CN101589166B - Metal formulations - Google Patents
Metal formulations Download PDFInfo
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- CN101589166B CN101589166B CN2008800030635A CN200880003063A CN101589166B CN 101589166 B CN101589166 B CN 101589166B CN 2008800030635 A CN2008800030635 A CN 2008800030635A CN 200880003063 A CN200880003063 A CN 200880003063A CN 101589166 B CN101589166 B CN 101589166B
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- China
- Prior art keywords
- powder
- metal powder
- cobalt
- cementing metal
- metallic substance
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 133
- 239000002184 metal Substances 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000009472 formulation Methods 0.000 title abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 180
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 102
- 239000010941 cobalt Substances 0.000 claims abstract description 102
- 239000000463 material Substances 0.000 claims abstract description 75
- 229910052742 iron Inorganic materials 0.000 claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 43
- 239000011230 binding agent Substances 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 230000000737 periodic effect Effects 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 140
- 235000013495 cobalt Nutrition 0.000 claims description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 89
- 229910002555 FeNi Inorganic materials 0.000 claims description 62
- 230000007797 corrosion Effects 0.000 claims description 28
- 238000005260 corrosion Methods 0.000 claims description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 238000005275 alloying Methods 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 8
- 230000002588 toxic effect Effects 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 231100000331 toxic Toxicity 0.000 claims description 6
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 5
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 4
- 229910039444 MoC Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims 22
- 238000007493 shaping process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 28
- 231100000419 toxicity Toxicity 0.000 description 28
- 230000001988 toxicity Effects 0.000 description 28
- 230000000694 effects Effects 0.000 description 18
- 238000005507 spraying Methods 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000000428 dust Substances 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 229910002546 FeCo Inorganic materials 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 239000000443 aerosol Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910002545 FeCoNi Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 210000004072 lung Anatomy 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 241000700159 Rattus Species 0.000 description 3
- 229910010069 TiCo Inorganic materials 0.000 description 3
- -1 and wherein Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 231100000086 high toxicity Toxicity 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 208000005069 pulmonary fibrosis Diseases 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000004482 other powder Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- 230000002110 toxicologic effect Effects 0.000 description 2
- 231100000759 toxicological effect Toxicity 0.000 description 2
- 231100000027 toxicology Toxicity 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- SKYGTJFKXUWZMD-UHFFFAOYSA-N ac1l2n4h Chemical compound [Co].[Co] SKYGTJFKXUWZMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000037 inhalation toxicity test Toxicity 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002075 main ingredient Substances 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
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a formulation which contains at least one hard material powder and at least two binder metal powders. Said formulation is characterized in that the cobalt is completely contained in the first binder metal powder and is prealloyed with one or more elements of groups 3 to 8 of the periodic system of elements, which are elements of the fourth period, and that at least one additional binder metal powder of the group of elementary powders including Fe, Ni, Al, Mn, Cr or the alloys thereof with each other is contained therein and the additional binder metal powders do not contain any cobalt in non-prealloyed form.
Description
Background technology
The formula that comprises powdery mechanically resistant material and powder binder metal is at industrial mechanically resistant material for the production of gummed especially or be used for the spraying powder of top coat.In the situation that carbide, the carbide that the most often uses is wolfram varbide; Other, such as titanium carbide, vanadium carbide, chromium carbide, tantalum carbide and niobium carbide or they each other mixture or the mixture of they and wolfram varbide often only as additive.Also may use nitride.Cobalt is the cementing metal of the most often using, but also uses the binder system that contains from 2 or the 3 kind of element of Fe, Co and Ni; In the spraying powder, also use for example Mn, Al, Cr.Other possible inorganic additives is metal-powder, such as tungsten, molybdenum and elemental carbon.If the mechanically resistant material of gummed contains as the titanium carbonitride of main ingredient to replace wolfram varbide, it is called as " sintering metal " so.Other possible mechanically resistant material is boride.
Usually use cobalt as the cementing metal in the mechanically resistant material of gummed and spraying powder, but also can use the alloy of nickel or Fe, Co and Ni.With regard to all situations, the binder phase after sintering or thermospray contains a certain proportion of for example tungsten, chromium, molybdenum and carbon from mechanically resistant material, and this is the result that exchanges with Carbide Phases generation element in liquid phase sintering or fusion.Powder binder metal used is element powders such as iron, nickel or cobalt dust or powdered alloy.
The binder phase of spraying powder not only can contain above-mentioned element and inorganic additives, can also contain other element, such as Al, rare earth element, yttrium.
In the past few decades, have been found that the incidence that has the pulmonary fibrosis of specificity appearance graphic in gummed mechanically resistant material industry obviously increases statistically, this is with the gummed mechanically resistant material operates powdery gummed mechanically resistant material or operation powdery formula is relevant in order to produce.This disease is also referred to as " gummed carbide lung (cementedcarbide lung) ", past and present be all the theme of many epidemiological studies and publication.In the custom production of the gummed mechanically resistant material that is undertaken by powder metallurgy production method (i.e. extruding and sintered powder mechanically resistant material/binder formula), the dust that causes release to suck due to the character of the method.If process the gummed mechanically resistant material at sintering or pre-sintered state by grinding machine, can form equally the superfine dust that sucks (" abrasive dust ").
The thermospray of the spraying powder of carbide-containing can cause equally and form superfine dust (" overspray ").
Similarly, approximately before 5 years, people are just known, if concentration is enough high, after suction, gummed mechanically resistant material dust also has hypertoxic effect to rat.Up to now, people also do not know the mechanism of action accurately.Two kinds of component wolfram varbides and cobalt do not have this effect individually.In order to improve the plan of occupational health, illustration mechanism and adopting does not have the surrogate that hypertoxic effect or hypertoxic effect reduce widely and receives great concern.
Summary of the invention
An object of the present invention is to provide the cobalt of certain formula, it can reduce toxicity on inhalation in the thermal spray process of described formula and in the Grinding Process of the ground finish (" grey processing ") of the gummed mechanically resistant material part of presintering and gummed mechanically resistant material.Can achieve this end by a kind of formula that comprises at least a hard material powder and at least two kinds of cementing metal powder, it is characterized in that, all cobalts be present in the first cementing metal powder and with one or more periodic table of elements in the element of 3-8 family pre-alloyed, there is at least a other cementing metal powder, this other cementing metal powder is from the powder of the mutual alloy of element of Fe, Ni, Al, Mn, Cr and these elements, and this other cementing metal powder does not contain the cobalt of any non-pre-alloyed form.
