the particles whose melting point is above the melting point of the matrix phase and which can thus act as crystallization nuclei for the melted matrix phase to achieve a fine-grained structure of the component. With a fine-grain structure, the total grain boundary area in the component is larger than with a coarse-grain structure, so that the oxides formed with the molybdenum or tungsten are distributed over a larger area without the oxygen content of the component having to be reduced. A weakening of the grain boundaries can be avoided in this way. In addition, a fine-grain structure leads to an increase in toughness. In principle, it is possible to adjust grain refinement by constitutional hypothermia. However, in order to achieve a sufficient effect, high levels of alloying elements are required, which cause constitutional hypothermia. These high contents cause an increase in strength, e.g. B. by mixed crystal formation or precipitates, whereby the ductility, expressed z. B. is significantly reduced by the fracture toughness. The provision according to the invention of particles with a melting point above the melting point of the matrix phase makes it possible to achieve a grain-refining effect without constitutional hypothermia or with a lower content of alloying elements which cause constitutional hypothermia. A component according to the invention is characterized in that the component contains particles whose melting point is above the melting point of the matrix phase. As already described, these particles lead to a fine-grained structure in the component and thus increase strength and toughness. The material used, from which the component is made, is preferably a powder. [0031] The presence of the particles is verified by conventional metallographic methods, for example by scanning or transmission electron microscopy. An additive manufacturing process according to the invention is characterized in that the starting powder contains [0033] - particles whose melting point is above the melting point of the matrix phase, and / or [0034] - at least one precursor substance (e.g. zirconium, hafnium, Contains tantalum, titanium, niobium, vanadium) for particles, the melting point of the particles being above the melting point of the matrix phase and the particles arising from the precursor substance when the particles of the starting powder are melted together in layers by means of laser or electron beam 4.11 AT 16 308 U2 2019-06-15 Austrian Patent Office [0035] - contains at least one component (e.g. zirconium, hafnium, tantalum, titanium, niobium, vanadium) which, in reaction with at least one component of a process gas atmosphere (e.g. Nitrogen) when the particles of the starting powder are melted together in layers by means of laser or electron beam, the melting point of which is above the melting point of the matrix phase. It is preferably provided that the step of providing a starting powder involves spheroidizing in the melting phase and / or granulating one Includes raw powder. All of the additive manufacturing methods known in the prior art, in particular those in which a large number of individual powder particles are melted together to form a solid structure by means of an energy-rich beam (laser or electron beam) can be used in the invention. A powder for use according to the invention in an additive manufacturing method, in particular an additive manufacturing method according to the invention, is characterized in that the powder contains [0039] particles whose melting point is above the melting point of the matrix phase of the particles, and / or [ Contains at least one precursor substance for particles, the melting point of the particles being above the melting point of the matrix phase of the particles and the particles arising from the precursor substance when the particles of the starting powder are melted together in layers by means of a laser or electron beam. The individual powder particles are preferred melted via an additive manufacturing process, whereby SLM (selective laser beam melting) or SEBM (selective electron beam melting) is advantageously used. [0042] The component is preferably built up in layers. For example, a powder layer is applied to a base plate using a doctor blade. The powder layer usually has a height of 10 to 150 μm. In the SEBM, the powder particles are first sintered to one another in a conductive manner using a defocused electron beam. Subsequently, the powder is locally melted by energy input using an electron beam. With the SLM, the powder can be melted locally using a laser beam. The beam creates a cellular weld pool with a line width of typically 30 microns to 200 microns. The laser or electron beam is guided over the powder layer. The entire powder layer or only part of the powder layer can be melted and subsequently solidified by suitable beam guidance. The melted and solidified areas of the powder layer are part of the finished component. The unmelted powder is not part of the manufactured component. Another layer of powder is then applied using a doctor blade and the laser or electron beam is again guided over this layer of powder. This creates a layered structure and a characteristic component structure. By guiding the electron or laser beam, a so-called scan structure is formed in each powder layer. Furthermore, a typical layer structure also forms in the direction of construction, which is determined by the application of a new powder layer. Both the scan structure and the individual layers can be recognized on the finished component. The structure of powder particles melted