EP0082438A1 - Procédé d'activation des surfaces pour la métallisation sans courant - Google Patents
Procédé d'activation des surfaces pour la métallisation sans courant Download PDFInfo
- Publication number
- EP0082438A1 EP0082438A1 EP82111461A EP82111461A EP0082438A1 EP 0082438 A1 EP0082438 A1 EP 0082438A1 EP 82111461 A EP82111461 A EP 82111461A EP 82111461 A EP82111461 A EP 82111461A EP 0082438 A1 EP0082438 A1 EP 0082438A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- palladium
- nickel
- minutes
- metallization
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000001465 metallisation Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000004913 activation Effects 0.000 title claims description 7
- 230000008569 process Effects 0.000 title description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- -1 palladium (II) organic compound Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 32
- 229910052759 nickel Inorganic materials 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000005062 Polybutadiene Substances 0.000 description 15
- 229920002857 polybutadiene Polymers 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 12
- 238000007747 plating Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000004816 latex Substances 0.000 description 10
- 229920000126 latex Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- HIDYYJFXCDZTHJ-UHFFFAOYSA-L acetonitrile;dichloropalladium Chemical compound CC#N.Cl[Pd]Cl HIDYYJFXCDZTHJ-UHFFFAOYSA-L 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 4
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HENYYBLMWDENHQ-UHFFFAOYSA-N benzonitrile palladium Chemical compound [Pd].N#CC1=CC=CC=C1 HENYYBLMWDENHQ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006289 polycarbonate film Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 210000003934 vacuole Anatomy 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910000634 wood's metal Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
Definitions
- the invention relates to a method for activating substrate surfaces for the purpose of chemical metallization.
- the polymer surface is changed so that caverns and vacuoles are formed.
- This is only possible with certain polymers, for example with 2-phase multicomponent grafts or copolymers, such as ABS polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene.
- 2-phase multicomponent grafts or copolymers such as ABS polymers, impact-resistant polystyrene or 2-phase homopolymers, such as partially crystalline polypropylene.
- working with chromosulfuric acid or other oxidants is associated with a deterioration in the physical properties, for example the notched impact strength or the electrical surface resistance of the polymeric base material.
- the ionogenic palladium is reduced either in an acidic tin (II) chloride bath or by introducing tin (II) chloride into a strongly hydrochloric acid palladium (II) chloride solution.
- the excess protective colloid must be removed from the substrate surface so that a reduction in the metal ions, e.g. of copper, nickel, gold and cobalt in the metallization shading is possible through the catalytic action of active palladium centers on the substrate surface.
- the object of the present invention was to provide a new, gentle and process-technically simple method for activating substrate surfaces for the purpose of electroless metallization, with which even hard-to-metallize surfaces can be provided with a well-adhering metal coating.
- organometallic compounds of palladium are used, the organic part of which are oligomeric, prepolymeric or polymeric compounds which contain double bonds.
- the invention therefore relates to a method for activating substrate surfaces for the purpose of electroless metallization, the surface to be metallized, preferably without prior etching, being wetted with an organopalladium (II) compound homogeneously distributed in a solvent, in particular an organic solvent, the solvent removed and the organopalladium (II) compound adhering to the surface to be metallized is reduced, characterized in that the organic part of the organometallic compound is an oligomeric, prepolymeric or polymeric compound which contains double bonds.
- oligomer, prepolymer and polymer are known to the person skilled in the art. Together, they comprise a molecular weight range of approximately 150 to 1,000,000, preferably 200 to 500,000.
- Preferred organic compounds are homo- and copolymers of conjugated dienes, e.g. Styrene-butadiene copolymers, and unsaturated polyesters.
- the metal can be bound to the oligomer, prepolymer or polymer or to the corresponding monomer, which would be followed by the corresponding polymer reaction. It is also possible to carry out the polymer reaction and metal bonding in one operation.
- the oligomeric, prepolymeric or polymeric compounds have, in addition to the groups which bind the metal to the polymer, further functional groups which are capable of binding the organometallic compound to the substrate to be activated or of a further polymer reaction.
