EP0328128A1 - Procédé relatif à l'adhérence entre des matériaux métalliques et des couches d'aluminium galvaniques ainsi que l'électrolyte non aqueux utilisé dans ce but - Google Patents
Procédé relatif à l'adhérence entre des matériaux métalliques et des couches d'aluminium galvaniques ainsi que l'électrolyte non aqueux utilisé dans ce but Download PDFInfo
- Publication number
- EP0328128A1 EP0328128A1 EP89102319A EP89102319A EP0328128A1 EP 0328128 A1 EP0328128 A1 EP 0328128A1 EP 89102319 A EP89102319 A EP 89102319A EP 89102319 A EP89102319 A EP 89102319A EP 0328128 A1 EP0328128 A1 EP 0328128A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- anhydrous
- nickel
- iron
- galvanic
- 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
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000007769 metal material Substances 0.000 title claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 8
- 239000004411 aluminium Substances 0.000 title abstract 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 8
- 239000010959 steel Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 15
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- -1 alkylene glycol Chemical compound 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052718 tin Chemical class 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000011135 tin Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 229940021013 electrolyte solution Drugs 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 2
- 150000003842 bromide salts Chemical class 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 229910001509 metal bromide Inorganic materials 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910001297 Zn alloy Inorganic materials 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000005269 aluminizing Methods 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CAPAZTWTGPAFQE-UHFFFAOYSA-N ethane-1,2-diol Chemical compound OCCO.OCCO CAPAZTWTGPAFQE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Definitions
- the invention relates to methods for the metal coating of metal materials, in particular of low-alloy, high-strength steels.
- the invention also relates to the non-aqueous electrolytes used in the above process.
- Certain metals such as copper, can be directly electroplated with aluminum after appropriate mechanical and / or chemical pretreatments to remove fat and / or oxide layers from the surface of the workpieces.
- metals such as, for example, iron materials and in particular special steels, generally no adhesive layers of galvanoaluminium can be obtained in the same way.
- DE-PS 22 60 191 (Siemens AG, priority: 08.12.1972) describes such a method, which is characterized in that at least the last process step, which is used to shape the workpieces, is carried out under an aprotic, water- and oxygen-free protective medium. In the examples, milling, sawing or sanding are mentioned as the last shaping process step.
- a decisive disadvantage of the two last-mentioned procedures is that during the electrodeposition of the metals serving as adhesion promoters, co-separation of hydrogen cannot be avoided.
- Low-alloy high-strength steels for example as shown in Table 1, are very sensitive to embrittlement to hydrogen. Aqueous electrolyte solutions are therefore unsuitable for coating such steels.
- the invention consequently relates to methods for the metal coating of metal materials, in particular low-alloy high-strength steels, which are characterized in that adhesion-promoting layers are electroplated from non-aqueous electrolytes Iron, iron and nickel, nickel, cobalt, copper or alloys of the above-mentioned metals or tin-nickel alloys are deposited on these metal materials and then subsequently galvanically aluminum is deposited in a manner known per se.
- a layer thickness of 1 to 4 ⁇ m is generally sufficient to ensure adhesion between the material, intermediate layer and galvanoaluminium layer.
- electrolytes are solutions of anhydrous metal salts of Fe, Co, Ni, Cu or Sn, in particular their anhydrous halides and / or the complex compounds of these metal halides with ethers, such as for example tetrahydrofuran, or with alcohols, such as ethanol, in anhydrous alkyl half ethers of a C2-C3 alkylene glycol of the formula in the R for C1 to C6 and phenyl, and R1 represents H or methyl, or mixtures of these solutions with the addition of anhydrous conductive salts, in particular lithium chloride, lithium bromide or corresponding tetraorganylammonium halides.
- ethers such as for example tetrahydrofuran
- alcohols such as ethanol
- Such soluble anodes are expediently those from the concerned metal or in the deposition of alloys used from the metals to be deposited or corresponding alloy anodes.