Astoundingly, have been found that the hypertoxic effect of the powdery formula of wolfram varbide and cobalt is based on the galvanic corrosion phenomenon, the bioavailability that it causes sucking rear cobalt increases.
And, it has surprisingly been found that, when the element of cobalt and iron or other periodic table of elements 3-8 family (transition group IIIa-VIIIa) is pre-alloyed, it is as the cementing metal in mechanically resistant material/binder formula, lose its toxicity on inhalation, but when these elements exist jointly with no-alloyed form and cobalt, but can not reduce the toxicity of cobalt.In principle, be positioned at cobalt left side and be preferably placed at its character of more easily having an effect of all because of metals of same period in periodictable, so can reduce corrosion tendency, and be difficult for the element of having an effect for example copper have opposite effect, even the alloyed copper that this point exists as additional phase also can be identified.
Advantageously, in the first cementing metal powder, the alloy companion of cobalt is the element of periodictable period 4 and 3-8 family.Particularly advantageously, in the first cementing metal powder, the alloy companion of cobalt is the element that is selected from Fe, Ni, Cr, Mn, Ti and Al.The first cementing metal powder can also contain other element, such as aluminium and/or copper.
Except the first cementing metal powder, usually need other cementing metal.Particularly advantageously, they are selected from iron powder, nickel powder, FeNi powdered alloy and pre-alloyed FeNi powdered alloy.
Mechanically resistant material is titanium carbide, vanadium carbide, molybdenum carbide, wolfram varbide or their mutual mixtures normally.These compounds are also the known catalyzer that is used for the aqueous medium oxygen reduction, and therefore as the catalyzer of burning, the mechanism of oxygen reduction is:
Co+1/2O
2+H
2O＝Co(OH)
2
In the situation that the spraying powder, the metal-powder of described at least a other interpolation can comprise Fe, Ni and for example other element, such as Al, Cr, Mn, Nb, Ta, Ti, but does not contain cobalt, in inevitable scope with unplanned in impurity.
Contain cobalt and fully the first cementing metal powder of alloying preferably contain the cobalt of 10-50 % by weight.Particularly preferably iron is 1: 1 or larger to the ratio of cobalt.Suitable composition is for example FeCo 50/50, FeCoNi 90/5/5.This powder can also comprise other iron family element ting.
Do not contain other cementing metal powder iron-based or Ni-based preferably of the cobalt of any non-pre-alloyed form, namely the total content of iron and nickel is at least 50%.The residuum of described other powder comprises at least 50% iron and nickel altogether.Advantageously, use powdered alloy composed as follows as other cementing metal powder: for example, to contain the FeNi powder of maximum 30%Fe, FeNi 50/50, FeNi 95/5.
The weight ratio of the first cementing metal powder and other powder preferably 1: 10-10: 1, particularly preferably 1: 5-5: 1.Those skilled in the art can select required ratio according to required stechiometry and existing powdered alloy.
Advantageously, the BET surface-area of other cementing metal powder is greater than 0.3m
2/ g, more advantageously greater than 0.5m
2/ g, particularly greater than 1m
2/ g.
In gummed mechanically resistant material and atomized powder footline industry, it is a kind of prior art from the element of Fe, Co, Ni and representative about the pre-alloyed powder that the binder phase of these elements forms that utilization contains two or more, and it utilizes two or three element powders to produce this formula.Although nearest modification can not reduce toxicity, can reduce or eliminate toxicity by making the complete alloying of binder system.Thisly come the powdered alloy of the hydrogen reducing of autoxidisable substance or other compound to buy from the market, have a lot of shortcomings but compare with element powders, for example higher oxygen level, extrudability are poor.Particularly Ni powder and Fe powder can be produced and can reach low-down oxygen level by carbonyl process, because the reduction potential of carbon monoxide is greater than the reduction potential of hydrogen, this is normally used for the production specific surface area greater than 1m
2The thin powdered alloy of/g.
Therefore, favourable formula is the formula that obtains by for the production of the method for mechanically resistant material/binder mixtures, utilizes a) pre-alloying powder of at least a chosen from Fe/cobalt and iron/nickel/cobalt; B) at least a element powders, its chosen from Fe, nickel, or be selected from and a) pre-alloying powder of different iron/nickel of component; C) hard material powder, wherein component a) and b) total composition comprise maximum 90% cobalt and the nickel of maximum 70 % by weight.Iron level is at least 10 % by weight advantageously.
In a favourable embodiment of the present invention, this is a kind of method of producing mechanically resistant material/binder mixtures as claimed in claim 1, wherein, total composition of binding agent is maximum 90 % by weight Co, maximum 70 % by weight Ni and at least 10 % by weight Fe, and wherein iron level satisfies with lower inequality
(Fe wherein: the weight percentage of iron, %Co: the weight percentage of cobalt, %Ni: the weight percentage of nickel),
At least use two kinds of adhesive powders, a kind of iron level of adhesive powder is lower than total composition of binding agent, the iron level of another kind of adhesive powder is higher than total composition of binding agent, and at least a adhesive powder is pre-alloyed from the element of at least two kinds of chosen from Fe, nickel and cobalt.
owing to occuring between binder phase and Carbide Phases and the chemical exchange between the molten particles of cementing metal powder in the liquid sintering process of thermal spray process neutralization for the production of the extruding formula of gummed mechanically resistant material, so, viewpoint of measures from material, utilize element powders enough, but from the toxicology viewpoint of measures, according to above example, make cobalt and minimum iron, nickel, manganese, the pre-alloyed ability of residuum of total composition of chromium or titanium and required cementing metal phase is enough, by pre-alloyed, for example, the content of iron and/or nickel or the content of other metal are fixed with the form of respective element powder (for example FeNi powdered alloy).
The program of this novel production formula may satisfy simultaneously two aspects (toxicology and oxygen level or control sintering after carbon content).Compare special-purpose pre-alloyed powder, it is also favourable utilizing pre-alloyed powder significantly to improve extrudability by part.