- groups which bind the metal to the polymer are carboxyl or ester groups.
- organometallic compounds used in accordance with the invention known low-molecular organometallic compounds with ligand exchange with the oligomers, prepolymers or polymers are reacted, or known organometallic compounds with ligand exchange with low-molecular compounds which are suitable for polymer production are reacted and the polymer reaction is then carried out.
- the organometallic compound can, for example, be dissolved or dispersed in the organic solvent, it can also be a rubbing of the organometallic compounds with the solvent.
- organometallic compound contains ligands which allow chemical fixation on the substrate surface, activation from the aqueous phase may also be possible.
- polar, protic and aprotic solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, acetone, methyl ethyl ketone, butanol, ethylene glycol and tetrahydrofuran are suitable as organic solvents.
- Suitable substrates for the process according to the invention are e.g. Steels, titanium, glass, quartz, ceramics, carbon, paper, polyethylene, polypropylene, ABS plastics, epoxy resins, polyesters and textile fabrics, threads and fibers made of polyamide, polyester, polyolefins, polyacrylonitrile, polyvinyl halides, cotton and wool, and mixtures thereof or from copolymers of the monomers mentioned.
- the organic solvent is removed.
- Low boiling solvents are preferred by evaporation, e.g. removed in vacuum.
- other methods such as extraction with a solvent in which the organometallic compounds are insoluble, are appropriate.
- the surfaces pretreated in this way must then be activated by reduction.
- the reducing agents customary in electroplating such as hydrazine hydrate, formaldehyde, hypophosphite or boranes, can preferably be used for this purpose. Of course there are others too Reducing agent possible.
- the reduction is preferably carried out in aqueous solution. However, other solvents such as alcohols, ethers, hydrocarbons can also be used. Of course, suspensions or slurries of the reducing agents can also be used.
- the surfaces activated in this way can be used directly for electroless metallization. However, it may also be necessary to rinse the surfaces of the reducing agent residues.
- a very particularly preferred embodiment of the method according to the invention consists in that the reduction in the metallization bath is carried out immediately with the reducing agent of the electroless metallization.
- This version represents a simplification of the electroless metallization that has not been possible until now.
- This very simple embodiment only consists of the three work steps: immersing the substrate in the solution of the organometallic compound, evaporating the solvent and immersing the surfaces thus activated in the metallization bath (reduction and Metallization).
- This embodiment is particularly suitable for nickel baths containing amine borane or copper baths containing formalin.
- metallising baths with nickel salts, C obaltsalzen, copper salts, gold salts and silver salts, or their mixtures with one another or with iron salts.
- Such metallization baths are known in the electroless metallization art.
- oligomeric, prepolymeric and polymeric organic palladium compounds can be used to produce directly activated moldings, using conventional technologies. These moldings can then be subjected to the reduction and metallization.
- oligomeric, prepolymeric and polymeric organometallic compounds applied to substrates can of course be subjected to further reactions, for example crosslinking or grafting.
- the electrical resistance of the chemically deposited nickel layer is so low that the polypropylene foil washed after the chemical metallization is galvanically coated with copper of approximately 4.2 ⁇ m in thickness in a galvanic copper plating bath at 1.0 amps after 30 minutes.
- a glass plate (100 x 80 mm) is ent with methylene chloride greased and then immersed for 30 seconds in a solution of 7.2 g palladed polybutadiene with 7.1% by weight palladium (based on the dry polybutadiene mass) in 1 1 methylene chloride, after evaporation of the solvent at room temperature according to Example 1, nickel-plated. After a minute, the plate is covered with a fine black nickel layer.
- the nickel layer After about 15 minutes, the nickel layer has a thickness of 0.15 ⁇ m and can be switched and reinforced as a cathode in common galvanic metallization baths.
- a metallized piece of fabric with a coating of 9 g / m 2 nickel is obtained.
- a glass plate (100 x 100 mm) is sprayed with the above-mentioned prepolymer solution (blowing agent Frigen), after drying according to Example 1 nickel-plated for 9 minutes.