together selectively to form a solid structure by means of an additive manufacturing process by means of a high-energy beam (preferably by means of a laser or electron beam) differs significantly from a structure produced by other processes, for example thermal spraying. In thermal spraying, individual spray particles are accelerated in a gas stream and hurled onto the surface of the component to be coated. The spray particles can be in molten or melted (plasma spraying) or solid (cold gas spraying) form. A layer formation takes place because the individual spray particles hit the component surface 5/11 AT 16 308 U2 2019-06-15 flatten the Austrian patent office, stick primarily through mechanical clamping and build up the spray layer in layers. A plate-like layer structure is formed. Layers produced in this way show a grain stretching perpendicular to the building direction in a plane parallel to the building direction with an average grain stretching ratio (Grain Aspect Ratio - GAR value; grain length to grain width ratio) well over 2 and thus differ significantly from layers produced by selective laser or electron beam melting / Components that also have an average grain stretching ratio significantly above 2 in a plane parallel to the building direction, but with a grain stretching parallel to the building direction. In one embodiment of a component according to the invention it is provided that the content of the component in the particles is so high that the matrix phase has an average grain area smaller than 10,000 square micrometers, preferably smaller than 5,000 square micrometers, particularly preferably smaller than 2,500 square micrometers. In one embodiment of a component according to the invention and / or the manufacturing method according to the invention and / or the use according to the invention, it is provided that an average size of the particles is less than 5 micrometers, preferably less than 1 micrometer. The average size of the particles is preferably greater than 10 nanometers. In one embodiment of a component according to the invention and / or the manufacturing method according to the invention it is provided that a volume content of the particles in the component is between 0.05 vol% and 10 vol%. Below 0.05% by volume, the grain-refining effect is not sufficient; above 10% by volume, the number of particles / volume (responsible for the grain size that arises) increases only slightly, so that volume contents greater than 10% by volume essentially only cause coarsening of the particles , but not a further reduction in grain size. However, these higher volume contents lead to a loss of ductility. The volume content can be measured in various ways, of which the following may be mentioned by way of example: - Determination of the composition of the particles and any dissolved proportions of the elements forming the particles by means of suitable analysis methods such as XRD, REM / EDX, TEM / EDX, microsensor. - Determination of the total content of the elements forming the particles by suitable methods such as ICP-OES, ICP-MS or RFA - Calculation of the particle content (dissolved portions of the elements forming the particles are not taken into account here). In one embodiment of a component according to the invention it is provided that the component has a fracture behavior at least in one plane of fracture with a transcrystalline fraction of more than 50%, preferably more than 80%, particularly preferably more than 90%, of the fracture surface. In one embodiment of a component according to the invention it is provided that the component is manufactured in layers in one direction of construction and preferably has an average grain extension in a plane parallel to the direction of construction less than 5, preferably less than 3. The low grain stretching ensures an isotropy of the mechanical properties that is sufficient for the customarily required use properties. In one embodiment of a component according to the invention and / or an additive manufacturing method according to the invention and / or a use of a powder according to the invention it is provided that the particles are selected individually or in any combination from a group comprising: - Oxides, preferably ZrO 2 - Carbides, preferably ZrC, NbC, MoC, TiC, TaC, HfC 6/11 AT 16 308 U2 2019-06-15 Austrian Patent Office [0058] - nitrides, preferably YN, TaN, HfN [0059] - borides, preferably TaB 2 , HfB 2 [0060] Which type of particle is preferably used depends on what the matrix phase of the component consists of. It is important to ensure that the melting point of the particles is above the melting point of the matrix phase of the component. The melting temperatures of the above compounds: YN (T m = 2670 ° C), MoC (T m = 2687 ° C), ZrO 2 (T m = 2715 ° C), Ta (T m = 2996 ° C), TaN (T m = 3090 ° C), TaB 2 (Tm = 3140 ° C), TiC (T m = 3160 ° C), Re (T m = 3180 ° C), HfB 2 (T m = 3250 ° C), HfN (T m = 3305 ° C), TaC (T m = 3880 ° C), HfC (T m = 3900 ° C), ZrC (T m = 3540 ° C), NbC (T m = 3500 ° C) are above that Melting temperature of molybdenum (T m = 2623 ° C) and partly above that of tungsten (T m = 3422 ° C). With regard to the use of a powder according to the invention, it is preferably provided that the powder has a particle size of less than 100 micrometers. With regard to the use of a powder according to the invention, it is provided in one embodiment that the particles of the powder have the particles, preferably in the form of fine precipitates. The advantage of this is that there can be no disadvantageous segregation when doctoring the powder