Therefore, as shown in table 1, the first and second cementing metal powder are particularly advantageous with the formula of the ratio existence of 1: 1:
Table 1:
| Numbering | The composition of the first cementing metal powder | The alloying element ratio of the first cementing metal powder | The composition of other cementing metal powder | The alloying element ratio of the second cementing metal powder |
| 1.01 | FeCo | 50∶50 | FeNi | 30∶70 |
| 1.02 | FeCoNi | 90∶5∶5 | FeNi | 30∶70 |
| 1.03 | FeCo | 50∶50 | FeNi | 50∶50 |
| 1.04 | FeCoNi | 90∶5∶5 | FeNi | 50∶50 |
| 1.05 | FeCo | 50∶50 | FeNi | 95∶5 |
| 1.06 | FeCoNi | 90∶5∶5 | FeNi | 95∶5 |
| 1.07 | CrCo | 50∶50 | FeNi | 30∶70 |
| 1.08 | CrCoNi | 90∶5∶5 | FeNi | 30∶70 |
| 1.09 | CrCo | 50∶50 | FeNi | 50∶50 |
| 1.10 | CrCoNi | 90∶5∶5 | FeNi | 50∶50 |
| 1.11 | CrCo | 50∶50 | FeNi | 95∶5 |
| 1.12 | CrCoNi | 90∶5∶5 | FeNi | 95∶5 |
| 1.13 | MnCo | 50∶50 | FeNi | 30∶70 |
| 1.14 | MnCoNi | 90∶5∶5 | FeNi | 30∶70 |
| 1.15 | MnCo | 50∶50 | FeNi | 50∶50 |
| 1.16 | MnCoNi | 90∶5∶5 | FeNi | 50∶50 |
| 1.17 | MnCo | 50∶50 | FeNi | 95∶5 |
| 1.18 | MnCoNi | 90∶5∶5 | FeNi | 95∶5 |
| 1.19 | TiCo | 50∶50 | FeNi | 30∶70 |
| 1.20 | TiCoNi | 90∶5∶5 | FeNi | 30∶70 |
| 1.21 | TiCo | 50∶50 | FeNi | 50∶50 |
| 1.22 | TiCoNi | 90∶5∶5 | FeNi | 50∶50 |
| 1.23 | TiCo | 50∶50 | FeNi | 95∶5 |
| 1.24 | TiCoNi | 90∶5∶5 | FeNi | 95∶5 |
| 1.25 | AlCo | 50∶50 | FeNi | 30∶70 |
| 1.26 | A1CoNi | 90∶5∶5 | FeNi | 30∶70 |
| 1.27 | AlCo | 50∶50 | FeNi | 50∶50 |
| 1.28 | AlCoNi | 90∶5∶5 | FeNi | 50∶50 |
| 1.29 | AlCo | 50∶50 | FeNi | 95∶5 |
| 1.30 | AlCoNi | 90∶5∶5 | FeNi | 95∶5 |
| 1.31 | VCo | 50∶50 | FeNi | 30∶70 |
| 1.32 | VCoNi | 90∶5∶5 | FeNi | 30∶70 |
| 1.33 | VCo | 50∶50 | FeNi | 50∶50 |
| 1.34 | VCoNi | 90∶5∶5 | FeNi | 50∶50 |
| 1.35 | VCo | 50∶50 | FeNi | 95∶5 |
| 1.36 | VCoNi | 90∶5∶5 | FeNi | 95∶5 |
| 1.37 | FeCoNi | 40∶20∶40 | FeNi | 50∶50 |
| 1.38 | FeCoNi | 40∶20∶40 | Ni | 100 |
| 1.39 | FeCoNi | 40∶20∶40 | Fe | 100 |
| 1.40 | CrCoNi | 40∶20∶40 | FeNi | 50∶50 |
| 1.41 | CrCoNi | 40∶20∶40 | Ni | 100 |
| 1.42 | CrCoNi | 40∶20∶40 | Fe | 100 |
| 1.43 | MnCoNi | 40∶20∶40 | FeNi | 50∶50 |
| 1.44 | MnCoNi | 40∶20∶40 | Ni | 100 |
| 1.45 | MnCoNi | 40∶20∶40 | Fe | 100 |
| 1.46 | TiCoNi | 40∶20∶40 | FeNi | 50∶50 |
| 1.47 | TiCoNi | 40∶20∶40 | Ni | 100 |
| 1.48 | TiCoNi | 40∶20∶40 | Fe | 100 |
| 1.49 | AlCoNi | 40∶20∶40 | FeNi | 50∶50 |
| 1.50 | AlCoNi | 40∶20∶40 | Ni | 100 |
| 1.51 | AlCoNi | 40∶20∶40 | Fe | 100 |
| 1.52 | VCoNi | 40∶20∶40 | FeNi | 50∶50 |
| 1.53 | VCoNi | 40∶20∶40 | Ni | 100 |
| 1.54 | VCoNi | 40∶20∶40 | Fe | 100 |
The formula of preferred table 2 and table 3.
Table 2: table 2 shows 54 kinds of formulas that are numbered 2.01-2.54, identical in the alloying element ratio of their the first cementing metal powder, other cementing metal powder and the first cementing metal powder and the second cementing metal powder and table 1, the first cementing metal powder and other cementing metal powder exist with the ratio of 1: 2.This means, in the situation that formula 2.01, the first powdered alloys are FeCo
50/50, other powdered alloy is FeNi 30/70, and the ratio of FeCo and FeNi is 1: 2.
Table 3: table 3 shows 54 kinds of formulas that are numbered 3.01-3.54, identical in the alloying element ratio of their the first cementing metal powder, other cementing metal powder and the first cementing metal powder and the second cementing metal powder and table 1, the first cementing metal powder and other cementing metal powder exist with the ratio of 2: 1.This means, in the situation that formula 3.01, the first powdered alloys are FeCo50/50, other powdered alloy is FeNi 30/70, and the ratio of FeCo and FeNi is 2: 1.