- a glass fiber reinforced epoxy resin plate (100 x 100 mm) is sprayed according to Example 12 with palladium-coated prepolymer solution, after drying the layer according to Example 1, nickel-plated in an alkaline nickel plating bath. After 9 minutes, a nickel layer 0.1 ⁇ m thick is measured.
- a 100 x 100 mm square of a woven fabric made of polyethylene terephthalate is sprayed according to Example 4 with palladed prepolymer solution (frigen as blowing agent) and, after the layer has dried, is nickel-plated according to Example 1. After just one minute, the fabric is covered with a fine layer of nickel. After 10 minutes the chemically deposited amount of nickel is 10 g / m 2 .
- Glass rods with a diameter of 8 mm and a length of 250 mm are coated with the above-mentioned palladed prepolymer solution by an immersion process, dried in a drying cabinet at 60 ° C. and then nickel-plated according to Example 1.
- the nickel layer After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 ⁇ m.
- the rods are removed from the bath, rinsed with distilled water and reinforced as a cathode according to Example 1 in a galvanic copper plating bath at 1.0 amp. To 20 ⁇ m.
- a 250 x 250 mm square of a wooden plate is made sprayed with the prepolymer solution.
- the lacquer layer is dried for 12 hours at room temperature and nickel-plated according to Example 1.
- the electrical resistance of the chemical nickel layer is so low that the wood-metal composite material can be reinforced as a cathode in a galvanic nickel plating bath at 1.5 amps.
- Example 7 10 g of the alkyd resin used in Example 7 (60% in xylene) are mixed with 0.8 g of benzonitrile palladium dichloride in 20 ml of toluene at 30 ° C., then concentrated to 15 ml at room temperature and under a water jet vacuum.
- a glass-fiber-reinforced epoxy resin plate is partially coated with the palladium-coated prepolymer solution mentioned in the screen printing process, after which it is nickel-plated at 60 ° C. in a drying cabinet according to Example 1.
- Glass rods with a diameter of 3 mm and a length of 250 mm are coated with the palladed prepolymer solution according to Example 15 by an immersion process, dried in a drying cabinet at 80 ° C. in 4.5 hours, then nickel-plated according to Example 1. After a chemical metallization time of approx. 6 minutes, the rods are covered with a nickel layer.
- Example 16 The palladed prepolymer listed in Example 16 is printed on a glass fiber reinforced epoxy resin plate (150 x 50 mm) using the screen printing process, the prepolymer mask is cured in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to Example 1.
- this printed circuit board is galvanically reinforced to 5 ⁇ m as the cathode in an acidic copper plating bath.
- the latex contains 31.5% by weight of solid with a 100% gel content and has a pH of 6.6 and an average particle diameter of 0.285 ⁇ m. Its swelling index in toluene is 5.0.
- Films (40 x 80 mm) are made from the palladed latex by casting on glass plates. The foils are annealed in a drying cabinet at 50 ° C. for 8 hours and then nickel-plated according to example 1.
- the electrical resistance of this chemical nickel layer is so low that the metallized metal-polymer composite material is reinforced to 15 ⁇ m in an acidic copper plating bath as the cathode.
- a 100 x 100 mm square of a 3 mm thick heat-resistant polycarbonate film is sprayed with a solution of 0.6 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride in 20 ml of n-butanol and 5 g of prepolymer solution according to Example 15, after evaporating the Solvent in the drying cabinet at 95 ° C for 10 minutes and then nickel-plated according to Example 1. After approx. 5 minutes the nickel layer has a thickness of approx. 0.2 ⁇ m.
- the sample is removed from the bath, carefully rinsed with distilled water, reinforced according to Example 1 at 1.2 amps with a 7.5 ⁇ m copper layer.
- a template for the production of printed circuits is placed on a 200 x 200 mm polyhydantoin film.
- the test specimen is sprayed with the coating solution (freezing as a blowing agent). After the solvent has evaporated, the stencil is removed from the film surface, the lacquer layer is cured in a drying cabinet at 50 ° C. in 5 hours and then nickel-plated according to Example 1.
