EP3688200A1 - Sintered molybdenum part - Google Patents
Sintered molybdenum partInfo
- Publication number
- EP3688200A1 EP3688200A1 EP18789316.9A EP18789316A EP3688200A1 EP 3688200 A1 EP3688200 A1 EP 3688200A1 EP 18789316 A EP18789316 A EP 18789316A EP 3688200 A1 EP3688200 A1 EP 3688200A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ppmw
- molybdenum
- boron
- content
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 119
- 239000011733 molybdenum Substances 0.000 claims abstract description 116
- 229910052796 boron Inorganic materials 0.000 claims abstract description 79
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 35
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000000523 sample Substances 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 35
- 238000005245 sintering Methods 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 16
- 238000003325 tomography Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 240000003834 Triticum spelta Species 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000000356 contaminant Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 32
- 238000005452 bending Methods 0.000 description 20
- 238000011161 development Methods 0.000 description 20
- 230000018109 developmental process Effects 0.000 description 20
- 238000003466 welding Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 238000007792 addition Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001887 electron backscatter diffraction Methods 0.000 description 8
- 238000005242 forging Methods 0.000 description 8
- 238000004663 powder metallurgy Methods 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 239000000156 glass melt Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009838 combustion analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002171 field ion microscopy Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
-
- 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
- B22F3/12—Both compacting and sintering
Definitions
- the present invention relates to a powder metallurgy solid state molybdenum sintered article and a process for producing such a molybdenum sintered article.
- Molybdenum due to its high melting point, low coefficient of thermal expansion and high thermal conductivity, is suitable for a variety of high performance applications, such as glass melt electrode material, high temperature furnace furnace components, heat sinks and X-ray anodes.
- a commonly used and large-scale process for the production of molybdenum and molybdenum-based materials is the powder metallurgy production route in which corresponding starting powders are pressed and then sintered, wherein in the case of several powders the pressing step is typically preceded by a mixing of the powders.
- powder-metallurgically produced molybdenum is distinguished by the fact that the microstructure is more fine-grained and more homogeneous due to the comparatively low sintering temperature (sintering temperature "0.8 * melting temperature)
- the powder metallurgy production route allows for the production of a greater variety of preforms (geometrically).
- molybdenum with its cubic space-centered crystal structure has a transition from ductile to brittle behavior - depending on the processing state - at or above room temperature (eg at 100 ° C) and is very brittle below this transition temperature.
- undeformed molybdenum and recrystallized molybdenum have a relatively low strength, in particular to bending and tensile loads, which also limits the scope (by forming, such as rolling or forging, these properties can be improved even with conventional molybdenum, with However, increasing recrystallization worsen again).
- molybdenum can not be welded, resulting in either th, flanging, etc.) or - to improve the welding properties - the addition of alloying elements (eg rhenium or zirconium) in the Mo base material or the use of welding consumables (eg
- the object of the present invention is to provide a molybdenum-based material which has a high strength and a good weldability and can be used universally in various applications.
- the molybdenum sintered part according to the invention has markedly increased ductility and increased strength, in particular with respect to bending and tensile loads Undeformed and / or (completely or partially) recrystallized state
- conventional molybdenum the deformation of larger components is problematic due to the low grain boundary strength, especially when forging thick rods (eg with starting diameters in the range of 200-240 mm) and when rolling thick sheets (eg with initial thicknesses in the range of 120-140 mm), crack formation, which occurs more intensively in the core of the bars / sheets, is problematic.
- the molybdenum sintered part according to the invention can also be produced and further processed on an industrial scale.
- the forming of large components, such as the forging of thick rods and the rolling of thick sheets, is possible in the molybdenum sintered part according to the invention while avoiding internal defects and grain boundaries.
- the molybdenum sintered part according to the invention eg in sheet form
- the low strength of conventional molybdenum is attributed to low grain boundary strength, which results in intercrystalline fracture behavior.
- the grain boundary strength of molybdenum is known to be due to a segregation of oxygen and optionally other elements, e.g. of nitrogen and phosphorus, decreased in the range of grain boundaries.
- the invention is based on the finding that even low contents of carbon and boron in combination lead to a significantly increased grain boundary strength and favorably influence the flow behavior of the material (which is responsible for the high ductility), if at the same time the oxygen content is low and the content of other materials is low Impurities (and W) are below the specified limits.
- the carbon content of the Oxygen content are kept low in the sintered part.
- the boron content there is no need for large amounts of carbon, which would be problematical especially in the case of glass melt components due to the then increasingly occurring outgassing.
- a powder-metallurgical molybdenum sintered part is understood to mean a component whose manufacture comprises the steps of pressing corresponding starting powders into a compact and sintering the compact.
- the production process may also have other steps, such as mixing and homogenizing (eg in a plowshare mixer) the powder to be pressed, etc ..