Therefore, the invention provides the metal formulations that comprises at least a hard material powder and at least two kinds of cementing metal powder, it is characterized in that, all cobalts be present in the first cementing metal powder and with one or more periodic table of elements in the element of period 4,3-8 family pre-alloyed, there is at least a other cementing metal powder, this other cementing metal powder is from the powder of the mutual alloy of element of Fe, Ni, Al, Mn, Cr and these elements, and this other cementing metal powder does not contain the cobalt of any non-pre-alloyed form;
Or
the metal formulations that comprises at least a hard material powder and at least two kinds of cementing metal powder, it is characterized in that, all cobalts are present in the first cementing metal powder and are pre-alloyed with the element of one or more periodic table of elements 3-8 family, there is at least a other cementing metal powder, this other cementing metal powder is from element of Fe, Ni, Al, Mn, the powder of the alloy that Cr and these elements are mutual, and this other cementing metal powder does not contain the cobalt of any non-pre-alloyed form, wherein, free corrosion potential between the mechanically resistant material of measuring in air saturation water when normal atmosphere and room temperature and the first cementing metal powder is less than 0.300 volt (preferably less than 0.280 volt), mechanically resistant material has straight polarity,
Or
The metal formulations that comprises at least a hard material powder and at least two kinds of cementing metal powder, it is characterized in that, all cobalts be present in the first cementing metal powder and with one or more periodic table of elements in the element of 3-8 family pre-alloyed, use at least a other cementing metal powder, this other cementing metal powder is selected from iron powder, nickel powder, FeNi powdered alloy and pre-alloyed FeNi powdered alloy, and this other cementing metal powder does not contain the cobalt of any non-pre-alloyed form.In these three kinds of metal formulations, the mechanically resistant material of existence can be titanium carbide, vanadium carbide, molybdenum carbide or wolfram varbide particularly more than all, and advantageously, their BET surface-area is greater than 0.3m
2/ g, more preferably greater than 0.5m
2/ g, special excellently greater than 1m
2/ g.
In yet another embodiment of the present invention, in above metal formulations in the first cementing metal powder the alloy companion of cobalt be the period 4 element;
Perhaps, in above metal formulations in the first cementing metal powder the alloy companion of cobalt be the element that is selected from Fe, Ni, Cr, Mn, Ti and Al;
Or
In above metal formulations, the first cementing metal powder can contain the element of other alloying, and aluminium and/or copper (Cu) can be used as other element.
In yet another embodiment of the present invention, except the first cementing metal powder, exist one or more to be selected from other cementing metal powder of iron powder, nickel powder, FeNi powdered alloy and pre-alloyed FeNi powdered alloy.
In these metal formulations, the free corrosion potential between the mechanically resistant material of measuring in air saturation water when normal atmosphere and room temperature and the first cementing metal powder is less than 0.300 volt more than all, and mechanically resistant material has straight polarity.
The mechanically resistant material that can exist can be titanium carbide, vanadium carbide, molybdenum carbide or wolfram varbide particularly, and advantageously, their BET surface-area is greater than 0.3m
2/ g, more preferably greater than 0.5m
2/ g, special excellently greater than 1m
2/ g.
In all this metal formulations, the weight ratio of the first cementing metal powder and other cementing metal powder advantageously 1: 10-10: 1.
All this metal formulations can advantageously contain: a) pre-alloying powder of at least a chosen from Fe/cobalt and iron/nickel/cobalt; B) at least a element powders, its chosen from Fe, nickel, or from a) the different pre-alloying powder that comprises iron and nickel of component; C) hard material powder, wherein component a) and b) total composition comprise maximum 90% cobalt and the nickel of maximum 70 % by weight.In this metal formulations, iron level is at least 10 % by weight advantageously.
In this metal formulations, the Co of advantageously maximum 90 % by weight of total composition of binding agent, the Ni of maximum 70 % by weight and the Fe of at least 10 % by weight, wherein iron level satisfies with lower inequality
This metal formulations is conducive to various application and can be for the production of gluing together mechanically resistant material or producing porous sintered agglomerate.
This porous agglomerate can obtain by the above a kind of metal formulations of sintering (not pushing).
Contain can be by the above a kind of metal formulations of sintering (not pushing) that obtain and thermal spray powder porous agglomerate that contain Al, yttrium and/or rare earth element be also suitable.
The present invention also provides the method for controlling the toxic effect that contains the cobalt metal formulations, it is characterized in that, and above a kind of metal formulations, advantageously, the metal formulations shown in table 1-3 is for the production of gummed mechanically resistant material or porous sintered agglomerate.
Usually, the invention provides the method for controlling the toxic effect contain the cobalt metal formulations, it is characterized in that, the element of cobalt and one or more periodic table of elements 3-8 family is pre-alloyed in metal formulations.
Therefore, the present invention also provides the method for controlling the toxic effect that contains the cobalt metal formulations, and wherein, metal formulations of the present invention, porous agglomerate of the present invention or thermal spray powder of the present invention are for the production of the article or the coating that are shaped.Contain in the method for toxic effect of cobalt metal formulations toxicological effect pulmonary fibrosis specifically and/or disease gummed carbide lung in control.
Because the high bioavailability of cobalt is based on the galvanic corrosion phenomenon, so, according to the present invention, free corrosion potential between the mechanically resistant material of measuring in air saturation water when normal atmosphere and room temperature and the first cementing metal powder less than 0.380 volt, preferably less than 0.330 volt, especially less than 0.300, particularly advantageously less than 0.280 volt, wolfram varbide has straight polarity.Fig. 1 has schematically shown experimental installation used.The positive electrode that reference number 1 representative is comprised of wolfram varbide (or other mechanically resistant material), 2 represent that 3 represent reaction medium-air saturation tap water by the binder metal negative potential that forms of cobalt of the present invention or binder metal formula for example.
Yet when cobalt and iron became alloy, even iron is more easily had an effect than cobalt, touch voltage also descended in surprise.The reason of this phenomenon is also unknown.Easily understand, the free corrosion potential of decline causes the motivating force of corrosion phenomenon to reduce or corrodes carrying out slowlyer, so bioavailability similarly reduces.Therefore, the free corrosion potential of the measuring apparatus described in embodiment 4 can serve as the indication of the expection toxicity on inhalation of mechanically resistant material/cementing metal formula.Another indication of expection toxicity on inhalation be when oxygen exists in the amount of the cementing metal of determining to dissolve in the time, described cementing metal contact the rear solution that just enters immediately at corresponding contact member with water.
