CN101018632A - 冶金涂覆颗粒 - Google Patents
冶金涂覆颗粒 Download PDFInfo
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- CN101018632A CN101018632A CNA03801582XA CN03801582A CN101018632A CN 101018632 A CN101018632 A CN 101018632A CN A03801582X A CNA03801582X A CN A03801582XA CN 03801582 A CN03801582 A CN 03801582A CN 101018632 A CN101018632 A CN 101018632A
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- 239000002245 particle Substances 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims abstract description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 239000010955 niobium Substances 0.000 claims abstract description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004767 nitrides Chemical class 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 metal oxide hydroxide compound Chemical class 0.000 claims description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 235000019580 granularity Nutrition 0.000 description 9
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 229940011182 cobalt acetate Drugs 0.000 description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 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 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910001029 Hf alloy Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- NUHXWPRATKOXDB-UHFFFAOYSA-L diazanium;cobalt(2+);disulfate Chemical compound [NH4+].[NH4+].[Co+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NUHXWPRATKOXDB-UHFFFAOYSA-L 0.000 description 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical group 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
Classifications
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
-
- 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
- B22F1/18—Non-metallic particles coated with metal
-
- 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
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明涉及一种用金属涂覆硬颗粒的方法，所述方法包括如下顺序的步骤(i)形成硬颗粒的含水浆液，(ii)向浆液添加一种或多种金属盐的水溶液，所述溶液具有从0.1m至1.6m的重量摩尔浓度，(iii)调节浆液/金属盐溶液的pH值在7至14之间，从而给硬颗粒涂覆金属盐，(iv)在升高的压力下将金属盐－涂覆颗粒浆液加热到一个升高的温度，以便将所述金属盐转化为金属氧化物，金属氧化物氢氧化物复合物(oxidehydroxide)，或金属氢氧化物，和(v)在所述升高的温度和压力下，将金属氧化物，金属氧化物氢氧化物复合物，或金属氢氧化物还原成组成金属，以形成所述金属涂覆硬颗粒，其中，硬颗粒是钨，钛，钽，铌，钼，铬，钒，锆，和铪中的一种或多种的碳化物，碳氮化物和氮化物中的一种或多种，所述金属是钴，镍和铁中的一种或多种。
