EP3688200B1 - Pièce frittée en molybdène et procédé de fabrication - Google Patents

Pièce frittée en molybdène et procédé de fabrication Download PDF

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EP3688200B1
EP3688200B1 EP18789316.9A EP18789316A EP3688200B1 EP 3688200 B1 EP3688200 B1 EP 3688200B1 EP 18789316 A EP18789316 A EP 18789316A EP 3688200 B1 EP3688200 B1 EP 3688200B1
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ppmw
content
molybdenum
boron
carbon
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German (de)
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EP3688200A1 (fr
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Karl Huber
Michael O'sullivan
Michael EIDENBERGER-SCHOBER
Robert Storf
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Plansee SE
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Plansee SE
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2207/00—Aspects of the compositions, gradients
    • B22F2207/01—Composition gradients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/45—Others, including non-metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only

Definitions

  • the present invention relates to a powder-metallurgical molybdenum sintered part in the form of a solid body and a method for producing such a molybdenum sintered part.
  • molybdenum Due to its high melting point, low thermal expansion coefficient and high thermal conductivity, molybdenum is suitable for various high-performance applications, such as a material for glass melting electrodes, for furnace components of high-temperature furnaces, for heat sinks and for X-ray anodes.
  • a frequently used and large-scale process for the production of molybdenum and molybdenum-based materials is the powder metallurgical production route, in which the corresponding starting powders are pressed and then sintered, with the pressing step typically being preceded by mixing the powders in the case of several powders.
  • molybdenum produced by powder metallurgy (hereinafter "powder metallurgy") is characterized by the fact that the structure is finer-grained and more homogeneous due to the comparatively low sintering temperature (sintering temperature ⁇ 0.8*melting point). There is no liquid phase segregation and the powder metallurgy fabrication route allows for a greater variety of preforms (in geometric terms) to be produced.
  • molybdenum with its body-centered cubic crystal structure, has a transition from ductile to brittle behavior depending on the processing state - at or above room temperature (e.g. at 100°C) and is very brittle below this transition temperature. Furthermore, undeformed molybdenum and recrystallized molybdenum have a relatively low strength, especially in relation to bending and tensile loads, which also limits the area of application (through forming, such as rolling or forging, these properties can also be improved with conventional molybdenum, with increasing recrystallization however, they deteriorate again).
  • molybdenum cannot be welded, which either requires complex connection methods (riveting, flanging, etc.) or - to improve the welding properties - the addition of alloying elements (e.g. rhenium or zirconium) to the Mo base material or the use of welding filler materials (e.g. rhenium).
  • alloying elements e.g. rhenium or zirconium
  • welding filler materials e.g. rhenium
  • 2017/0044646 A1 which contains certain proportions of vanadium (V), carbon (C), niobium (Nb), titanium (Ti), boron (B), tungsten (W), tantalum (Ta), hafnium (Hf) and ruthenium (Ru ) teaches in combination known.
  • V vanadium
  • carbon C
  • niobium Nb
  • titanium Ti
  • boron B
  • Ta tantalum
  • Ru ruthenium
  • the object of the present invention is to provide a molybdenum-based material that has high strength and good weldability and can be used universally in different applications.
  • the molybdenum sintered part according to the invention has significantly increased ductility and increased strength, in particular with regard to bending and tensile loads. This is particularly true when compared to conventional molybdenum in the undeformed and/or (fully or partially) recrystallized condition.
  • conventional molybdenum the Forming larger components is problematic due to the low grain boundary strength.
  • forging thick bars e.g. with starting diameters of 200-240 mm
  • rolling thick sheets e.g.
  • the molybdenum sintered part according to the invention can also be produced and further processed on an industrial scale.
  • the molybdenum sintered part according to the invention With the molybdenum sintered part according to the invention, the forming of large components, such as the forging of thick rods and the rolling of thick sheets, is possible while avoiding internal defects and grain boundary cracks.
  • the molybdenum sintered part according to the invention eg in the form of sheet metal
  • the low strength of conventional molybdenum is attributed to low grain boundary strength, which leads to intergranular fracture behavior.
  • the grain boundary strength of molybdenum is known to be reduced by segregation of oxygen and possibly other elements, such as nitrogen and phosphorus, in the area of the grain boundaries.
  • the invention is based on the finding that even low levels of carbon and boron in combination lead to significantly increased grain boundary strength and have a favorable effect on the flow behavior of the material (responsible for the high ductility) if the oxygen content is low and the content of other impurities ( and W) are below the specified limits.
  • the carbon content of the Oxygen content can be kept low in the sintered part.
  • the boron content large amounts of carbon are not required, which would be problematic, especially in the case of glass melting components, due to the increased outgassing that then occurs.