- the powder metallurgy molybdenum sintered part thus has a typical for powder metallurgy microstructure, the will be readily apparent to those skilled in the art.
- This microstructure is characterized by its fine granularity (typical particle 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. With “good” or “complete” sintering (the density is then> 93% of the theoretical density for molybdenum and there is no open porosity), these pores appear at the grain boundaries as well as rounded cavities in the interior of the resulting sintered grains. The investigation of these characteristic features is carried out in cross-section by light microscopy or electron microscopy).
- the powder metallurgy molybdenum sintered part according to the invention may also have been subjected to further processing steps, such as a forming (rolling, forging, etc.), so that it is then present in a Umform Quilt, a subsequent annealing, etc .. Furthermore, it can also be coated and / or be connected to other components, such as by welding or soldering.
- the details of the shares according to the invention as well as the information relating to the further developments explained below relate to the respective reference taken element (eg Mo, B, C, O or W), regardless of whether this is present in the molybdenum sintered element in elemental or bonded form.
- the proportions of the different elements are determined by chemical analysis.
- the proportions of most of the metallic elements eg Al, Hf, Ti, K, Zr, etc.
- ICP-MS mass spectrometry with inductively coupled plasma
- the boron content is determined by the analytical method ICP- OES (inductively coupled plasma optical emission spectroscopy)
- the carbon content via combustion analysis and the oxygen content via carrier gas hot extraction.
- the indication "ppmw” expresses the weight fraction multiplied by 10 -6 .
- the specified limit values can in principle be maintained stably even over thick component thicknesses, in particular the advantageous properties can be realized industrially independent of the respective component geometry, sheet thickness, etc.
- 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 sintering thickness, a slight decrease in the boron content and / or the carbon content towards the surface or a slight increase in the Oxygen content to the surface, even if the limits are then possibly no longer complied with in a near-surface area (with a thickness of 0.1 mm, for example) is particularly critical and then such molybdenum sintered parts are still from the present Invention includes, if sufficient thick core or, more generally, at least one sufficiently thick layer of the sintered part remains in which the claimed limit values are met, so that at least in this core or in this layer, cracking or crack propagation (eg due to a forming step) is avoided or avoided is significantly slowed down.
- a core designed according to the invention is at least twice as thick as the total thickness of the surface-near regions within which the claimed limit values are no longer fully or partially fulfilled.
- grading of the composition may also take place only during subsequent treatment steps of the molybdenum sintered part, such as, for example, during forming (rolling, forging, extrusion, etc.), in the event of subsequent melting. hung, in a welding process, etc., occur or amplify even further.
- the boron content and the carbon content are each 5 ppmw.
- certified contents of boron and carbon are typically also specifiable above 5 ppmw.
- boron and carbon below a respective proportion of 5 ppmw are also clearly detectable and their proportions can be determined quantitatively (at least if the respective proportion is> 2 ppmw), but the proportions are Depending on the analytical procedure, this area can sometimes no longer be certified as a certified value.
- the total fraction "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 “40" .40 ppmw
- the carbon content “C” is in the range of 5 "C” -S 30 ppmw, more preferably in the range of 15 -S “C” 20 ppmw.
- elements (B, C) in such a high and at the same time in sufficient amount in the molybdenum sintered part that their beneficial interaction is clearly felt, but at the same time the carbon contained and The boron contained does not yet adversely affect the different applications.
- the effect of carbon is to keep the oxygen content in the molybdenum sintered body low and of boron to allow for a sufficiently low carbon content while achieving high ductility and high strength.
- the oxygen content "O” is in the range of 5 “O" -S 15 ppmw. According to previous knowledge, the oxygen accumulates in the region of the grain boundaries (segregation) and leads to a lowering of the grain boundary strength. Accordingly, an overall low oxygen content is advantageous.
- the setting of such a low oxygen content succeeds both by the use of starting powders with a low oxygen content (eg ⁇ 600 ppmw, in particular ⁇ 500 ppmw), the sintering in Vacuum, under protective gas (eg argon) or preferably in a reducing atmosphere (especially in a hydrogen atmosphere or in an atmosphere with H2 partial pressure), as well as by the provision of a sufficient carbon content 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 H2 partial pressure
- the maximum amount of contamination by zirconium (Zr), hafnium (Hf), titanium (Ti), vanadium (V) and aluminum (AI) is 50 ppmw in total.
- the proportion of each element of this group (Zr, Hf, Ti, V, AI) is -15 ppmw in each case.
- the maximum proportion of impurities due to silicon (Si), rhenium (Re) and potassium (K) is 20 ppmw in total.
- the proportion of each element of this group (Si, Re, K) in each case is preferably 10 ppmw, in particular -S 8 ppmw.