- test specimen is removed from the metallization bath and the partial nickel coating in a galvanic copper plating bath is increased to 5 ⁇ m at 0.9 amp./dm 2 .
- lacquer (15% strength in xylene) based on 1,4-polyisoprene with diazole crosslinker are mixed with 0.4 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride palladium dichloride with stirring and nitrogen injection within one hour added in 5 ml of methylene chloride.
- a 25 x 80 mm, 1.5 mm thick glass fiber reinforced epoxy resin plate is coated with the above-mentioned lacquer by immersion, irradiated with a mercury lamp for 15 minutes after evaporation of the solvent and nickel-plated according to Example 1.
- the nickel coating is so thick that it can be reinforced in a galvanic copper plating bath.
- the underside of the carpet has a nickel layer.
- Isobutyl vinyl ether palladium dichloride is obtained in an analogous manner from the acetonitrile palladium dichloride and isobutyl vinyl ether, melting point: 57-60 ° C.
- a cetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride, mixed with oligomeric polybutadiene, stirred for 30 minutes at room temperature and freed from solvent and acetonitrile in vacuo.
- a cetonitrile palladium dichloride is 5% by weight dissolved in methylene chloride. Butadiene is introduced and the solvent and acetonitrile are distilled off in vacuo.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3150985 | 1981-12-23 | ||
DE19813150985 DE3150985A1 (de) | 1981-12-23 | 1981-12-23 | Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0082438A1 true EP0082438A1 (fr) | 1983-06-29 |
EP0082438B1 EP0082438B1 (fr) | 1985-10-09 |
Family
ID=6149500
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82111461A Expired EP0082438B1 (fr) | 1981-12-23 | 1982-12-10 | Procédé d'activation des surfaces pour la métallisation sans courant |
Country Status (4)
Country | Link |
---|---|
US (2) | US4493861A (fr) |
EP (1) | EP0082438B1 (fr) |
JP (1) | JPS58113366A (fr) |
DE (2) | DE3150985A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3419755A1 (de) * | 1984-05-26 | 1985-11-28 | Bayer Ag, 5090 Leverkusen | Chemisches versilberungsbad |
EP0250867A1 (fr) * | 1986-06-16 | 1988-01-07 | International Business Machines Corporation | Procédé d'activation en vue d'un dépôt de métal par voie chimique |
DE3938710A1 (de) * | 1989-11-17 | 1991-05-23 | Schering Ag | Komplexverbindungen mit oligomerem bis polymerem charakter |
DE19941043A1 (de) * | 1999-08-28 | 2001-03-01 | Bosch Gmbh Robert | Bekeimungsbad und Verfahren zur Bekeimung von pulverförmigen Werkstoffen, Verfahren zur Metallisierung eines bekeimten pulverförmigen Werkstoffs und Verfahren zur Herstellung metallisch begrenzter Hohlkörper |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3242162A1 (de) * | 1982-11-13 | 1984-05-17 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von verbundwerkstoffen |
DE3248778A1 (de) * | 1982-12-31 | 1984-07-12 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung metallisierter poroeser festkoerper |
PH23907A (en) * | 1983-09-28 | 1989-12-18 | Rohm & Haas | Catalytic process and systems |
US4719145A (en) * | 1983-09-28 | 1988-01-12 | Rohm And Haas Company | Catalytic process and systems |
DE3339856A1 (de) * | 1983-11-04 | 1985-05-15 | Bayer Ag, 5090 Leverkusen | Verfahren zur haftaktivierung von polyamidsubstraten fuer die stromlose metallisierung |