Description
技术领域
本发明涉及一种用粘结料金属制造冶金涂覆颗粒的方法，还涉及由此形成的颗粒。
背景技术
在粉末冶金制造硬质合金或金属陶瓷的初始阶段，金属例如钨，钛，钽，铌，钼，铬，钒，锆，和铪的硬质合金，碳氮化物和/或氮化物(以下称之为“硬颗粒”)与适当的粘结料金属(典型的如钴，镍，铁，或者两种或多种这些金属的结合)混合。为了获得最终的密实烧结合金的最佳机械性能，最好尽可能实现均匀地混合。传统上，这是通过将组成的粉末一起磨碎来实现：在球式，棒式或研磨机式粉碎磨机中，利用硬质合金研磨体和载液例如水，乙醇，丙酮或己烷。生成的浆液添加适当的润滑剂(例如固体石蜡，聚乙二醇等)，并通过公知的方法(例如喷雾干燥)干燥和凝聚，以形成自由流动的结块。这种结块适合在自动压力机中压实，以形成几何结构，然后，在大气中或真空中烧结以形成成品或半成品元件，以用作工具或磨损部件。该工艺令人满意地适合制造硬颗粒，粒度在从0.8至5um，但在该范围外就会出现问题。对于更细的粒度，需要与至少与硬颗粒一样细的粘结料金属粉末混合，这会导致金属粉末由于粉尘和自燃产生的健康和安全问题。而且，公知的细粉机械研磨的低效率导致研磨时间过长。对于更大的粒度，研磨工艺变的效率过高，除了混合还粉碎了硬颗粒。
已经提出若干替代的方法来解决上述研磨问题：
1)向硬颗粒添加钴(作为粘结料金属)形成卤化盐溶液，通过使之经过具有还原气氛(例如氢或合成气体)的还原炉，以便将卤化物转换成金属，从而实现干燥并随后将产品还原。
2)添加粘结料金属作为氧化物，以便其高度易碎性能大大加速了其与磨碎的碳的混合。然后，生成的混合的粉末必须经过具有惰性气氛(例如氮或氩)，或还原气氛(例如氢气或合成气体)的炉子，以便将氧化物转换成金属。
3)在适当的溶剂中形成硬颗粒的浆液，粘结料金属在该溶剂中溶解形成金属盐(例如醋酸盐，氯化物等)，使溶剂蒸发(通常采用搅拌)，在硬颗粒上或之间使粘结料金属盐细微沉淀。然后，该干燥的混合物必须与上述1)相同方式通过炉处理。
4)在通过炉处理之前，除了溶解的粘结相化学沉淀(如草酸盐或苹果酸盐等)外，与上述1)相同。
在上述每种情况下，产品仍然必须均匀地与润滑剂混合，并凝聚以便将其转换成适合使用的材料。这样，与标准的研磨方法相比，上述工艺必然导致更大的成本。
其它方法旨在用粘结相直接涂覆给硬颗粒涂覆，例如：
1)以电解方式向硬颗粒电镀钴。尽管这看起来会带来令人满意的结果，实践中所必须的保持与大量颗粒电接触的困难导致该技术无用。
2)采用非电解镀层的方式对硬颗粒镀钴。在该工艺中，硬颗粒的浆液和一种或多种钴盐(例如氯化钴，硫酸钴，硫酸铵钴等)的水溶液用化学还原剂进行处理，这可以是：
(i)包含次磷酸盐或硼氢化物的盐。这些分别在磷化钴和硼化钴中留下剩余物。尽管这种剩余物可以接受，或者甚至是期望，在一些用途中，公知的，其在烧结硬质合金中的存在是有害的。
(ii)化学还原剂，例如肼或甲醛。这些都很昂贵，并带来严重的健康，安全和环境危险。
(iii)乙二醇或其它多羟基化合物。还原剂的分解产生的反应产物在母液中聚集，其处置需要焚化或类似处理。
(iv)在升高的温度和压力下用氢直接还原。尽管该工艺对于镍是令人满意的，连续的钴沉淀的晶核形成和生长仅通过成核剂例如硫化物和氰化物实现，这两种成核剂是危险的，或者通过有机催化剂例如硫代乙酰胺(一种公知的致癌物质)，或者通过利用催化剂例如氯化钯(一种昂贵的贵金属)预处理硬颗粒，和/或通过预涂覆镍(它可以是或不是粘结相的期望成分)。
发明内容
本发明的一个目的是提供一种制造涂覆硬颗粒的新颖的工艺，该工艺可避免或减轻与现有技术的方法相关的问题。
根据本发明，提供一种用金属涂覆硬颗粒的方法，所述方法包括如下顺序的步骤：
(i)形成硬颗粒的含水浆液，
(ii)向浆液添加一种或多种金属盐的水溶液，所述溶液具有从0.1m至1.6m的重量摩尔浓度，
(iii)调节浆液/金属盐溶液的PH值在7至14之间，从而给硬颗粒涂覆金属盐，
(iv)在升高的压力下将金属盐-涂覆颗粒浆液加热到一个升高的温度，以便将所述金属盐转化为金属氧化物，金属氧化物氢氧化物复合物(oxidehydroxide)，或金属氢氧化物，和
(v)在所述升高的温度和压力下，将金属氧化物，金属氧化物氢氧化物复合物，或金属氢氧化物还原成组成金属，以形成所述金属涂覆硬颗粒，
其中，硬颗粒是钨，钛，钽，铌，钼，铬，钒，锆，和铪中的一种或多种的碳化物，碳氮化物和氮化物中的一种或多种，并且
其中所述金属是钴，镍和铁中的一种或多种。