layer. With regard to the use of a powder according to the invention, it is provided in one exemplary embodiment that the powder is a mixture which contains particles comprising molybdenum and / or tungsten and particles whose melting point is above the melting point of the matrix phase. The advantage here is that the raw materials are easily available. With regard to the use of a powder according to the invention, one exemplary embodiment provides that the at least one precursor substance for the particles, the melting point of which is above the melting point of the matrix phase, is at least partially present as a layer on particles of the powder. In one embodiment of the component according to the invention it is provided that the component has an alloy element or several alloy elements which, in the case of molybdenum and the molybdenum-based alloy, for MoO 2 and / or MoO 3 ] - in the case of tungsten and the tungsten-based alloy for WO 2 and / or WO 3 and [0071] - in the case of the molybdenum-tungsten based alloy for at least one oxide from the group MoO 2 , MoO 3 , WO 2 and WO 3 At least in the temperature range> 1500 ° C has or has a reducing effect, at least one of the alloy elements being present both in at least partially non-oxidized form and in oxidized form. In one embodiment of an additive manufacturing process according to the invention, it is provided that the starting powder provided has at least one element which, in the case of molybdenum and the molybdenum-based alloy, for MoO 2 and / or MoO 3 , in the case of tungsten and the tungsten based alloy for WO 2 and / or WO 3 and in the case of the molybdenum-tungsten-based alloy for at least one oxide of the group MoO 2 , MoO 3 , WO 2 and WO 3 has a reducing effect at least in the temperature range> 1500 ° C. and in the starting powder provided is present in at least partially non-oxidized form and that at least one of the reducing elements is at least partially present as an oxide in the component produced. In one embodiment of a powder according to the invention it is provided that the powder further comprises one or more elements, which in the case of 7/11 AT 16 308 U2 2019-06-15 Austrian patent office Molybdenum and the molybdenum-based alloy for MoO 2 and / or MoO 3 , in the case of tungsten and the tungsten-based alloy for WO 2 and / or WO 3 and in the case of the molybdenum-tungsten-based alloy for at least one oxide from the group MoO 2 MoO 3 , WO 2 and WO 3 have a reducing effect at least in the temperature range> 1500 ° C., and that at least one reducing element is present in at least partially non-oxidized form. By the measures described above, it is possible to prevent the formation of molybdenum. To reduce tungsten oxides, in particular at the grain boundaries, by offering the oxygen in the form of the reducing, at least one alloy element or reducing element, a more attractive reaction partner. The oxygen content of the component is therefore not reduced, but the oxygen is at least partially, preferably largely, in an oxide form which is solid (at room temperature) and is formed with the alloy element (s). The oxygen bound in this way can no longer have an adverse effect on the grain boundary strength. Suitable alloying elements having a reducing action or reducing elements can be found in a simple manner by the person skilled in the art in tables. Thus, with the help of Gibb's energy (free enthalpy) or with the help of the Richardson-Ellingham diagram, the elements which have a reducing effect on molybdenum or tungsten oxide can be found on the basis of the differences between their free standard enthalpies of formation. This makes it possible in a simple manner to find elements which are suitable as reducing agents for molybdenum or tungsten oxide. The alloying element preferably has a reducing effect for all molybdenum oxides (eg MoO 2 , MoO 3 ) or for all tungsten oxides (eg WO 2 , WO 3 ), regardless of their stoichiometry. So that the alloying element can reliably bind the oxygen in the form of an oxide, the alloying element must have a reducing effect on molybdenum and / or tungsten oxide at least in the temperature range> 1500 ° C. At temperatures <1500 ° C, the reaction kinetics are too low, so that re-oxidation of molybdenum or tungsten no longer occurs. The alloying element preferably has a reducing effect in the temperature range from room temperature to liquidus temperature for molybdenum and / or tungsten oxide. It is preferably provided that at least one of the alloy elements is an element from group 2, 3 or 4 of the periodic table, preferably titanium, zirconium or hafnium. For example, it can be provided that the component contains HfC, ZrO 2 or HfO 2 . The proof that the alloying element is present in the component in at least partially non-oxidized and in oxidized form can be done by customary methods, such as XRD, microsensor, ICP-OES, ICP-MS, RFA, REM / EDX, TEM / EDX and carrier gas hot extraction. The quantitative determination of the alloying element content takes place, for example, via ICP-OES or ICP-MS, the quantitative determination of the oxygen content by hot gas extraction or XRF. Whether the alloying element is present both in oxidized form and in non-oxidized form can be determined by XRD and, in the case of low contents, by spatially resolving methods, such as, for example, microsonde, REM / EDX or TEM / EDX. It can preferably be provided that the particles whose melting point is above the melting point of the matrix phase themselves act as these alloying elements or reducing elements, that is to say they assume a double role.