- Potassium is said to have the effect of lowering 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 oxygen accumulation in the region of the grain boundaries by binding the oxygen (oxygen getter) and in turn to increase the grain boundary strength.
- they are sometimes suspected of reducing ductility, especially if they are present in larger quantities.
- Re and V are attributed a ductilizing effect, ie they could in principle be used to increase the ductility.
- additives (elements / compounds) implies that they may also interfere with the application and conditions of use of the Mo sintered part.
- the molybdenum sintered part has a total content of molybdenum and tungsten of> 99.97% by weight.
- the proportion of tungsten within the specified limits of 330 ppmw) is not critical for the hitherto known applications and is typically already due to Mo recovery and powder production.
- the molybdenum sintered part has a molybdenum content of> 99.97% by weight, ie it consists almost exclusively of molybdenum.
- the proportion very low on other impurities Accordingly, according to these developments - taken individually and in particular in combination - a broadly usable molybdenum sintered part with high purity is provided.
- the carbon and the boron in total amount to at least 70% by weight, based on the total content of carbon and boron, in dissolved form (ie they do not form a separate phase).
- the carbon and the boron are in solution at least to a large extent (for example> 70% by weight, in particular> 90% by weight), they can segregate to the grain boundaries and fulfill the above-described effect to a particularly high degree.
- the specified limits are also observed individually by each of the elements B and C.
- the boron and the carbon in the Mo base material are finely distributed and enriched in the region of the large-angle grain boundaries.
- a large-angle grain boundary exists when an angular difference of> 15 ° is required to bring the crystallographic orientation of adjacent grains into coincidence, which can be determined via EBSD (English: 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.
- boron and carbon are the starting powders in the powder metallurgical production as pure as possible element (B, C) or as pure as possible compound, ie with as few other impurities (apart from the possibly to be added connecting partner of B and / or C, such as Mo, N, C, etc.), and added as fine as possible powder become.
- Boron can be used, for example, as molybdenum Dänborid (M02B), as boron carbide (B4C), as boron nitride (BN) or elemental as amorphous or crystalline boron are added.
- Carbon can be added, for example, as graphite or as molybdenum carbide (MoC, M02C).
- the boron-containing powder (compound / element, grain size, grain morphology, etc.) and the carbonaceous powder (compound / element, grain size, grain morphology, etc.), the amounts thereof and the sintering conditions (temperature profile, maximum Sintering temperature, holding times, sintering atmosphere) are coordinated such that the boron and the carbon after the sintering process as evenly as possible and finely distributed with the respective desired proportion and in the most constant possible concentration over the thickness of the respective molybdenum sintered part away.
- boron and carbon if they are freely available at the temperatures in question, react at least proportionally with oxygen from the starting powders and optionally additionally with oxygen from the sintering atmosphere and escape as gas. In order nevertheless to achieve the desired boron and carbon content in the finished molybdenum sintered part, correspondingly higher amounts of boron and / or carbonaceous powders have to be added to the starting powders.
- the tendency for it to volatilize during the sintering process and to discharge it as an environmentally harmful gas into the atmosphere can be counteracted by matching the boron-containing powder and the sintering conditions in such a way that the boron does not react such a period of time and / or after such a temperature increase is available as a reaction partner (eg because only then does the boron-containing compound decompose or the boron-containing powder only releases the boron for reaction due to its morphology, coating, etc.), if the oxygen from the starting powders has reacted, at least for the most part, with deviating reactants (eg hydrogen, carbon, etc.) and has escaped as gas.
- deviating reactants eg 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 in the starting powders as low as possible and also only a moderately increased amount of carbon and boron-containing powders (in comparison to the C and B contents to be obtained in the Mo sintered part), preferably a reducing atmosphere (h atmosphere or h partial pressure), alternatively a protective gas (eg Argon) or a vacuum in the sintering process is selected and in that the boron-containing powder and the temperature profile during the sintering process are coordinated so that the boron is released only when the oxygen from the starting powders reacts at least to a large extent already with different reactants Has.
- a protective gas eg Argon
- a vacuum in the sintering process is selected and in that the boron-containing powder and the temperature profile during the sintering process are coordinated so that the boron is released only when the oxygen from the starting powders reacts at least to a large extent already with different reactants Has.
- the proportion of carbon and boron in total in the region of the grain boundary section is at least one and a half times as high as in the region of the grain interior of the adjacent grain, at least at one grain boundary section of a large-angle grain boundary and the adjoining grain;
- the proportion of carbon and boron in total in the region of the grain boundary portion is at least two times as high, more preferably at least three times as high, as in the region of the grain interior of the adjacent grain.
- the specified relations are also fulfilled individually by each of the elements B and C.
- 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 atomic probe tomography.
- the cylinder axis is in particular perpendicular to the plane which is spanned by the grain boundary section in the area to be examined.