令人惊奇的，本发明人发现在上述特定条件下，在步骤(iii)后，粘结料金属盐(作为离子金属络合物)均匀地吸收在硬颗粒的表面上。利用现有技术的方法不可能实现这样均匀的涂覆。
最好，该方法有效地制造小于1um厚度的涂层。该涂层可以是连续的涂层，其中，基本上所有颗粒的表面完全由涂层覆盖，或者部分涂覆，其中大量颗粒的部分表面保持未涂覆。
在步骤(ii)中使用的盐可以是金属的任何可溶于水的盐，并最好选自氯化物，醋酸盐，和水合物中的一种或多种。最优选的实例包括氯化钴(II)，醋酸钴(II)或(III)，和醋酸钴[(II)]四水合物。最好盐(s)的重量摩尔浓度约为0.4m。
最好，通过添加一种或多种氨，和取代或未取代氢氧化季铵(例如氢氧化铵，四甲基氢氧化铵，二乙基二甲基氢氧化铵，和四乙基氢氧化铵)，实施步骤(iii)。最好pH值调节至约8和9之间。
步骤(iv)最好在约150至300℃实施，更好的是在约200℃实施。步骤(iv)的优选的压力范围为25-35巴(2.5-3.5Mpa)。在一个优选实施例中，步骤(iv)(最好步骤(v)在高压釜中实施，这种情况下，压力最好是自生压力。最好，在步骤(iv)期间的至少一段时间搅动浆液。最好，步骤(iv)实施至多约3小时，最好加热速率为约1℃/分钟。
最好，通过向浆液引入氢气，来实施步骤(v)。更好的是，在从10至50巴1至5Mpa)的局部压力下添加氢，最好，在约30巴(3Mpa)的局部压力下添加氢。最好步骤(v)实施约2小时。
本发明还涉及利用本发明的方法生产的涂覆硬颗粒，还涉及包括这种硬颗粒的密实的和烧结的部件。
具体实施方式
现在仅通过举例来描述本发明的实例。
硬颗粒形成水成浆液，这里的pH值控制在7至14之间。如果硬颗粒结块，通过本领域公知的技术实施解开结块。PH值的控制可以通过添加氨，和/或四元氢氧化物来实现。在该浆液中添加粘结料金属的一种或多种适当的盐的水溶液，其重量摩尔浓度在0.1m和1.6m之间。如前所述，在步骤(iii)后，粘结料金属盐均匀地吸收到硬颗粒的表面上。这种情况通过用钴盐处理时碳化钨的电位的改变来证明，这表明水溶液中碳化钨表面正常酸性已经改变为典型钴合成物的基本特性。
然后，硬颗粒/金属盐混合物放置在高压釜中并加热，同时在其自生压力下搅动。然后，氢在特定压力下进入高压釜中达特定时间。
然后，高压釜冷却，降压，并清除剩余的氢。现在涂覆的颗粒通过沉积，或过滤与浆液分离，然后，再与例如水，酒精混成浆液，或者其混合物与适当的压制润滑剂例如聚乙二醇混合，并喷雾干燥，以获得期望的结块粉末。约99％的初始粘结料金属还原成最终产品，作为粘附到硬颗粒上的细微散布的金属，无须添加前述活化剂和/或成核剂，通过杂凝聚步骤可避免使用该活化剂和/或成核剂。剩余1％的初始粘结料金属在过滤后留在水相溶液中。这可以在随后的程序组中再使用，不存在有毒的或有害的分解产品或副产品，因为仅产生水，二氧化碳和氮。
实例1
具有0.4um粒度的94g碳化钨粉在室温下与醋酸钴II的0.4m溶液混合成浆液，对应添加6g钴。当搅动浆液时，添加0.880氨溶液，以便溶液调节至PH9。搅动继续30分钟，然后，浆液放置在高压釜中，高压釜关闭，并用惰性气体(氮或氩)净化。然后，在自生压力下，温度增加到200℃，然后氢引入以便保持30巴(3Mpa)的压力达2小时。高压釜被允许冷却和降压，然后用惰性气体净化。浆液从高压釜倒空，固相通过沉积倾滤而分离，随后进行清洗和干燥。
对所得粉末的分析表明它包含6％的作为金属的钴。然后，粉末与适当的压制润滑剂，例如与固体石蜡或者聚乙二醇混合，这在行业中是标准的，并在模型中加压，随后在真空炉中在1410℃减润滑(de-lubricated)并烧结。冶金和高分辨率金相检查显示极佳的钴分布，且没有碳化钨晶粒毗连、钴沉淀色料或多孔性。
实例2
具有8μm粒度的90g碳化钨粉末在室温下与0.4m的醋酸钴(II)溶液和0.4m的醋酸镍(II)溶液混合成浆液，对应添加8g钴和2g镍。随后的处理与上述实例1所述相同。
对生成粉末的分析表明它包含作为金属的8％的钴和2％的镍。然后，粉末与适当的压制润滑剂混合，并在模型中加压，随后在真空炉中在1450℃下减润滑并烧结。冶金和高分辨率金相检查显示极佳的钴分布，且没有碳化钨细粒毗连、钴沉淀色料或多孔性。
实例3
具有0.2um粒度的91.2g碳化钨粉末，以及具有0.3um粒度的0.3g碳化钒和具有0.3um粒度的0.5g碳化铬在室温下与0.4m的醋酸钴(II)溶液混合成浆液，对应添加8g钴。随后的处理与上述实例1所述相同。
对生成粉末的分析表明它包含作为金属的8％的钴。然后，粉末与适当的压制润滑剂混合，并在模型中加压，随后在真空炉中在1360℃下减润滑并烧结。冶金和高分辨率进行检查显示极佳的钴分布，且没有碳化钨细粒毗连、钴沉淀色料或多孔性。在1500X放大倍数下，在每个观察领域，平均烧结的粒度小于0.4um，小于一个颗粒的平均粒度大于2um。
Claims (17)