权利要求:
Claims (18) [1] 1. Component with a matrix phase made of at least one material, selected from a group comprising molybdenum, a molybdenum-based alloy, tungsten, a tungsten-based alloy and a molybdenum-tungsten-based alloy, which is produced by means of laser or electron beam in an additive manufacturing process is, the molybdenum content, the tungsten content or the total content of molybdenum and tungsten is greater than 85 at%, characterized in that the component contains particles whose melting point is above the melting point of the matrix phase. [2] 2. The component according to claim 1, wherein an average particle size of the particles is less than 5 micrometers. [3] 3. Component according to at least one of the preceding claims, wherein a volume content of the particles in the component is between 0.05 vol% and 10 vol%. [4] 4. The component according to at least one of the preceding claims, wherein the component has at least in a fracture plane a fracture behavior with a transcrystalline fraction of more than 50% of the fracture surface. [5] 5. Component according to at least one of the preceding claims, wherein the component was manufactured in an additive manufacturing process along a direction of construction and wherein an average grain stretching in a plane parallel to the direction of construction is less than 5. [6] 6. Component according to at least one of the preceding claims, wherein the particles are selected individually or in any combination from a group comprising: - Oxides, preferably ZrO 2 , HfO 2 - carbides, preferably ZrC, NbC, MoC, TiC, TaC, HfC - nitrides, preferably YN, TaN, HfN - Borides, preferably TaB 2 , HfB 2 [7] 7. Additive manufacturing method for producing a component, in particular a component according to at least one of the preceding claims, comprising at least the following steps: - Providing a starting powder from at least one material selected from a group comprising molybdenum, a molybdenum-based alloy, tungsten, a tungsten-based alloy and a molybdenum-tungsten-based alloy - Layer-wise melting together of the particles of the starting powder by means of laser or electron beam, whereby a matrix phase is formed, the molybdenum content, the tungsten content or the total content of molybdenum and tungsten in the matrix phase being greater than 85 at%, characterized in that the starting powder - Contains particles whose melting point is above the melting point of the matrix phase, and / or contains at least one precursor substance for particles, the melting point of the particles being above the melting point of the matrix phase and the particles arising from the at least one precursor substance when the particles of the starting powder are melted together in layers by means of laser or electron beam, and / or - Contains at least one component which forms particles in reaction with at least one component of a process gas atmosphere when the particles of the starting powder are melted together in layers, the melting point of which is above the melting point of the matrix phase 9.11 AT 16 308 U2 2019-06-15 Austrian patent office [8] 8. The manufacturing method according to the preceding claim, wherein the step of providing the starting powder comprises spheroidizing in the melting phase and / or granulating a raw powder. [9] 9. Manufacturing method according to at least one of the two preceding claims, wherein an average size of the particles is less than 5 microns. [10] 10. Manufacturing method according to at least one of claims 7 to 9, wherein a volume content of the particles in the component is between 0.05 vol% and 10 vol%. [11] 11. The manufacturing method according to at least one of claims 7 to 10, wherein the starting powder provided has at least one element which in the case of molybdenum and the molybdenum-based alloy for MoO 2 and / or MoO 3 , in the case of tungsten and the tungsten-based Alloy for WO 2 and / or WO 3 and in the case of the molybdenum-tungsten-based alloy for at least one oxide of the group MoO 2 , MoO 3 , WO 2 and WO 3 has a reducing effect at least in the temperature range> 1500 ° C. and in the starting powder provided in at least partially non-oxidized form is present and that at least one of the reducing elements is at least partially present as an oxide in the component (8) produced. [12] 12. Use of a powder which comprises particles of at least one material selected from a group comprising molybdenum, a molybdenum-based alloy, tungsten, a tungsten-based alloy and a molybdenum-tungsten-based alloy, the particles having a matrix phase and wherein the molybdenum content, the tungsten content or the total content of molybdenum and tungsten in the matrix phase is greater than 85 at%, characterized in that the powder - Contains particles whose melting point is above the melting point of the matrix phase of the particles, and / or contains at least one precursor substance for particles, the melting point of the particles being above the melting point of the matrix phase of the particles and the particles arising from the at least one precursor substance when the