- the metal (II) compounds are expediently used; in the deposition of Cu one generally starts from Cu (I) compounds.
- Ni is described as less good because it is brittle
- Co as less good because it is black, spongy.
- adhesion-promoting layers for galvanoaluminium is not known, but this must be done, in particular because of the properties of the Ni or Co-layers such as brittleness or spongy character are doubted
- water components introduced by the metal salts the co-separation of hydrogen remains unavoidable and the associated risk of embrittlement of the materials by hydrogen is maintained.
- NiCl2 ⁇ 6H2O in ethylene glycol (1,2-ethanediol) also works from AJ Dill (Plating 1972 , 59 (11), 1048-1052, Galvano-Organo 1974 , 43, 151-156) a water-containing metal salt. The co-separation of hydrogen cannot therefore be avoided.
- the anhydrous metal salts are preferably the anhydrous metal dichlorides or dibromides in the case of Fe, Co and Ni or copper (I) chloride or bromide or their addition compounds with alcohols, such as, for example, methanol or ethanol, or with ethers, such as, for example, diethyl ether, THF or dimethoxyethane , used.
- Alkyl half ethers of an alkylene glycol such as 1-alkoxy-2-hydroxyethane or 1-alkoxy-2-hydroxypropane, in particular the easily and inexpensively accessible half ethers of 1,2-ethanediol ROCH2CH2OH, preferably those with R methyl, ethyl, propyl or isopropyl, are used as solvents or those of 1,2-propanediol, in particular CH3CH (OH) CH2OCH3, used.
- concentrations of conductive salt, especially lithium bromide, should be of approximately the same to twice the order of magnitude.
- the electrolysis temperatures are between room temperature and approx. 120 ° C. Temperatures between 50 and 80 ° C. are preferred. Good, uniform and shiny metal layers made of Fe, Co, Ni or Cu can be achieved with current densities between 0.2 and 1.5 A / dm2, 0.5 to 1.0 A / dm2 are preferred, see Table 1.
- alloy deposits mixtures of solutions of the metal salts of the alloy components are generally used according to the invention.
- the anodes can then be either those made of appropriate alloys or a plurality of electrodes made of the metals of the individual alloy components. If there is a large electrolyte supply, it is possible to work only with the anode made from one of the alloy components. The concentration of the other alloy component must then be refreshed from time to time in the solution by adding the appropriate salt. If the deposition tendencies of the individual metals are very different, electrolytes containing only the salt of the more difficult to deposit metal can also be used when using alloy anodes.
- the electrolyses are carried out in closed vessels in an inert gas atmosphere of, for example, argon and / or laughing gas and / or nitrogen.
- the workpieces are first washed with the solvent of the electrolyte.
- the workpieces are washed with dry toluene and then transferred to the aluminizing bath via an inert gas lock.
- a particular advantage of such a procedure is that no new oxide or water layer can be formed on the metal surface. Furthermore, there is no need for subsequent, complex drying processes before entering the aluminizing bath, such as treatment with fluorocarbons containing wetting agents.
- a cylindrical glass vessel with an edge ground flat at the top serves as the electrolysis cell and can be firmly closed with a lid made of insulating material.
- a cathode made of the material to be coated for example WL-1.6359, is suspended from the lid between two anode plates made of the electrochemically dissolvable metal, for example nickel.
- the attachments of the electrodes also serve as power supply.
- the dry cell is filled with inert gas, such as argon or nitrogen.
- a solution of 0.05 mol NiCl2 ⁇ 0.63 THF and 0.05 mol LiBr in 1 liter CH3OCH2CH2OH is used as the electrolyte to coat the cathode with nickel. Electrolysis is carried out at 60 ° C.
- the anodic and cathodic current yields are quantitative in relation to the amount of current.
- the workpieces are washed with the solvent of the electrolyte and dried in a stream of inert gas.
- the workpieces are then washed with dry toluene and transferred to the aluminizing bath via an inert gas lock.