- an averaged plane which is at a minimum distance from the grain boundary section over the observed area (for the alignment and positioning of the cylindrical area to be examined) is to be used.
- a three-dimensional, cylindrical region spaced apart from the grain boundary section (or optionally to the associated, averaged plane) by its center by 10 nm in the cylinder axis direction becomes equal Dimensions and the same orientation (ie the same orientation and position of the cylinder axis of the examined, cylindrical area) used. It is important to ensure that the area of the grain interior at the same time from other large-angle grain boundaries sufficient, preferably spaced by at least 10 nm.
- the three-dimensional, cylindrical regions (of the interior of the grain and of the grain boundary section) each have a (circular) diameter of 10 nm, the associated circular surface of the cylindrical regions being aligned perpendicular to the associated cylinder axis (resulting from the cylinder shape).
- the proportion of boron and carbon in atomic percent is determined.
- the proportions determined in this way either of boron and carbon in total or, alternatively, also of the individual elements in each case, are set in relation to the region of the grain interior, in each case from the region of the grain boundary section, as will be explained in more detail below.
- Atomic probe tomography is a high-resolution characterization method for solids. Needle-shaped tips ("probe tip”) approximately 100 nm in diameter are cooled to about 60K and removed by field evaporation The position of the atom and the mass-to-charge ratio for each detected atom (ion) are determined using a position-sensitive detector and time-of-flight mass spectrometer For a more detailed description of atomic probe tomography, see MK Miller, A. Cerezo, MG Hetherington, GDW Smith, Atomic specimen field ion microscopy, Clarendon Press, Oxford, 1996.
- FIG. 5 also FIG. 5 and its description. At least the elements B and C are displayed. Based on the knowledge that these elements accumulate in the region of the large-angle grain boundaries, the position of the large-angle grain boundary in the three-dimensional reconstruction can be made visible by the compression of elements B and C occurring there.
- a measuring cylinder which is decisive for the evaluation and has a diameter of 10 nm (in accordance with the above information) is positioned in the three-dimensional reconstruction in such a way that a grain boundary section (as planar as possible and sufficiently far from other large-angle grain boundaries) Large-angle grain boundary within the measuring cylinder is that the cylinder axis of the measuring cylinder - as described above for the investigated cylindrical areas - is aligned perpendicular to the plane defined by the grain boundary portion plane.
- the grain boundary section is preferably located substantially in the center of the measuring cylinder relative to the cylinder axis of the measuring cylinder.
- the measuring cylinder is to be positioned and its length (along the cylinder axis) so long to choose (eg 30 nm), that not only the cylindrical portion of the grain boundary portion, but also the cylindrical portion of the grain interior, each having a thickness of 5 nm and their centers are spaced apart along the cylinder axis by 10 nm, each completely within the measuring cylinder.
- a one-dimensional concentration profile is determined (see Fig. 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 in each case 10 nm 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.
- the concentration, determined for each slice, of at least the elements B and C (individually and possibly also in total) is plotted along the length of the cylinder axis. (see Fig.
- the five adjoining slices of the measuring cylinder are selected in which the sum of the measured concentrations of B and C (B and C calculated for each measuring point in total) is the maximum.
- the five adjacent disks are selected whose central disk is spaced apart by 10 nm from the central disk of the cylindrical portion of the grain boundary portion.
- the proportions of B, C and the sum of B and C are determined by the proportions (in atomic percent) of these elements (B, C, and B and C in total ) is summed up for the five relevant slices of the respective area to be examined and then the sum is divided by five. Then, the values obtained for the area of the grain boundary portion can 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 to a forming process (rolling, forging, extrusion, etc.).
- the molybdenum sintered part is at least partially reshaped and has a preferential orientation of the large-angle grain boundaries and / or large-angle grain boundary sections perpendicular to the main deformation direction, which is determined by EBSD analysis of a metallographic micrograph of a cross-sectional plane along the deformation direction, in which For example, circumferentially around a grain trained) large-angle grain boundaries and (made for example with an open beginning and end) large-angle grain boundary sections are made determinable.
- the molybdenum sintered part according to the invention can be formed particularly well and with a low reject rate. Even when forging thick rods (eg with starting diameters in the range of 200-240 mm) and when rolling thick sheets (eg with starting thicknesses in the range of 120-140 mm) cracking occurs, which occurs in conventional molybdenum reinforced in the core of the rods / sheets, avoided.
- the molybdenum Sintered part has a forming structure, that is, there are typically no clear single-grain grain wide-angle grain boundaries as they appear immediately after the sintering step, but only large angle grain boundary sections, each with an open beginning and an open one Have end.