1.一种用金属涂覆硬颗粒的方法，所述方法包括如下顺序的步骤：
(i)形成硬颗粒的含水浆液，
(ii)向浆液添加一种或多种金属盐的水溶液，所述溶液具有从0.1m至1.6m的重量摩尔浓度，
(iii)调节浆液/金属盐溶液的pH值在7至14之间，从而给硬颗粒涂覆金属盐，
(iv)在升高的压力下将金属盐-涂覆颗粒浆液加热到一个升高的温度，以便将所述金属盐转化为金属氧化物、金属氧化物氢氧化物复合物、或金属氢氧化物，和
(v)在所述升高的温度和压力下，将金属氧化物、金属氧化物氢氧化物复合物、或金属氢氧化物还原成组成金属，从而形成所述金属涂覆的硬颗粒，其中，硬颗粒是钨、钛、钽、铌、钼、铬、钒、锆和铪中的一种或多种的碳化物、碳氮化物和氮化物中的一种或多种，所述金属是钴、镍和铁中的一种或多种。
2.如权利要求1所述的方法，其特征在于该方法可以制造厚度小于1um的涂层。
3.如权利要求1或2所述的方法，其特征在于该涂层是连续的涂层，其中，基本上所有颗粒的表面完全由涂层覆盖。
4.如上述权利要求中任一所述的方法，其特征在于在步骤(ii)中使用的盐是可溶于水的金属盐，它最好选自氯化物、醋酸盐和其水合物中的一种或多种。
5.如上述权利要求中任一所述的方法，其特征在于一种或多种盐的重量摩尔浓度约为0.4m。
6.如上述权利要求中任一所述的方法，其特征在于通过添加一种或多种氨且取代或未取代氢氧化季铵，来实施步骤(iii)。
7.如上述权利要求中任一所述的方法，其特征在于在步骤(iii)中，pH值调节至约8和9之间。
8.如上述权利要求中任一所述的方法，其特征在于步骤(iv)在约150至300℃实施。
9.如上述权利要求中任一所述的方法，其特征在于步骤(iv)的压力范围为2.5-3.5Mpa。
10.如上述权利要求中任一所述的方法，其特征在于步骤(iv)和步骤(V)在高压釜中实施。
11.如上述权利要求中任一所述的方法，其特征在于在步骤(iv)期间的至少一段时间搅动浆液。
12.如上述权利要求中任一所述的方法，其特征在于步骤(iv)实施至多约3小时，最好加热速率为约1℃/分钟。
13.如上述权利要求中任一所述的方法，其特征在于通过向浆液引入氢气，来实施步骤(v)。
14.如权利要求13所述的方法，其特征在于在从1至5Mpa的局部压力下添加氢。
15.如上述权利要求中任一所述的方法，其特征在于步骤(v)实施约2小时。
16.如实例1至3中任意一项所述的方法。
17.如权利要求1至16中任一权利要求的方法所制造的硬颗粒。
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| CN102292177A (zh) * | 2009-01-22 | 2011-12-21 | 住友电气工业株式会社 | 冶金用粉末的制法、压粉磁芯的制法、压粉磁芯以及线圈部件 |
| CN103418785A (zh) * | 2012-05-23 | 2013-12-04 | 北京航空航天大学 | 一种耐腐蚀钛/氧化钌复合粉体的制备方法 |
| CN109790024A (zh) * | 2016-10-05 | 2019-05-21 | 埃克森美孚化学专利公司 | 制备金属氮化物和金属碳化物的方法 |
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| CN101090786A (zh) * | 2004-12-27 | 2007-12-19 | 优米科尔公司 | 硬质金属用复合粉末 |
| US8679207B2 (en) * | 2006-03-30 | 2014-03-25 | Komatsu Ltd. | Wear resisting particle and wear resisting structure member |
| EP3527306A1 (de) | 2018-02-14 | 2019-08-21 | H.C. Starck Tungsten GmbH | Pulver umfassend beschichtete hartstoffpartikel |
| WO2020168163A1 (en) * | 2019-02-14 | 2020-08-20 | Arcanum Alloys, Inc. | Methods and systems for coating a steel substrate |
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| US2119488A (en) * | 1936-07-31 | 1938-05-31 | Sirian Wire And Contact Compan | Alloys and process of making same |