- the "tape test” is a quantitative comparative method that enables liability assessments to be carried out in a simple manner. For this purpose, an adhesive strip is first pressed firmly onto the galvanic layer and then quickly torn off. In the event of poor or moderate adhesion, the galvanic layer and the adhesive strip come off the material base. If the adhesion is good, only small areas of the electroplating layer are detached and if the adhesion is very good, the bonding of the electroplating layer to the base is completely preserved.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Laminated Bodies (AREA)
- Secondary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Prevention Of Electric Corrosion (AREA)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3804303 | 1988-02-12 | ||
| DE3804303A DE3804303A1 (de) | 1988-02-12 | 1988-02-12 | Verfahren zur haftvermittlung zwischen metallwerkstoffen und glavanischen aluminiumschichten und hierbei eingesetzte nichtwaessrige elektrolyte |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0328128A1 true EP0328128A1 (fr) | 1989-08-16 |
| EP0328128B1 EP0328128B1 (fr) | 1992-04-08 |
| EP0328128B2 EP0328128B2 (fr) | 1995-09-20 |
Family
ID=6347224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89102319A Expired - Lifetime EP0328128B2 (fr) | 1988-02-12 | 1989-02-10 | Procédé relatif à l'adhérence entre des matériaux métalliques et des couches d'aluminium galvaniques ainsi que l'électrolyte non aqueux utilisé dans ce but |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4925536A (fr) |
| EP (1) | EP0328128B2 (fr) |
| JP (1) | JP2824267B2 (fr) |
| AT (1) | ATE74630T1 (fr) |
| CA (1) | CA1337690C (fr) |
| DE (2) | DE3804303A1 (fr) |
| DK (1) | DK64789A (fr) |
| ES (1) | ES2032341T5 (fr) |
| IE (1) | IE61700B1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1524336A1 (fr) * | 2003-10-18 | 2005-04-20 | Aluminal Oberflächtentechnik GmbH & Co. KG | Pièces à usiner recouvertes d'un alliage aluminium-magnesium |
| DE102017201559A1 (de) | 2017-01-31 | 2018-08-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Atmosphärendruckplasmaverfahren zur Herstellung von plasmapolymeren Beschichtungen |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992004484A1 (fr) * | 1989-04-20 | 1992-03-19 | Tokin Corporation | Bain galvanoplastique utilisant un solvant organique pour le plaquage d'aimants permanents a compose intermetallique r2t14b |
| US8225481B2 (en) * | 2003-05-19 | 2012-07-24 | Pratt & Whitney Rocketdyne, Inc. | Diffusion bonded composite material and method therefor |
| DE102008048109B4 (de) * | 2008-04-17 | 2015-01-29 | Ks Aluminium-Technologie Gmbh | Verfahren zur Herstellung eines metallischen Bauteils und Verwendung eines Zylinderteils als Grundkörper zur Durchführung des Verfahrens |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2012846A1 (de) * | 1969-03-24 | 1970-10-08 | United States Atomic Energy Commission, Washington, D.C. | Elektroplattierlösung und Elektroplattierverfahren |
| DE3112834A1 (de) * | 1981-03-31 | 1982-10-14 | Siemens AG, 1000 Berlin und 8000 München | "metallbeschichtete eisenwerkstoffe" |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5334711B2 (fr) * | 1971-09-16 | 1978-09-21 | ||
| JPS5137082B2 (fr) * | 1972-03-31 | 1976-10-13 | ||
| EP0195791A1 (fr) * | 1984-09-17 | 1986-10-01 | Eltech Systems Corporation | Revetement protecteur |
-
1988
- 1988-02-12 DE DE3804303A patent/DE3804303A1/de not_active Withdrawn
-
1989
- 1989-02-02 US US07/305,838 patent/US4925536A/en not_active Expired - Fee Related
- 1989-02-10 IE IE42489A patent/IE61700B1/en not_active IP Right Cessation
- 1989-02-10 EP EP89102319A patent/EP0328128B2/fr not_active Expired - Lifetime
- 1989-02-10 CA CA000590782A patent/CA1337690C/fr not_active Expired - Fee Related
- 1989-02-10 AT AT89102319T patent/ATE74630T1/de not_active IP Right Cessation
- 1989-02-10 JP JP1032540A patent/JP2824267B2/ja not_active Expired - Lifetime
