EP2038441B1 - Process for producing shaped refractory metal bodies - Google Patents
Process for producing shaped refractory metal bodies Download PDFInfo
- Publication number
- EP2038441B1 EP2038441B1 EP07765458.0A EP07765458A EP2038441B1 EP 2038441 B1 EP2038441 B1 EP 2038441B1 EP 07765458 A EP07765458 A EP 07765458A EP 2038441 B1 EP2038441 B1 EP 2038441B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- tungsten
- molybdenum
- heavy metal
- alloy
- 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.)
- Not-in-force
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- 238000000034 method Methods 0.000 title claims description 33
- 230000008569 process Effects 0.000 title description 12
- 239000003870 refractory metal Substances 0.000 title description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 58
- 239000010937 tungsten Substances 0.000 claims description 58
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 57
- 239000011230 binding agent Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 43
- 229910001385 heavy metal Inorganic materials 0.000 claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 239000000956 alloy Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 229930182556 Polyacetal Natural products 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 230000005670 electromagnetic radiation Effects 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims 1
- 238000005096 rolling process Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 15
- 239000004014 plasticizer Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 4
- 238000009760 electrical discharge machining Methods 0.000 description 4
- 238000001887 electron backscatter diffraction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl phosphate compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 3
- 230000002706 hydrostatic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 238000003698 laser cutting Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 241000273930 Brevoortia tyrannus Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010038743 Restlessness Diseases 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- 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
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- 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
- B22F3/24—After-treatment of workpieces or articles
-
- 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
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- 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
- C22F1/18—High-melting or refractory metals or alloys based thereon
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- 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
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
Definitions
- the present invention relates to a method for the production of sheets of tungsten heavy metal or molybdenum alloy and their use. Due to their high density of 17 to 18.6 g / cm 3 , tungsten heavy metal alloys are suitable for shielding short-wave electromagnetic radiation, for example. They are therefore often used for radiation protection or beam guidance in X-ray equipment. Other applications include balancing weights in the aerospace and automotive industries or molded components for aluminum die casting molds. Tungsten heavy metal alloys consist of about 90% to about 97% by weight tungsten. The remainder is binder metal. Such sheets are commercially available in thicknesses of about 0.4 mm to about 1.2 mm, but have by rolling anisotropic material properties and an anisotropic microstructure (based on tungsten) on. Tungsten heavy metal components are usually sintered close to the final shape and then machined or, in the case of flat components, produced from sheet metal.
- US 3,155,502 discloses a method for producing shaped articles, wherein first a refractory metal powder with water-soluble organic binders . Lubricants and a small amount of water is mixed. The mixture is extruded into a green body and can be further compacted in a cold rolling step and then sintered in an inert atmosphere.
- EP 0 325 179 describes a process for the production of sheets from a tungsten heavy metal alloy, in which the constituents of the alloy are mixed in a liquid medium to a slurry in which the liquid constituents are sucked off. From the dried slurry, a planar shaped body is prepared, which is dried and sintered to a density of at least 90% of the theoretical density of the alloy. The sintered shaped body is then rolled in further steps to the desired final thickness.
- This object is achieved by a method for the production of shaped articles from a tungsten heavy metal alloy and from molybdenum alloys, wherein a slurry for film casting is produced from a tungsten heavy metal alloy or molybdenum alloy, a film is poured from the slurry and the film is debinded and sintered after drying, to get a sheet.
- the molded article according to the invention is generally available as a sheet or as a sheet metal by, for example, stamping, stamping or forming. Other suitable forming methods for obtaining the molded article include, for example, bending, water jet or laser cutting, spark erosion, and machining.
- tungsten heavy metal alloy or molybdenum alloy means materials selected from the group consisting of tungsten heavy metal alloys, tungsten, tungsten alloys, molybdenum and molybdenum alloys. The method according to the invention can thus be used advantageously for many materials.
- the objects obtained by the process according to the invention have these features and thus solve this task.
- Film casting is a cost effective process for producing planar components for a variety of applications in the electrical industry, such. As chip substrates, piezo actuators and multilayer capacitors. In recent years, however, interest in film casting has grown significantly for other, new product areas. With conventional methods for the production of ceramic components, such as dry pressing, slip casting or extrusion, the economic production of large-area, flat, thin, defect-free and homogeneous substrates, which have sufficient green strength, tight dimensional tolerances and a smooth surface is extremely difficult or even impossible ,
- Suitable shaping methods include, for example, bending, water jet or laser cutting, spark erosion and machining.
- An object of the invention is a method as defined in claims 1 to 5.
- Another object is the use as defined in any one of claims 6 to 11.
- a slurry for film casting is prepared from a tungsten heavy metal alloy or molybdenum alloy, cast from the slurry a film on a substrate and the film is debind after drying and sintered to obtain the sheet, the film by pulling the pad is brought in the drawing direction by pouring cut to the desired thickness.
- tungsten metal powder or molybdenum metal powder is first mixed with a metal binder, also in the form of a metal powder.
- the metallic binder is usually an alloy containing metals selected from the group consisting of nickel, iron, copper with each other or with other metals.
- an alloy of tungsten or molybdenum may be used with the metallic binder in the form of a metal powder.
- metal binder can be used advantageously nickel / iron and nickel / copper alloys.
- the metallic binder is usually made of nickel, iron, copper, cobalt, manganese, molybdenum and / or aluminum.
- the tungsten or molybdenum content is from 60% by weight to 98% by weight, advantageously from 78% by weight to 97% by weight, in particular from 90% by weight to 95% by weight, or 90.2% by weight .-% to 95.5 wt .-%.
- the nickel content is 1 wt .-% to 30 wt .-%, advantageously 2 wt .-% to 15 wt .-%, or 2.6 wt .-% to 6 wt .-%, or 3 wt .-% to 5.5% by weight.
- the iron content is 0 wt .-% to 15 wt .-%, advantageously 0.1 wt .-% to 7 wt .-%, in particular 0.2 wt .-% to 5.25 wt .-% or 0.67 Wt .-% to 4.8 wt .-%.
- the copper content is 0 wt .-% to 5 wt .-%, advantageously 0.08 wt .-% to 4 wt .-%, in particular 0.5 wt .-% to 3 wt .-% or 0.95 wt. % to 2.1% by weight.
- the cobalt content is 0 wt .-% to 2 wt .-%, advantageously 0.1 wt .-% to 0.25 wt .-% or 0.1 wt .-% to 0.2 wt .-%.
- the manganese content is 0 wt.% To 0.15 wt.%, Preferably 0.05 wt .-% to 0.1 wt .-%.
- the aluminum content is 0 to 0.2 wt .-%, preferably 0.05 to 0.15 Wt .-%, or 0.1 wt .-%.
- the tungsten content is from 60 1 wt .-% to 30 wt .-% to 80 wt .-% to 30 wt .-%, if only iron and nickel are used as a metallic binder. In this case, optionally 0 to 0.2% by weight of aluminum may be advantageous.
- the tungsten or molybdenum powder or alloy powder advantageously has a specific surface area of about 0.1 m 2 / g to about 2 m 2 / g, the particle size is usually less than 100 .mu.m, in particular less than 63 .mu.m.
- This mixture is then introduced into a solvent which preferably contains a dispersant and then deagglomerated, for example in a ball mill or other suitable device.
- the dispersant prevents agglomeration of the powder particles, lowers the viscosity of the slurry and results in a higher green density of the cast film.
- Polyester / polyamine condensation polymers such as Hypermer KD1 from Uniqema are advantageously used as the dispersant; however, those skilled in the art will be aware of other suitable materials such as fish oil (Menhaden Fish Oil Z3) or alkyl phosphate compounds (ZSCHIMMER & SCHWARZ KF 1001).
- solvents it is possible to use polar organic solvents, for example esters, ethers, alcohols or ketones, such as methanol, ethanol, n-propanol, n-butanol, diethyl ether, tert-butyl methyl ether, methyl acetate, ethyl acetate, acetone, ethyl methyl ketone or mixtures thereof ,
- the solvent used is an azeotropic mixture of two solvents, for example a mixture of ethanol and ethyl methyl ketone in a ratio of 31.8 to 68.2 percent by volume.
- This mixture is ground, for example, in a ball mill or other suitable mixing unit and thereby homogenized. This process is generally carried out for about 24 hours to obtain the first mixture.
- the polymeric binder may be added in the preparation of the first mixture, optionally with additional solvent and optionally a plasticizer.
- the polymeric binder can also be added in the preparation of the second mixture.
- the polymeric binder may be added in part both in the preparation of the first mixture and in part in the preparation of the second mixture.
- a solvent or solvent mixture may be used and the polymeric binder added with another solvent or solvent mixture such that a desired solvent mixture (e.g., an azeotropic mixture) does not set until after the addition of the polymeric binder.
- a desired solvent mixture e.g., an azeotropic mixture
- the polymeric binder must meet many requirements. It serves primarily to combine individual powder particles when drying together, should be soluble in the solvent and be well compatible with the dispersant.
- the addition of the polymeric binder greatly influences the viscosity of the slurry. Advantageously, it causes only a slight increase in viscosity and at the same time has a stabilizing effect on the dispersion.
- the polymeric binder must burn out without residue.
- the polymeric binder provides good strength and handleability of the green sheet. An optimal polymeric binder reduces the tendency of drying cracks in the green sheet and does not hinder solvent evaporation by forming a dense surface layer.
- polymeric binder it is generally possible to use polymers or polymer formulations having a low ceiling temperature, such as polyacetal, polyacrylates or methacrylates or its copolymers (acrylic resins such as ZSCHIMMER & SCHWARZ KF 3003 and KF 3004), as well as polyvinyl alcohol or its derivatives such as polyvinyl acetate or Polyvinyl butyral (KURARAY Mowital SB 45 H, FERRO Butvar B-98, and B-76, KURARAY Mowital SB 60 H).