| FR866944A (fr) * | 1940-05-17 | 1941-09-18 | Préparation d'alliages par frittage | |
| CA916484A (en) * | 1971-04-15 | 1972-12-12 | Kunda Wasyl | Cobalt coated core powders |
| JPS588530B2 (ja) * | 1978-03-10 | 1983-02-16 | 株式会社東芝 | 真空開閉器用電極材の製造方法 |
| US4801472A (en) * | 1987-08-24 | 1989-01-31 | Gte Product Corporation | Process for coating tungsten carbide with cobalt metal |
| SE504244C2 (sv) * | 1994-03-29 | 1996-12-16 | Sandvik Ab | Sätt att tillverka kompositmaterial av hårdämnen i en metallbindefas |
| SE9500473D0 (sv) * | 1995-02-09 | 1995-02-09 | Sandvik Ab | Method of making metal composite materials |
| SE507211C2 (sv) * | 1995-09-29 | 1998-04-27 | Sandvik Ab | Sätt att tillverka ett belagt hårdämnespulver |
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| SE510749C2 (sv) * | 1997-12-22 | 1999-06-21 | Sandvik Ab | Sätt att framställa ett metallkompositmaterial innehållande hårda partiklar och bindemetall |
| DE19962015A1 (de) * | 1999-12-22 | 2001-06-28 | Starck H C Gmbh Co Kg | Pulvermischungen bzw. Verbundpulver, Verfahren zu ihrer Herstellung und ihre Verwendung in Verbundwerkstoffen |
| US20030097907A1 (en) * | 2001-11-28 | 2003-05-29 | Carroll Daniel F. | Methods of producing composite powders |
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2003
- 2003-09-12 CN CNA03801582XA patent/CN101018632A/zh active Pending
- 2003-09-12 EP EP03797770A patent/EP1539410A1/en not_active Withdrawn
- 2003-09-12 WO PCT/SE2003/001432 patent/WO2004026509A1/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102292177A (zh) * | 2009-01-22 | 2011-12-21 | 住友电气工业株式会社 | 冶金用粉末的制法、压粉磁芯的制法、压粉磁芯以及线圈部件 |
| CN103418785A (zh) * | 2012-05-23 | 2013-12-04 | 北京航空航天大学 | 一种耐腐蚀钛/氧化钌复合粉体的制备方法 |
| CN103418785B (zh) * | 2012-05-23 | 2016-05-25 | 北京航空航天大学 | 一种耐腐蚀钛/氧化钌复合粉体的制备方法 |
| CN109790024A (zh) * | 2016-10-05 | 2019-05-21 | 埃克森美孚化学专利公司 | 制备金属氮化物和金属碳化物的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004026509A1 (en) | 2004-04-01 |
| EP1539410A1 (en) | 2005-06-15 |
| GB0221999D0 (en) | 2002-10-30 |
| GB2399824A (en) | 2004-09-29 |
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