- 1989-02-10 ES ES89102319T patent/ES2032341T5/es not_active Expired - Lifetime
- 1989-02-10 DE DE8989102319T patent/DE58901105D1/de not_active Expired - Lifetime
- 1989-02-10 DK DK064789A patent/DK64789A/da not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2012846A1 (de) * | 1969-03-24 | 1970-10-08 | United States Atomic Energy Commission, Washington, D.C. | Elektroplattierlösung und Elektroplattierverfahren |
| DE3112834A1 (de) * | 1981-03-31 | 1982-10-14 | Siemens AG, 1000 Berlin und 8000 München | "metallbeschichtete eisenwerkstoffe" |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1524336A1 (fr) * | 2003-10-18 | 2005-04-20 | Aluminal Oberflächtentechnik GmbH & Co. KG | Pièces à usiner recouvertes d'un alliage aluminium-magnesium |
| WO2005035835A3 (fr) * | 2003-10-18 | 2005-06-23 | Aluminal Oberflaechentechnik | Pieces a usiner enduites d'un alliage aluminium-magnesium |
| DE102017201559A1 (de) | 2017-01-31 | 2018-08-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Atmosphärendruckplasmaverfahren zur Herstellung von plasmapolymeren Beschichtungen |
| WO2018141802A1 (fr) | 2017-01-31 | 2018-08-09 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Procédé à plasma à pression atmosphérique pour fabriquer des revêtements en polymère plasma |
Also Published As
| Publication number | Publication date |
|---|---|
| IE890424L (en) | 1989-08-12 |
| ATE74630T1 (de) | 1992-04-15 |
| IE61700B1 (en) | 1994-11-16 |
| CA1337690C (fr) | 1995-12-05 |
| ES2032341T5 (es) | 1995-11-16 |
| DE3804303A1 (de) | 1989-08-24 |
| ES2032341T3 (es) | 1993-02-01 |
| DK64789A (da) | 1989-08-13 |
| DK64789D0 (da) | 1989-02-10 |
| JPH01247593A (ja) | 1989-10-03 |
| US4925536A (en) | 1990-05-15 |
| JP2824267B2 (ja) | 1998-11-11 |
| EP0328128B2 (fr) | 1995-09-20 |
| DE58901105D1 (de) | 1992-05-14 |
| EP0328128B1 (fr) | 1992-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3428345C2 (fr) | ||
| DE3048083C2 (de) | Verfahren zur chemischen Entfernung von Oxidschichten von Gegenständen aus Titan oder Titanlegierungen | |
| EP2899299A1 (fr) | Électrolyte au chrome trivalent et méthode de déposition du chrome métallique | |
| DE19523307A1 (de) | Verchromungsverfahren unter Verwendung von trivalentem Chrom | |
| EP2283170A1 (fr) | Bains d'électrolyte au pd et au pd-ni | |
| EP3253906B1 (fr) | Électrolyte pour placage électrolytique | |
| Rashwan et al. | Electrodeposition and characterization of thin layers of Zn–Co alloys obtained from glycinate baths | |
| DE2822463A1 (de) | Verfahren zum kathodischen aufbringen eines chromhaltigen schutzueberzugs | |
| DE2430250A1 (de) | Verfahren zum galvanischen abscheiden von metallen und elektrolytbad zur durchfuehrung des verfahrens | |
| DE3710368A1 (de) | Waessriges saures bad und verfahren fuer die galvanische abscheidung einer zink-nickel-legierung | |
| CA1129805A (fr) | Electrodeposition a l'alliage de ruthenium et d'iridium | |
| DE2114119A1 (de) | Verfahren zur elektrolytischen Abscheidung von Ruthenium und Elektrolysebad zur Durchfuehrung dieses Verfahrens | |
| EP0328128B2 (fr) | Procédé relatif à l'adhérence entre des matériaux métalliques et des couches d'aluminium galvaniques ainsi que l'électrolyte non aqueux utilisé dans ce but | |
| DE2724730A1 (de) | Verfahren und elektrolyt zum abscheiden von chromhaltigen umwandlungsschutzueberzuegen | |
| DE2917019C2 (de) | Verfahren zur Metallisierung von Verbundmaterial und dazu geeignete Badzusammensetzung | |
| EP2635724B1 (fr) | Procédé de placage de chrome dur à partir d'un électrolyte sans cr(vi) | |
| DE68905429T2 (de) | Verfahren fuer das zinn-elektroplattieren von metallischem material. | |
| DE3347593C2 (fr) | ||
| EP2989236B1 (fr) | Liquides électro-conducteurs à base de complexes métal-diphosphonate | |
| Levason et al. | Studies of platinum electroplating baths: Part V: Solutions derived from Pt (NO2) 42− in aqueous acid | |