- polyacetal polyacrylates or methacrylates or its copolymers
- polyvinyl alcohol or its derivatives such as polyvinyl acetate or Polyvinyl butyral (KURARAY Mowital SB 45 H, FERRO Butvar B-98, and B-76, KURARAY Mowital SB 60 H).
- plasticizer plasticizer additives
- plasticizer additives which cause by lowering the glass transition temperature of the polymeric binder, a higher flexibility of the green sheet.
- the plasticizer penetrates into the network structure of the polymeric binder, which causes the intermolecular frictional resistance and thus the viscosity of the slurry to be reduced.
- the plasticizer used is advantageously a benzyl phthalate (FERRO Santicizer 261A).
- Binders and plasticizers can be added as binder suspension or binder solution.
- the binder suspension is advantageously composed of polyvinyl butyral and benzyl phthalate at a ratio of 1: 1, by weight.
- the second mixture is obtained.
- the second mixture has a solids content of about 30 to 60 percent by volume.
- the solvent content is usually less than 45 percent by volume.
- the proportion of organic compounds other than the solvent, such as polymeric binder, dispersant and plasticizer, is generally 5 to 15% by volume in total.
- the second mixture has a specific viscosity which is in the range from 1 Pa ⁇ s to 7 Pa ⁇ s.
- the second mixture After homogenizing the second mixture, it is conditioned in casting charges and degassed.
- the conditioned slurry is slowly stirred in a special pressure vessel and evacuated at reduced pressure. This is a common process step, which is known in principle to the person skilled in the art, so that the optimal conditions can be found with a small number of experiments.
- the slurry thus obtained, or the homogenized, conditioned and degassed second mixture is then used for film casting.
- the slip is poured onto a base and brought to a certain thickness with a squeegee.
- a film casting installation is also used which has an in FIG. 1 having pictured casting shoe.
- the slip 4 is filled and is brought by pulling the pad 5 in the drawing direction 6 by the Gellozier 3 to the desired thickness.
- a base can advantageously be used on one side silicone coated plastic film, which consists for example of PET (polyethylene terephthalate); in principle, however, other films are also suitable, which can withstand the forces occurring during pulling and have low adhesion to the dried slip.
- the surface of the film may also be patterned to impart a surface texture to the finished sheet.
- silicone-coated PET films having a thickness of about 100 ⁇ m are suitable.
- the thickness of the cast film depends on the cutting height, the hydrostatic pressure in the casting shoe, and the pulling rate.
- the slip height In order to achieve a constant hydrostatic pressure, the slip height must be kept constant via a corresponding filling and level control.
- the in FIG. 1 Shown Doppelschg hassleschuh improves compliance with a constant hydrostatic pressure in the second chamber, which is formed by the cutting 1 and 2 and allows very accurate compliance with a desired film thickness.
- foils up to 40 cm wide can be easily cast.
- the belt speed varies between 15 m / h (meters per hour) and 30 m / h.
- the set cutting heights depend on the desired film thickness and are between 50 .mu.m and 2000 .mu.m, in particular between 500 .mu.m and 2000 .mu.m.
- the film thickness after drying is about 30% of the cutting height.
- the thickness of the sintered sheets depends on the z-shrinkage during sintering.
- the shrinkage of the dried film is about 20% during sintering.
- the cast metal powder films dry continuously in the drying channel of the casting plant in a temperature range of 25 - 70 ° C.
- the drying channel is flowed through in countercurrent with air.
- the high solvent vapor concentrations during drying necessitate a drying channel that complies with the explosion protection guidelines.
- the film can be processed for example by cutting, punching or machining.
- thin welding rods, rings, crucibles, boats or isotope containers can be obtained.
- film parts are folded or assembled, for example, to pipes, boats or larger crucibles, wherein the film can also be glued.
- an adhesive for example, unconsumed slip or unconsumed binder suspension can be used.
- the article obtained from the film can be subjected to the further process steps.
- Debinding means removing as far as possible residue-free organic constituents required for film casting, such as polymeric binders and plasticizers from the material. If residues remain in the form of carbon, this leads to the formation of carbides, such as tungsten carbide, in the subsequent sintering process.
- Debindering takes place in a thermal process.
- the films are heated with a suitable temperature profile.
- FIG. 2 shows an example of a suitable temperature profile.
- the organic components are first softened and possibly liquid.
- Polymeric components such as the polymeric binder or dispersant are advantageously depolymerized, therefore, as mentioned above, a low ceiling temperature of these components is advantageous.
- these liquid phases should evaporate and be removed via the atmosphere. The temperature is expected to rise so fast that no low-volatile cracking products.
- These lead to carbon deposits in the form of soot To increase the vapor pressure is heated to 600 ° C under a vacuum of 50 - 150 mbar absolute, whereby a better evaporation of the liquid phase is achieved.
- the atmosphere in the furnace chamber must be rinsed.
- nitrogen is used in a proportion of about 2% by volume of hydrogen or less.
- the hydrogen content advantageously has the effect that the furnace atmosphere is free of oxygen and oxidation of the metal powders is avoided.
- Debinding is completed up to about 600 ° C.
- the components at this stage are a weakly bound powder packing.
- the thermal process is increased to about 800 ° C. There arise manageable, very brittle components that can be subjected to the following sintering step.
- the film is sintered.
- the sintering temperature is between about 1300 ° C and about 1600 ° C, especially 1400 ° C and 1550 ° C. Typically, the sintering times are about 2 hours to 8 hours. It is preferably sintered in a hydrogen atmosphere, in a vacuum or under an inert gas such as nitrogen or a noble gas such as argon with the addition of hydrogen. After sintering, there is a dense sheet with up to 100% of the theoretical density. The sintering can take place in batch or push furnaces.
- the debindered and sintered foils are to be sintered on suitable sintered bases.
- the films to be sintered with a smooth, flat cover, so that discarding of the film is avoided during the sintering process.
- several films can be superimposed, which additionally increases the sintering capacity.
- the stacked films are preferably separated from each other by sintering pads.
- As sintering substrate are preferably ceramic plates or films which do not react with the tungsten heavy metal alloy under the sintering conditions. There are, for example, in question: alumina, aluminum nitride, boron nitride, silicon carbide or zirconium oxide. Furthermore, the surface quality of the sintered substrate is decisive for the surface quality of the film to be sintered.
- the sheet may be rolled under conditions known in the art. It is rolled depending on the thickness of the sheet between about 1100 ° C and room temperature. Sheets approximately 2 mm thick are rolled at high temperatures, while foils can be rolled at room temperature.
- rolling in the method according to the invention unlike the prior art, serves less to reduce the thickness, but it is intended Above all, the rippling of the sheet eliminated and the surface quality can be improved.
- annealing to reduce internal stresses can be performed.
- the annealing is generally carried out at temperatures of 600 ° C to 1000 ° C in a vacuum or under protective gas or reducing atmosphere. If necessary, the steps of rolling and annealing may be repeated until the desired surface quality and, if necessary, thickness have been achieved.
- the method according to the invention allows the production of sheets of a tungsten heavy metal alloy or molybdenum alloy which have a thickness of less than 0.4 mm.
- the density of the sheet is 17 g / cm 3 to 18.6 g / cm 3 , preferably 17.3 g / cm 3 to 18.3 g / cm 3 .
- the method according to the invention allows the production of sheets from a tungsten heavy metal alloy or molybdenum alloy, which has an isotropic microstructure based on tungsten or molybdenum.
- an isotropic microstructure is understood to mean a uniform mixture of the crystallographic orientations without a preferred orientation, as well as an approximately round grain shape of the tungsten phase or molybdenum phase.
- Sheets and films produced by rolling in accordance with the prior art preferably have ⁇ 100> and ⁇ 110> orientations parallel to the normal direction of the sheet (see FIG. 11 ). These preferred orientations are part of a typical rolling texture as seen from the pole figures (see FIG. 12 ) can be read.
- This formation of the crystallographic texture is accompanied by the oblong expression of the grain shape along the rolling direction (cf. Fig. 3 and Fig. 9 ).
- FIG. 7 no crystallographic preferred direction along the standard of brass read (see. Fig. 7 and Fig. 11 ).
- the pole pieces ( FIG. 8 ) have an intensity maximum of 2.0, but this is compared to the maximum intensity of 4.7 in the pole pieces for the rolled sheet ( FIG.
- the thickness of the sheets described is advantageously less than 1.5 mm, in particular less than 0.5 mm, especially less than 0.4 mm.
- the sheets of the invention have as another property that the strength and bendability are independent of direction.
- the open porosity of the sheets of the invention is low and is 20 percent or less.
- the sheets contain the materials described above. Iron should not be used if the material is to be non-magnetic.
- an alloy powder of the composition W-0.2% Fe-5.3% Ni-2.1% Cu-0.2% Fe was used to produce a tungsten heavy metal sheet.
- the powder had a specific surface area of 0.6 m 2 / g and a particle size of less than 63 ⁇ m.
- the alloy powder was in a ball mill with 0.3 kg of polyester / polyamine condensation polymer (UNIQEMA Hypermer KD1) and 2.3 l of a mixture of 31.8 vol .-% ethanol and 68.2 vol .-% ethyl methyl ketone for 24 hours in ground and homogenized in a ball mill.
- FIG. 3 shows the microstructure of the obtained tungsten heavy metal sheet, the image vertical is parallel to the lead normal, the image horizontal parallel to the drawing direction.
- FIGS. 5 and 6 show pictures of the microstructure of the obtained tungsten heavy metal sheet, FIG. 5 with the image vertical parallel to the sheet normal and the image horizontal parallel to the rolling direction, FIG. 5 with the image vertical parallel to the lead normals and the image horizontals parallel to the transverse direction. In FIG. 5 is a slight stretch to see in FIG. 6 is a flattening of the particles recognizable.
- FIG. 7 represents the microstructure (cf. FIG. 3 ), in which the color of the tungsten particles indicates the crystal direction of the grain, which is parallel to the normal direction of the sheet (compare to Figure 7a: color code).