DE3339857A1 (de) * | 1983-11-04 | 1985-05-15 | Bayer Ag, 5090 Leverkusen | Verfahren zur vorbehandlung von polyamidsubstraten fuer die stromlose metallisierung |
DE3407114A1 (de) * | 1984-02-28 | 1985-09-05 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von leiterplatten |
DE3424065A1 (de) * | 1984-06-29 | 1986-01-09 | Bayer Ag, 5090 Leverkusen | Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung |
JPS62149884A (ja) * | 1985-12-24 | 1987-07-03 | Nippon Mining Co Ltd | 無電解銅めつきの前処理方法 |
JPH0694592B2 (ja) * | 1986-04-22 | 1994-11-24 | 日産化学工業株式会社 | 無電解メッキ法 |
US5182135A (en) * | 1986-08-12 | 1993-01-26 | Bayer Aktiengesellschaft | Process for improving the adherency of metallic coatings deposited without current on plastic surfaces |
US4910072A (en) * | 1986-11-07 | 1990-03-20 | Monsanto Company | Selective catalytic activation of polymeric films |
US5075037A (en) * | 1986-11-07 | 1991-12-24 | Monsanto Company | Selective catalytic activation of polymeric films |
JP2760984B2 (ja) * | 1987-02-26 | 1998-06-04 | 株式会社東芝 | 絶縁ゲート型サイリスタ |
JPH01104782A (ja) * | 1987-07-02 | 1989-04-21 | Fuji Photo Film Co Ltd | 無電解メッキ用触媒材料およびそれを用いた金属化材料 |
DE3743780A1 (de) * | 1987-12-23 | 1989-07-06 | Bayer Ag | Verfahren zur verbesserung der haftfestigkeit von stromlos abgeschiedenen metallschichten auf polyimidoberflaechen |
US5030742A (en) * | 1988-12-16 | 1991-07-09 | Ciba-Geigy Corporation | Ultrathin layers of palladium(O) complexes |
US5227223A (en) * | 1989-12-21 | 1993-07-13 | Monsanto Company | Fabricating metal articles from printed images |
US5279899A (en) * | 1992-03-17 | 1994-01-18 | Monsanto Company | Sulfonated polyamides |
US5517338A (en) * | 1992-10-20 | 1996-05-14 | Monsanto Company | Composite mirrors |
US5419954A (en) * | 1993-02-04 | 1995-05-30 | The Alpha Corporation | Composition including a catalytic metal-polymer complex and a method of manufacturing a laminate preform or a laminate which is catalytically effective for subsequent electroless metallization thereof |
DE4319759A1 (de) * | 1993-06-15 | 1994-12-22 | Bayer Ag | Pulvermischungen zum Metallisieren von Substratoberflächen |
US20040031404A1 (en) * | 2002-08-19 | 2004-02-19 | John Dixon | Seamless embossing shim |
US8465469B2 (en) * | 2002-09-12 | 2013-06-18 | Medtronic Vascular, Inc. | Reinforced catheter and methods of making |
CN1329554C (zh) * | 2004-01-13 | 2007-08-01 | 长沙力元新材料股份有限公司 | 非金属基材表面化学镀覆金属的方法及其采用的前处理体系 |
KR101459515B1 (ko) * | 2006-10-23 | 2014-11-07 | 후지필름 가부시키가이샤 | 표면 금속막 재료와 그 제작방법, 금속패턴 재료와 그 제작방법, 폴리머층 형성용 조성물, 니트릴기 함유 폴리머와 그 합성방법, 니트릴기 함유 폴리머를 사용한 조성물, 및 적층체 |
JP5470503B2 (ja) * | 2010-05-04 | 2014-04-16 | ユニ−ピクセル・ディスプレイズ・インコーポレーテッド | 導電性パターンを伴う微細構造表面の製作方法 |
US8591637B2 (en) * | 2010-12-14 | 2013-11-26 | Rohm And Haas Electronic Materials Llc | Plating catalyst and method |
US8591636B2 (en) | 2010-12-14 | 2013-11-26 | Rohm And Haas Electronics Materials Llc | Plating catalyst and method |
Citations (1)
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US3523824A (en) * | 1966-12-29 | 1970-08-11 | Ibm | Metallization of plastic materials |
Family Cites Families (10)
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FR1553822A (fr) * | 1965-08-13 | 1969-01-17 | ||
US3560257A (en) * | 1967-01-03 | 1971-02-02 | Kollmorgen Photocircuits | Metallization of insulating substrates |
US3488166A (en) * | 1967-01-13 | 1970-01-06 | Ibm | Method for activating plastics,subsequent metallization and article of manufacture resulting therefrom |
US3501332A (en) * | 1967-04-28 | 1970-03-17 | Shell Oil Co | Metal plating of plastics |
US3900320A (en) * | 1971-09-30 | 1975-08-19 | Bell & Howell Co | Activation method for electroless plating |
US3956041A (en) * | 1972-07-11 | 1976-05-11 | Kollmorgen Corporation | Transfer coating process for manufacture of printing circuits |
US3998602A (en) * | 1975-02-07 | 1976-12-21 | Carl Horowitz | Metal plating of polymeric substrates |
DE2727245C3 (de) * | 1977-06-16 | 1980-06-26 | Brintzinger, Hans, Prof. Dr., 7750 Konstanz | Polymergebundene CyclopentadienylÜbergangsmetall-Verbindungen und ihre Ligand-Substitutions-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren |
DE3025307A1 (de) * | 1980-07-04 | 1982-01-28 | Bayer Ag, 5090 Leverkusen | Verfahren zur aktivierung von oberflaechen fuer die stromlose metallisierung |
DE3148280A1 (de) * | 1981-12-05 | 1983-06-09 | Bayer Ag, 5090 Leverkusen | Verfahren zur aktivierung von substratoberflaechen fuer die stromlose metallisierung |
-
1981
- 1981-12-23 DE DE19813150985 patent/DE3150985A1/de not_active Withdrawn
-
1982
- 1982-12-10 EP EP82111461A patent/EP0082438B1/fr not_active Expired
- 1982-12-10 DE DE8282111461T patent/DE3266873D1/de not_active Expired
- 1982-12-13 US US06/449,043 patent/US4493861A/en not_active Expired - Fee Related
- 1982-12-23 JP JP57225100A patent/JPS58113366A/ja active Granted
-
1984
- 1984-10-25 US US06/664,668 patent/US4622411A/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US3523824A (en) * | 1966-12-29 | 1970-08-11 | Ibm | Metallization of plastic materials |
Non-Patent Citations (2)
Title |
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IBM TECHNICAL DISCLOSURE BULLETIN, Band 11, Nr. 8, Januar 1969, Seite 1001, New York, USA * |
IBM TECHNICAL DISCLOSURE BULLETIN, Band 13, Nr. 5, Oktober 1970, Seite 1200, New York, USA * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3419755A1 (de) * | 1984-05-26 | 1985-11-28 | Bayer Ag, 5090 Leverkusen | Chemisches versilberungsbad |
EP0250867A1 (fr) * | 1986-06-16 | 1988-01-07 | International Business Machines Corporation | Procédé d'activation en vue d'un dépôt de métal par voie chimique |
DE3938710A1 (de) * | 1989-11-17 | 1991-05-23 | Schering Ag | Komplexverbindungen mit oligomerem bis polymerem charakter |
DE19941043A1 (de) * | 1999-08-28 | 2001-03-01 | Bosch Gmbh Robert | Bekeimungsbad und Verfahren zur Bekeimung von pulverförmigen Werkstoffen, Verfahren zur Metallisierung eines bekeimten pulverförmigen Werkstoffs und Verfahren zur Herstellung metallisch begrenzter Hohlkörper |
DE19941043B4 (de) * | 1999-08-28 | 2004-04-29 | Robert Bosch Gmbh | Bekeimungsbad und Verfahren zur Bekeimung von pulverförmigen Werkstoffen, Verfahren zur Metallisierung eines bekeimten pulverförmigen Werkstoffs und Verfahren zur Herstellung metallisch begrenzter Hohlkörper |
Also Published As
Publication number | Publication date |
---|---|
DE3266873D1 (en) | 1985-11-14 |
JPH026834B2 (fr) | 1990-02-14 |
US4622411A (en) | 1986-11-11 |
DE3150985A1 (de) | 1983-06-30 |
JPS58113366A (ja) | 1983-07-06 |
US4493861A (en) | 1985-01-15 |
EP0082438B1 (fr) | 1985-10-09 |
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