particles of the starting powder are melted together in layers by means of laser or electron beam and for an additive manufacturing process, in particular for an additive manufacturing method according to at least one of claims 7 to 11 is used. [13] 13. Use of a powder according to the preceding claim, wherein the particles of the powder have the particles, preferably in the form of fine precipitates. [14] 14. Use of a powder according to at least one of claims 12 or 13, wherein the powder is a mixture which contains particles containing molybdenum, a molybdenum-based alloy, tungsten, a tungsten-based alloy or a molybdenum-tungsten-based alloy and particles whose melting point is above the melting point of the matrix phase. [15] 15. Use of a powder according to at least one of claims 12 to 14, wherein the at least one precursor substance for the particles whose melting point is above the melting point of the matrix phase is at least partially present as a layer on particles of the powder. [16] 16. Use of a powder according to at least one of claims 12 to 15, wherein an average particle size of the particles whose melting point is above the melting point of the matrix phase of the particles is less than 5 micrometers. [17] 17. Use of a powder according to at least one of claims 12 to 16, wherein a volume content of the particles whose melting point is above the melting point of the matrix phase of the particles in the powder is between 0.05 vol% and 10 vol%. 10/11 AT 16 308 U2 2019-06-15 Austrian patent office [18] 18. Use of a powder according to at least one of claims 12 to 17, wherein the powder further comprises one or more elements, which in the case of molybdenum and the molybdenum-based alloy for MoO 2 and / or MoO 3 , in the case of tungsten and the tungsten-based alloy for WO 2 and / or WO 3 and in the case of the molybdenum-tungsten-based alloy for at least one oxide from the group MoO 2 , MoO 3 , WO 2 and WO 3 at least in the temperature range> 1500 ° C. has a reducing effect, and at least one reducing element is present in at least partially non-oxidized form.
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引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 EP3892404A1|2020-04-08|2021-10-13|Heraeus Deutschland GmbH & Co KG|Additive fabrication of refractory metals with reduced degree of contamination|DE102010049910A1|2010-10-28|2012-05-03|Eads Deutschland Gmbh|Method for targeted material change during the selective laser melting process| JP5394582B1|2012-06-07|2014-01-22|株式会社アライドマテリアル|Molybdenum heat-resistant alloy| CN103074532A|2013-01-10|2013-05-01|南京航空航天大学|Method for preparing solid solution toughened wolfram-base composite material through laser rapid forming| CN111251604A|2014-06-20|2020-06-09|福吉米株式会社|Powder material for powder laminate molding and powder laminate molding method using same| CN107027315B|2014-07-03|2020-02-14|攀时奥地利公司|Method for producing a layer| GB2552907A|2015-04-24|2018-02-14|Halliburton Energy Services Inc|Mesoscale reinforcement of metal matrix composites| US10386801B2|2015-08-03|2019-08-20|Baker Hughes, A Ge Company, Llc|Methods of forming and methods of repairing earth-boring tools| JP6656911B2|2015-12-22|2020-03-04|株式会社フジミインコーポレーテッド|Modeling materials for use in powder additive manufacturing| US20190032175A1|2017-02-01|2019-01-31|Hrl Laboratories, Llc|Aluminum alloys with grain refiners, and methods for making and using the same| US11117193B2|2017-02-01|2021-09-14|Hrl Laboratories, Llc|Additive manufacturing with nanofunctionalized precursors| JP2020511317A|2017-02-28|2020-04-16|スリーエム イノベイティブ プロパティズ カンパニー|Metal bond abrasive article and method for manufacturing metal bond abrasive article|
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申请号 | 申请日 | 专利标题 ATGM50191/2018U|AT16308U3|2018-11-19|2018-11-19|Additively manufactured refractory metal component, additive manufacturing process and powder|ATGM50191/2018U| AT16308U3|2018-11-19|2018-11-19|Additively manufactured refractory metal component, additive manufacturing process and powder| JP2021527249A| JP2022507758A|2018-11-19|2019-10-03|Additional refractory metal parts, additional manufacturing methods and powders| US17/294,845| US20220016699A1|2018-11-19|2019-10-03|Additively-manufactured refractory metal component, additive manufacturing process, and powder| EP19787135.3A| EP3883708A1|2018-11-19|2019-10-03|Additively-manufactured refractory metal component, additive manufacturing process, and powder| KR1020217017492A| KR20210091750A|2018-11-19|2019-10-03|Additive Manufacturing Refractory Metal Components, Additive Manufacturing Methods and Powders| CN201980076144.6A| CN113039028A|2018-11-19|2019-10-03|Refractory metal component produced by additive method, additive method and powder| PCT/AT2019/060326| WO2020102834A1|2018-11-19|2019-10-03|Additively-manufactured refractory metal component, additive manufacturing process, and powder| TW108137056A| TW202020178A|2018-11-19|2019-10-15|Fire-proof metal part made with additive, process for production with additive and powder| 相关专利
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