- FIG. 7 shows a uniform distribution of all colors, so that no crystallographic preferred direction with respect to the sheet normal is recognizable.
- the texture is represented in the form of pole figures.
- FIG. 8 shows a relatively restless texture with no apparent rolling texture.
- a tungsten heavy metal sheet with a density of 17.5 g / cm 3 which was obtained by rolling and contained an amount of 92.4% tungsten and 7.6% metallic binder, was investigated analogously.
- element powders in the composition W-0.2% Fe-5.3% Ni-2.1% Cu-0.2% Fe were mixed in a ball mill and ground.
- the powder mixture was isostatically pressed at 1500 bar and then sintered at 1450 ° C in a hydrogen atmosphere.
- An approximately 10 mm thick plate of the sintered material was brought by multiple hot / hot rolling by about 20% each with subsequent annealing to a thickness of about 1 mm.
- the preheating temperature of about 1300 ° C is reduced at 10 mm thickness with decreasing thickness. In the last rolling step is preheated only at about 300 ° C.
- FIG. 9 shows the microstructure of the obtained tungsten heavy metal sheet, the image vertical is parallel to the lead normal, the image horizontal parallel to the rolling direction.
- FIG. 10 shows the microstructure of the obtained Tungsten heavy metal sheet, the image vertical is parallel to the metal standard, the image horizontal is parallel to the transverse direction. In both pictures it can be clearly seen that the tungsten particles were stretched in the rolling direction by the rolling process.
- FIG. 10 shows the microstructure across the rolling direction. The tungsten particles are slightly flattened.
- FIG. 8 represents the microstructure (cf. FIG. 9 ), wherein the color of the tungsten particles indicates the crystal direction of the grain, which is parallel to the normal direction of the sheet (cf. Figure 7a : Color code). In contrast to FIG. 7 dominate in FIG. 11 red and blue colors. It can It can be read that the stretched tungsten particles have aligned preferably ⁇ 100> and ⁇ 110> directions parallel to the sheet normal.
- FIG. 12 the texture is represented in the form of pole figures. In FIG. 12 is contrary to FIG. 8 to recognize a clear difference between the transverse and rolling direction. Therefore, due to the orientation of the tungsten particles, the sheet has anisotropic material properties within the sheet plane.
- Table 1 are further examples of compositions which are processed as in Example 1 into sheets. Tungsten is filled in wt .-% to a total of 100 wt .-% (identified by "ad 100").
- Table 2 consists of 136 sheets using molybdenum instead of tungsten and the content of the metal binder components nickel, iron, copper, cobalt, manganese or aluminum as shown in Table 1 in weight percent. No.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Blechen aus Wolframschwermetalllepierunp oder Motybdänlegierung sowie deren Verwendung. Wolframschwermetalllegierungen sind aufgrund ihrer hohen Dichte von 17 bis 18,6 g/cm3 beispielsweise dazu geeignet, kurzwellige elektromagnetische Strahlung abzuschirmen. Sie werden daher häufig zum Strahlungsschutz oder zur Strahlführung in Röntgengeräten eingesetzt. Andere Anwendungen sind zum Beispiel Ausgleichsgewichte in der der Luftfahrt- und Automobilindustrie oder Formbauteile für Aluminiumdruckgussformen.
Wolframschwermetalllegierungen bestehen zu etwa 90 Gew.-% bis etwa 97 Gew.-% aus Wolfram. Der restliche Anteil sind Bindermetalle. Derartige Bleche sind in Dicken von etwa 0,4 mm bis etwa 1,2 mm kommerziell erhältlich, weisen durch Walzbehandlung jedoch anisotrope Werkstoffeigenschaften und ein anisotrope Mikrostruktur (bezogen auf Wolfram) auf.
Wolframschwermetallbauteile werden meist endformnah gesintert und anschließend spanend bearbeitet oder im Falle von flachen Bauteilen aus Blechen hergestellt.The present invention relates to a method for the production of sheets of tungsten heavy metal or molybdenum alloy and their use. Due to their high density of 17 to 18.6 g / cm 3 , tungsten heavy metal alloys are suitable for shielding short-wave electromagnetic radiation, for example. They are therefore often used for radiation protection or beam guidance in X-ray equipment. Other applications include balancing weights in the aerospace and automotive industries or molded components for aluminum die casting molds.
Tungsten heavy metal alloys consist of about 90% to about 97% by weight tungsten. The remainder is binder metal. Such sheets are commercially available in thicknesses of about 0.4 mm to about 1.2 mm, but have by rolling anisotropic material properties and an anisotropic microstructure (based on tungsten) on.
Tungsten heavy metal components are usually sintered close to the final shape and then machined or, in the case of flat components, produced from sheet metal.
Bei der Herstellung von Wolframschwermetallblechen und auch Blechen aus Molybdänlegierungen treten verschiedene Probleme auf:
- Zwischen zwei Glühschritten kann im Allgemeinen nur eine sehr begrenzte Walzverformung eingebracht werden. Bei zu starker Walzverformung reißen die Bleche ein und werden unbrauchbar. Typische, erlaubte Verformungsgrade liegen unter 20 % zwischen zwei Glühschritten. Bei Blechdicken unter 0,4 mm ist es notwendig mehr als 4 Glühungen durchzuführen. Dadurch wird das Verfahren signifikant erschwert, wenn dünne Bleche hergestellt werden sollen.
- Die gewalzten, dünnen Bleche können aufgrund ihrer Länge nur schwer in üblichen Produktionsöfen geglüht werden können. Platzsparendes Aufwickeln ist wegen der Sprödigkeit der Bleche nicht durchführbar, so dass meist eine große Anzahl kleiner Bleche verarbeitet werden muss. Hierdurch wird die Herstellung dünner Bleche mit einer Dicke von 0,5 mm oder weniger signifikant erschwert.
- Die bekannten Bleche zeigen bedingt durch das Herstellungsverfahren anisotrope, das heißt richtungsabhängige, Werkstoffeigenschaften innerhalb der Blechebene sowie eine Textur, bei welcher die <100>- und <110>-Richtungen parallel zur Blechnormalen ausgerichtet sind.
- In general, only a very limited rolling deformation can be introduced between two annealing steps. If the rolling deformation is too high, the sheets break and become unusable. Typical allowable degrees of deformation are below 20% between two anneals. For sheet thicknesses below 0.4 mm, it is necessary to perform more than 4 anneals. This significantly complicates the process when thin sheets are to be made.
- The rolled, thin sheets can be difficult to anneal in conventional production ovens because of their length. Space-saving winding is not feasible because of the brittleness of the sheets, so that usually a large number of small sheets must be processed. This will be the Making thin sheets with a thickness of 0.5 mm or less significantly more difficult.
- Due to the manufacturing process, the known metal sheets show anisotropic, that is directional, material properties within the sheet metal plane and a texture in which the <100> and <110> directions are aligned parallel to the sheet metal standard.
Es war die Aufgabe der vorliegenden Erfindung, ein technisch einfacheres Herstellungsverfahren für derartige Bleche mit einer geringen Dicke bereitzustellen. Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung von geformten Gegenständen aus einer Wolframschwermetallegierung und aus Molybdänlegierungen, wobei aus einer Wolframschwermetallegierung oder Molybdänlegierung ein Schlicker zum Foliengießen hergestellt wird, aus dem Schlicker eine Folie gegossen wird und die Folie nach dem Trocknen entbindert und gesintert wird, ein Blech zu erhalten. Der geformte Gegenstand gemäß der Erfindung ist im Allgemeinen ein Blech oder aus einem Blech durch beispielsweise Stanzen, Prägen oder Umformen erhältlich. Weitere geeignete Formgebungsverfahren zum Erhalt des geformten Gegenstandes sind beispielsweise Biegen, Wasserstrahl- oder Laserschneiden, Funkenerosion und spanende Bearbeitung.It was the object of the present invention to provide a technically simpler manufacturing method for such sheets with a small thickness. This object is achieved by a method for the production of shaped articles from a tungsten heavy metal alloy and from molybdenum alloys, wherein a slurry for film casting is produced from a tungsten heavy metal alloy or molybdenum alloy, a film is poured from the slurry and the film is debinded and sintered after drying, to get a sheet. The molded article according to the invention is generally available as a sheet or as a sheet metal by, for example, stamping, stamping or forming. Other suitable forming methods for obtaining the molded article include, for example, bending, water jet or laser cutting, spark erosion, and machining.
Unter dem Begriff Wolframschwermetallegierung oder Molybdänlegierung sind im Sinne der vorliegenden Erfindung Materialien ausgewählt aus der Gruppe bestehend aus Wolframschwermetalllegierungen, Wolfram, Wolframlegierungen, Molybdän und Molybdänlegierungen zu verstehen. Das Verfahren gemäß der Erfindung ist somit für zahlreiche Materialien vorteilhaft einsetzbar.For the purposes of the present invention, the term tungsten heavy metal alloy or molybdenum alloy means materials selected from the group consisting of tungsten heavy metal alloys, tungsten, tungsten alloys, molybdenum and molybdenum alloys. The method according to the invention can thus be used advantageously for many materials.
Es war eine weitere Aufgabe, einen geformten Gegenstand aus einer Wolframschwermetallegierung oder Molybdänlegierung, welches eine isotrope Mikrostruktur bezogen auf Wolfram bzw. Molybdän, aufweist, bereitzustellen, welcher isotrope Eigenschaften besitzt. Die nach dem Verfahren gemäß der Erfindung erhaltenen Gegenstände weisen diese Merkmale auf und lösen somit diese Aufgabe.It was another object to provide a molded article of tungsten heavy metal alloy or molybdenum alloy having an isotropic microstructure with respect to tungsten and molybdenum, respectively, which has isotropic properties. The objects obtained by the process according to the invention have these features and thus solve this task.
Das Foliengießen ist ein kostengünstiges Verfahren zur Herstellung planarer Komponenten für verschiedenste Anwendungen in der Elektroindustrie, wie z. B. Chipsubstrate, Piezoaktuatoren und Mehrschichtkondensatoren. In den letzten Jahren ist jedoch das Interesse am Foliengießen für andere, neue Produktbereiche stark gewachsen. Mit herkömmlichen Verfahren zur Herstellung von keramischen Bauteilen, wie Trockenpressen, Schlickerguss oder Extrusion ist die wirtschaftliche Herstellung von großflächigen, ebenen, dünnen, defektfreien und homogenen Substraten, die eine ausreichende Grünfestigkeit, enge Maßtoleranzen und eine glatte Oberfläche aufweisen, überaus schwierig oder gar nicht möglich.Film casting is a cost effective process for producing planar components for a variety of applications in the electrical industry, such. As chip substrates, piezo actuators and multilayer capacitors. In recent years, however, interest in film casting has grown significantly for other, new product areas. With conventional methods for the production of ceramic components, such as dry pressing, slip casting or extrusion, the economic production of large-area, flat, thin, defect-free and homogeneous substrates, which have sufficient green strength, tight dimensional tolerances and a smooth surface is extremely difficult or even impossible ,
Gemäß dem derzeitigen Stand der Technik umfasst das Verfahren zur Herstellung von Blechen aus Wolframschwermetalllegierungen oder Molybdänlegierungen im Allgemeinen folgende Schritte:
- Metallpulver mischen (z.B. Wolfram und metallischer Binder)
- mahlen
- pressen
- sintern
mehrfaches Wiederholen der Schritte - walzen
- glühen
bis die gewünschte Blechstärke erreicht ist - richten
- Mix metal powder (eg tungsten and metallic binder)
- grind
- press
- sinter
repeating the steps several times - roll
- glow
until the desired thickness is reached - judge
Anschließend werden die Bleche zum gewünschten Bauteil verarbeitet. Geeignete Formgebungsverfahren sind beispielsweise Biegen, Wasserstrahl- oder Laserschneiden, Funkenerosion und spanende Bearbeitung.Subsequently, the sheets are processed to the desired component. Suitable shaping methods include, for example, bending, water jet or laser cutting, spark erosion and machining.
Ein Gegenstand der Erfindung ist ein Verfahren wie in den Ansprüchen 1 bis 5 definiert.An object of the invention is a method as defined in
Ein weiterer Gegenstand ist die Verwendung wie in einem der Ansprüche 6 bis 11 definiert.Another object is the use as defined in any one of
Bei dem Verfahren gemäß der Erfindung wird aus einer Wolframschwermetallegierung oder Molybdänlegierung ein Schlicker zum Foliengießen hergestellt, aus dem Schlicker eine Folie auf eine Unterlage gegossen und die Folie nach dem Trocknen entbindert und gesintert, um das Blech zu erhalten, wobei die Folie durch Ziehen der Unterlage in Ziehrichtung durch Gießschneiden auf die gewünschte Dicke gebracht wird.In the method according to the invention, a slurry for film casting is prepared from a tungsten heavy metal alloy or molybdenum alloy, cast from the slurry a film on a substrate and the film is debind after drying and sintered to obtain the sheet, the film by pulling the pad is brought in the drawing direction by pouring cut to the desired thickness.
Das Verfahren ist insbesondere ein Verfahren zur Herstellung von Blechen aus einer Wolframschwermetallegierung oder Molybdänlegierung enthaltend die Schritte
- Bereitstellen eines Pulvers aus einer Wolframschwermetallegierung oder Molybdänlegierung;
- Mischen mit Lösemittel, Dispergator und gegebenenfalls polymerem Binder, um eine erste Mischung zu erhalten;
- Mahlen und Homogenisieren der ersten Mischung;
- Hinzufügen von Plastifizierer und gegebenenfalls weiterem Lösemittel und / oder polymerem Binder, um eine zweite Mischung zu erhalten;
- Homogenisieren der zweiten Mischung;
- Entgasen der zweiten Mischung;
- Foliengießen der zweiten Mischung;
- Trocknen der gegossenen Folie;
- Entbindern der gegossenen Folie;
- Sintern der Folie, um ein erstes Schwermetallblech zu erhalten.
- Providing a tungsten heavy metal alloy or molybdenum alloy powder;
- Mixing with solvent, dispersant and optionally polymeric binder to obtain a first mixture;
- Grinding and homogenizing the first mixture;
- Adding plasticizer and optionally further solvent and / or polymeric binder to obtain a second mixture;
- Homogenizing the second mixture;
- Degassing the second mixture;
- Film casting the second mixture;
- Drying the cast film;
- Debinding the cast film;
- Sintering the foil to obtain a first heavy metal sheet.
In einer vorteilhaften Ausführung enthält das Verfahren zusätzlich noch die Schritte
- Walzen und Glühen des ersten Schwermetallbleches, um ein zweites Schwermetallblech zu erhalten;
- gegebenenfalls Wiederholen des Walzen und Glühens, bis die gewünschte Oberflächenstruktur und Dicke erreicht ist;
- Richten des zweiten Schwermetallbleches.
- Rolling and annealing the first heavy metal sheet to obtain a second heavy metal sheet;
- optionally repeating the rolling and annealing until the desired surface texture and thickness is achieved;
- Straightening the second heavy metal sheet.
In dem Verfahren gemäß der Erfindung wird zunächst Wolframmetallpulver oder Molybdänmetallpulver mit einem metallischen Binder, ebenfalls in Form eines Metallpulvers, miteinander gemischt. Der metallische Binder ist üblicherweise eine Legierung enthaltend Metalle ausgewählt aus der Gruppe bestehend aus Nickel, Eisen, Kupfer miteinander oder mit anderen Metallen. Alternativ kann auch eine Legierung von Wolfram oder Molybdän mit dem metallischen Binder in Form eines Metallpulvers eingesetzt werden. Als metallische Binder lassen sich vorteilhaft Nickel/Eisen- und Nickel/Kupfer-Legierungen verwenden.In the process according to the invention, tungsten metal powder or molybdenum metal powder is first mixed with a metal binder, also in the form of a metal powder. The metallic binder is usually an alloy containing metals selected from the group consisting of nickel, iron, copper with each other or with other metals. Alternatively, an alloy of tungsten or molybdenum may be used with the metallic binder in the form of a metal powder. As metal binder can be used advantageously nickel / iron and nickel / copper alloys.
Der metallische Binder besteht in der Regel aus Nickel, Eisen, Kupfer, Kobalt, Mangan, Molybdän und/oder Aluminium.The metallic binder is usually made of nickel, iron, copper, cobalt, manganese, molybdenum and / or aluminum.
Der Wolfram- oder Molybdängehalt beträgt von 60 Gew.-% bis 98 Gew.-%, vorteilhaft von 78 Gew.-% bis 97 Gew.%, insbesondere 90 Gew.-% bis 95 Gew.-%, oder 90,2 Gew.-% bis 95,5 Gew.-%.The tungsten or molybdenum content is from 60% by weight to 98% by weight, advantageously from 78% by weight to 97% by weight, in particular from 90% by weight to 95% by weight, or 90.2% by weight .-% to 95.5 wt .-%.
Der Nickelgehalt beträgt 1 Gew.-% bis 30 Gew.-%, vorteilhaft 2 Gew.-% bis 15 Gew.-%, oder 2,6 Gew.-% bis 6 Gew.-%, oder 3 Gew.-% bis 5,5 Gew.-%.The nickel content is 1 wt .-% to 30 wt .-%, advantageously 2 wt .-% to 15 wt .-%, or 2.6 wt .-% to 6 wt .-%, or 3 wt .-% to 5.5% by weight.
Der Eisengehalt beträgt 0 Gew.-% bis 15 Gew.-%, vorteilhaft 0,1 Gew.-% bis 7 Gew.-%, insbesondere 0,2 Gew.-% bis 5,25 Gew.-% oder 0,67 Gew.-% bis 4,8 Gew.-%. Der Kupfergehalt beträgt 0 Gew.-% bis 5 Gew.-%, vorteilhaft 0,08 Gew.-% bis 4 Gew.-%, insbesondere 0,5 Gew.-% bis 3 Gew.-% oder 0,95 Gew.-% bis 2,1 Gew.-%. Der Kobaltgehalt beträgt 0 Gew.-% bis 2 Gew.-%, vorteilhaft 0,1 Gew.-% bis 0,25 Gew.-% oder 0,1 Gew.-% bis 0,2 Gew.-%.The iron content is 0 wt .-% to 15 wt .-%, advantageously 0.1 wt .-% to 7 wt .-%, in particular 0.2 wt .-% to 5.25 wt .-% or 0.67 Wt .-% to 4.8 wt .-%. The copper content is 0 wt .-% to 5 wt .-%, advantageously 0.08 wt .-% to 4 wt .-%, in particular 0.5 wt .-% to 3 wt .-% or 0.95 wt. % to 2.1% by weight. The cobalt content is 0 wt .-% to 2 wt .-%, advantageously 0.1 wt .-% to 0.25 wt .-% or 0.1 wt .-% to 0.2 wt .-%.
Der Mangangehalt beträgt 0 Gew.% bis 0,15 Gew.%, vorteilhaft 0,05 Gew.-% bis 0,1 Gew.-%. Der Aluminiumgehalt beträgt 0 bis 0,2 Gew.-%, vorteilhaft 0,05 bis 0,15 Gew.-%, oder 0,1 Gew.-%. Vorteilhaft liegt der Wolframgehalt bei 60 1 Gew.-% bis 30 Gew.-% bis 80 Gew.-% bis 30 Gew.-%, wenn nur Eisen und Nickel als metallischer Binder verwendet werden. In diesem Fall können optional 0 bis 0,2 Gew.-% Aluminium vorteilhaft sein.The manganese content is 0 wt.% To 0.15 wt.%, Preferably 0.05 wt .-% to 0.1 wt .-%. The aluminum content is 0 to 0.2 wt .-%, preferably 0.05 to 0.15 Wt .-%, or 0.1 wt .-%. Advantageously, the tungsten content is from 60 1 wt .-% to 30 wt .-% to 80 wt .-% to 30 wt .-%, if only iron and nickel are used as a metallic binder. In this case, optionally 0 to 0.2% by weight of aluminum may be advantageous.
Das Wolfram- oder Molybdänpulver bzw. Legierungspulver hat vorteilhaft eine spezifische Oberfläche von etwa 0,1 m2/g bis etwa 2 m2/g, die Teilchengröße beträgt meist weniger als 100 µm, insbesondere weniger als 63 µm. Diese Mischung wird anschließend in ein Lösemittel eingebracht, welches vorzugsweise einen Dispergator enthält und anschließend deagglomeriert, beispielsweise in eine Kugelmühle oder einer anderen geeigneten Vorrichtung.The tungsten or molybdenum powder or alloy powder advantageously has a specific surface area of about 0.1 m 2 / g to about 2 m 2 / g, the particle size is usually less than 100 .mu.m, in particular less than 63 .mu.m. This mixture is then introduced into a solvent which preferably contains a dispersant and then deagglomerated, for example in a ball mill or other suitable device.
Der Dispergator verhindert das Agglomerieren der Pulverteilchen, senkt die Viskosität des Schlickers und führt zu einer höheren Gründichte der gegossenen Folie. Als Dispergator werden vorteilhaft Polyester/Polyamin-Kondensationspolymere, wie beispielsweise Hypermer KD1 der Firma Uniqema eingesetzt; dem Fachmann sind jedoch weitere geeignete Materialien bekannt, wie beispielsweise Fischöl (Menhaden Fish Oil Z3) oder Alkylphosphatverbindungen (ZSCHIMMER & SCHWARZ KF 1001).The dispersant prevents agglomeration of the powder particles, lowers the viscosity of the slurry and results in a higher green density of the cast film. Polyester / polyamine condensation polymers such as Hypermer KD1 from Uniqema are advantageously used as the dispersant; however, those skilled in the art will be aware of other suitable materials such as fish oil (Menhaden Fish Oil Z3) or alkyl phosphate compounds (ZSCHIMMER & SCHWARZ KF 1001).
Als Lösemittel lassen sich vorteilhaft polare organische Lösungsmittel verwenden, wie beispielsweise Ester, Ether, Alkohole oder Ketone, wie Methanol, Ethanol, n-Propanol, n-Butanol, Diethylether, tert.-Butylmethylether, Essigsäuremethylester, Essigsäureethylester, Aceton, Ethylmethylketon oder deren Mischungen. Vorzugsweise wird als Lösemittel ein azeotropes Gemisch zweier Lösemittel verwendet, beispielsweise ein Gemisch aus Ethanol und Ethylmethylketon im Verhältnis von 31,8 zu 68,2 Volumenprozent.As solvents it is possible to use polar organic solvents, for example esters, ethers, alcohols or ketones, such as methanol, ethanol, n-propanol, n-butanol, diethyl ether, tert-butyl methyl ether, methyl acetate, ethyl acetate, acetone, ethyl methyl ketone or mixtures thereof , Preferably, the solvent used is an azeotropic mixture of two solvents, for example a mixture of ethanol and ethyl methyl ketone in a ratio of 31.8 to 68.2 percent by volume.
Dieses Gemisch wird beispielsweise in einer Kugelmühle oder einem anderen geeigneten Mischaggregat gemahlen und dabei homogenisiert. Dieser Vorgang wird im Allgemeinen etwa 24 Stunden lang durchgeführt und so die erste Mischung erhalten.This mixture is ground, for example, in a ball mill or other suitable mixing unit and thereby homogenized. This process is generally carried out for about 24 hours to obtain the first mixture.
Der polymere Binder kann bei der Herstellung der ersten Mischung zugefügt werden, optional mit weiterem Lösemittel und gegebenenfalls einem Plastifizierer. In einer alternativen Ausführungsform lässt sich der polymere Binder auch bei der Herstellung der zweiten Mischung zugeben. In einer alternativen Ausführungsform kann der polymere Binder zum Teil sowohl bei der Herstellung der ersten Mischung zugefügt werden als auch zum Teil bei der Herstellung der zweiten Mischung. Diese Variante hat den Vorteil, dass nach Zugabe eines Teiles des polymeren Binders in die erste Mischung diese Mischung stabiler ist und eine geringere oder keine Sedimentation zeigt.The polymeric binder may be added in the preparation of the first mixture, optionally with additional solvent and optionally a plasticizer. In an alternative embodiment, the polymeric binder can also be added in the preparation of the second mixture. In an alternative embodiment, the polymeric binder may be added in part both in the preparation of the first mixture and in part in the preparation of the second mixture. These Variant has the advantage that after adding a portion of the polymeric binder in the first mixture, this mixture is more stable and shows less or no sedimentation.
Meist wird ein Gemisch aus Plastifizierer, polymerem Binder und Lösemittel zugefügt. Hierbei können die gleichen Lösemittel wie oben beschrieben werden.Mostly a mixture of plasticizer, polymeric binder and solvent is added. Here, the same solvents as described above.
Alternativ kann zur Herstellung der ersten Mischung ein Lösemittel oder Lösemittelgemisch verwendet werden und der polymere Binder mit einem anderen Lösemittel oder Lösemittelgemisch zugesetzt werden, so dass sich ein gewünschtes Lösemittelgemisch (z.B. ein azeotropes Gemisch) erst nach der Zugabe des polymeren Binders einstellt.Alternatively, to prepare the first mixture, a solvent or solvent mixture may be used and the polymeric binder added with another solvent or solvent mixture such that a desired solvent mixture (e.g., an azeotropic mixture) does not set until after the addition of the polymeric binder.
Der polymere Binder, muß viele Anforderungen erfüllen. Er dient vorwiegend dazu, einzelne Pulverteilchen beim Trocknen miteinander zu verbinden, soll im Lösemittel löslich und gut mit dem Dispergator verträglich sein. Die Zugabe des polymeren Binders beeinflusst die Viskosität des Schlickers stark. Vorteilhaft bewirkt er nur eine geringe Viskositätserhöhung und besitzt gleichzeitig eine stabilisierende Wirkung auf die Dispersion. Der polymere Binder muss rückstandsfrei ausbrennen. Zusätzlich sorgt der polymere Binder für eine gute Festigkeit und Handhabbarkeit der Grünfolie. Ein optimaler polymerer Binder reduziert die Tendenz von Trocknungsrissen in der Grünfolie und behindert nicht die Lösemittelverdampfung durch die Ausbildung einer dichten Oberflächenschicht. Als polymerer Binder lassen sich generell Polymere oder Polymerzubereitungen mit einer niedrigen Ceiling-Temperatur verwenden, wie beispielsweise Polyacetal, Polyacrylate oder -methacrylate oder dessen Copolymere (Acrylharze wie ZSCHIMMER & SCHWARZ KF 3003 und KF 3004), sowie Polyvinylalkohol oder dessen Derivate, wie Polyvinylacetat oder Polyvinylbutyral (KURARAY Mowital SB 45 H, FERRO Butvar B-98, und B-76, KURARAY Mowital SB 60 H).The polymeric binder must meet many requirements. It serves primarily to combine individual powder particles when drying together, should be soluble in the solvent and be well compatible with the dispersant. The addition of the polymeric binder greatly influences the viscosity of the slurry. Advantageously, it causes only a slight increase in viscosity and at the same time has a stabilizing effect on the dispersion. The polymeric binder must burn out without residue. In addition, the polymeric binder provides good strength and handleability of the green sheet. An optimal polymeric binder reduces the tendency of drying cracks in the green sheet and does not hinder solvent evaporation by forming a dense surface layer. As the polymeric binder, it is generally possible to use polymers or polymer formulations having a low ceiling temperature, such as polyacetal, polyacrylates or methacrylates or its copolymers (acrylic resins such as ZSCHIMMER & SCHWARZ KF 3003 and KF 3004), as well as polyvinyl alcohol or its derivatives such as polyvinyl acetate or Polyvinyl butyral (KURARAY Mowital SB 45 H, FERRO Butvar B-98, and B-76, KURARAY Mowital SB 60 H).
Als Plastifizierer (Weichmacher) werden Additive verwendet, welche durch Herabsetzung der Glastemperatur des polymeren Binders eine höhere Flexibilität der Grünfolie bewirken.As plasticizer (plasticizer) additives are used, which cause by lowering the glass transition temperature of the polymeric binder, a higher flexibility of the green sheet.
Der Plastifizierer dringt in die Netzwerkstruktur des polymeren Binders ein, was dazu führt, dass der intermolekulare Reibungswiderstand und damit die Viskosität des Schlickers herabgesetzt wird. Durch Einstellung eines geeigneten Weichmacher-/Binderverhältnisses und durch die Kombination von verschiedenen Weichmachertypen lassen sich Folieneigenschaften wie Reißfestigkeit und Dehnbarkeit steuern.The plasticizer penetrates into the network structure of the polymeric binder, which causes the intermolecular frictional resistance and thus the viscosity of the slurry to be reduced. By setting a suitable plasticizer / binder ratio and by combining different Plasticizer types can be used to control film properties such as tear resistance and ductility.
Als Plastifizierer wird vorteilhaft ein Benzylphthalat (FERRO Santicizer 261A) eingesetzt.The plasticizer used is advantageously a benzyl phthalate (FERRO Santicizer 261A).
Binder und Plastifizierer lassen sich als Bindersuspension oder Binderlösung zum zugeben. Die Bindersuspension setzt sich vorteilhaft aus Polyvinylbutyral und Benzylphthalat mit einem Verhältnis 1:1, bezogen auf das Gewicht, zusammen.Binders and plasticizers can be added as binder suspension or binder solution. The binder suspension is advantageously composed of polyvinyl butyral and benzyl phthalate at a ratio of 1: 1, by weight.
Nach der Zugabe des polymeren Binders, gegebenenfalls mit weiterem Lösemittel und optional mit Plastifizierer, wird die zweite Mischung erhalten.After the addition of the polymeric binder, optionally with further solvent and optionally with plasticizer, the second mixture is obtained.
Die zweite Mischung weist einen Feststoffanteil von ca. 30 bis 60 Volumenprozent auf. Der Lösemittelanteil ist meist kleiner als 45 Volumenprozent. Der Anteil an vom Lösemittel verschiedenen organischen Verbindungen, wie polymerer Binder, Dispergator und Plastifizierer beträgt in der Summe meist 5 bis 15 Volumenprozent. Je nach Zusammensetzung besitzt die zweite Mischung eine bestimmte Viskosität, die im Bereich von 1 Pa·s bis 7 Pa·s liegt.The second mixture has a solids content of about 30 to 60 percent by volume. The solvent content is usually less than 45 percent by volume. The proportion of organic compounds other than the solvent, such as polymeric binder, dispersant and plasticizer, is generally 5 to 15% by volume in total. Depending on the composition, the second mixture has a specific viscosity which is in the range from 1 Pa · s to 7 Pa · s.
Diese wird -meist für weitere 24 Stunden- in einem geeigneten Mischaggregat, wie einer Kugelmühle, homogenisiert.This is-mostly for a further 24 hours-homogenized in a suitable mixing unit, such as a ball mill.
Nach dem Homogenisieren der zweiten Mischung wird diese in Gießchargen konditioniert und entgast. Der konditionierte Schlicker wird in einem speziellen Druckbehälter langsam gerührt und bei Unterdruck evakuiert. Dies ist ein üblicher Verfahrensschritt, der dem Fachmann prinzipiell bekannt ist, so dass die optimalen Bedingungen mit einer geringen Anzahl an Versuchen aufzufinden sind. Der so erhaltene Schlicker, bzw. die homogenisierte, konditionierte und entgaste zweite Mischung wird anschließend zum Foliengießen verwendet.After homogenizing the second mixture, it is conditioned in casting charges and degassed. The conditioned slurry is slowly stirred in a special pressure vessel and evacuated at reduced pressure. This is a common process step, which is known in principle to the person skilled in the art, so that the optimal conditions can be found with a small number of experiments. The slurry thus obtained, or the homogenized, conditioned and degassed second mixture is then used for film casting.
Im einfachsten Fall wird der Schlicker auf eine Unterlage gegossen und mit einem Rakel auf eine bestimmte Dicke gebracht.In the simplest case, the slip is poured onto a base and brought to a certain thickness with a squeegee.
Bei dem erfindungsgemäßen Verfahren wird dabei auch eine Foliengießanlage eingesetzt, welche einen in
Für einen Schlicker mit konstanten Eigenschaften hängt die Dicke der gegossenen Folie von der Schneidenhöhe, vom hydrostatischen Druck im Gießschuh und der Ziehgeschwindigkeit ab. Um einen konstanten hydrostatischen Druck zu erreichen, muss die Schlickerhöhe über eine entsprechende Befüllung und Niveauregulierung konstant gehalten werden. Der in
Im Allgemeinen beträgt die Foliendicke nach dem Trocknen ca. 30 % der Schneidenhöhe. Die Dicke der gesinterten Bleche ist abhängig von der z-Schwindung beim Sintern. Die Schwindung der getrockneten Folie beträgt beim Sintern ca. 20 %. Die gegossenen Metallpulverfolien trocknen kontinuierlich im Trocknungskanal der Gießanlage in einem Temperaturbereich von 25 - 70 °C. Der Trocknungskanal wird im Gegenstrom mit Luft durchströmt. Die hohen Lösemitteldampfkonzentrationen beim Trocknen bedingen einen Trocknungskanal, der den Explosions-Schutzrichtlinien entspricht.In general, the film thickness after drying is about 30% of the cutting height. The thickness of the sintered sheets depends on the z-shrinkage during sintering. The shrinkage of the dried film is about 20% during sintering. The cast metal powder films dry continuously in the drying channel of the casting plant in a temperature range of 25 - 70 ° C. The drying channel is flowed through in countercurrent with air. The high solvent vapor concentrations during drying necessitate a drying channel that complies with the explosion protection guidelines.
Die genauen Verfahrensbedingungen hängen von der Zusammensetzung des verwendeten Schlickers und den Parametern der verwendeten Foliengießanlage ab. Der Fachmann kann durch eine geringe Anzahl an Routineversuchen die geeigneten Einstellungen herausfinden.The exact process conditions depend on the composition of the slip used and the parameters of the film caster used. The person skilled in the art can find out the suitable settings through a small number of routine tests.
Um unterschiedlich geformte Gegenstände herzustellen kann die Folie beispielsweise durch Schneiden, Stanzen oder auch spanend bearbeitet werden. Hierdurch lassen sich beispielsweise dünne Schweißstäbe, Ringe, Tiegel, Schiffchen oder Isotopenbehälter erhalten. Für komplexer geformte Gegenstände können auch ausgeschnittene Folienteile beispielsweise zu Rohren, Schiffchen oder größeren Tiegeln gefaltet oder zusammengesetzt werden, wobei sich die Folie auch kleben lässt. Als Klebstoff ist beispielsweise unverbrauchter Schlicker oder unverbrauchte Bindersuspension verwendbar. Anschließend kann der aus der Folie erhaltene Gegenstand den weiteren Verfahrensschritten unterzogen werden.In order to produce differently shaped objects, the film can be processed for example by cutting, punching or machining. As a result, for example, thin welding rods, rings, crucibles, boats or isotope containers can be obtained. For more complex shaped objects can also cut out film parts are folded or assembled, for example, to pipes, boats or larger crucibles, wherein the film can also be glued. As an adhesive, for example, unconsumed slip or unconsumed binder suspension can be used. Subsequently, the article obtained from the film can be subjected to the further process steps.
Nach dem Trocknen der Folie wird diese entbindert. Entbinderung bedeutet die möglichst rückstandsfreie Entfernung aller zum Foliengießen benötigten organischen Bestandteile wie polymerer Binder und Weichmacher aus dem Material. Falls Rückstände in Form von Kohlenstoff zurückbleiben führt dies im folgenden Sinterprozess zur Bildung von Karbiden, beispielsweise von Wolframkarbid.After drying the film, this is debinded. Debinding means removing as far as possible residue-free organic constituents required for film casting, such as polymeric binders and plasticizers from the material. If residues remain in the form of carbon, this leads to the formation of carbides, such as tungsten carbide, in the subsequent sintering process.
Die Entbinderung erfolgt in einem thermischen Prozess. Hierbei werden die Folien mit einem geeigneten Temperaturprofil aufgeheizt.
Zur Erhöhung des Dampfdruckes wird bis 600°C unter einem Vakuum von 50 - 150 mbar absolut erwärmt, wodurch eine bessere Verdampfung der Flüssigphase erzielt wird.Debindering takes place in a thermal process. Here, the films are heated with a suitable temperature profile.
To increase the vapor pressure is heated to 600 ° C under a vacuum of 50 - 150 mbar absolute, whereby a better evaporation of the liquid phase is achieved.
Zum Abtransport der verdampften organischen Bestandteile muss die Atmosphäre im Ofenraum gespült werden. Hierzu wird Stickstoff mit einem Anteil von etwa 2 Vol.-% Wasserstoff oder weniger verwendet. Der Wasserstoffanteil bewirkt vorteilhaft, dass die Ofenatmosphäre frei von Sauerstoff ist und eine Oxidation der Metallpulver vermieden wird.To remove the evaporated organic components, the atmosphere in the furnace chamber must be rinsed. For this purpose, nitrogen is used in a proportion of about 2% by volume of hydrogen or less. The hydrogen content advantageously has the effect that the furnace atmosphere is free of oxygen and oxidation of the metal powders is avoided.
Das Entbindern ist bis etwa 600°C abgeschlossen. Bei den Bauteilen handelt es sich in diesem Stadium um eine schwach gebundene Pulverpackung. Um einDebinding is completed up to about 600 ° C. The components at this stage are a weakly bound powder packing. To one
Ansintern der Pulverkörner zu erreichen wird der thermische Prozess bis etwa 800°C erhöht. Es entstehen handhabbare, sehr spröde Bauteile, die dem folgenden Sinterschritt unterworfen werden können.To achieve sintering of the powder grains, the thermal process is increased to about 800 ° C. There arise manageable, very brittle components that can be subjected to the following sintering step.
Nach dem Entbindern wird die Folie gesintert. Je nach Legierungszusammensetzung liegt die Sintertemperatur zwischen etwa 1300°C und etwa 1600°C, insbesondere 1400°C und 1550°C. typischerweise liegen die Sinterzeiten bei ca. 2 h bis 8 h. Es wird vorzugsweise in einer Wasserstoffatmosphäre, im Vakuum oder unter Schutzgas wie Stickstoff oder einem Edelgas wie Argon evtl. unter Beimengung von Wasserstoff gesintert. Nach dem Sintern liegt ein dichtes Blech mit bis zu 100 % der theoretischen Dichte vor. Das Sintern kann in Batch- oder Durchschuböfen stattfinden. Die entbinderten und angesinterten Folien sind auf geeigneten Sinteruntelagen zu sintern. Dabei ist es vorteilhaft die zu sinternden Folien mit einer glatten, ebenen Abdeckung zu beschweren, damit ein Verwerfen der Folie während des Sintervorgangs vermieden wird. Dazu können auch mehrere Folien übereinander gelegt werden, wodurch zusätzlich die Sinterkapazität erhöht wird. Die gestapelten Folien sind vorzugsweise durch Sinterunterlagen voneinander zu trennen. Als Sinterunterlage eignen sich vorzugsweise keramische Platten oder Folien, welche unter den Sinterbedingungen nicht mit der Wolframschwermetalllegierung reagieren. Es kommen hierfür beispielsweise in Frage: Aluminiumoxid, Aluminiumnitrid, Bornitrid, Siliziumcarbid oder Zirkonoxid. Ferner ist die Oberflächenqualität der Sinterunterlage entscheidend für die Oberflächenqualität der zu sinternden Folie. Defekte können sich unmittelbar auf der Folie abbilden oder zu Anhaftungen während des Sinterns führen. Anhaftungen führen häufig zu Rissbildung oder zum Verzug der Folien, da die Schwindung während des Sinterns behindert wird. Zum Reduzieren der Welligkeit und/oder der Verbesserung der Oberflächenqualität kann vorteilhaft ein Walzschritt angeschlossen werden. Das Blech kann unter Bedingungen, die aus dem bisherigen Stand der Technik bekannt sind gewalzt werden. Dabei wird je nach Dicke des Blechs zwischen ca. 1100°C und Raumtemperatur gewalzt. Bleche mit ca. 2 mm Dicke werden bei hohen Temperaturen gewalzt, während Folien bei Raumtemperatur gewalzt werden können. Das Walzen dient in dem Verfahren gemäß der Erfindung im Gegensatz zum Stand der Technik jedoch weniger dem Reduzieren der Dicke, sondern es soll vor allem die Welligkeit des Blechs beseitigt und die Oberflächenqualität verbessert werden.
Zur Herstellung besonders dünner Bleche kann allerdings auch zur Dickenreduktion gewalzt werden.
Abschließend kann eine Glühung zur Reduzierung innerer Spannungen durchgeführt werden. Das Glühen wird im Allgemeinen bei Temperaturen von 600°C bis 1000°C im Vakuum oder unter Schutzgas bzw. reduzierender Atmosphäre durchgeführt.
Die Schritte des Walzen und Glühens können gegebenenfalls wiederholt werden, bis die gewünschte Oberflächenqualität und gegebenenfalls Dicke erreicht wurden.After debinding, the film is sintered. Depending on the alloy composition, the sintering temperature is between about 1300 ° C and about 1600 ° C, especially 1400 ° C and 1550 ° C. Typically, the sintering times are about 2 hours to 8 hours. It is preferably sintered in a hydrogen atmosphere, in a vacuum or under an inert gas such as nitrogen or a noble gas such as argon with the addition of hydrogen. After sintering, there is a dense sheet with up to 100% of the theoretical density. The sintering can take place in batch or push furnaces. The debindered and sintered foils are to be sintered on suitable sintered bases. It is advantageous to weight the films to be sintered with a smooth, flat cover, so that discarding of the film is avoided during the sintering process. For this purpose, several films can be superimposed, which additionally increases the sintering capacity. The stacked films are preferably separated from each other by sintering pads. As sintering substrate are preferably ceramic plates or films which do not react with the tungsten heavy metal alloy under the sintering conditions. There are, for example, in question: alumina, aluminum nitride, boron nitride, silicon carbide or zirconium oxide. Furthermore, the surface quality of the sintered substrate is decisive for the surface quality of the film to be sintered. Defects can be imaged directly on the film or lead to adhesion during sintering. Buildup often results in cracking or distortion of the films as shrinkage during sintering is hindered. To reduce the waviness and / or the improvement of the surface quality, a rolling step can be advantageously connected. The sheet may be rolled under conditions known in the art. It is rolled depending on the thickness of the sheet between about 1100 ° C and room temperature. Sheets approximately 2 mm thick are rolled at high temperatures, while foils can be rolled at room temperature. However, rolling in the method according to the invention, unlike the prior art, serves less to reduce the thickness, but it is intended Above all, the rippling of the sheet eliminated and the surface quality can be improved.
For the production of particularly thin sheets, however, can also be rolled to reduce the thickness.
Finally, an annealing to reduce internal stresses can be performed. The annealing is generally carried out at temperatures of 600 ° C to 1000 ° C in a vacuum or under protective gas or reducing atmosphere.
If necessary, the steps of rolling and annealing may be repeated until the desired surface quality and, if necessary, thickness have been achieved.
Das Verfahren gemäß der Erfindung erlaubt die Herstellung von Blechen aus einer Wolframschwermetallegierung oder Molybdänlegierung, welche eine Dicke von weniger als 0,4 mm aufweisen. Die Dichte des Bleches liegt bei 17 g/cm3 bis 18,6 g/ cm3, vorzugsweise bei 17,3 g/ cm3 bis 18,3 g/ cm3. Das Verfahren gemäß der Erfindung erlaubt die Herstellung von Blechen aus einer Wolframschwermetallegierung oder Molybdänlegierung, welches eine isotrope Mikrostruktur bezogen auf Wolfram bzw. Molybdän, aufweist. Unter einer isotropen Mikrostruktur wird gemäß der Erfindung eine gleichmäßige Mischung der kristallographischen Orientierungen ohne eine Vorzugsorientierung verstanden, sowie eine annähernd runde Kornform der Wolframphase bzw. Molybdänphase.
Bleche und Folien, die gemäß dem Stand der Technik durch Walzen hergestellt werden, weisen bevorzugt <100>- und <110>-Orientierungen parallel zur Normalenrichtung des Blechs auf (siehe
Sheets and films produced by rolling in accordance with the prior art preferably have <100> and <110> orientations parallel to the normal direction of the sheet (see
Die offene Porosität der Bleche der Erfindung ist gering und liegt bei 20 Prozent oder weniger.
Als metallischen Binder enthalten die Bleche die oben beschriebenen Materialien. Eisen sollte nicht verwendet werden, wenn das Material unmagnetisch sein soll.The open porosity of the sheets of the invention is low and is 20 percent or less.
As a metallic binder, the sheets contain the materials described above. Iron should not be used if the material is to be non-magnetic.
50 kg eines Legierungspulvers der Zusammensetzung W-0,2%Fe-5,3%Ni-2,1%Cu-0,2%Fe wurde zur Herstellung eines Wolframschwermetallbleches eingesetzt. Das Pulver besaß eine spezifische Oberfläche von 0,6 m2/g und eine Teilchengröße von kleiner als 63 µm. Das Legierungspulver wurde in einer Kugelmühle mit 0,3 kg Polyester/Polyamin-Kondensationspolymer (UNIQEMA Hypermer KD1) und 2,3 l eines Gemisches aus 31,8 Vol.-% Ethanol und 68,2 Vol.-% Ethylmethylketon für 24 Stunden in einer Kugelmühle gemahlen und homogenisiert. Anschließend wurde eine Menge von 2,5 kg eines Gemisches von 0,7 kg Polyvinylbutyral (Kuraray Mowital SB 45 H), 0,7 kg Benzylphthalat (FERRO Santicizer 261A) und 1,5 l eines Gemisches aus 31,8 Vol.-% Ethanol und 68,2 Vol.-% Ethylmethylketon als Lösemittel zugegeben und für weitere 24 Stunden homogenisiert. Anschließend wurde die Mischung in Gießchargen konditioniert und entgast. Der erhaltene Schlicker besaß eine Viskosität von 3,5 Pa·s. Die Dichte des Schlickers betrug 7 g/cm3. Der Schlicker wurde anschließend auf einer Gießanlage unter Verwendung eines Doppelkammergießschuhs auf einer silikonbeschichteten PET-Folie mit einer Ziehgeschwindigkeit von 30 m/h zu einem Band mit einer Länge von 15 m, einer Breite von 40 cm und einer Dicke von 1100 µm ausgezogen und bei einer Temperatur von 35° C für 24 Stunden getrocknet. Anschließend wurde die erhaltene Grünfolie in einem Vakuum von 50 mbar und dem in
Das erhaltene Blech wurde bei 1200°C gewalzt und anschließend 2 Stunden bei einer Temperatur von 800 °C in reduzierender Atmosphäre geglüht. Das erhaltene Wolframschwermetallblech enthielt 92,4 % Wolfram und 7,6 % des metallischen Binders. Das Blech besaß eine Dichte von 17,5 g/cm3.
Die kristallographische Textur wurde durch EBSD- (Electron Back-Scatter Diffraction) Messungen bestimmt.
In den
In the
Ein Wolframschwermetallblech einer Dichte von 17,5 g/cm3, welches durch Walzen erhalten wurde und eine Menge von 92,4% Wolfram und 7,6% metallischem Binder enthielt wurde analog untersucht.
Dazu wurden Elementpulver in der Zusammensetzung W-0,2%Fe-5,3%Ni-2,1%Cu-0,2% Fe in einer Kugelmühle gemischt und gemahlen. Anschließend wurde die Pulvermischung isostatisch bei 1500 bar gepresst und dann bei 1450°C in einer Wasserstoffatmosphäre gesintert. Eine ca. 10 mm starke Platte des gesinterten Materials wurde durch mehrfaches Heiß/Warmwalzen um jeweils ca. 20 % mit jeweils anschließender Glühbehandlung auf eine Stärke von ca. 1 mm gebracht. Dabei wird die Vorglühtemperatur von ca. 1300°C bei 10 mm Stärke mit abnehmender Dicke reduziert. Im letzten Walzschritt wird nur mit etwa 300°C vorgewärmt.A tungsten heavy metal sheet with a density of 17.5 g / cm 3 , which was obtained by rolling and contained an amount of 92.4% tungsten and 7.6% metallic binder, was investigated analogously.
To this end, element powders in the composition W-0.2% Fe-5.3% Ni-2.1% Cu-0.2% Fe were mixed in a ball mill and ground. Subsequently, the powder mixture was isostatically pressed at 1500 bar and then sintered at 1450 ° C in a hydrogen atmosphere. An approximately 10 mm thick plate of the sintered material was brought by multiple hot / hot rolling by about 20% each with subsequent annealing to a thickness of about 1 mm. The preheating temperature of about 1300 ° C is reduced at 10 mm thickness with decreasing thickness. In the last rolling step is preheated only at about 300 ° C.
Wolframschwermetallblechs, die Bildvertikale befindet sich parallel zur Blechnormalen, die Bildhorizontale befindet sich parallel zur Querrichtung. In beiden Bildern ist deutlich zu erkennen, dass die Wolframpartikel durch den Walzprozess in Walzrichtung gestreckt wurden.
Tungsten heavy metal sheet, the image vertical is parallel to the metal standard, the image horizontal is parallel to the transverse direction. In both pictures it can be clearly seen that the tungsten particles were stretched in the rolling direction by the rolling process.
Die kristallographische Textur wurde durch EBSD-(Electron Back-Scatter Diffraction) Messungen bestimmt.
In
In
In der folgenden Tabelle 1 finden sich weitere Beispiele für Zusammensetzungen, welche wie in Beispiel 1 zu Blechen verarbeitet werden. Wolfram wird in Gew.-% zu insgesamt 100 Gew.-% aufgefüllt (kenntlich gemacht durch "ad 100").
Claims (11)
- Method for manufacturing a metal sheet, with a thickness of less than 0.4 mm, made of a tungsten heavy metal alloy or a molybdenum alloy, having an isotropic microstructure based on molybdenum or tungsten, wherein
a slip for foil casting is produced from a tungsten heavy metal alloy or molybdenum alloy,
a foil is cast from the slip onto a substrate and, after drying, the foil is freed of binder and sintered in order to obtain the metal sheet, wherein the foil is brought to the desired thickness by drawing the substrate in the drawing direction through casting blades. - Method according to Claim 1, characterized in that the tungsten heavy metal alloy or molybdenum alloy comprises
78% by weight to 97% by weight tungsten or molybdenum,
2% by weight to 15% by weight nickel,
0.1% by weight to 7% by weight iron,
0.08% by weight to 4% by weight copper. - Method according to either or both of Claims 1 and 2, characterized in that the polymeric binder is selected from the group consisting of polyacetal, poly(meth)acrylate and copolymers thereof, polyvinyl alcohol and derivatives thereof, in particular polyvinyl butyral.
- Method according to one or more of Claims 1 to 3, characterized in that the second mixture has a viscosity in the region of 1 to 7 Pas.
- Method according to one or more of Claims 1 to 4, characterized in that the sintering temperature is in the range between 1300 and 1600°C.
- Use of a metal sheet, with a thickness of less than 0.4 mm, made of a tungsten heavy metal alloy or a molybdenum alloy, having an isotropic microstructure based on molybdenum or tungsten, wherein the tungsten heavy metal alloy or molybdenum alloy comprises
78% by weight to 97% by weight tungsten or molybdenum,
2% by weight to 15% by weight nickel,
0.1% by weight to 7% by weight iron,
0.08% by weight to 4% by weight copper, and wherein the metal sheet has a density of 17-18.6 g/cm3, for shielding from short-wavelength electromagnetic radiation or for radiation protection or for beam guiding in X-ray devices. - Use according to Claim 6, wherein the isotropic microstructure contains an even mixture of crystallographic orientations without a preferred orientation.
- Use according to Claim 7, wherein(I) the distribution of the crystallographic orientations varies by less than 30% over each surface parallel to the surface normal, and(II) the distribution of the crystallographic orientations varies by less than 30% over each surface perpendicular to the surface normal.
- Use according to Claim 7 or 8, wherein the crystallographic orientations are the <100> and <110> orientations.
- Use according to one or more of Claims 6 to 9, wherein the strength and flexibility are direction-independent.
- Use according to one or more of Claims 6 to 10, wherein the open porosity is 20% or less.
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PL07765458T PL2038441T3 (en) | 2006-06-22 | 2007-06-18 | Process for producing shaped refractory metal bodies |
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PCT/EP2007/055986 WO2007147792A1 (en) | 2006-06-22 | 2007-06-18 | Process for producing shaped refractory metal bodies |
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US (2) | US20110206944A1 (en) |
EP (1) | EP2038441B1 (en) |
JP (2) | JP5661278B2 (en) |
CN (1) | CN101473054B (en) |
DK (1) | DK2038441T3 (en) |
ES (1) | ES2558877T3 (en) |
HK (1) | HK1132017A1 (en) |
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DE102011115866A1 (en) * | 2011-10-13 | 2013-04-18 | Karlsruher Institut für Technologie | Metal pipe; Use of a metal tube as a structural component; Method for producing a metal pipe; metallic structural component; divertor |
JP5847196B2 (en) * | 2011-12-07 | 2016-01-20 | 株式会社アライドマテリアル | Tungsten sintered alloy |
DE102012006998A1 (en) | 2012-04-10 | 2013-12-12 | H.C. Starck Ceramics Gmbh | Producing wear-resistant film useful for producing wear-resistant coatings on components, comprises producing a green film comprising hard material particles, and compacting the green film |
DE102012217182A1 (en) | 2012-09-24 | 2014-03-27 | Siemens Aktiengesellschaft | Producing a refractory metal component |
DE102012217191A1 (en) | 2012-09-24 | 2014-03-27 | Siemens Aktiengesellschaft | Producing a refractory metal component |
DE102012217188A1 (en) | 2012-09-24 | 2014-03-27 | Siemens Aktiengesellschaft | Producing a refractory metal component |
DE102012109782A1 (en) | 2012-10-15 | 2014-04-17 | Karlsruher Institut für Technologie | layer composite |
KR101675713B1 (en) * | 2013-06-04 | 2016-11-11 | 에이치. 씨. 스타아크 아이앤씨 | Slip and pressure casting of refractory metal bodies |
CN104588651A (en) * | 2014-10-31 | 2015-05-06 | 成都易态科技有限公司 | Flexible multi-hole metal foil and manufacturing method thereof |
DE102015218408A1 (en) | 2015-09-24 | 2017-03-30 | Siemens Aktiengesellschaft | Component and / or surface of a refractory metal or a refractory metal alloy for thermocyclic loads and manufacturing method thereto |
CN106141507B (en) * | 2016-07-01 | 2018-08-24 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of the ceramic granule reinforced composite material film of low content of organics |
CN106756379B (en) * | 2017-01-10 | 2019-01-25 | 广州市华司特合金制品有限公司 | Tungsten alloy barricade and the electronic information card for being provided with tungsten alloy barricade |
JP7174476B2 (en) | 2017-03-31 | 2022-11-17 | Jx金属株式会社 | tungsten target |
JP7191390B2 (en) * | 2017-05-16 | 2022-12-19 | エルジー・ケム・リミテッド | METHOD OF MANUFACTURING METAL FOAM |
CN109518054A (en) * | 2019-01-15 | 2019-03-26 | 株洲市美力迪实业有限公司 | A kind of broaching tool material and preparation method thereof and broaching tool |
CN110903020A (en) * | 2019-11-27 | 2020-03-24 | 株洲硬质合金集团有限公司 | Temperature-uniforming plate for 3D glass hot bending machine and preparation method and application thereof |
CN113462942A (en) * | 2021-07-02 | 2021-10-01 | 西安华力装备科技有限公司 | Preparation method of high-yield tungsten alloy material |
CN114480935B (en) * | 2022-01-20 | 2022-11-29 | 广东工业大学 | Tungsten-based alloy with grain size having gradient effect and preparation method thereof |
CN115029597A (en) * | 2022-06-02 | 2022-09-09 | 安泰天龙钨钼科技有限公司 | Method for preparing tungsten and tungsten alloy sheets |
CN114769593A (en) * | 2022-06-02 | 2022-07-22 | 安泰科技股份有限公司 | Method for preparing molybdenum and molybdenum alloy foil |
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US3155502A (en) * | 1960-08-12 | 1964-11-03 | Union Carbide Corp | Powder metallurgy |
US3403009A (en) | 1964-08-10 | 1968-09-24 | Minnesota Mining & Mfg | Refractory metal structures |
GB1121646A (en) * | 1964-08-10 | 1968-07-31 | Minnesota Mining & Mfg | Sintered metal articles |
US3324699A (en) * | 1965-01-04 | 1967-06-13 | Gen Electric | Production of non-earing molybdenum sheet |
US4491559A (en) * | 1979-12-31 | 1985-01-01 | Kennametal Inc. | Flowable composition adapted for sintering and method of making |
EP0325179A1 (en) * | 1988-01-14 | 1989-07-26 | GTE Products Corporation | Process for producing tungsten heavy alloy sheet |
US4777015A (en) * | 1988-01-14 | 1988-10-11 | Gte Products Corporation | Process for producing tungsten heavy alloy sheet using a metallic salt binder system |
JPH09235641A (en) * | 1996-02-28 | 1997-09-09 | Toho Kinzoku Kk | Tungsten heavy alloy sheet its production |
US6447715B1 (en) * | 2000-01-14 | 2002-09-10 | Darryl D. Amick | Methods for producing medium-density articles from high-density tungsten alloys |
JP2002030372A (en) * | 2000-07-12 | 2002-01-31 | Allied Material Corp | Thin and deformed superheavy alloy sheet and its production method |
US20070172378A1 (en) * | 2004-01-30 | 2007-07-26 | Nippon Tungsten Co., Ltd. | Tungsten based sintered compact and method for production thereof |
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WO2007147792A1 (en) | 2007-12-27 |
US20110206944A1 (en) | 2011-08-25 |
DK2038441T3 (en) | 2016-02-01 |
US10549350B2 (en) | 2020-02-04 |
CN101473054A (en) | 2009-07-01 |
JP2009541584A (en) | 2009-11-26 |
HK1132017A1 (en) | 2010-02-12 |
PL2038441T3 (en) | 2016-04-29 |
CN101473054B (en) | 2012-07-04 |
JP5661278B2 (en) | 2015-01-28 |
EP2038441A1 (en) | 2009-03-25 |
US20170050244A1 (en) | 2017-02-23 |
ES2558877T3 (en) | 2016-02-09 |
JP2014098209A (en) | 2014-05-29 |
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