The reason of toxicity on inhalation phenomenon can only interact to explain with the height of organism with the dust that is inhaled into, it must be the synergy between two kinds of component cobalts and mechanically resistant material, because have been found that in them, any one does not show this character individually, this learns from document.And, owing to having been found that in the present invention toxicity depends on the intensity of the geometrical contact of two kinds of components, so the seemingly possible explanation of toxicological effect of increase of the bioavailability that is caused by corrosion.The gummed mechanically resistant material is called as the crevice corrosion composition for a long time always.For example, become known for cobalt in the water base cooling fluid optimum solvation gummed mechanically resistant material of grinding gummed mechanically resistant material.Megede (
Frankfurt a.Main, 1985) theoretical detailed inspection mechanism wherein: under the existence of water and oxygen, cobalt corrodes and forms by the oxygen reduction principle hydroxide layer that effects on surface has passivation.In the hydroxide anion forming process, wolfram varbide catalysis transfer transport makes corrosion greatly accelerate and carry out partly.Therefore, the passivation of hydroxide layer is undermined.Similarly, this has also explained and why has found wolfram varbide in gummed carbide lung and do not find that cobalt-cobalt obviously is corroded and absorbs with accelerated manner again.The bioavailability increase of the low dose that causes thus/concentration cobalt causes chronic disease (pulmonary fibrosis or " gummed carbide lung "), causes the hypertoxicity phenomenon in the high density situation.The bioavailability of cobalt has side effect to organism, and its mechanism is not also illustrated up to now fully.It is upper or make the reactive oxygen species material such as the peroxide anionic stabilization by forming complex compound that tentative explanation comprises that ionic cobalt is added DNA to, and this is the effect of well-known cobalt.
In the situation that gummed mechanically resistant material and carbide spraying powder, by adding chromium carbide or chromium metal can improve solidity to corrosion in formula, solidity to corrosion is measured by the chemical erosion to binding agent.In both cases, after sintering or thermospray, chromium partly is present in binding agent with alloy form.If the concentration of chromium enough high (this can control by the mode of carbon balance) in binding agent, the solidity to corrosion of gluing together so mechanically resistant material or sprayed coating is much bigger, therefrom can draw such conclusion, in the situation that this gummed mechanically resistant material of grinding or spraying excessively, the toxicity of dust must be significantly less than pure WC-Co.Can be by further improving solidity to corrosion with nickel Partial Replacement cobalt, similarly, this is the industrial practice in gummed mechanically resistant material situation.
Corrosion speed when in a word, the severe toxicity effect of gummed mechanically resistant material dust exists to water and oxygen is relevant.By making cobalt and (for example) iron become alloy, can reduce free corrosion potential, cause the pre-alloyed violent toxicity on inhalation that contains the cobalt formula of cobalt and iron obviously to reduce.This viewpoint is subject to the support that following research is found, when air exists, the gummed mechanically resistant material that binder phase contains cobalt and iron has better resistance to oxidation acid corrosion (TU Wien, the paper of Wittmann (thesis by Wittmann), 2002) than the material of pure cobalt binder.
Can foretell, some intermediates during the gummed mechanically resistant material is produced are toxicity on inhalation especially, comprises particularly the dust from the ground finish (" grey processing ") of presintering gummed mechanically resistant material part.At this, formula be extruded and at lower than the temperature of melt eutectic sintering (" presintering ") so that the sintered compact that pending ground finish arranged is because the sintering bridge obtains enough physical strengths.Under this state, sintered compact remains porous, no longer contains any organic additive, and the powder of use is also unbalanced in formula, so cobalt still mainly exists with element form.This point is combined with the vesicular structure of grinding dust, means that very high toxicity on inhalation is in accordance with expectation.Even in the situation that not only use cobalt metal powder in the production of described formula but also the use iron metal powder, can not expect that toxicity can reduce, because in fact the phase mutual diffusion (formation of=alloy) between cobalt and iron particle does not occur in the presintering process.
So the spraying powder of making from particulate state formula sintering is because its size is difficult to be dispersed in air, but the toxicity of the fines that sucks that forms due to the internal friction in the powder treatment process but very high (seeing embodiment 1e).
For example, formula of the present invention can be used for producing gummed mechanically resistant material or porous sintered agglomerate, and this porous sintered agglomerate can be advantageously used in the thermal spray powder.The gummed mechanically resistant material that has based on the binder system of (especially) FeCoNi all provides the technical superiority of the material that is better than pure cobalt binder according to forming in many application, therefore, they are favourable according to the present invention.
According to the present invention, pre-alloyed powder is the metal-powder that contains the adhesive composition that relates to Fe, Co and Ni content, and each powder particle exists with the atomic dispersion form.In meaning of the present invention, pre-alloyed powder can be the powdered alloy of being made by melt atomizing or the powdered alloy that obtains by precipitation and reduction, for example described in US-B-6554885, EP-A-1079950 and the document wherein quoted, perhaps, can produce by other suitable substantially method such as carbonyl process, plasma method, CVD etc.; The powdered alloy that can obtain by precipitation and reduction described in US-B-6554885, EP-A-1079950 and the document wherein quoted, is for example favourable.The production of carbide spraying powder is corresponding to the production of granular formula in the production of gummed mechanically resistant material, but pellet is not extruded, but similarly lower than or little higher than the temperature of minimum eutectic temperature under sintering, then classification.In this step, the organic additive of existence is removed.The particle that obtains in this way remains porous, has the sintering neck between the particle that represents cementing metal phase and mechanically resistant material.
The binder phase of spraying powder can also contain other element, such as Al, rare earth element, yttrium except containing above-mentioned element and inorganic additives.
Formula for the production of gummed mechanically resistant material and spraying powder not only contains above-mentioned inorganic components usually, also contain organic additive, such as paraffin, polyoxyethylene glycol, inhibitor, they help further processing and process, and no longer are present in the spraying powder but no longer be present in the gummed mechanically resistant material or after lighting.These formulas can become particle by for example spraying drying.Also may there be softening agent (being used for extruding) for example polyethylene and paraffin, wedding agent such as carboxylic acid and dispersion agent.
The industry custom formula that is comprised of mechanically resistant material and cementing metal always contains aerobic because owing to processing in air, grinding in waterborne liquid and mixing and subsequently drying, the surface coverage of powder water and oxyhydroxide.The oxygen that exists in heat treatment process subsequently with formula in be present in carbide in carbon or the carbon of element form react to form carbon monoxide and carbonic acid gas, therefore, upset sintered compact or the metal content of spraying powder and the balance between carbon content, and this balance must be kept strictly.In a word, the oxygen level of formula must remain on alap level, in order to can control better the metal/carbon balance.
Embodiment
Embodiment
Britain Camb Heng Tingdeng life science company limited (Huntingdon Life Sciences Ltd.) represents that the applicant implements as all embodiment that suck research, and these researchs are stipulated by EEC (appendix II.5.2.3).The powder atomization that makes examine is aerosol, it is blown into is placed with the indoor of 10 rats.Aerocolloidal concentration is in mg/l, and mean particle size is in μ m.Ratio with the particle of percentage ratio record＞7 μ m; Hour be abbreviated as h.Dust concentration in measuring chamber and particle size distribution (Marple cascade impactor 298 types (Marple Cascade Impactor Mod.), by State of Georgia, US Atlanta Ge Lisi white-Arthur Andersen company limited (Graseby Andersen Inc.) makes).After 4 hours, determine the quantity of that die or dying rat, sum is recorded as mortality ratio.
Embodiment 1) toxicity on inhalation of WC/Co formula
A) produce the tungsten-cobalt carbide matrix material described in WO 01/46484 A1.It contains 10% cobalt.In this matrix material, cobalt granule contacts very close with tungsten carbide particle.When the concentration of 0.25mg/l, the result that sucks experiment is 100% mortality ratio.Indoor mean particle size is 2.5 μ m, and 90% particle is less than 7 μ m.
B) produce the mixture of wolfram varbide and cobalt metal powder, wherein contain the cobalt of 10 % by weight, repeat to suck experiment under three concentration:
| Effective concentration | Mortality ratio | Mean particle size | The ratio of＜7 μ m |
| 0.24 | 30 | 4 | 75 |
| 0.52 | 100 | 4.2 | 74 |
C) produce the mixture of cobalt and wolfram varbide, wherein contain 6% cobalt.When effective aerosol load of 0.26mg/l, the result that sucks experiment is: 0%, but stopping after the indoor introducing aerosol 3 days, 20% death.Mean particle size is 3.8 μ m, all particles 79% less than 7 μ m.
D) grind the mixture (wherein containing 10% cobalt) of wolfram varbide and cobalt, make it mix 4h as the dispersion in hexane.1h before grinding end, adding paraffin in order to make the ratio of paraffin in formula is (based on solids content) 2 % by weight.After grinding and mixing 4h, remove hexane in order to form the powder that contains paraffin by vacuum distilling.Use this powder to implement to suck experiment under three aerosol loads, obtain following result:
| Effective aerosol load | Mortality ratio | Mean particle size | The ratio of＜7 μ m |
| 0.24 | 0％ | 3.2 | 87 |
| 1.08 | 20％ | 4.2 | 83 |
E) inspection contains 17% cobalt and has the fixedly porous sintered tungsten carbide-cobalt dust of size-grade distribution of 5-30mm in inhalation test, obtain following result: effectively aerosol load floats in the 1.01-0.93mg/l scope, mortality ratio is 60%, the indoor mean particle size of surveying is 5.2-5.6 μ m, and approximately 20% particle is less than 7 μ m.
This result demonstration, the toxicity on inhalation of WC/Co formula depends on various factors.
Embodiment a) shows high toxicity.Due to its mode of production, it provides contact measurement value maximum between cobalt granule and tungsten carbide particle.
Embodiment b) toxicity is less, and the cobalt granule of this powdered mixture and the contact between WC particle will be lacked a lot.
Embodiment c) similarly again show the effect that reduces, the cobalt contents of this powdered mixture reduces.
Embodiment d) implement with two concentration, show less toxic effect.Due to the grinding of masher, the contact meeting between cobalt granule and tungsten carbide particle is very strong, so the hydrophobization effect (hydrophobicization) that the paraffin (2 % by weight are corresponding to 25 volume %) that the reason that toxicity reduces is existence causes.
Embodiment e) show the toxicity of the general powder that is used for thermal spray.Should be noted that because particle is thicker, only the part powder can enter in lung herein, but great mortality ratio still occurs.
, can see a)-f) time when comparing embodiment, the ability in entering lung and arbitrarily the hydrophobization reagent of content, the contact strength between Co and WC is the major effect parameter that acts on the toxicity on inhalation degree.
Embodiment 2) toxicity on inhalation of WC/FeCo formula
A) comprise 70.6% wolfram varbide, 14.8% cobalt and 12.2% iron from the general industry gummed carbide lapping powder of final processing (grind gummed carbide), show 70% mortality ratio in sucking experiment.Effectively aerosol load is 0.28mg/l, and mean particle size is 4.3 μ m.All particles 76% less than 7 μ m.
B) as embodiment 1d) described in, grind the mixture that comprises 90% wolfram varbide, 5% iron powder and 5% cobalt metal powder in masher, but do not add paraffin.Due to the deformation process that grinding causes, iron and cobalt mutually combine, and part is mechanically smeared mutually, but do not become alloy.Use 2 results that suck experiment of this powder as follows:
| Effective aerosol load | Mortality ratio | Mean particle size | The ratio of＜7 μ m |
| 0.25 | 0 | 2.8 | 86 |
| 1.03 | 30％ | 3.2 | 85 |
C) described in WO 01/46484 A1, produce the matrix material that contains 5% iron, 5% cobalt and 90% wolfram varbide.Herein, iron and cobalt fully form alloy mutually.In one sucks experiment, obtain following result:
| Effective aerosol load | Mortality ratio | Mean particle size | The ratio of＜7 μ m |
| 0.988 | 0 | 3 | 94 |
| 5.03 | 0 | 3.7 | 84 |
As the general industry lapping powder from the final processing grinding of carbide (gummed), compare, embodiment a) shows very high toxicity.12% iron level is to be caused by the wearing and tearing of abrasive disk and other pollutent, but irrelevant with the final processing of the gummed carbide with iron content binder system.Therefore, this iron level does not occur pre-alloyed with cobalt.This lapping powder is not the formula in meaning of the present invention, because it is not produced in the target mode, and cobalt is not pre-alloyed with iron.
Embodiment b), use element powders Fe and Co to make, its toxicity order of magnitude is similar to the formula of the masher grinding that contains 5%Co (there is no other additive).
Embodiment c) even also do not show any toxicity when the concentration of 5mg/l, although in this case, WC particle and the 1a as embodiment that contacts between pre-alloyed FeCo particle) in strong, and the mode of production of matrix material is similar.
Embodiment 3) toxicity on inhalation of WC/FeNi formula
Use the mixture of 10% pre-alloyed FeNi 50/50 and 90% wolfram varbide to implement to suck experiment.Wherein, even when effective aerosol load of 0.53-5.22mg/l, mortality ratio is also 0%.
This embodiment shows that this is owing to the shortage of cobalt without violent toxicity on inhalation appearance.
Embodiment 4): the free corrosion potential of WC/Co and WC/FeCo contact member
In thermocompressor in the time of 2200 ℃ the hot pressing tungsten-carbide powder take production density as 15.68g/cm
3The solid of (corresponding to theoretical density).And, extruding cobalt metal powder and pre-alloyed iron-cobalt metal powder (cobalt contents: 50%) to obtain almost having the DB of theoretical density in the time of 1000 ℃.In first experiment, by two kinds of solid members being provided and being used for measuring the power stage electrode of touch voltage and this device partly being immersed the air saturation tap water, measure the touch voltage of electrochemistry galvanic couple tungsten carbide/cobalt.When two solids do not contact mutually, record the difference of 0.330 volt, cobalt has negative polarity with respect to wolfram varbide.This difference stands for freedom corrosion potential.When solid contacts (short circuit), record the difference of 0.04mV, observe reversal of poles.
Use the solid members of being made by FeCo to replace the cobalt solid members to repeat this measurement.The free corrosion potential value that records is 0.240 volt, and polarity is kept former state.When FeCo contacts with the wolfram varbide solid, record the difference of 0.007mV, reversal of poles occurs.
When mutual comparing embodiment 1)-3) time, very clear, the existence of the element cobalt that contacts with wolfram varbide is the prerequisite that necessity of toxicity on inhalation occurs, still, when cobalt and the iron of equal umber are pre-alloyed, at least 20 times required of concentration increases or more.
Embodiment 4) show, the touch voltage between WC and cobalt or free corrosion potential (according to electrochemistry law known to those skilled in the art, it depends on molecule oxygen concentration in water fatefully) have played significant effect.The 0.33V that herein records can compare (R﹠amp by the value 0.301-0.384V that the potential determination of gummed carbide obtains with the people such as Mori fully; HM 21,135 (2003)).Yet when cobalt and iron became alloy, even iron is more easily had an effect than cobalt, touch voltage also descended in surprise.The reason of this phenomenon is also unknown.Can easily see, the free corrosion potential of decline causes the motivating force of corrosion phenomenon to reduce or corrodes carrying out slowlyer, so bioavailability similarly reduces.Therefore, the free corrosion potential of the measuring apparatus described in embodiment 4 can serve as the indication of the mechanically resistant material of expection/cementing metal formula toxicity on inhalation.Another indication of expection toxicity on inhalation be when oxygen exists in the amount of the cementing metal of determining to dissolve in the time, described cementing metal contact the rear solution that just enters immediately at corresponding contact member with water.
Fig. 2 shows aerosol load with respect to the chart of mortality ratio, and it is assigned to each embodiment.
Claims (22)
1. the metallic substance that comprises at least a hard material powder and at least two kinds of cementing metal powder, it is characterized in that, all cobalts be present in the first cementing metal powder and with one or more periodic table of elements in the element of period 4,3-8 family pre-alloyed, and there is at least a other cementing metal powder, this other cementing metal powder is from the powder of the mutual alloy of element of Fe, Ni, Al, Mn, Cr and these elements, and this other cementing metal powder does not contain the cobalt of any non-pre-alloyed form.
2. the metallic substance that comprises at least a hard material powder and at least two kinds of cementing metal powder, it is characterized in that, all cobalts are present in the first cementing metal powder and are pre-alloyed with the element of one or more periodic table of elements 3-8 family, and there is at least a other cementing metal powder, this other cementing metal powder is from element of Fe, Ni, Al, Mn, the powder of the alloy that Cr and these elements are mutual, and this other cementing metal powder does not contain the cobalt of any non-pre-alloyed form, wherein, free corrosion potential between the mechanically resistant material of measuring in air saturation water when normal atmosphere and room temperature and the first cementing metal powder is less than 0.300 volt, described mechanically resistant material has straight polarity.
3. the metallic substance that comprises at least a hard material powder and at least two kinds of cementing metal powder, it is characterized in that, all cobalts be present in the first cementing metal powder and with one or more periodic table of elements in the element of 3-8 family pre-alloyed, and use at least a other cementing metal powder, this other cementing metal powder is selected from iron powder, nickel powder, FeNi powdered alloy and pre-alloyed FeNi powdered alloy, and this other cementing metal powder does not contain the cobalt of any non-pre-alloyed form.
4. metallic substance as claimed in claim 2, is characterized in that, in described the first cementing metal powder, the alloy companion of cobalt is the element of period 4.
5. metallic substance as claimed in claim 1 or 2, is characterized in that, in described the first cementing metal powder, the alloy companion of cobalt is the element that is selected from Fe, Ni, Cr, Mn, Ti and Al.
6. metallic substance as described in any one in claim 1-4, is characterized in that, described the first cementing metal powder can contain other element of alloy form.
7. metallic substance as claimed in claim 6, is characterized in that, Al and/or Cu are as other element.
8. as the described metallic substance of any one in claim 1-2,4 and 7, it is characterized in that, except the first cementing metal powder, use one or more to be selected from other cementing metal powder of iron powder, nickel powder, FeNi powdered alloy and pre-alloyed FeNi powdered alloy.
9. metallic substance as described in any one in claim 1 and 3, it is characterized in that, free corrosion potential between the mechanically resistant material of measuring in air saturation water when normal atmosphere and room temperature and the first cementing metal powder is less than 0.300 volt, and described mechanically resistant material has straight polarity.