- a larger portion (eg at least 60%, in particular at least 70%) of the large-angle grain boundary sections is inclined more towards the direction perpendicular to the main deformation direction (or partly also exactly parallel thereto) than inclined towards the main deformation direction, which means EBSD analysis of a metallographic micrograph of a cross-sectional plane along the Hauptumformides in which the large-angle grain boundary sections are made visible, can be determined.
- the molybdenum sintered part according to the invention lies at least in sections (possibly also completely) In a partially or completely recrystallized structure, significantly higher ductility and strength values are achieved compared to conventional molybdenum with a partially or completely recrystallized structure.
- the molybdenum sintered part (formed in particular in sheet metal form) is connected via a welded connection to a further molybdenum sintered part (in particular formed in sheet metal form), both molybdenum sintered parts according to the present invention and, if appropriate, according to one or more of the developments are formed and wherein a weld zone of the welded joint has a molybdenum content of> 99.93 wt.% Has.
- the molybdenum sintered parts according to the invention can be significantly better welded compared to conventional molybdenum. As indicated by the specified molybdenum content of the weld zone, no addition of filler metal is required.
- the welded joint has high ductility and strength values, in particular, depending on the welding process and the welding conditions, strains 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). Substantial improvements have been achieved in particular in laser beam welding and in TIG welding (tungsten arc welding).
- the present invention further relates to a method for producing a molybdenum sintered part which has a molybdenum content of> 99.93 wt.%, A boron content "B"of> 3 ppmw and a carbon content “C”of> 3 ppmw, the total fraction being BuC “is 50 ppmw, an oxygen content" O “in the range of 3 ppmw.s” O "20 ppmw, a maximum tungsten content of ⁇ 330 ppmw and a maximum content of other impurities of ⁇ 300 ppmw, characterized by the following steps:
- the boron- and carbon-containing powders may likewise be molybdenum powder containing a corresponding proportion of boron and / or carbon. It is essential that the starting powder, which is used for pressing the green compact, contains sufficient amounts of boron and carbon and these additives are distributed as uniformly and finely as possible in the starting powder.
- the step of sintering comprises a heat treatment for a residence time of 45 minutes to 12 hours (h), preferably of 1-5 hours, at temperatures in the range of 1,800 ° C - 2,100 ° C.
- the sintering step is carried out under vacuum, under a protective gas (e.g., argon), or preferably in a reducing atmosphere (especially in a hydrogen atmosphere or in an H2 partial pressure atmosphere).
- Fig. 1 Diagram of a 3-point bending test of samples of different molybdenum sintered parts
- FIG. 2 Corresponding diagram representation as in FIG. 1, taking up further samples of molybdenum sintered parts
- FIG. 3 Diagram of the elongation at break of different molybdenum sintered parts in the tensile test
- FIG. 4 Diagram of the breaking strength of different molybdenum sintered parts in a tensile test
- FIG. 5 Three-dimensional images determined by atomic probe tomography
- Figs. 1 and 2 The bending angles shown in Figs. 1 and 2 for the various molybdenum sintered parts were determined by a 3-point bending test.
- the 3-point bending test was carried out in accordance with DIN EN ISO 7438 with a correspondingly designed test device.
- FIGS. 1 and 2 the maximum bending angle reached in each case for the various test specimens at the test temperatures specified in each case is plotted before breakage of the test specimen occurred.
- this bending angle is characteristic of the ductility, ie the higher the achievable bending angle, the higher is the ductility. tivity of the respective molybdenum sintered part.
- the transition from ductile to brittle behavior can be shown by the temperature dependence of the maximum achievable bending angle.
- the test specimens according to the invention achieve significantly higher bending angles at the same test temperature, in particular at a test temperature of 60 ° C, the test sample "30B15C” reaches a bending angle of 99 °, the test sample "15B15C” a bending angle of 94 ° and the test sample "Mo pure” only a bending angle of about 2.5 °.
- the test sample "30B15C” reaches a bending angle of 82 °, the test sample “15B15C” a bending angle of 40 ° and the test sample "Mo pure” only a bending angle of about 2.5 ° Shows bending angle for the individual test samples, 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 1 10 ° C at "Mo pure" to -10 ° C at "30B15C” and to 0 ° C at "15B15C". The transition from brittle to ductile behavior is attributed to the temperature at which a bending angle of 20 ° is reached for the first time. Furthermore, a comparison of the test samples
- FIGS. 3 and 4 show the results of tensile tests carried out in accordance with DIN EN ISO 6892-1 Verf.B on appropriately dimensioned test bars of the molybdenum sintered parts "Mo-pure”, “30B15C”, “15B15C”, “150B”, “70B”, “30B”, “150C”, “70C”.
- 3 shows the elongation at break (as a percentage of the change in length ⁇ in relation to the initial length L) of the various test bars, while the fracture strength Rm (in MPa, megapascal) of the various test bars is shown in FIG.