  • a low proportion of boron in combination with a comparatively low proportion of carbon is sufficient to achieve the desired high ductility and strength values.
  • a powder-metallurgical molybdenum sintered part is understood to mean a component whose production includes the steps of pressing corresponding starting powder to form a compact and sintering the compact.
  • the manufacturing process can also have further steps, such as mixing and homogenizing (e.g. in a plowshare mixer) the powder to be pressed, etc Specialist is readily recognizable.
  • This microstructure is characterized by its fine grain (typical grain sizes in particular in the range of 30-60 ⁇ m). Furthermore, the pores are distributed uniformly over the entire cross section through the sintered part.
  • the powder-metallurgical molybdenum sintered part according to the invention can also have been subjected to further processing steps, such as forming (rolling, forging, etc.), so that it is then in a formed structure, subsequent annealing, etc.. It can also be coated and / or connected to other components, such as by welding or soldering.
  • the details of the proportions according to the invention and the details regarding the further developments explained below relate to the respective taken element (eg Mo, B, C, O or W), regardless of whether this is present in the molybdenum sinter in elemental or combined form.
  • the proportions of the different elements are determined by chemical analysis.
  • the proportions of most metallic elements e.g. Al, Hf, Ti, K, Zr, etc.
  • the ICP-MS analysis method mass spectroscopy with inductively coupled plasma
  • the boron proportion using the ICP-OES analysis method optical emission spectroscopy with inductively coupled plasma
  • the carbon content via combustion analysis combustion analysis
  • oxygen content via hot extraction analysis carrier gas hot extraction
  • ppmw expresses the proportion by weight multiplied by 10 -6 .
  • the specified limit values can also be stably maintained over thick components; in particular, the advantageous properties can be realized on an industrial scale independently of the respective component geometry, sheet metal thickness, etc. It was observed that the boron content and the carbon content decrease slightly towards the surface of the sintered part, while the oxygen content is relatively constant through the sintered part thickness. A slight decrease in the boron content and/or the carbon content towards the surface or a slight increase in the oxygen content towards the surface, even if the limit values may not be in an area close to the surface (with a thickness of 0.1 mm, for example).
  • a grading of the composition can optionally only occur during subsequent treatment steps of the molybdenum sintered part, such as during reshaping (rolling, forging, extrusion, etc.), during subsequent annealing, during a welding process, etc., occur or increase further.
  • the boron content and the carbon content are each ⁇ 5 ppmw.
  • certified content information for boron and carbon can typically be specified above 5 ppmw.
  • boron and carbon below a respective proportion of 5 ppmw can also be clearly detected and their proportions can be determined quantitatively (at least if the respective proportion is ⁇ 2 ppmw), but the proportions in in this area - depending on the analysis method - sometimes no longer specified as a certified value.
  • the total proportion "BuC" of carbon and boron is in the range of 25 ppmw ⁇ "BuC" ⁇ 40 ppmw.
  • the boron content "B” is in the range of 5 ppmw ⁇ "B" ⁇ 45 ppmw, more preferably in the range of 10 ppmw ⁇ "B" ⁇ 40 ppmw.
  • the proportion of carbon “C” is in the range of 5 ⁇ “C” ⁇ 30 ppmw, more preferably in the range of 15 ⁇ “C” ⁇ 20 ppmw.
  • both elements (B, C) are contained in the molybdenum sintered part in such a high and at the same time in such a sufficient quantity that their advantageous interaction is clearly noticeable, but at the same time the carbon and the boron contained does not yet have a negative effect in the various applications.
  • the effect of carbon is to keep the oxygen content low in the molybdenum sinter and of boron to allow a sufficiently low carbon content while achieving high ductility and high strength.
  • the oxygen content "O" is in the range of 5 ⁇ "O" ⁇ 15 ppmw. According to current knowledge, the oxygen accumulates in the area of the grain boundaries (segregation) and leads to a reduction in grain boundary strength. Accordingly, an overall low oxygen content is advantageous. Setting such a low oxygen content is possible both by using starting powders with a low oxygen content (eg ⁇ 600 ppmw, in particular ⁇ 500 ppmw), sintering in the Vacuum, under protective gas (eg argon) or preferably in a reducing atmosphere (especially in a hydrogen atmosphere or in an atmosphere with H 2 partial pressure), and by providing a sufficient proportion of carbon in the starting powders.
  • a low oxygen content eg ⁇ 600 ppmw, in particular ⁇ 500 ppmw
  • protective gas eg argon
  • a reducing atmosphere especially in a hydrogen atmosphere or in an atmosphere with H 2 partial pressure
  • the maximum proportion of impurities from zirconium (Zr), hafnium (Hf), titanium (Ti), vanadium (V) and aluminum (Al) is ⁇ 50 ppmw in total.
  • the proportion of each element of this group (Zr, Hf, Ti, V, Al) is preferably ⁇ 15 ppmw.
  • the maximum proportion of impurities from silicon (Si), rhenium (Re) and potassium (K) is ⁇ 20 ppmw in total.
  • the proportion of each element of this group (Si, Re, K) is preferably ⁇ 10 ppmw, in particular ⁇ 8 ppmw.
  • the effect attributed to potassium is that it reduces the grain boundary strength, which is why the lowest possible proportion is desirable.
  • Zr, Hf, Ti, Si and Al are oxide formers and could in principle be used to counteract an enrichment of oxygen in the area of the grain boundaries by binding the oxygen (oxygen getter) and thus in turn to increase the grain boundary strength. In some cases, however, they are suspected of reducing ductility, especially when they are present in large quantities.
  • a ductilizing effect is ascribed to Re and V, ie they could in principle be used to increase the ductility.
  • the addition of additives means that they can also have a disruptive effect depending on the application and conditions of use of the Mo sintered part.
  • the molybdenum sintered part has a total proportion of molybdenum and tungsten of ⁇ 99.97% by weight.
  • the proportion of tungsten within the specified limit values ( ⁇ 330 ppmw) is not critical for the previously known applications and is typically already due to the Mo extraction and powder production.
  • the molybdenum sintered part has a molybdenum content of ⁇ 99.97% by weight, ie it consists almost entirely of molybdenum.
  • the carbon and the boron are in total at least 70% by weight, based on the total content of carbon and boron, in dissolved form (they do not therefore form a separate phase).
  • Investigations on sintered molybdenum parts according to the invention have shown that a small proportion of the boron may be present as the Mo 2 B phase, although this is not critical to a small extent.
  • the carbon and the boron are at least to a large extent (eg ⁇ 70% by weight, in particular ⁇ 90% by weight) in solution, they can segregate at the grain boundaries and fulfill the effect explained above to a particularly high degree.
  • each of the elements B and C individually also satisfies the specified limit values.
  • the boron and the carbon are finely distributed in the Mo base material and enriched in the area of the large-angle grain boundaries.
  • a high-angle grain boundary is present when an angular difference of ⁇ 15° is required to match the crystallographic alignment of adjacent grains, which can be determined by EBSD (electron backscatter diffraction). Due to the fine distribution and the enrichment in the area of the large-angle grain boundaries, boron and carbon can exert their positive influence on the grain boundary strength to a particularly high degree.
  • An essential aspect for achieving this fine distribution and a high enrichment at least along as many large-angle grain boundaries as possible (and possibly also along small-angle grain boundaries) is that the boron and carbon are added to the starting powders during powder metallurgical production as the purest possible element (B , C) or as a compound that is as pure as possible, ie with as few other impurities as possible (apart from the compound partner of B and/or C that may be added, such as Mo, N, C, etc.), and as a powder that is as fine as possible.
  • Boron for example, as molybdenum boride (Mo 2 B), as boron carbide (B 4 C), as boron nitride (BN) or elementary as amorphous or crystalline boron.
  • Carbon can be added, for example, as graphite or as molybdenum carbide (MoC, Mo 2 C).
  • the sintering conditions temperature profile, maximum sintering temperature, Holding times, sintering atmosphere
  • boron and carbon if they are freely available at the temperatures in question, react at least partially with oxygen from the starting powders and possibly also with oxygen from the sintering atmosphere and escape as gas. In order to still achieve the desired boron and carbon content in the finished molybdenum sintered part, correspondingly higher amounts of boron- and/or carbon-containing powders must be added to the starting powders.
  • the tendency for it to volatilize during the sintering process and be emitted into the atmosphere as an environmentally harmful gas can be counteracted by matching the boron-containing powder and the sintering conditions in such a way that the boron is only released after such a Duration and / or after such a temperature increase as a reactant is available (e.g. because only then does the boron-containing compound decompose or the boron-containing powder only releases the boron due to its morphology, coating, etc. to the reaction) if the Oxygen from the starting powders has at least largely reacted with different reactants (e.g. hydrogen, carbon, etc.) and has escaped as a gas.
  • reactants e.g. hydrogen, carbon, etc.
  • a gradation of the composition across the thickness of the Mo sintered part can be largely suppressed by keeping the oxygen content as low as possible in the starting powders and only using a moderately increased amount of carbon and boron-containing powders (compared to the achievable C and B portions in the Mo sintered part) is added, preferably a reducing atmosphere (H 2 atmosphere or H 2 partial pressure), alternatively a protective gas (e.g argon) or a vacuum is selected during the sintering process and the boron-containing powder and the temperature profile during the sintering process are coordinated in such a way that the boron is only released when the oxygen from the starting powders has already reacted, at least to a large extent, with other reactants Has.
  • a protective gas e.g argon
  • the total proportion of carbon and boron in the area of the grain boundary section is at least one and a half times as high as in the area of the grain interior of the adjacent grain;
  • the proportion of carbon and boron in total in the area of the grain boundary section is at least twice as high, more preferably at least three times as high as in the area of the grain interior of the adjacent grain.
  • each of the elements B and C satisfies the specified relationships.
  • the proportions of the individual elements (B, C) and the sum of the elements (B and C) are each determined in atomic percent (at%) by means of three-dimensional atom probe tomography.
  • a three-dimensional, cylindrical region with a cylinder axis running perpendicular to the grain boundary section and with a thickness of 5 nm (nanometers) running along the cylinder axis is selected for the region of the grain boundary section, which is placed centrally around the grain boundary section in relation to the cylinder axis direction (According to the measurement method that is decisive here and explained in detail below, this is the range of 5 nm thickness within which the sum of the measured concentrations of B and C is maximum).
  • the cylinder axis runs perpendicularly to the plane that is spanned by the grain boundary section in the region to be examined.
  • a mean plane that maintains a minimum distance to the grain boundary section over the observed area is to be used (for the orientation and positioning of the cylindrical region to be examined).
  • a three-dimensional cylindrical region spaced with its center by 10 nm in the cylinder axis direction from the grain boundary portion (or, if necessary, from the associated average plane) becomes the same Dimensions and the same orientation (ie the same alignment and position of the cylinder axis of the cylinder-shaped area to be examined) is used. It is important to ensure that the region of the interior of the grain is at the same time sufficiently spaced apart from other large-angle grain boundaries, preferably by at least 10 nm.
  • the three-dimensional, cylindrical areas (of the grain interior as well as the grain boundary section) each have a (circular) diameter of 10 nm, with the associated circular area of the cylindrical areas being aligned perpendicular to the associated cylinder axis (resulting from the cylindrical shape).
  • the proportion of boron and carbon is determined in atomic percent. Subsequently, the proportions determined in this way, either of boron and carbon in total or alternatively also of the individual elements, are set in relation to the area of the grain boundary section and the area of the interior of the grain, as will be explained in more detail below.
  • Atom probe tomography is a high-resolution characterization method for solids. Needle-shaped tips ("sample tip") with a diameter of about 100nm are cooled to temperatures of about 60K and removed by field evaporation. The position of the atom and the mass-to-charge ratio for each detected atom (ion) is determined using a position-sensitive detector and time-of-flight mass spectrometer. A more detailed description of atom probe tomography can be found in MK Miller, A Cerezo, MG Hetherington, GDW Smith, Atom probe field ion microscopy, Clarendon Press, Oxford, 1996 .
  • a three-dimensional reconstruction of the sample tip used in the molybdenum sintered part according to the invention is first carried out (cf. also figure 5 and their description). At least elements B and C are displayed. Based on the knowledge that these elements accumulate in the area of the large-angle grain boundaries, the position of the large-angle grain boundary can be made visible in the three-dimensional reconstruction by the compression of elements B and C occurring there.
  • a measuring cylinder which is relevant for the evaluation and has a diameter of 10 nm (according to the information given above), is positioned in the three-dimensional reconstruction in such a way that a grain boundary section (as flat as possible and spaced sufficiently far from other large-angle grain boundaries) of the Large-angle grain boundary within the measuring cylinder is that the cylinder axis of the measuring cylinder - as described above for the cylindrical areas to be examined - is aligned perpendicular to the plane spanned by the grain boundary section.
  • the grain boundary section is preferably located essentially in the center of the measuring cylinder in relation to the cylinder axis of the measuring cylinder.
  • the measuring cylinder must be positioned and its length (along the cylinder axis) chosen so long (e.g. 30 nm) that not only the cylindrical area of the grain boundary section, but also the cylindrical area of the grain interior, each of which has a thickness of 5 nm and whose centers are spaced apart by 10 nm along the cylinder axis, each lie entirely within the measuring cylinder.
  • a one-dimensional concentration profile is then determined (cf. 6 and the associated description).
  • the measuring cylinder is divided along its cylinder axis into cylindrical disks with a respective disk thickness of 1 nm (diameter 10 nm in each case corresponding to the diameter of the measuring cylinder).
  • the concentration (in atomic percent) of at least the elements B and C (and optionally other elements such as O, N, Mo, etc.) is determined for each of these discs.
  • the concentration of at least the elements B and C (individually and possibly also in total) determined for each disk is plotted against the length of the cylinder axis in a diagram (see. 6 ), whereby one measuring point per nanometer is to be entered according to the subdivision.
  • the five adjacent discs of the measuring cylinder where the sum of the measured concentrations of B and C (B and C calculated for each measuring point in total) is maximum are selected as the cylindrical area of the grain boundary section to be examined.
  • the five adjacent disks are selected, the central disk of which is spaced by 10 nm from the central disk of the cylindrical region of the grain boundary section.
  • the proportions of B, C and the sum of B and C are determined for the area of the grain boundary section and correspondingly for the area of the interior of the grain by calculating the proportions (in atomic percent) of these elements (B, C, or B and C in total ) is summed up for the five relevant panes of the area to be examined and then the sum is divided by five.
  • the values thus obtained for the area of the grain boundary section can then be related to the area of the grain interior.
  • the molybdenum sintered part according to the invention can also be subjected to further processing steps, in particular forming (rolling, forging, extrusion, etc.).
  • the sintered molybdenum part is deformed at least in sections and has a preferred orientation of the large-angle grain boundaries and/or large-angle grain boundary sections perpendicular to the main direction of deformation, which can be determined by means of EBSD analysis of a metallographic microsection of a cross-sectional plane along the direction of deformation, in which the (e.g. circumferential high angle grain boundaries formed around a grain and the high angle grain boundary sections (e.g. formed with an open beginning and end) visualized can be determined.
  • the molybdenum sintered part according to the invention can be shaped particularly well and with a low scrap rate. Even when forging thick bars (e.g. with starting diameters in the range of 200-240 mm) and rolling thick sheets (e.g. with starting thicknesses in the range of 120-140mm), cracking, which occurs more frequently with conventional molybdenum, in the core of the bars/sheets, avoided.
  • the molybdenum sintered part a deformed structure, i.e. there are typically no clear large-angle grain boundaries surrounding individual grains, as they occur immediately after the sintering step, but only large-angle grain boundary sections, each of which has an open beginning and an open end.
  • sections of the large-angle grain boundaries of the original grains are still recognizable as they were immediately after the sintering step.
  • Dislocations and new large-angle grain boundary sections are also formed as a result of the deformation.
  • the original grains, as they were immediately after the sintering step, if they are still recognizable, are severely squashed and distorted due to the deformation.
  • the preferred direction of the recognizable large-angle grain boundary sections runs perpendicular to the main direction of deformation. In particular, a larger proportion (e.g.
  • At least 60%, in particular at least 70%) of the large-angle grain boundary sections in terms of length is more inclined to the direction perpendicular to the main forming direction (or in some cases exactly parallel to it) than inclined to the main forming direction, which is EBSD analysis of a metallographic micrograph of a cross-sectional plane along the main forming direction, in which the high-angle grain boundary sections are made visible.
  • a heat treatment e.g. stress-relief annealing at temperatures in the range of 650-850°C and a duration in the range of 2-6 h; recrystallization annealing at temperatures in the range of 1000-1300°C and a duration in range of 1-3 hours.
  • a heat treatment e.g. stress-relief annealing at temperatures in the range of 650-850°C and a duration in the range of 2-6 h; recrystallization annealing at temperatures in the range of 1000-1300°C and a duration in range of 1-3 hours.
  • the molybdenum sintered part according to the invention is at least partially (if necessary also completely ) in a partially or fully recrystallized structure. Compared to conventional molybdenum with a partially or fully recrystallized structure, significantly higher ductility and strength values are achieved.
  • the sintered molybdenum part (in particular in the form of sheet metal) is connected to a further sintered molybdenum part (in particular in the form of sheet metal) via a welded joint, with both sintered molybdenum parts being formed in accordance with the present invention and optionally in accordance with one or more of the further developments and wherein a weld zone of the welded joint has a molybdenum content of ⁇ 99.93% by weight.
  • the molybdenum sintered parts according to the invention can be welded much better than conventional molybdenum. As is evident from the specified molybdenum content of the weld zone, no filler material is required.
  • the welded connection has high ductility and strength values, in particular, depending on the welding process and the welding conditions, elongations of >8% in the tensile test (according to DIN EN ISO 6892-1 Verf.B) and bending angles of up to 70° in bending tests according to DIN EN ISO 7438) measured. Significant improvements have been achieved in particular in laser beam welding and TIG welding (tungsten inert gas welding).
  • the powders containing boron and carbon can likewise be molybdenum powder, which contains a corresponding proportion of boron and/or carbon. It is essential that the starting powder used for pressing the green compact contains sufficient amounts of boron and carbon and that these additives are distributed as evenly and finely as possible in the starting powder.
  • the sintering step comprises a heat treatment for a residence time of from 45 minutes to 12 hours (h), preferably from 1-5 h, at temperatures in the range of 1800°C - 2100°C.
  • the sintering step is carried out in a vacuum, under a protective gas (eg argon) or preferably in a reducing atmosphere (in particular in a hydrogen atmosphere or in an atmosphere with H 2 partial pressure).
  • the molybdenum sintered parts had the following compositions (if relevant to the present invention): 30B15C 15B15C 30B B70 B150 C70 C150 Mon in B portion [ppmw] 30 15 30 70 150 ⁇ 5 ⁇ 5 ⁇ 5 C content [ppmw] 15 15 9 8th 9 70 150 6 O content [ppmw] 9 9 8th 5 6 7 ⁇ 5 14 W component [ppmw] ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 ⁇ 330 330 330 330 330 330 330 330 Other impurities. [ppmw] ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇ 300 ⁇
  • test specimens designed according to the invention achieve significantly higher bending angles at the same test temperature.
  • test sample "30B15C” achieves a bending angle of 99°
  • test sample "15B15C” a bending angle of 94°
  • test sample "Mo pure” only a bending angle of approx. 2.5°.
  • test specimen "30B15C” achieves a bending angle of 82°, test specimen “15B15C” a bending angle of 40° and test specimen "Mo pure” only a bending angle of approx. 2.5°.
  • the transition from ductile to brittle behavior in molybdenum sintered parts according to the invention can be shifted to significantly lower temperatures, in particular from 110° C. for "Mo pure” to -10° C. for "30B15C”. and at 0°C at "15B15C”.
  • the transition from brittle to ductile behavior is assigned to the temperature at which a bending angle of 20° is reached for the first time.
  • test samples "30B15C” and “15B15C” show that a slightly higher addition of boron leads to a further increase in ductility, especially in the temperature range from approx. -20°C to 50°C, while the ductility is comparable in the remaining temperature ranges is.
  • a B content of 15 ppmw and a C content of 15 ppmw will already be sufficient for many applications, especially if the aim is to keep the content of additional elements as low as possible.
  • FIG 5 is a three-dimensional reconstruction of a sample tip of a molybdenum sintered part according to the invention, determined by atom probe tomography "15B15C" shown.
  • the position of the C atoms in the tip of the sample is shown in red in this representation, that of the B atoms in violet, that of the O atoms in blue and that of the N atoms in green.
  • the Mo atoms are indicated as small dots in order to visualize the shape of the tip of the sample.
  • the positions of the various atoms are also clearly recognizable in a gray scale representation (taken place in the patent specification) on the basis of the different gray scales.
  • the three-dimensional reconstruction is also described qualitatively in the following and also quantitatively by the one-dimensional concentration profile of the 6 added.
  • a measuring cylinder 4 is placed in the three-dimensional reconstruction by the measuring software in such a way that its cylinder axis 6 is perpendicular to the the grain boundary section 2 spanned plane runs.
  • a measuring cylinder 4 with a length of 20 nm (along the cylinder axis) and a diameter of 10 nm was selected.
  • the grain boundary section 2 lies centrally (relative to the cylinder axis 6) within the measuring cylinder 4.
  • those five adjacent disks (each having a thickness of 1 nm) of the measuring cylinder 4 are selected as the three-dimensional cylindrical region representative of the grain boundary section, in which the sum of the measured concentrations of B and C is maximum. In the present case, these are the measured values at the "distances" of 9, 10, 11, 12 and 13 nm.
  • the five adjacent disks are selected as the cylindrical region of the interior of the grain to be examined, the central disk of which is 10 nm away from the central disk of the cylindrical Area of the grain boundary portion is spaced. This would be in the representation of 6 the measured values at the distances 3, 2, 1, 0, -1 (the latter value is not covered by the measuring cylinder in this case). Subsequently, for these two areas (of the grain boundary section as well as of the grain interior), the total proportions of B, C and of B and C are determined and set in relation to one another, as described in detail above.
  • the proportion of carbon and boron, both individually and in total, in the area of the grain boundary section is at least three times as high as in the area of the interior of the adjacent grain. Furthermore is off 6 (as well as from figure 5 ) it can be seen that B and C (particularly in the interior of the grain) are finely and evenly distributed and are strongly enriched in the area of the large-angle grain boundaries.
  • Molybdenum powder which was produced by hydrogen reduction, was used for the powder-metallurgical production of a molybdenum sintered part according to the invention.
  • the grain size according to Fisher (FSSS according to ASTM B330) was 4.7 ⁇ m.
  • the molybdenum powder had impurities of 10 ppmw carbon, 470 ppmw oxygen, 135 ppmw tungsten and 7 ppmw iron.
  • the compacts produced in this way (round rods of 480 kg each) were sintered in indirectly heated sintering plants (i.e. heat transfer to the sintered material via thermal radiation and convection) at a temperature of 2050°C for a period of 4 hours in a hydrogen atmosphere and then cooled.
  • the sintered rods obtained in this way had a boron content of 22 ppmw, a carbon content of 12 ppmw and an oxygen content of 7 ppmw.
  • the tungsten content and the content of other metallic impurities remained unchanged.
  • the sintered molybdenum rods according to the invention were deformed on a radial forging machine at a temperature of 1200° C., the diameter being reduced from 240 to 165 mm.
  • the ultrasonic examination of the 100% dense bar showed no cracks on the inside either, and metallographic sections confirmed this finding.
  • a cross-sectional area is produced through the molybdenum sintered part to be examined.
  • a corresponding ground surface is prepared in particular by embedding, grinding, polishing and etching the cross-sectional area obtained, with the surface then being ion-polished (to remove the deformation structure on the surface caused by the grinding process).
  • the measuring arrangement is such that the electron beam strikes the prepared ground surface at an angle of 20°.
  • the distance between the electron source (here: field emission cathode) and the sample is 16.2 mm and the distance between the sample and the EBSD camera (here: "DigiView IV” ) is 16 mm.
  • the information given in parentheses relates to the device types used by the applicant, although in principle other device types that enable the functions described can also be used in a corresponding manner.
  • the acceleration voltage is 20 kV
  • a magnification of 500x is set and the distance between the individual pixels on the sample, which are scanned one after the other, is 0.5 ⁇ m.
  • large-angle grain boundaries e.g. formed circumferentially around a grain
  • large-angle grain boundary sections e.g. formed with an open beginning and end
  • a grain boundary angle that is greater than or equal to the minimum rotation angle of 15°
  • the scanning electron microscope large-angle grain boundaries or large-angle grain boundary sections are always determined and displayed between two grid points within the examined sample surface if an orientation difference of the respective crystal lattices of ⁇ 15° is determined between the two grid points.
  • the smallest angle that is required to convert the respective crystal lattices that are present at the grid points to be compared into one another is used as the orientation difference.
  • This process is performed on each raster point in relation to all raster points surrounding it. In this way, a grain boundary pattern of high-angle grain boundaries and/or high-angle grain boundary sections is obtained within the examined sample area.

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Claims (13)

  1. Pièce frittée à base de molybdène, issue de la métallurgie des poudres, se trouvant sous forme de corps solide, en une composition constituée par les proportions suivantes :
    a. une proportion de molybdène ≥ 99,93% en poids,
    b. une proportion de bore "B" ≥ 3 ppm en poids et une proportion de carbone "C" ≥ 3 ppm en poids, la proportion totale "BeC" de carbone et de bore se situant dans la plage de 15 ppm en poids ≤ "BeC" ≤ 50 ppm en poids,
    c. une proportion d'oxygène "O" dans la plage de 3 ppm en poids ≤ "O" ≤ 20 ppm en poids,
    d. une proportion maximale de tungstène ≤ 330 ppm en poids et
    e. une proportion maximale d'autres impuretés ≤ 300 ppm en poids, de préférence la proportion maximale d'impuretés provoquées par le zirconium (Zr), le hafnium (Hf), le titane (Ti), le vanadium (V) et l'aluminium (Al) en somme étant ≤ 50 ppm en poids et de préférence la proportion maximale d'impuretés provoquées par le silicium (Si), le rhénium (Re) et le potassium (K) en somme étant ≤ 20 ppm en poids.
  2. Pièce frittée à base de molybdène selon la revendication 1, caractérisée en ce que la proportion de bore "B" se situe dans la plage de 5 ≤ "B" ≤ 45 ppm en poids.
  3. Pièce frittée à base de molybdène selon la revendication 1 ou 2, caractérisée en ce que la proportion de carbone "C" se situe dans la plage de 5 ≤ "C" ≤ 30 ppm en poids.
  4. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce que la proportion d'oxygène "O" se situe dans la plage de 5 ≤ "O" ≤ 15 ppm en poids.
  5. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce que la proportion maximale d'impuretés provoquées par le zirconium (Zr), le hafnium (Hf), le titane (Ti), le vanadium (V) et l'aluminium (Al) en somme est ≤ 50 ppm en poids et en ce que la proportion maximale d'impuretés provoquées par le silicium (Si), le rhénium (Re) et le potassium (K) en somme est ≤ 20 ppm en poids.
  6. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce que celle-ci présente une proportion totale de molybdène et de tungstène ≥ 99,97% en poids.
  7. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce que le carbone et le bore se trouvent, en somme, à raison d'au moins 70% en poids par rapport à la teneur totale en carbone et en bore, sous forme dissoute.
  8. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce qu'au moins au niveau d'une section limite de grain (2) d'une limite de grain à grand angle et d'un grain adjacent, la proportion de carbone et de bore, en somme dans la zone de la section limite de grain (2), est au moins une fois et demi plus élevée que dans la zone de l'intérieur du grain adjacent, mesurée en pour cent en atome au moyen de la tomographie par sonde atomique tridimensionnelle, où, pour la zone de la section limite de grain (2), on sélectionne une zone cylindrique tridimensionnelle présentant un axe de cylindre (6) s'étendant perpendiculairement à la section limite de grain (2) et présentant une épaisseur s'étendant le long de l'axe de cylindre (6) de 5 nm, qui est placée de manière centrale autour de la section limite de grain (2) par rapport à la direction de l'axe de cylindre et, pour la zone de l'intérieur du grain, on utilise une zone cylindrique tridimensionnelle de mêmes dimensions et de même orientation écartée en son centre de 10 nm dans la direction de l'axe de cylindre de la section limite de grain (2).
  9. Pièce frittée à base de molybdène selon la revendication 7, caractérisée en ce que la proportion de carbone et de bore, en somme, dans la zone de la section limite de grain (2) est au moins trois fois plus élevée que dans la zone de l'intérieur du grain adjacent.
  10. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle est façonnée au moins par sections et présente une orientation préférentielle de la limite de grain à grand angle et/ou des sections limites de grain à grand angle perpendiculaire à la direction principale de façonnage.
  11. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle se trouve au moins par sections sous forme d'une structure partiellement ou complètement recristallisée.
  12. Pièce frittée à base de molybdène selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle est reliée par l'intermédiaire d'un assemblage par soudage à une autre pièce frittée à base de molybdène qui est conçue selon l'une quelconque des revendications précédentes, une zone de soudure de l'assemblage par soudage présentant une proportion de molybdène ≥ 99,93% en poids.
  13. Procédé pour la préparation d'une pièce frittée à base de molybdène, qui est constituée par une proportion de molybdène ≥ 99,93% en poids, une proportion de bore "B" ≥ 3 ppm en poids une proportion de carbone "C" ≥ 3 ppm en poids, la proportion totale "BeC" de carbone et de bore se situant dans la plage de 15 ppm en poids ≤ "BeC" ≤ 50 ppm en poids, une proportion d'oxygène "O" dans la plage de 3 ppm en poids ≤ "O" ≤ 20 ppm en poids, une proportion maximale de tungstène ≤ 330 ppm en poids et une proportion maximale d'autres impuretés ≤ 300 ppm en poids, de préférence la proportion maximale d'impuretés provoquées par le zirconium (Zr), le hafnium (Hf), le titane (Ti), le vanadium (V) et l'aluminium (Al) en somme étant ≤ 50 ppm en poids et de préférence la proportion maximale d'impuretés provoquées par le silicium (Si), le rhénium (Re) et le potassium (K) en somme étant ≤ 20 ppm en poids, présentant les étapes suivantes:
    a. pressage d'un mélange de poudre constitué par de la poudre de molybdène et par une poudre contenant du bore et du carbone, en un corps cru ;
    b. frittage du corps cru dans une atmosphère protégeant contre l'oxydation pendant une durée de séjour d'au moins 45 minutes à des températures dans la plage de 1600°C-2200°C.
EP18789316.9A 2017-09-29 2018-09-07 Pièce frittée en molybdène et procédé de fabrication Active EP3688200B1 (fr)

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ATGM217/2017U AT15903U1 (de) 2017-09-29 2017-09-29 Molybdän-Sinterteil
PCT/AT2018/000071 WO2019060932A1 (fr) 2017-09-29 2018-09-07 Pièce frittée en molybdène

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CN113418946B (zh) * 2021-07-30 2022-08-09 贵研检测科技（云南）有限公司 一种金属钌的高标定率ebsd制样方法
CN115261634B (zh) * 2022-07-25 2024-02-06 金堆城钼业股份有限公司 一种低钾钼基体、制备方法及应用
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US20200306832A1 (en) 2020-10-01
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WO2019060932A1 (fr) 2019-04-04
ES2923151T3 (es) 2022-09-23
CN111164227A (zh) 2020-05-15
CN111164227B (zh) 2022-07-26
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AT15903U1 (de) 2018-08-15
TW201920707A (zh) 2019-06-01
JP7273808B2 (ja) 2023-05-15

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