10. metallic substance as described in any one in claim 1-4 and 7, is characterized in that, described mechanically resistant material contains titanium carbide, vanadium carbide, molybdenum carbide or wolfram varbide.
11. metallic substance as claimed in claim 10 is characterized in that, the BET surface-area of described mechanically resistant material is greater than 0.3m
2/ g.
12. as the described metallic substance of any one in claim 1-4,7 and 11, it is characterized in that, the weight ratio of described the first cementing metal powder and described other one or more cementing metal powder is 1:10-10:1.
13. as the described metallic substance of any one in claim 1-4,7 and 11, it is characterized in that, it contains a) pre-alloying powder of at least a chosen from Fe/cobalt and iron/nickel/cobalt; B) at least a element powders, its chosen from Fe, nickel, or from a) different pre-alloyed powder that formed by iron/nickel of component; C) hard material powder, wherein component a) and b) total composition comprise maximum 90% cobalt and the nickel of maximum 70 % by weight.
14. metallic substance as claimed in claim 13 is characterized in that, described iron level is at least 10 % by weight.
15. metallic substance as claimed in claim 1 is characterized in that, total composition of described binding agent is the Ni of the Co of maximum 90 % by weight, maximum 70 % by weight and the Fe of at least 10 % by weight, and wherein iron level satisfies with lower inequality
16. the application of the described metallic substance of any one in producing the gummed mechanically resistant material in claim 1-15.
17. the application of the described metallic substance of any one in producing porous sintered agglomerate in claim 1-15.
18. the porous agglomerate, it is not by in the situation that push and the described metallic substance of any one in claim 1-15 is carried out sintering obtain.
19. the thermal spray powder, it comprises the described porous agglomerate of claim 18 and Al and/or rare earth element.
20. thermal spray powder as claimed in claim 19 is characterized in that described rare earth element is yttrium.
21. a control contains the method for the toxic effect of cobalt metallic substance, it is characterized in that, with the described metallic substance of any one in claim 1-15 for the production of gummed mechanically resistant material or porous sintered agglomerate.
22. a control contains the method for the toxic effect of cobalt metallic substance, it is characterized in that, with object or the coating for the production of shaping of the described metallic substance of any one, the described agglomerate of claim 18 or the described thermal spray powder of claim 19 or 20 in claim 1-15.
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| DE102007004937.6 | 2007-01-26 | ||
| DE102007004937A DE102007004937B4 (en) | 2007-01-26 | 2007-01-26 | metal formulations |
| PCT/EP2008/050845 WO2008090208A1 (en) | 2007-01-26 | 2008-01-25 | Metal formulations |
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| CN101589166A CN101589166A (en) | 2009-11-25 |
| CN101589166B true CN101589166B (en) | 2013-06-26 |
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| US (1) | US20100077887A1 (en) |
| EP (1) | EP2126148A1 (en) |
| JP (1) | JP2010516896A (en) |
| KR (1) | KR20090107554A (en) |
| CN (1) | CN101589166B (en) |
| BR (1) | BRPI0807178A2 (en) |
| CA (1) | CA2674928A1 (en) |
| DE (1) | DE102007004937B4 (en) |
| MX (1) | MX2009007484A (en) |
| RU (1) | RU2483833C2 (en) |
| WO (1) | WO2008090208A1 (en) |
| ZA (1) | ZA200904268B (en) |
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| CN102179511A (en) * | 2011-04-21 | 2011-09-14 | 北京矿冶研究总院 | Preparation method of porous MCrAlY alloy powder for thermal spraying |
| ES2628422T3 (en) | 2011-05-27 | 2017-08-02 | H.C. Starck Gmbh | FeNi binder with universal applicability |
| DE102011112435B3 (en) * | 2011-09-06 | 2012-10-25 | H.C. Starck Gmbh | Cermet powder, process for producing a cermet powder, use of the cermet powder, process for producing a coated part, coated part |
| DE102013220040A1 (en) | 2013-10-02 | 2015-04-02 | H.C. Starck Gmbh | Sintered spray powder based on molybdenum carbide |
| CN104400080B (en) * | 2014-09-23 | 2017-04-05 | 宁波市荣科迈特数控刀具有限公司 | A kind of depth drill |
| CN104625078B (en) * | 2015-02-14 | 2018-01-09 | 江苏和鹰机电科技有限公司 | Hard alloy cutter for cutting carbon fiber or glass fibre and preparation method thereof |
| CN104831216A (en) * | 2015-05-09 | 2015-08-12 | 芜湖鼎恒材料技术有限公司 | Ni-Co-Mo-Mn nanocoating material and preparation method thereof |
| CN104831213A (en) * | 2015-05-09 | 2015-08-12 | 安徽鼎恒再制造产业技术研究院有限公司 | Ni-Co-Mo-Mn material and preparation method thereof |
| KR20190021816A (en) * | 2017-08-24 | 2019-03-06 | 주식회사 포스코 | Metal alloy powder and method for producing the same |
| TWI804570B (en) * | 2018-01-31 | 2023-06-11 | 日商博邁立鋮股份有限公司 | Composite rolls made of superhard alloy and superhard alloy for rolling |
| CN109280838B (en) * | 2018-11-30 | 2020-11-06 | 宇龙精机科技（浙江）有限公司 | Titanium-cobalt alloy and preparation method thereof |
| CN111826569A (en) * | 2020-07-21 | 2020-10-27 | 广东正信硬质材料技术研发有限公司 | Wear-resistant high-hardness hard alloy drilling tool and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| MX2009007484A (en) | 2009-07-22 |
| DE102007004937A1 (en) | 2008-07-31 |
| US20100077887A1 (en) | 2010-04-01 |
| WO2008090208A1 (en) | 2008-07-31 |
| DE102007004937B4 (en) | 2008-10-23 |
| CN101589166A (en) | 2009-11-25 |
| BRPI0807178A2 (en) | 2014-05-27 |
| CA2674928A1 (en) | 2008-07-31 |
| RU2009132002A (en) | 2011-03-10 |
| RU2483833C2 (en) | 2013-06-10 |
| EP2126148A1 (en) | 2009-12-02 |
| JP2010516896A (en) | 2010-05-20 |
| ZA200904268B (en) | 2010-08-25 |
| KR20090107554A (en) | 2009-10-13 |
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