| DE3108202A1 (de) | Verfahren zur elektrolytischen abscheidung von schichten von nickellegierungen mit legierungselementen | |
| DE2743847A1 (de) | Verfahren zur galvanischen abscheidung von nickel und kobalt alleine oder als binaere oder ternaere legierungen | |
| DE19610361A1 (de) | Bad und Verfahren für die galvanische Abscheidung von Halbglanznickel | |
| DE2818780A1 (de) | Galvanisches bad zum elektroplattieren von chrom oder chromlegierungen | |
| DE2333096B2 (de) | Galvanisch aufgebrachter mehrschichtiger Metallüberzug und Verfahren zu seiner Herstellung |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE |
|
| 17P | Request for examination filed |
Effective date: 19890920 |
|
| 17Q | First examination report despatched |
Effective date: 19910717 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE |
|
| REF | Corresponds to: |
Ref document number: 74630 Country of ref document: AT Date of ref document: 19920415 Kind code of ref document: T |
|
| ITF | It: translation for a ep patent filed | ||
| REF | Corresponds to: |
Ref document number: 58901105 Country of ref document: DE Date of ref document: 19920514 |
|
| ET | Fr: translation filed | ||
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| 26 | Opposition filed |
Opponent name: SIEMENS AG GR PA 8 Effective date: 19930108 |
|
| NLR1 | Nl: opposition has been filed with the epo |
Opponent name: SIEMENS AG |
|
| EPTA | Lu: last paid annual fee | ||
| EAL | Se: european patent in force in sweden |
Ref document number: 89102319.4 |
|
| PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
| 27A | Patent maintained in amended form |
Effective date: 19950920 |
|
| AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH DE ES FR GB IT LI LU NL SE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN |
|
| ET3 | Fr: translation filed ** decision concerning opposition | ||
| NLR2 | Nl: decision of opposition | ||
| GBTA | Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977) |
Effective date: 19951018 |
|
| ITF | It: translation for a ep patent filed | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Kind code of ref document: T5 Effective date: 19951116 |
|
| NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19990218 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20000114 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20000117 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20000122 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20000124 Year of fee payment: 12 Ref country code: LU Payment date: 20000124 Year of fee payment: 12 Ref country code: FR Payment date: 20000124 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20000125 Year of fee payment: 12 Ref country code: AT Payment date: 20000125 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000208 Year of fee payment: 12 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010210 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010210 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010210 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010211 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010212 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010228 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010228 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010228 |
|
| BERE | Be: lapsed |
Owner name: STUDIEN G.- KOHLE M.B.H. Effective date: 20010228 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010901 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20010210 |
|
| EUG | Se: european patent has lapsed |
Ref document number: 89102319.4 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011031 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20010901 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011201 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20020916 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050210 |
|
| PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |