EP1975282A1 - Electrolyte and method for separating decorative and technical layers from black ruthenium - Google Patents
Electrolyte and method for separating decorative and technical layers from black ruthenium Download PDFInfo
- Publication number
- EP1975282A1 EP1975282A1 EP07006380A EP07006380A EP1975282A1 EP 1975282 A1 EP1975282 A1 EP 1975282A1 EP 07006380 A EP07006380 A EP 07006380A EP 07006380 A EP07006380 A EP 07006380A EP 1975282 A1 EP1975282 A1 EP 1975282A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- electrolyte
- ruthenium
- phosphonic acid
- phosphonic
- 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
- 239000003792 electrolyte Substances 0.000 title claims abstract description 61
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 12
- 150000003007 phosphonic acid derivatives Chemical class 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 claims abstract description 11
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 4
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 9
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 1-acetylamino-2,2,2 -trichloroethyl Chemical group 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229940120146 EDTMP Drugs 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 208000035220 Dyserythropoietic Congenital Anemia Diseases 0.000 claims description 3
- YAWYUSRBDMEKHZ-UHFFFAOYSA-N [2-hydroxyethyl(phosphonomethyl)amino]methylphosphonic acid Chemical compound OCCN(CP(O)(O)=O)CP(O)(O)=O YAWYUSRBDMEKHZ-UHFFFAOYSA-N 0.000 claims description 3
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 3
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- WCJYZAIHHQFLSS-UHFFFAOYSA-N (1-benzamido-2,2,2-trichloroethyl)phosphonic acid Chemical compound OP(O)(=O)C(C(Cl)(Cl)Cl)NC(=O)C1=CC=CC=C1 WCJYZAIHHQFLSS-UHFFFAOYSA-N 0.000 claims description 2
- SIXJDNRSTUBUBM-UHFFFAOYSA-N (1-benzamido-2,2-dichloroethenyl)phosphonic acid Chemical compound OP(O)(=O)C(=C(Cl)Cl)NC(=O)C1=CC=CC=C1 SIXJDNRSTUBUBM-UHFFFAOYSA-N 0.000 claims description 2
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 claims description 2
- UIQSKEDQPSEGAU-UHFFFAOYSA-N 1-Aminoethylphosphonic Acid Chemical compound CC(N)P(O)(O)=O UIQSKEDQPSEGAU-UHFFFAOYSA-N 0.000 claims description 2
- DELJNDWGTWHHFA-UHFFFAOYSA-N 1-azaniumylpropyl(hydroxy)phosphinate Chemical compound CCC(N)P(O)(O)=O DELJNDWGTWHHFA-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WFCQGBOETURRDK-UHFFFAOYSA-N [2-amino-1,1,1-trichloro-3-(furan-2-yl)-3-oxopropan-2-yl]phosphonic acid Chemical compound ClC(Cl)(Cl)C(P(O)(O)=O)(N)C(=O)C1=CC=CO1 WFCQGBOETURRDK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- SPDJZXXKQOBLBT-UHFFFAOYSA-N n-[6-[bis[hydroxy(methoxy)phosphoryl]amino]hexyl]-n-[hydroxy(methoxy)phosphoryl]-methoxyphosphonamidic acid Chemical compound COP(O)(=O)N(P(O)(=O)OC)CCCCCCN(P(O)(=O)OC)P(O)(=O)OC SPDJZXXKQOBLBT-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- BQIYVTCUMQVDEJ-UHFFFAOYSA-N (1-amino-1-phosphonooctyl)phosphonic acid Chemical compound CCCCCCCC(N)(P(O)(O)=O)P(O)(O)=O BQIYVTCUMQVDEJ-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- HPPXSNUAVNMIES-UHFFFAOYSA-N [(4-chlorophenyl)-hydroxymethyl]phosphonic acid Chemical compound OP(=O)(O)C(O)C1=CC=C(Cl)C=C1 HPPXSNUAVNMIES-UHFFFAOYSA-N 0.000 claims 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000005137 deposition process Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OZMCKSGKGHEMGG-UHFFFAOYSA-N (1-acetamido-2,2,2-trichloroethyl)phosphonic acid Chemical compound CC(=O)NC(C(Cl)(Cl)Cl)P(O)(O)=O OZMCKSGKGHEMGG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LMCWAAVARQXGCR-UHFFFAOYSA-N NCCNCCN.ClC1=CC=C(C=C1)C(O)P(O)(O)=O Chemical compound NCCNCCN.ClC1=CC=C(C=C1)C(O)P(O)(O)=O LMCWAAVARQXGCR-UHFFFAOYSA-N 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 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
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 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
- 239000000383 hazardous chemical Substances 0.000 description 1
- QSIBMCLAMXSMRM-UHFFFAOYSA-N hexane-1,6-diamine methylphosphonic acid Chemical compound CP(O)(O)=O.CP(O)(O)=O.CP(O)(O)=O.CP(O)(O)=O.NCCCCCCN QSIBMCLAMXSMRM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
Definitions
- the invention relates to a ruthenium electrolyte, which is suitable for the deposition of decorative and technical layers with particular blackness. Furthermore, the invention relates to a method for the deposition of decorative and technical layers of ruthenium with special blackness ("black-ruthenium”) on jewelry, decorative items, durable goods and technical items.
- black-ruthenium ruthenium with special blackness
- Durable consumer goods and technical articles, jewelery and decorative goods are finished with thin oxidation-stable metal layers to protect against corrosion and / or for visual enhancement. These layers must be mechanically stable and should not show tarnish or signs of wear even after prolonged use.
- a proven means for producing such layers are electroplating processes, which can be used to obtain a variety of metal and alloy layers in high quality form. Examples well-known from everyday life are galvanic bronze and brass layers on doorknobs or buttons, chrome plating of vehicle parts, galvanized tools or gold plating on watch straps.
- a particular challenge in the field of galvanic finishing is the production of oxidation-stable and mechanically strong metal coatings in black color, which can be interesting not only in the decorative and decorative sector but also for technical applications, for example in the field of solar technology. Only a few metals are available for producing oxidation-stable, black layers.
- ruthenium, rhodium and nickel are suitable.
- the use of the precious metal rhodium is limited to the jewelry sector because of the high raw material costs.
- the use of cost-effective nickel and nickel-containing alloys is especially in the jewelry and durable goods sector only in exceptional cases and in compliance with strict conditions possible, since it is nickel and nickel-containing Metal layers around contact allergens is.
- the use of ruthenium is a useful alternative for all described applications.
- Electrolytes for producing black ruthenium layers in electroplating processes are known in the art.
- the most common baths contain ruthenium in complexed form with sulfamic acid or ruthenium as nitridochloro or nitridobromo complex.
- JP 63259095 a process for ruthenium electroplating using a bath containing 5 g / l ruthenium and 100 to 150 g / l amidosulfonic acid.
- the WO 2001/011113 discloses a ruthenium electrolyte containing ruthenium sulfate and sulfamic acid (amidosulfonic acid).
- a blackening additive a thio compound is used. To protect the thio compound from decomposition by anodic oxidation, a sacrificial substance must also be added.
- An electrolyte for the electrodeposition of low-stress, crack-resistant ruthenium layers contains ruthenium in complexed with amidosulfuric acid and pyridine or N-alkylated pyridinium salts.
- US 4,375,392 claims an acidic electrolyte for depositing ruthenium on various substrates containing a complex of ruthenium and amidosulfonic acid present in a molar ratio of 4 to 10 moles of amidosulfonic acid per mole of ruthenium and in appropriate concentration, and containing a second compound of a metal selected from the group containing nickel, cobalt, iron, tin, lead and magnesium. The concentration of the second metal is chosen so that crack-free ruthenium layers can be deposited.
- the pH of the bath is between 0.1 and 2.2.
- DE 1 959 907 describes the use of the dinuclear ruthenium complex [Ru 2 NCl x Br 8-x (H 2 O) 2 ] 3- in an electroplating plating bath.
- the nitrido-chloro complex [Ru 2 NCl 8 (H 2 O) 2 ] 3- is used.
- This nitridochloro complex of ruthenium is also used in the aqueous, non-acidic bath for electrodeposition of ruthenium, which is used in the US 4,297,178 is described. It also contains oxalic acid or an oxalate.
- the invention relates to a ruthenium electrolyte which contains, in addition to 1 to 20 g / l of ruthenium, one or more compounds selected from the group consisting of dicarboxylic and tricarboxylic acids, benzenesulfonic acid, N-containing aromatics, and amino acids or derivatives of said compounds, and in which moreover 0.01 to 10 g / l of a thio compound is used as a blackening additive.
- JP 2054792 contains, in addition to an inorganic ruthenium salt, preferably ruthenium sulfate, and an inorganic acid, preferably sulfuric acid, a "metal of group III", preferably Sc, Y, In or Ga.
- black layers For the finishing of jewelery and decorative objects, black layers must have a perfect optical adhesive quality in addition to an excellent mechanical adhesion. If necessary, they must be able to be produced in a glossy or matt form and with a very deep blackness. The same applies to applications in the technical field, in particular in solar technology. Blackcoats for processing consumer goods must also meet high mechanical stability requirements. In particular, they must not show any black abrasion even with frequent use for a long time.
- ruthenium baths described in the prior art which meet these requirements are either dependent on the use of toxicologically harmful compounds such as thio compounds as blackening additive or contain another transition metal to ensure the required mechanical adhesion, making it difficult to guide the bath during the deposition process.
- the present invention was therefore based on the object of providing a non-toxic electrolyte for depositing layers of ruthenium with particular blackness ("black ruthenium”), with which black layers can be produced in a galvanic standard process, which are characterized by high mechanical properties Stability, in particular by abrasion resistance even with frequent use, distinguished and which can be generated in various degrees of gloss preserving gloss.
- black ruthenium ruthenium with particular blackness
- an electrolyte which contains one or more phosphonic acid derivatives as a blackening additive.
- a method is provided, with the use of the electrolyte according to the invention decorative and technical layers of ruthenium with special blackness (“black-ruthenium”) can be applied to jewelry, Dekorgüter, consumer goods and technical items, wherein the substrates to be coated in be immersed in the electrolyte of the invention.
- Non-toxic in the sense of this document is understood to mean that in the so-called electrolyte according to the invention no substances are contained, which according to the regulations in force in Europe for handling dangerous goods and hazardous substances as “toxic” (T) or “very toxic "(T + ) are to be classified.
- Ruthenium is used in the form of a water-soluble compound, preferably as a binuclear anionic nitrido-halo-complex compound of the formula [Ru 2 N (H 2 O) 2 X 8 ] 3- wherein X is a halide ion. Particularly preferred is the chloro complex [Ru 2 N (H 2 O) 2 Cl 8 ] 3- .
- the amount of the complex compound in the electrolyte of the invention is chosen so that the volume concentration of the ruthenium after complete dissolution of the compound between 0.2 and 20 grams per liter of electrolyte, calculated as ruthenium metal, is. More preferably, the final electrolyte contains from 1 to 15 grams of ruthenium per liter of electrolyte, most preferably from 3 to 10 grams of ruthenium per liter of electrolyte.
- the blackening of the electrodeposited ruthenium layers is achieved by selectively inhibiting the rate of deposition from the plating bath.
- an inhibitor and thus as a blackening additive one or more phosphonic acid derivatives are contained in the bath according to the invention.
- the compounds used are preferably the compounds aminophosphonic acid AP, 1-aminomethylphosphonic acid AMP, amino-tris (methylenephosphonic acid) ATMP, 1-aminoethylphosphonic acid AEP, 1-aminopropylphosphonic acid APP, (1-acetylamino-2,2,2-trichloroethyl) -phosphonic acid, Amino-1-phosphona-actyl) -phosphonic acid, (1-benzoylamino-2,2,2-trichloroethyl) -phosphonic acid, (1-benzoylamino-2,2-dichlorovinyl) -phosphonic acid, (4-chlorophenyl-hydroxymethyl) -phosphonic acid Diethylenetriamine penta (methylenephosphonic acid) DTPMP, ethylenediamine tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP, hydroxyethyl-amino-d
- Particular preference is given to using one or more compounds selected from the group consisting of amino-tris (methylenephosphonic acid) ATMP, diethylenetriamine-penta (methylenephosphonic acid) DTPMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid ) HEDP, hydroxyethylamino-di (methylenephosphonic acid) HEMPA, hexamethylenediamine tetra (methylphosphonic acid) HDTMP, salts derived therefrom or condensates derived therefrom, or combinations thereof.
- amino-tris methylenephosphonic acid
- DTPMP diethylenetriamine-penta
- EDTMP ethylenediamine-tetra (methylenephosphonic acid)
- 1-hydroxyethane- (1,1-di-phosphonic acid ) HEDP hydroxyethylamino-di (methylenephosphonic acid) HEMPA
- HEMPA
- Amino-tris (methylenephosphonic acid) ATMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP and 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP and salts derived therefrom or condensates derived therefrom are outstandingly suitable in particular for the coating of decorative and consumer goods , or combinations thereof.
- the concentration of the blackening additive determines the degree of blackening of the layer to be produced. It must be chosen so that the desired depth of blackening is achieved, but must not be too high. If the concentration of the blackening additive is chosen too high, current densities must be selected in order to ensure economical deposition rates, in which the adhesive strength of the resulting ruthenium layer is no longer guaranteed.
- the electrolyte according to the invention preferably contains between 0.1 and 20 grams of phosphonic acid derivatives per liter of electrolyte, more preferably 1 to 10 grams of phosphonic acid derivatives per liter of electrolyte. If dark gray, not deep black dyeings are to be achieved, 0.1 to 4 grams of phosphonic acid derivatives in liters of electrolyte are preferred.
- the phosphonic acid derivatives used are gloss-preserving.
- the color of the resulting Layer can be adjusted in all variants from light black to deep black, without changing their characteristic gloss.
- the pH of the bath according to the invention is preferably between 0 and 3, particularly preferably between 0.5 and 2.
- the electrolyte according to the invention may contain inorganic mineral acids, preferably selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, nitrous acid, amidosulfonic acid , Sulfuric acid, sulfuric acid, disulfuric acid, dithionic acid, disulfurous acid and dithionic acid, or combinations thereof.
- hydrochloric acid hydrobromic acid, sulfamic acid and sulfuric acid or combinations thereof are suitable.
- the preferred volume concentration of inorganic mineral acid is between 0 and 50 grams per liter of electrolyte, more preferably between 0 and 40 grams per liter of electrolyte.
- Particularly suitable electrolytes for the deposition of uniform, decorative black ruthenium layers contain between 1 and 10 grams of sulfuric acid per liter of electrolyte.
- the electrolyte may contain, in addition to ruthenium and the phosphonic acid derivatives, organic additives which take over the function of the wetting agent.
- the addition of one or more compounds is preferably selected from the group of the alkanesulfonic acids or the ionic and nonionic surfactants or combinations thereof. Alkanesulfonic acids are particularly suitable.
- the erfuidungswele bath is suitable for the deposition of layers of pure ruthenium, but not for the deposition of ruthenium alloys. Except ruthenium, the electrolyte contains no transition metal ions.
- the described ruthenium electrolyte which is the subject of the present invention, is particularly suitable for the deposition of decorative deep black-glossy layers, for example, on jewelery and decorative objects. It can preferably be used in drum and frame coating processes.
- the pieces of jewelery, decorative goods, consumer goods or technical articles (collectively referred to as substrates) to be coated dip into the electrolyte according to the invention and form the cathode.
- the electrolyte is preferably tempered in a range of 20 to 80 ° C.
- Particularly decorative layers are obtained at electrolyte temperatures of 60 to 70 ° C.
- a current density of 0.01 to 10 A / dm 2 is preferably set, particularly preferably 0.05 to 5 A / dm 2 .
- the chosen value is also determined by the type of coating process. In a drum coating process, the preferred current density is between 0.05 to 1 A / dm 2 . In frame coating processes, a current density of 0.5 to 5 A / dm 2 leads to optically flawless black ruthenium layers.
- Insoluble anodes are suitable for carrying out the galvanic deposition process from the acidic ruthenium bath according to the invention.
- Anodes are preferably used from a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon” DLC) or combinations thereof.
- an inventive electrolyte was used, which in addition to 2.5 g / L ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- 15 g / L 1-hydroxyethane (1,1-di phosphonic acid) HEDP dissolved in water as a blackening additive and containing 20 g / L sulfuric acid.
- the electrolyte had a pH of 0.8.
- the substrates were provided with mechanically stable, abrasion-resistant black layers, which are considered optically flawless in the consumer goods sector.
- a slight irregularity in the layer thickness of the layers obtained limits the use of this bath according to the invention to applications outside the jewelry area.
- an electrolyte according to the invention was used, the 5 g / L ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- and 1.5 g / L ethylenediamine tetra (methylenephosphonic) EDTMP as Blackening additive contained in water.
- 4 g / L sulfuric acid was added to the electrolyte so that the pH at the beginning of the deposition was 1.3.
- suitable substrates were finished at a set current density of 0.5 to 3 A / dm 2 with black ruthenium layers.
- the electrolyte was heated at 60 to 70 ° C.
- the layers obtained had a very good mechanical stability, showed a deep black color and high gloss.
- the optical quality of the layers thus produced was so high that the suitability of this bath according to the invention is also given for the jewelry and decor area.
- a further bath according to the invention was investigated which contained 5 g / l of ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- and 5 g / l of amino-tris (methylenephosphonic acid) ATMP in water.
- the pH of the bath was adjusted to 1.4 with 4 g / L sulfuric acid.
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Abstract
Description
Die Erfindung betrifft einen Ruthenium-Elektrolyten, der sich zur Abscheidung von dekorativen und technischen Schichten mit besonderer Schwärze eignet. Weiterhin betrifft die Erfindung ein Verfahren zur Abscheidung von dekorativen und technischen Schichten aus Ruthenium mit besonderer Schwärze ("Schwarz-Ruthenium") auf Schmuckstücke, Dekorgüter, Gebrauchsgüter und technische Gegenstände.The invention relates to a ruthenium electrolyte, which is suitable for the deposition of decorative and technical layers with particular blackness. Furthermore, the invention relates to a method for the deposition of decorative and technical layers of ruthenium with special blackness ("black-ruthenium") on jewelry, decorative items, durable goods and technical items.
Gebrauchsgüter und technische Gegenstände, Schmuckstücke und Dekorgüter werden zum Schutz vor Korrosion und/oder zur optischen Aufwertung mit dünnen oxidationsstabilen Metallschichten veredelt. Diese Schichten müssen mechanisch stabil sein und sollen auch bei längerem Gebrauch keine Anlauffarben oder Abnutzungserscheinungen zeigen. Ein probates Mittel zur Erzeugung solcher Schichten sind galvanische Verfahren, mit denen eine Vielzahl von Metall- und Legierungsschichten in qualitativ hochwertiger Form erhalten werden können. Aus dem Alltag gut bekannte Beispiele sind galvanische Bronze- und Messingschichten auf Türklinken oder Knöpfen, Chromüberzüge von Fahrzeugteilen, verzinkte Werkzeuge oder Goldüberzüge auf Uhrenarmbändern.Durable consumer goods and technical articles, jewelery and decorative goods are finished with thin oxidation-stable metal layers to protect against corrosion and / or for visual enhancement. These layers must be mechanically stable and should not show tarnish or signs of wear even after prolonged use. A proven means for producing such layers are electroplating processes, which can be used to obtain a variety of metal and alloy layers in high quality form. Examples well-known from everyday life are galvanic bronze and brass layers on doorknobs or buttons, chrome plating of vehicle parts, galvanized tools or gold plating on watch straps.
Eine besondere Herausforderung im Bereich der galvanischen Veredelung stellt die Erzeugung oxidationsstabiler und mechanisch belastbarer Metallschichten in schwarzer Farbe dar, die außer im Dekor- und Schmuckbereich auch für technische Anwendungen beispielsweise im Bereich der Solartechnik interessant sein können. Zur Erzeugung oxidationsstabiler, schwarzer Schichten stehen nur wenige Metalle zur Verfügung. Neben Ruthenium eignen sich Rhodium und Nickel. Die Verwendung des Edelmetalls Rhodium ist wegen der hohen Rohstoffkosten auf den Schmuckbereich beschränkt. Die Verwendung von kostengünstigem Nickel und Nickel-haltigen Legierungen ist insbesondere im Schmuck- und Gebrauchsgüterbereich nur noch in Ausnahmefällen und unter Beachtung strenger Auflagen möglich, da es sich bei Nickel und Nickel-haltigen Metallschichten um Kontaktallergene handelt. Die Verwendung von Ruthenium stellt eine sinnvolle Alternative für alle beschriebenen Anwendungsfelder dar.A particular challenge in the field of galvanic finishing is the production of oxidation-stable and mechanically strong metal coatings in black color, which can be interesting not only in the decorative and decorative sector but also for technical applications, for example in the field of solar technology. Only a few metals are available for producing oxidation-stable, black layers. In addition to ruthenium, rhodium and nickel are suitable. The use of the precious metal rhodium is limited to the jewelry sector because of the high raw material costs. The use of cost-effective nickel and nickel-containing alloys is especially in the jewelry and durable goods sector only in exceptional cases and in compliance with strict conditions possible, since it is nickel and nickel-containing Metal layers around contact allergens is. The use of ruthenium is a useful alternative for all described applications.
Elektrolyte zur Erzeugung von schwarzen Rutheniumschichten in galvanischen Veredelungsverfahren sind im Stand der Technik bekannt. Die gängigsten Bäder enthalten Ruthenium in mit Amidosulfonsäure komplexierter Form oder Ruthenium als Nitridochloro- oder Nitridobromokomplex.Electrolytes for producing black ruthenium layers in electroplating processes are known in the art. The most common baths contain ruthenium in complexed form with sulfamic acid or ruthenium as nitridochloro or nitridobromo complex.
Beispielsweise beschreibt die
In
Zur Veredelung von Schmuck und Dekorgütern müssen schwarze Schichten neben einer exzellenten mechanischen Haftfestigkeit eine einwandfreie optische Qualität aufweisen. Sie müssen bei Bedarf in glänzender oder matter Form und mit sehr tiefer Schwärze herstellbar sein. Entsprechendes gilt für Anwendungen im technischen Bereich, insbesondere in der Solartechnik. Schwarzschichten zur Veredelung von Gebrauchsgütern müssen darüber hinaus hohen Anforderungen an die mechanische Stabilität genügen. Insbesondere dürfen sie auch bei häufigem Gebrauch über längere Zeit keinen schwarzen Abrieb zeigen.For the finishing of jewelery and decorative objects, black layers must have a perfect optical adhesive quality in addition to an excellent mechanical adhesion. If necessary, they must be able to be produced in a glossy or matt form and with a very deep blackness. The same applies to applications in the technical field, in particular in solar technology. Blackcoats for processing consumer goods must also meet high mechanical stability requirements. In particular, they must not show any black abrasion even with frequent use for a long time.
Die im Stand der Technik beschriebenen Rutheniumbäder, die diesen Anforderungen genügen, sind entweder auf die Verwendung toxikologisch bedenklicher Verbindungen wie Thioverbindungen als Schwärzungszusatz angewiesen oder enthalten zur Gewährleistung der geforderten mechanischen Haftfestigkeit ein weiteres Übergangsmetall, was die Führung des Bades während des Abscheideprozesses erschwert.The ruthenium baths described in the prior art which meet these requirements are either dependent on the use of toxicologically harmful compounds such as thio compounds as blackening additive or contain another transition metal to ensure the required mechanical adhesion, making it difficult to guide the bath during the deposition process.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, einen nicht giftigen Elektrolyten zur Abscheidung von Schichten aus Ruthenium mit besonderer Schwärze ("Schwarz-Ruthenium") zur Verfügung zu stellen, mit dem in einem galvanischen Standardverfahren Schwarzschichten erzeugt werden können, die sich durch hohe mechanische Stabilität, insbesondere durch Abriebbeständigkeit auch bei häufigem Gebrauch, auszeichnen und die darüber hinaus in verschiedenen Schwärzegraden glanzerhaltend erzeugt werden können.The present invention was therefore based on the object of providing a non-toxic electrolyte for depositing layers of ruthenium with particular blackness ("black ruthenium"), with which black layers can be produced in a galvanic standard process, which are characterized by high mechanical properties Stability, in particular by abrasion resistance even with frequent use, distinguished and which can be generated in various degrees of gloss preserving gloss.
Diese Aufgabe wird durch einen Elektrolyten gelöst, der ein oder mehrere Phosphonsäurederivate als Schwärzungszusatz enthält. Außerdem wird ein Verfahren zur Verfügung gestellt, mit dem unter Verwendung des erfindungsgemäßen Elektrolyten dekorative und technische Schichten aus Ruthenium mit besonderer Schwärze ("Schwarz-Ruthenium") auf Schmuckstücke, Dekorgüter, Gebrauchsgüter und technische Gegenstände aufgebracht werden können, wobei die zu beschichtenden Substrate in den erfindungsgemäßen Elektrolyten eingetaucht werden.This object is achieved by an electrolyte which contains one or more phosphonic acid derivatives as a blackening additive. In addition, a method is provided, with the use of the electrolyte according to the invention decorative and technical layers of ruthenium with special blackness ("black-ruthenium") can be applied to jewelry, Dekorgüter, consumer goods and technical items, wherein the substrates to be coated in be immersed in the electrolyte of the invention.
Unter "nicht giftig" im Sinne dieser Schrift wird dabei verstanden, daß in dem so bezeichneten, erfindungsgemäßen Elektrolyten keine Stoffe enthalten sind, die gemäß den in Europa gültigen Verordnungen zum Umgang mit gefährlichen Gütern und Gefahrstoffen als "giftig" (T) oder "sehr giftig" (T+) einzustufen sind."Non-toxic" in the sense of this document is understood to mean that in the so-called electrolyte according to the invention no substances are contained, which according to the regulations in force in Europe for handling dangerous goods and hazardous substances as "toxic" (T) or "very toxic "(T + ) are to be classified.
Ruthenium wird in Form einer wasserlöslichen Verbindung eingesetzt, bevorzugt als zweikernige, anionische Nitridohalogenokomplexverbindung der Formel [Ru2N(H2O)2X8]3-, wobei X ein Halogenidion ist. Besonders bevorzugt ist der Chlorokomplex [Ru2N(H2O)2Cl8]3-. Die Menge der Komplexverbindung im erfindungsgemäßen Elektrolyten wird so gewählt, daß die Volumenkonzentration des Rutheniums nach vollständigem Lösen der Verbindung zwischen 0,2 und 20 Gramm pro Liter Elektrolyt, berechnet als Ruthenium-Metall, liegt. Besonders bevorzugt enthält der fertige Elektrolyt 1 bis 15 Gramm Ruthenium pro Liter Elektrolyt, ganz besonders bevorzugt 3 bis 10 Gramm Ruthenium pro Liter Elektrolyt.Ruthenium is used in the form of a water-soluble compound, preferably as a binuclear anionic nitrido-halo-complex compound of the formula [Ru 2 N (H 2 O) 2 X 8 ] 3- wherein X is a halide ion. Particularly preferred is the chloro complex [Ru 2 N (H 2 O) 2 Cl 8 ] 3- . The amount of the complex compound in the electrolyte of the invention is chosen so that the volume concentration of the ruthenium after complete dissolution of the compound between 0.2 and 20 grams per liter of electrolyte, calculated as ruthenium metal, is. More preferably, the final electrolyte contains from 1 to 15 grams of ruthenium per liter of electrolyte, most preferably from 3 to 10 grams of ruthenium per liter of electrolyte.
Die Schwarzfärbung der galvanisch erzeugten Rutheniumschichten wird dadurch erreicht, daß die Abscheiderrate aus dem galvanischen Bad gezielt inhibiert wird. Als Inhibitor und somit als Schwärzungszusatz sind im erfindungsgemäßen Bad ein oder mehrere Phosphonsäurederivate enthalten.The blackening of the electrodeposited ruthenium layers is achieved by selectively inhibiting the rate of deposition from the plating bath. As an inhibitor and thus as a blackening additive, one or more phosphonic acid derivatives are contained in the bath according to the invention.
Bevorzugt eingesetzt werden die Verbindungen Aminophosphonsäure AP, 1-Aminomethylphosphonsäure AMP, Amino-tris(methylenphosphonsäure) ATMP, 1-Aminoethylphosphonsäure AEP, 1-Aminopropylphosphonsäure APP, (1-Acetylamino-2,2,2-trichloroethyl)-phosphonsäure, (1-Amino-1-phosphona-actyl)-phosphonsäure, (1-Benzoylamino-2,2,2-trichloroethyl)-phosphonsäure, (1-Benzoylamino-2,2-dichlorovinyl)-phosphonsäure, (4-Chlorophenyl-hydroxymethyl)-phosphonsäure, Diethylentriaminpenta(methylenphosphonsäure) DTPMP, Ethylendiamin-tetra(methylenphosphonsäure) EDTMP, 1-Hydroxyethan-(1,1-di-phosphonsäure) HEDP, Hydroxyethyl-amino-di(methylenphosphonsäure) HEMPA, Hexamethylendiamin-tetra(methylphosphonsäure) HDTMP, ((Hydroxymethyl-phosphonomethyl-amino)-methyl)-phasphonsäure, Nitrilotris(methylenphosphonsäure) NTMP, 2,2,2-Trichloro-1-(furan-2-carbonyl)-amino-ethylphosphonsäure, davon abgeleitete Salze oder davon abgeleitete Kondensate, oder Kombinationen davon.The compounds used are preferably the compounds aminophosphonic acid AP, 1-aminomethylphosphonic acid AMP, amino-tris (methylenephosphonic acid) ATMP, 1-aminoethylphosphonic acid AEP, 1-aminopropylphosphonic acid APP, (1-acetylamino-2,2,2-trichloroethyl) -phosphonic acid, Amino-1-phosphona-actyl) -phosphonic acid, (1-benzoylamino-2,2,2-trichloroethyl) -phosphonic acid, (1-benzoylamino-2,2-dichlorovinyl) -phosphonic acid, (4-chlorophenyl-hydroxymethyl) -phosphonic acid Diethylenetriamine penta (methylenephosphonic acid) DTPMP, ethylenediamine tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP, hydroxyethyl-amino-di (methylenephosphonic acid) HEMPA, hexamethylenediamine-tetra (methylphosphonic acid) HDTMP, ((hydroxymethyl-phosphonomethyl-amino ) -methyl) -phasphonic acid, nitrilotris (methylenephosphonic acid) NTMP, 2,2,2-trichloro-1- (furan-2-carbonyl) -amino-ethylphosphonic acid, salts derived therefrom or condensates derived therefrom, or combinations thereof.
Besonders bevorzugt verwendet werden eine oder mehrere Verbindungen ausgewählt aus der Gruppe bestehend aus Amino-tris(methylenphosphonsäure) ATMP, Diethylentriamin-penta(methylenphosphonsäure) DTPMP, Ethylendiamin-tetra(methylenphosphonsäure) EDTMP, 1-Hydroxyethan-(1,1-di-phosphonsäure) HEDP, Hydroxyethylamino-di(methylenphosphonsäure) HEMPA, Hexamethylendiamin-tetra(methylphosphonsäure) HDTMP, davon abgeleitete Salze oder davon abgeleitete Kondensate, oder Kombinationen davon.Particular preference is given to using one or more compounds selected from the group consisting of amino-tris (methylenephosphonic acid) ATMP, diethylenetriamine-penta (methylenephosphonic acid) DTPMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid ) HEDP, hydroxyethylamino-di (methylenephosphonic acid) HEMPA, hexamethylenediamine tetra (methylphosphonic acid) HDTMP, salts derived therefrom or condensates derived therefrom, or combinations thereof.
Insbesondere für die Beschichtung von Dekor- und Gebrauchsgütern hervorragend geeignet sind Amino-tris(methylenphosphonsäure) ATMP, Ethylendiamin-tetra(methylenphosphonsäure) EDTMP und 1-Hydroxyethan-(1,1-di-phosphonsäure) HEDP sowie davon abgeleitete Salze oder davon abgeleitete Kondensate, oder Kombinationen davon.Amino-tris (methylenephosphonic acid) ATMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP and 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP and salts derived therefrom or condensates derived therefrom are outstandingly suitable in particular for the coating of decorative and consumer goods , or combinations thereof.
Die Konzentration des Schwärzungszusatzes bestimmt den Schwärzegrad der zu erzeugenden Schicht. Sie muß so gewählt werden, daß die gewünschte Tiefenschwärze erreicht wird, darf jedoch nicht zu hoch sein. Wird die Konzentration des Schwärzungszusatzes zu hoch gewählt, so müssen, um wirtschaftliche Abscheideraten sicherzustellen, Stromdichten gewählt werden, bei denen die Haftfestigkeit der resultierenden Rutheniumschicht nicht mehr gewährleistet ist. Bevorzugt enthält der erfindungsgemäße Elektrolyt zwischen 0,1 und 20 Gramm Phosphonsäurederivate pro Liter Elektrolyt, besonders bevorzugt 1 bis 10 Gramm Phosphonsäurederivate pro Liter Elektrolyt. Sollen dunkelgraue, nicht tiefschwarze Färbungen erzielt werden, sind 0,1 bis 4 Gramm Phosphonsäurederivate im Liter Elektrolyt bevorzugt.The concentration of the blackening additive determines the degree of blackening of the layer to be produced. It must be chosen so that the desired depth of blackening is achieved, but must not be too high. If the concentration of the blackening additive is chosen too high, current densities must be selected in order to ensure economical deposition rates, in which the adhesive strength of the resulting ruthenium layer is no longer guaranteed. The electrolyte according to the invention preferably contains between 0.1 and 20 grams of phosphonic acid derivatives per liter of electrolyte, more preferably 1 to 10 grams of phosphonic acid derivatives per liter of electrolyte. If dark gray, not deep black dyeings are to be achieved, 0.1 to 4 grams of phosphonic acid derivatives in liters of electrolyte are preferred.
Die eingesetzten Phosphonsäurederivate wirken glanzerhaltend. Durch eine geeignete Auswahl von Art und Menge der Phosphonsäurederivate kann die Farbe der resultierenden Schicht in allen Varianten von leichtschwarz bis tiefschwarz eingestellt werden, ohne ihren charakteristischen Glanz zu verändern.The phosphonic acid derivatives used are gloss-preserving. By a suitable choice of the type and amount of phosphonic acid derivatives, the color of the resulting Layer can be adjusted in all variants from light black to deep black, without changing their characteristic gloss.
Einen wichtigen Einfluß auf die Führbarkeit des Elektrolyten während des Abscheidevorgangs und die Qualität der resultierenden schwarzen Rutheniumschichten hat der pH-Wert des erfindungsgemäßen Bades. Er liegt bevorzugt zwischen 0 und 3, besonders bevorzugt zwischen 0,5 und 2. Zur Einstellung des pH-Wertes kann der erfindungsgemäße Elektrolyt anorganische Mineralsäuren enthalten, bevorzugt ausgewählt aus der Gruppe bestehend aus Salzsäure, Bromwasserstoffsäure, Iodwasserstoffsäure, Salpetersäure, Salpetrige Säure, Amidosulfonsäure, Schwefelsäure, Schwefelige Säure, Dischwefelsäure, Dithionsäure, Dischweflige Säure und Dithionige Säure oder Kombinationen davon. Insbesondere eignen sich Salzsäure, Bromwasserstoffsäure, Amidosulfonsäure und Schwefelsäure oder Kombinationen davon. Je nachdem, welches Phosphonsäurederivat in welcher Konzentration eingesetzt und welche Mineralsäure gewählt wird, beträgt die bevorzugte Volumenkonzentration der anorganischen Mineralsäure zwischen 0 und 50 Gramm pro Liter Elektrolyt, besonders bevorzugt zwischen 0 und 40 Gramm pro Liter Elektrolyt. Für die Abscheidung von gleichmäßigen, dekorativen Schwarz-Rutheniumschichten besonders gut geeignete Elektrolyte enthalten zwischen 1 und 10 Gramm Schwefelsäure pro Liter Elektrolyt.An important influence on the conductivity of the electrolyte during the deposition process and the quality of the resulting black ruthenium layers, the pH of the bath according to the invention. It is preferably between 0 and 3, particularly preferably between 0.5 and 2. To adjust the pH, the electrolyte according to the invention may contain inorganic mineral acids, preferably selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, nitrous acid, amidosulfonic acid , Sulfuric acid, sulfuric acid, disulfuric acid, dithionic acid, disulfurous acid and dithionic acid, or combinations thereof. In particular, hydrochloric acid, hydrobromic acid, sulfamic acid and sulfuric acid or combinations thereof are suitable. Depending on which phosphonic acid derivative is used at which concentration and which mineral acid is chosen, the preferred volume concentration of inorganic mineral acid is between 0 and 50 grams per liter of electrolyte, more preferably between 0 and 40 grams per liter of electrolyte. Particularly suitable electrolytes for the deposition of uniform, decorative black ruthenium layers contain between 1 and 10 grams of sulfuric acid per liter of electrolyte.
Der Elektrolyt kann außer Ruthenium und den Phosphonsäurederivaten organische Zusätze enthalten, die die Funktion des Netzmittels übernehmen. Bevorzugt ist der Zusatz einer oder mehrerer Verbindungen ausgewählt aus der Gruppe der Alkansulfonsäuren oder der ionischen und nicht-ionischen Tenside oder Kombinationen davon, Besonders gut geeignet sind Alkansulfonsäuren.The electrolyte may contain, in addition to ruthenium and the phosphonic acid derivatives, organic additives which take over the function of the wetting agent. The addition of one or more compounds is preferably selected from the group of the alkanesulfonic acids or the ionic and nonionic surfactants or combinations thereof. Alkanesulfonic acids are particularly suitable.
Das erfuidungsgemäße Bad eignet sich zur Abscheidung von Schichten aus reinem Ruthenium, jedoch nicht zur Abscheidung von Rutheniumlegierungen. Außer Ruthenium enthält der Elektrolyt keine Übergangsmetallionen.The erfuidungsgemäße bath is suitable for the deposition of layers of pure ruthenium, but not for the deposition of ruthenium alloys. Except ruthenium, the electrolyte contains no transition metal ions.
Der beschriebene Ruthenium-Elektrolyt, der Gegenstand der vorliegenden Erfindung ist, eignet sich besonders gut zur Abscheidung von dekorativen tiefschwarz-glänzenden Schichten beispielsweise auf Schmuckstücke und Dekorgüter. Er kann bevorzugt in Trommel- und Gestellbeschichtungsverfahren eingesetzt werden.The described ruthenium electrolyte, which is the subject of the present invention, is particularly suitable for the deposition of decorative deep black-glossy layers, for example, on jewelery and decorative objects. It can preferably be used in drum and frame coating processes.
In einem entsprechenden Verfahren zur galvanischen Aufbringung von Schwarz-Rutheniumschichten tauchen die zu beschichtenden Schmuckstücke, Dekorgüter, Gebrauchsgüter oder technischen Gegenstände (zusammenfassend als Substrate bezeichnet) in den erfindungsgemäßen Elektrolyten ein und bilden die Kathode. Der Elektrolyt wird bevorzugt in einem Bereich von 20 bis 80°C temperiert. Besonders dekorative Schichten werden bei Elektrolyt-Temperaturen von 60 bis 70°C erhalten.In a corresponding process for the electroplating of black ruthenium layers, the pieces of jewelery, decorative goods, consumer goods or technical articles (collectively referred to as substrates) to be coated dip into the electrolyte according to the invention and form the cathode. The electrolyte is preferably tempered in a range of 20 to 80 ° C. Particularly decorative layers are obtained at electrolyte temperatures of 60 to 70 ° C.
Um haftfeste, gleichmäßige Schichten zu erhalten, sollte eine maximale Stromdichte von 10 Ampere pro Quadratdezimeter [A/dm2] nicht überschritten werden. Oberhalb dieses Wertes werden amorphe Rutheniumanteile abgeschieden. Dadurch werden die Schichten ungleichmäßig und zeigen bei mechanischer Belastung dunklen Abrieb. Bevorzugt wird eine Stromdichte von 0,01 bis 10 A/dm2 eingestellt, besonders bevorzugt 0,05 bis 5 A/dm2. Der gewählte Wert wird auch von der Art des Beschichtungsverfahrens bestimmt. In einem Trommelbeschichtungsverfahren liegt die bevorzugte Stromdichte zwischen 0,05 bis 1 A/dm2. In Gestellbeschichtungsverfahren führt eine Stromdichte von 0,5 bis 5 A/dm2 zu optisch einwandfreien Schwarz-Rutheniumschichten.To obtain adherent, even layers, a maximum current density of 10 amperes per square decimeter [A / dm 2 ] should not be exceeded. Above this value, amorphous ruthenium components are deposited. As a result, the layers are uneven and show dark abrasion under mechanical stress. A current density of 0.01 to 10 A / dm 2 is preferably set, particularly preferably 0.05 to 5 A / dm 2 . The chosen value is also determined by the type of coating process. In a drum coating process, the preferred current density is between 0.05 to 1 A / dm 2 . In frame coating processes, a current density of 0.5 to 5 A / dm 2 leads to optically flawless black ruthenium layers.
Zur Durchführung des galvanischen Abscheidevorgangs aus dem erfindungsgemäßen, sauren Rutheniumbad eignen sich unlösliche Anoden. Bevorzugt werden Anoden aus einem Material ausgewählt aus der Gruppe bestehend aus platiniertem Titan, Graphit, Iridium-Übergangsmetall-Mischoxid und speziellem Kohlenstoffmaterial ("Diamond Like Carbon" DLC) oder Kombinationen davon eingesetzt.Insoluble anodes are suitable for carrying out the galvanic deposition process from the acidic ruthenium bath according to the invention. Anodes are preferably used from a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon" DLC) or combinations thereof.
Die folgenden Beispiele sollen die Erfindung näher erläutern:The following examples are intended to explain the invention in more detail:
Zur Abscheidung schwarzer Schichten auf Gebrauchsgütern wurde ein erfindungsgemäßer Elektrolyt verwendet, der neben 2,5 g/L Ruthenium in [Ru2NCl8(H2O)2]3- 15 g/L 1-Hydroxyethan-(1,1-di-phosphonsäure) HEDP gelöst in Wasser als Schwärzungszusatz und 20 g/L Schwefelsäure enthielt. Der Elektrolyt hatte einen pH-Wert von 0,8.For the deposition of black layers on consumer goods, an inventive electrolyte was used, which in addition to 2.5 g / L ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- 15 g / L 1-hydroxyethane (1,1-di phosphonic acid) HEDP dissolved in water as a blackening additive and containing 20 g / L sulfuric acid. The electrolyte had a pH of 0.8.
In einem Gestellbeschichtungsverfahren wurden entsprechende Substrate bei einer Stromdichte von 2 - 10 A/dm2 beschichtet, wobei der Elektrolyt bei 60°C temperiert wurde.In a rack coating process corresponding substrates were coated at a current density of 2-10 A / dm 2 , wherein the electrolyte was heated at 60 ° C.
Nach Beendigung des Abscheidevorgangs waren die Substrate mit mechanisch stabilen, abriebfesten schwarzen Schichten versehen, die im Gebrauchsgüterbereich als optisch einwandfrei gelten. Eine leichte Unregelmäßigkeit in der Schichtdicke der erhaltenen Schichten beschränkt die Verwendung dieses erfindungsgemäßen Bades auf Anwendungen außerhalb des Schmuckbereiches.After completion of the deposition process, the substrates were provided with mechanically stable, abrasion-resistant black layers, which are considered optically flawless in the consumer goods sector. A slight irregularity in the layer thickness of the layers obtained limits the use of this bath according to the invention to applications outside the jewelry area.
Zur Erzeugung von Schwarz-Rutheniumschichten auf Dekorgütern wurde ein erfindungsgemäßer Elektrolyt verwendet, der 5 g/L Ruthenium in [Ru2NCl8(H2O)2]3- und 1,5 g/L Ethylendiamin-tetra(methylenphosphonsäure) EDTMP als Schwärzungszusatz in Wasser enthielt. Zur Einstellung des pH-Werts wurden dem Elektrolyten 4 g/L Schwefelsäure zugesetzt, so daß der pH-Wert zu Beginn der Abscheidung 1,3 betrug.For the production of black ruthenium layers on decorative items, an electrolyte according to the invention was used, the 5 g / L ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- and 1.5 g / L ethylenediamine tetra (methylenephosphonic) EDTMP as Blackening additive contained in water. To adjust the pH, 4 g / L sulfuric acid was added to the electrolyte so that the pH at the beginning of the deposition was 1.3.
In einer Gestellapparatur wurden geeignete Substrate bei einer eingestellten Stromdichte von 0,5 bis 3 A/dm2 mit schwarzen Rutheniumschichten veredelt. Während des Abscheidevorgangs wurde der Elektrolyt bei 60 bis 70°C temperiert.In a rack apparatus, suitable substrates were finished at a set current density of 0.5 to 3 A / dm 2 with black ruthenium layers. During the deposition process, the electrolyte was heated at 60 to 70 ° C.
Die erhaltenen Schichten wiesen eine sehr gute mechanische Stabilität auf, zeigten eine tiefschwarzer Farbe und hohen Glanz. Die optische Qualität der so erzeugten Schichten war so hoch, daß die Eignung dieses erfindungsgemäßen Bades auch für den Schmuck- und Dekorbereich gegeben ist.The layers obtained had a very good mechanical stability, showed a deep black color and high gloss. The optical quality of the layers thus produced was so high that the suitability of this bath according to the invention is also given for the jewelry and decor area.
Es wurde ein weiteres erfindungsgemäßes Bad untersucht, das 5 g/L Ruthenium in [Ru2NCl8(H2O)2]3- und 5 g/L Amino-tris(methylenphosphonsäure) ATMP in Wasser enthielt. Der pH-Wert des Bades wurde mit 4 g/L Schwefelsäure auf 1,4 eingestellt.A further bath according to the invention was investigated which contained 5 g / l of ruthenium in [Ru 2 NCl 8 (H 2 O) 2 ] 3- and 5 g / l of amino-tris (methylenephosphonic acid) ATMP in water. The pH of the bath was adjusted to 1.4 with 4 g / L sulfuric acid.
In einem Gestellbeschichtungsverfahren wurden bei einer eingestellten Stromdichte von 0,5 bis 2,5 A/dm2 und einer Temperierung des Bades bei 60°C ebenfalls gleichmäßige, tiefschwarze Schichten von hoher optischer Güte erhalten.In a frame coating process uniform, deep black layers of high optical quality were obtained at a set current density of 0.5 to 2.5 A / dm 2 and a temperature of the bath at 60 ° C.
Claims (13)
dadurch gekennzeichnet,
daß der Elektrolyt ein oder mehrere Phosphonsäurederivate als Schwärzungszusatz enthält.Non-toxic electrolyte for the deposition of decorative and technical coatings of ruthenium with special blackness ("black ruthenium"),
characterized,
that the electrolyte contains one or more phosphonic acid derivatives as a blackening.
dadurch gekennzeichnet,
daß Ruthenium als zweikernige, anionische Rutheniumnitridohalogenokomplexverbindung der Formel [Ru2N(H2O)2X8]3- vorliegt.An electrolyte according to claim 1,
characterized,
that ruthenium is present as a dinuclear, anionic Rutheniumnitridohalogenokomplexverbindung the formula [Ru 2 N (H 2 O) 2 X 8 ] 3- .
dadurch gekennzeichnet,
daß die Volumenkonzentration des Rutheniums zwischen 0,2 und 20 Gramm pro Liter Elektrolyt, berechnet als Ruthenium-Metall, liegt.Electrolyte according to claim 2,
characterized,
that the volume concentration of ruthenium between 0.2 and 20 grams per liter of electrolyte, calculated as ruthenium metal, is located.
dadurch gekennzeichnet,
daß der Elektrolyt frei ist von weiteren Übergangsmetallionen.Electrolyte according to claim 2,
characterized,
that the electrolyte is free of further transition metal ions.
dadurch gekennzeichnet,
daß er als Phosphonsäure eine oder mehrere Verbindungen ausgewählt aus der Gruppe bestehend aus Aminophosphonsäure AP, 1-Aminomethylphosphonsäure AMP, Amino-tris(methylenphosphonsäure) ATMP, 1-Aminoethylphosphonsäure AEP, 1-Aminopropylphosphonsäure APP, (1-Acetylamino-2,2,2-trichloroethyl)-phasphonsäure, (1-Amino-1-phosphono-octyl)-phosphonsäure, (1-Benzoylamino-2,2,2-trichloroethyl)-phosphonsäure, (1-Benzoylamino-2,2-dichlorovinyl)-phosphonäure, (4-Chlorophenyl-hydroxymethyl)-phosphonsäure, Diethylentriaminpenta(methylenphosphonsäure) DTPMP, Ethylendiamin-tetra(methylenphosphonsäure) EDTMP, 1-Hydroxyethan-(1,1-di-phosphonsäure) HEDP, Hydroxyethylamino-di(methylenphosphonsäure) HEMPA, Hexamethylendiamin-tetra(methylphosphonsäure) HDTMP, ((Hydroxymethyl-phosphonomethyl-amino)-methyl)-phosphonsäure, Nitrilo-tris(methylenphosphonsäure) NTMP, 2,2,2-Trichloro-1-(furan-2-carbonyl)-amino-ethylphosphonsäure, davon abgeleitete Salze oder davon abgeleitete Kondensate, oder Kombinationen davon enthält.Electrolyte according to claim 2,
characterized,
in that it contains as phosphonic acid one or more compounds selected from the group consisting of aminophosphonic acid AP, 1-aminomethylphosphonic acid AMP, amino-tris (methylenephosphonic acid) ATMP, 1-aminoethylphosphonic acid AEP, 1-aminopropylphosphonic acid APP, (1-acetylamino-2,2,2 -trichloroethyl) -phasphonic acid, (1-amino-1-phosphono-octyl) -phosphonic acid, (1-benzoylamino-2,2,2-trichloroethyl) -phosphonic acid, (1-benzoylamino-2,2-dichlorovinyl) -phosphonic acid, (4-chlorophenylhydroxymethyl) phosphonic acid, diethylenetriaminepenta (methylenephosphonic acid) DTPMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP, hydroxyethylamino-di (methylenephosphonic acid) HEMPA, hexamethylenediamine-tetra (methylphosphonic acid) HDTMP, ((hydroxymethyl-phosphonomethyl-amino) -methyl) -phosphonic acid, nitrilo-tris (methylenephosphonic acid) NTMP, 2,2,2-trichloro-1- (furan-2-carbonyl) -amino-ethylphosphonic acid, salts derived therefrom or derived therefrom condensates, or combinations thereof.
dadurch gekennzeichnet,
daß er zwischen 0,1 und 20 Gramm Phophonsäurederivate pro Liter Elektrolyt enthält.Electrolyte according to claim 5,
characterized,
that it contains between 0.1 and 20 grams of phophonic acid per liter of electrolyte.
dadurch gekennzeichnet,
daß der pH-Wert des Elektrolyten zwischen 0 und 3 liegt.Electrolyte according to claim 5,
characterized,
that the pH of the electrolyte is between 0 and 3.
dadurch gekennzeichnet,
daß der Elektrolyt anorganische Mineralsäuren ausgewählt aus der Gruppe bestehend aus Salzsäure, Bromwasserstoffsäure, Iodwasserstoffsäure, Salpetersäure, Salpetrige Säure, Amidosulfonsäure, Schwefelsäure, Schwefelige Säure, Dischwefelsäure, Dithionsäure, Dischweflige Säure und Dithionige Säure oder Kombinationen davon enthält.Electrolyte according to claim 7,
characterized,
that the electrolyte contains inorganic mineral acids selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, nitrous acid, amidosulfonic acid, sulfuric acid, sulfurous acid, disulfuric acid, dithionic acid, disulfurous acid and dithionous acid or combinations thereof.
dadurch gekennzeichnet,
daß der Elektrolyt als Netzmittel eine oder mehrere Verbindungen ausgewählt aus der Gruppe der Alkansulfonsäuren oder der ionischen und nicht-ionischen Tenside oder Kombinationen davon.Electrolyte according to one of claims 5 to 8,
characterized,
that the electrolyte as a wetting agent one or more compounds selected from the group of alkanesulfonic acids or the ionic and nonionic surfactants or combinations thereof.
dadurch gekennzeichnet,
daß ein Elektrolyt verwendet wird, der ein oder mehrere Phosphonsäurederivate als Schwärzungszusatz enthält.Process for the electroplating of decorative and technical layers of ruthenium of special blackness ("black ruthenium") on jewelery, decorative objects, consumer goods and technical articles, the substrates to be coated being immersed in an electrolyte containing ruthenium in dissolved form,
characterized,
that an electrolyte is used which contains one or more phosphonic acid derivatives as a blackening additive.
dadurch gekennzeichnet,
daß der Elektrolyt im Bereich 20 bis 80°C temperiert wird.Method according to claim 10,
characterized,
that the electrolyte is heated in the range 20 to 80 ° C.
dadurch gekennzeichnet,
daß eine Stromdichte eingestellt wird, die im Bereich 0,01 bis 10 Ampere pro Quadratdezimeter liegt.Method according to claim 11,
characterized,
that a current density is set which is in the range of 0.01 to 10 amperes per square decimeter.
dadurch gekennzeichnet,
daß unlösliche Anoden aus einem Material ausgewählt aus der Gruppe bestehend aus platiniertem Titan, Graphit, Iridium-Übergangsmetall-Mischoxid und speziellem Kohlenstoffmaterial ("Diamon Like Carbon" DLC) oder Kombinationen dieser Anoden verwendet werden.Method according to claim 12,
characterized,
that insoluble anodes made of a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ( "Diamon Like Carbon" DLC) or combinations of these anodes are used.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07006380A EP1975282B1 (en) | 2007-03-28 | 2007-03-28 | Electrolyte and method for electroplating decorative and technical layers of black ruthenium. |
| AT07006380T ATE449201T1 (en) | 2007-03-28 | 2007-03-28 | ELECTTOLYTE AND METHOD FOR DEPOSING DECORATIVE AND TECHNICAL LAYERS MADE OF BLACK RUTHENIUM |
| DE502007002036T DE502007002036D1 (en) | 2007-03-28 | 2007-03-28 | Electrolysis and method of deposition of dekoraium |
| BRPI0809382-2A BRPI0809382A2 (en) | 2007-03-28 | 2008-03-05 | ELECTROLYTE AND METHOD FOR DEPOSITING DECORATIVE AND BLACK RUTENIUM LAYERS |
| KR1020097020293A KR101416253B1 (en) | 2007-03-28 | 2008-03-05 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
| US12/532,296 US8211286B2 (en) | 2007-03-28 | 2008-03-05 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
| PCT/EP2008/001751 WO2008116545A1 (en) | 2007-03-28 | 2008-03-05 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
| JP2010500099A JP5449130B2 (en) | 2007-03-28 | 2008-03-05 | Method for depositing electrolyte and decorative and technical layers of black ruthenium |
| CN2008800147422A CN101675185B (en) | 2007-03-28 | 2008-03-05 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
| TW097108314A TWI427195B (en) | 2007-03-28 | 2008-03-10 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
| HK10103898.5A HK1138044A1 (en) | 2007-03-28 | 2010-04-21 | Electrolyte and method for depositing decorative and technical layers of black ruthenium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07006380A EP1975282B1 (en) | 2007-03-28 | 2007-03-28 | Electrolyte and method for electroplating decorative and technical layers of black ruthenium. |
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| Publication Number | Publication Date |
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| EP1975282A1 true EP1975282A1 (en) | 2008-10-01 |
| EP1975282B1 EP1975282B1 (en) | 2009-11-18 |
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| EP07006380A Active EP1975282B1 (en) | 2007-03-28 | 2007-03-28 | Electrolyte and method for electroplating decorative and technical layers of black ruthenium. |
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| Country | Link |
|---|---|
| US (1) | US8211286B2 (en) |
| EP (1) | EP1975282B1 (en) |
| JP (1) | JP5449130B2 (en) |
| KR (1) | KR101416253B1 (en) |
| CN (1) | CN101675185B (en) |
| AT (1) | ATE449201T1 (en) |
| BR (1) | BRPI0809382A2 (en) |
| DE (1) | DE502007002036D1 (en) |
| HK (1) | HK1138044A1 (en) |
| TW (1) | TWI427195B (en) |
| WO (1) | WO2008116545A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012171856A2 (en) | 2011-06-17 | 2012-12-20 | Umicore Galvanotechnik Gmbh | Electrolyte and its use for the deposition of black ruthenium coatings and coatings obtained in this way |
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| CN107722361B (en) * | 2017-09-26 | 2020-01-10 | 同济大学 | Preparation method of nano amino trimethylene magnesium phosphonate loaded reduced graphene oxide flame retardant |
| DE102019109188B4 (en) * | 2019-04-08 | 2022-08-11 | Umicore Galvanotechnik Gmbh | Use of an electrolyte for the deposition of anthracite/black rhodium/ruthenium alloy layers |
| CN110965088A (en) * | 2019-08-27 | 2020-04-07 | 周大福珠宝金行（深圳）有限公司 | Ancient restoring process of gold and ancient restoring gold |
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| WO2012171856A2 (en) | 2011-06-17 | 2012-12-20 | Umicore Galvanotechnik Gmbh | Electrolyte and its use for the deposition of black ruthenium coatings and coatings obtained in this way |
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| Publication number | Publication date |
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| CN101675185B (en) | 2011-04-13 |
| DE502007002036D1 (en) | 2009-12-31 |
| US20100051468A1 (en) | 2010-03-04 |
| ATE449201T1 (en) | 2009-12-15 |
| WO2008116545A1 (en) | 2008-10-02 |
| KR20090123928A (en) | 2009-12-02 |
| JP2010522277A (en) | 2010-07-01 |
| KR101416253B1 (en) | 2014-07-09 |
| BRPI0809382A2 (en) | 2014-09-09 |
| TW200914650A (en) | 2009-04-01 |
| CN101675185A (en) | 2010-03-17 |
| HK1138044A1 (en) | 2010-08-13 |
| US8211286B2 (en) | 2012-07-03 |
| TWI427195B (en) | 2014-02-21 |
| JP5449130B2 (en) | 2014-03-19 |
| EP1975282B1 (en) | 2009-11-18 |
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