- FIG. 5 shows a three-dimensional reconstruction of a sample tip of a molybdenum probe according to the invention determined by atomic probe tomography.
- the position of the C atoms in the sample tip is red, that of the B atoms violet, that of the O atoms blue and that of the N atoms green, and the Mo atoms as In a grayscale representation (in the patent specification), the positions of the various atoms are clearly recognizable by the different shades of gray 6, and in particular also in FIG.
- the quantitative determination of the segregation of B and C in the region of the grain boundary portion relative to the region of the grain interior is made by the measurement software Measuring cylinder 4 placed in the three-dimensional reconstruction so that its cylinder axis 6 is perpendicular to the plane defined by the Korngren- zen 2 plane.
- the grain boundary section 2 is located centrally (relative to the cylinder axis 6) within the measuring cylinder 4.
- Fig. 6 shows the thus obtained linear concentration profile in a diagram.
- the grain This range can be seen by the sharp increase in the concentration of elements B and C (see, in particular, the values in the range of 9 nm-13 nm along the "distance" axis.)
- the oxygen is in the range of Grain limit only slightly increased and the N content is essentially constant at a low level, which is advantageous in terms of grain boundary strength.
- the five adjacent disks are selected as the cylindrical region of the interior of the grain to be examined, whose central disk is separated by 10 nm from the central disk of the 6, the measured values would be at the distances 3, 2, 1, 0, -1 (the latter value in this case does not encompass the measuring cylinder) (the grain boundary portion as well as the grain inside) the proportions of B, C as well as of B and C in total determined and set in relation to each other, as described above in detail Percentage of carbon and boron in each case as well as in total in the region of the grain boundary section at least three times as high as in the region of the grain interior of the adjacent Furthermore, it can be seen from FIG. 6 (as well as from FIG. 5) that B and C (especially in the interior of the grain) are finely and uniformly distributed and highly enriched in the region of the large-angle grain boundaries.
- molybdenum powder which was prepared by hydrogen reduction, was used. Fisher's grain size (FSSS to ASTM B330) was 4.7 pm.
- the molybdenum powder had impurities of 10 ppmw carbon, 470 ppmw oxygen, 135 ppmw tungsten and 7 ppmw iron.
- the thus produced compacts (round bars of 480 kg each) were sintered in indirectly heated sintering equipment (i.e., heat transfer to the sintered material by heat radiation and convection) at a temperature of 2050 ° C for 4 hours in a hydrogen atmosphere and then cooled.
- the sintered rods thus obtained 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 proportion of other metallic impurities remained unchanged.
- the molybdenum sintered rods according to the invention were deformed on a radial forging machine at a temperature of 1200 ° C, with a diameter reduction from 240 to 165 mm was made.
- the ultrasound examination of the 100% dense rod showed no cracks in the interior, and metallographic sections confirmed this finding.
- Microstructural investigations showed that a uniform, relatively fine-grained microstructure was also formed in the area of the weld zone.
- the welded molybdenum sintered parts also showed a comparatively high ductility in the area of the welded joint, which was confirmed in the bending test in which the bending angle of> 70 ° was achieved.
- a cross-sectional area is produced by the molybdenum sintered part to be examined.
- the preparation of a corresponding ground surface takes place in particular by embedding, grinding, polishing and etching of the cross-sectional area obtained, the surface being subsequently polished by an ion (for removing the deformation structure on the surface resulting from the grinding process).
- the measuring arrangement is such that the electron beam impinges on the prepared ground surface at an angle of 20 °.
- large-angle grain boundaries eg circumferentially formed around a grain
- large-angle grain boundary sections eg with an open beginning and end having a grain boundary angle greater than or equal to the minimum rotation angle of 15 °
- the orientation difference used is in each case the smallest angle which is required in order to convert the respective crystal lattices which are present at the grid points to be compared into one another. This process is performed at each grid point with respect to all grid points surrounding it. In this way, a grain boundary pattern of large-angle grain boundaries and / or large-angle grain boundary sections is obtained within the examined sample area.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ATGM217/2017U AT15903U1 (en) | 2017-09-29 | 2017-09-29 | Molybdenum sintered part |
PCT/AT2018/000071 WO2019060932A1 (en) | 2017-09-29 | 2018-09-07 | Sintered molybdenum part |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3688200A1 true EP3688200A1 (en) | 2020-08-05 |
EP3688200B1 EP3688200B1 (en) | 2022-06-22 |
Family
ID=63142276
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18789316.9A Active EP3688200B1 (en) | 2017-09-29 | 2018-09-07 | Molybdenum sintered part and method of manufacturing |
Country Status (8)
Country | Link |
---|---|
US (1) | US11925984B2 (en) |
EP (1) | EP3688200B1 (en) |
JP (1) | JP7273808B2 (en) |
CN (1) | CN111164227B (en) |
AT (1) | AT15903U1 (en) |
ES (1) | ES2923151T3 (en) |
TW (1) | TWI763918B (en) |
WO (1) | WO2019060932A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT17259U1 (en) * | 2020-11-13 | 2021-10-15 | Plansee Se | HIGH TEMPERATURE FORMING TOOL |
CN113637884B (en) * | 2021-07-20 | 2022-07-08 | 深圳大学 | High-performance molybdenum alloy and preparation method thereof |
CN113418946B (en) * | 2021-07-30 | 2022-08-09 | 贵研检测科技(云南)有限公司 | High-calibration-rate EBSD sample preparation method for ruthenium metal |
CN115261634B (en) * | 2022-07-25 | 2024-02-06 | 金堆城钼业股份有限公司 | Low-potassium molybdenum matrix, preparation method and application |
CN115418517B (en) * | 2022-09-15 | 2024-05-14 | 宁波江丰电子材料股份有限公司 | Preparation method of molybdenum-copper alloy for electronic packaging |
CN115572877B (en) * | 2022-10-08 | 2023-06-09 | 郑州大学 | Preparation method of molybdenum-niobium or molybdenum-tantalum alloy |
CN118166230B (en) * | 2024-05-15 | 2024-07-19 | 安庆瑞迈特科技有限公司 | Improved tungsten/molybdenum alloy material powder metallurgy method |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT285966B (en) * | 1968-10-11 | 1970-11-25 | Plansee Metallwerk | Sintered molybdenum-boron alloy |
JPS4940763B1 (en) * | 1969-09-10 | 1974-11-05 | ||
JPS54116313A (en) | 1978-03-02 | 1979-09-10 | Nat Res Inst Metals | Production of molybdenum material or sintered molybdenum material with excellent low temperature tenacity |
JPS55164071A (en) | 1979-06-08 | 1980-12-20 | Sumitomo Electric Ind Ltd | Manufacture of coated and sintered alloy parts |
JPS5853703B2 (en) * | 1980-07-08 | 1983-11-30 | 株式会社東芝 | Molybdenum material with excellent hot workability |
AT377584B (en) * | 1981-06-25 | 1985-04-10 | Klima & Kaelte Gmbh | CORNER CONNECTION TO METAL FRAME |
JPS59116356A (en) | 1982-12-22 | 1984-07-05 | Toshiba Corp | Molybdenum alloy |
JP4199406B2 (en) | 2000-03-29 | 2008-12-17 | 株式会社アライドマテリアル | Molybdenum material and manufacturing method thereof |
JP2006002178A (en) * | 2004-06-15 | 2006-01-05 | Hitachi Metals Ltd | Method for producing pure molybdenum or molybdenum alloy thin strip |
DE102005003445B4 (en) | 2005-01-21 | 2009-06-04 | H.C. Starck Hermsdorf Gmbh | Metal substrate material for the anode plates of rotary anode X-ray tubes, method for producing such a material and method for producing an anode plate using such a material |
CN101611165B (en) * | 2007-01-12 | 2012-03-21 | 新日铁高新材料 | Process for producing molybdenum-based sputtering target plate |
JP5484756B2 (en) | 2009-03-13 | 2014-05-07 | 株式会社アライドマテリアル | Molybdenum plate and method for manufacturing molybdenum plate |
TW201103987A (en) * | 2009-07-22 | 2011-02-01 | China Steel Corp | Method for manufacturing molybdenum based sheet |
CN102703788B (en) | 2012-06-26 | 2014-01-22 | 洛阳爱科麦钨钼制品有限公司 | Boron-doped TZM (molybdenum-titanium-zirconium) alloy |
US9238852B2 (en) | 2013-09-13 | 2016-01-19 | Ametek, Inc. | Process for making molybdenum or molybdenum-containing strip |
CN106715738B (en) | 2014-04-23 | 2020-12-29 | 奎斯泰克创新公司 | Tough high-temperature molybdenum-based alloy |
CN105618768B (en) * | 2015-12-28 | 2018-09-25 | 安泰天龙(天津)钨钼科技有限公司 | A kind of preparation method of high-compactness pure tungsten, pure molybdenum and its alloy material |
-
2017
- 2017-09-29 AT ATGM217/2017U patent/AT15903U1/en unknown
-
2018
- 2018-09-04 TW TW107131004A patent/TWI763918B/en active
- 2018-09-07 JP JP2020517783A patent/JP7273808B2/en active Active
- 2018-09-07 WO PCT/AT2018/000071 patent/WO2019060932A1/en unknown
- 2018-09-07 EP EP18789316.9A patent/EP3688200B1/en active Active
- 2018-09-07 ES ES18789316T patent/ES2923151T3/en active Active
- 2018-09-07 CN CN201880063038.XA patent/CN111164227B/en active Active
- 2018-09-07 US US16/649,489 patent/US11925984B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2020535318A (en) | 2020-12-03 |
US20200306832A1 (en) | 2020-10-01 |
US11925984B2 (en) | 2024-03-12 |
WO2019060932A1 (en) | 2019-04-04 |
ES2923151T3 (en) | 2022-09-23 |
CN111164227A (en) | 2020-05-15 |
CN111164227B (en) | 2022-07-26 |
TWI763918B (en) | 2022-05-11 |
EP3688200B1 (en) | 2022-06-22 |
AT15903U1 (en) | 2018-08-15 |
TW201920707A (en) | 2019-06-01 |
JP7273808B2 (en) | 2023-05-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3688200B1 (en) | Molybdenum sintered part and method of manufacturing | |
EP3109889B1 (en) | Rotating anode | |
DE2927079C2 (en) | ||
DE69014085T2 (en) | Oxidation-resistant alloys with a low coefficient of expansion. | |
AT16217U1 (en) | Additive manufactured component | |
EP3802898B1 (en) | Density-optimized molybdenum alloy | |
WO2015061816A9 (en) | Sputtering target and production method | |
DE69702949T2 (en) | Composite carbide powder for use in cemented carbide and process for its manufacture | |
WO2019120347A1 (en) | Particle reinforced high temperature material | |
DE4219469A1 (en) | Component subject to high temperatures, in particular turbine blade, and method for producing this component | |
DE1558632C3 (en) | Application of deformation hardening to particularly nickel-rich cobalt-nickel-chromium-molybdenum alloys | |
DE102008050716A1 (en) | X-ray rotary anode plate and method for its production | |
WO2018058158A1 (en) | Sputtering target | |
DE102004063052A1 (en) | Nanoparticle-reinforced molybdenum alloys for X-ray targets and process for their preparation | |
DE112016003045T5 (en) | Casting material and method for producing a casting material | |
DE3637930C1 (en) | Mfg. composite material for armour piercing ammunition - using alloy powder contg. tungsten@, nickel@, iron@, copper@, titanium@, aluminium@ and/or molybdenum@ | |
AT15459U1 (en) | anode | |
DE102023135181A1 (en) | hard metal | |
DE102007054455B3 (en) | Method for producing a metallic composite | |
DE102021128591A1 (en) | Process for producing a cemented carbide body | |
DE112022001739T5 (en) | Carbide and cutting tool | |
WO2022233491A1 (en) | Method for manufacturing a cemented-carbide body | |
DE112022001856T5 (en) | ALUMINUM ALLOY FOR CASTING AND ALUMINUM CASTING PROVIDED BY THE USE AND CASTING THEREOF | |
DE102021120273A1 (en) | Process for the production of a cemented carbide material with a reinforced binder phase |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20200303 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20210203 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B22F 3/12 20060101ALN20220214BHEP Ipc: B22F 3/10 20060101ALN20220214BHEP Ipc: B22F 3/04 20060101ALN20220214BHEP Ipc: B22F 3/02 20060101ALN20220214BHEP Ipc: C22F 1/16 20060101ALI20220214BHEP Ipc: B22F 5/00 20060101ALI20220214BHEP Ipc: C22C 27/04 20060101ALI20220214BHEP Ipc: C22C 1/04 20060101AFI20220214BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20220329 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: STORF, ROBERT Inventor name: EIDENBERGER-SCHOBER, MICHAEL Inventor name: O'SULLIVAN, MICHAEL Inventor name: HUBER, KARL |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502018010005 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1499816 Country of ref document: AT Kind code of ref document: T Effective date: 20220715 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 Effective date: 20220718 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: NO Ref legal event code: T2 Effective date: 20220622 |
|
REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2923151 Country of ref document: ES Kind code of ref document: T3 Effective date: 20220923 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220923 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220922 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221024 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20221022 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502018010005 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20230323 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220907 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: RO Payment date: 20230824 Year of fee payment: 6 Ref country code: NO Payment date: 20230922 Year of fee payment: 6 Ref country code: NL Payment date: 20230920 Year of fee payment: 6 Ref country code: IE Payment date: 20230920 Year of fee payment: 6 Ref country code: GB Payment date: 20230920 Year of fee payment: 6 Ref country code: AT Payment date: 20230921 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20230920 Year of fee payment: 6 Ref country code: DK Payment date: 20230925 Year of fee payment: 6 Ref country code: DE Payment date: 20230920 Year of fee payment: 6 Ref country code: BE Payment date: 20230920 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20231124 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230927 Year of fee payment: 6 Ref country code: CH Payment date: 20231001 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220622 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20180907 |