EP3712302A1 - Electrolytic nickel plating composition and electrolytic nickel plating method using the same composition - Google Patents
Electrolytic nickel plating composition and electrolytic nickel plating method using the same composition Download PDFInfo
- Publication number
- EP3712302A1 EP3712302A1 EP20161027.6A EP20161027A EP3712302A1 EP 3712302 A1 EP3712302 A1 EP 3712302A1 EP 20161027 A EP20161027 A EP 20161027A EP 3712302 A1 EP3712302 A1 EP 3712302A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- nickel plating
- nickel
- ions
- electrolytic nickel
- Prior art date
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- Granted
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 34
- 238000007747 plating Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 9
- -1 tri-hydroxybenzene compound Chemical class 0.000 claims abstract description 51
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- WQGWDDDVZFFDIG-UHFFFAOYSA-N trihydroxybenzene Natural products OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 12
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 11
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012928 buffer substance Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KYGZCKSPAKDVKC-UHFFFAOYSA-N Oxolinic acid Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC2=C1OCO2 KYGZCKSPAKDVKC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- IKQCSJBQLWJEPU-UHFFFAOYSA-N 2,5-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1 IKQCSJBQLWJEPU-UHFFFAOYSA-N 0.000 description 1
- QMWGSOMVXSRXQX-UHFFFAOYSA-N 3-sulfobenzoic acid Chemical class OC(=O)C1=CC=CC(S(O)(=O)=O)=C1 QMWGSOMVXSRXQX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- 241000935974 Paralichthys dentatus Species 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 238000007714 electro crystallization reaction Methods 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000004701 malic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- AYGJDUHQRFKLBG-UHFFFAOYSA-M sodium;1,1-dioxo-1,2-benzothiazol-3-olate;dihydrate Chemical compound O.O.[Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 AYGJDUHQRFKLBG-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 230000007704 transition Effects 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
Definitions
- the invention relates to a composition according to the preamble of claim 1 and a method for electrolytic nickel plating according to the preamble of claim 8.
- Nickel baths consist of a mixture of nickel sulfate, nickel chloride, sodium saccharine or allyl sulfonate (so-called primary gloss carriers), secondary gloss carriers, which generally have an alkyne group as functionality, and boric acid as a so-called conductive salt or buffer substance.
- the application range of such nickel baths is in a pH range from 3.5 to 4.8.
- boric acid-free compositions are increasing offered and used for electrolytic nickel plating.
- these compositions generally have the disadvantage that the nickel layers deposited therefrom are less shiny and, in particular, less leveled.
- GB 244,167 A discloses the use of a small amount of hydroquinone as a reducing agent of iron, which is present as an impurity in the anodes and leads to pore formation in the nickel layer.
- DE 865 695 B discloses the use of phenolic compounds as brighteners in nickel baths with high fluoride concentrations.
- composition which comprises 2-phenyl-5-benzimidazole sulfonic acid, salts thereof or mixtures thereof as the buffer substance.
- the invention is based on the object of providing a composition for electrolytic nickel plating which has properties on the Substrate generated nickel layer enables the same or better than those that can be achieved with a boric acid-containing composition.
- the invention is based on the object of providing a corresponding method for electrolytic nickel plating using such a composition.
- an improved composition for electrolytic nickel plating comprises one or more sources of nickel ions and a mono-, di- or tri-hydroxybenzene compound, preferably a hydroquinone compound, or their salts or mixtures thereof.
- a composition for electrolytic nickel plating in the context of this invention means a nickel bath which is used for the galvanic deposition of a nickel layer on a substrate, the nickel ion source being nickel sulfate, nickel chloride and / or nickel sulfamate.
- the mono-, di- or tri-hydroxybenzene compound preferably has a pKa value between 6.5 and 12.5.
- a monohydroxybenzene compound can be, for example, phenolsulfonic acid, a di-hydroxybenzene compound, for example pyrocatechol, resorcinol or hydroquinone, a tri-hydroxybenzene compound, for example, pyrogallol, phloroglucinol or hydroxyhydroquinone, but these are not restricted to this.
- hydroquinone (I) or its salts are very particularly preferred.
- the composition comprises an additional source of sulfoxyl ions and / or an additional source of carboxylate ions.
- the additional source of sulfoxylate ions or the additional source of carboxylate ions is used as a weak complexing agent and, together with the mono-, di- or tri-hydroxybenzene compound, serves as a buffer substance.
- the source of sulfoxylate ions or the source of carboxylate ions likewise has a pKa value in the range from 6.5 to 12.5 and / or ⁇ 3.
- a pH of the composition of 3 to 9 can be achieved. If sulfoxylate or carboxylate sources with pKa values between 3 and 6.5 are used, these must not exceed a concentration of more than 1 g / l.
- a new buffer area is made possible, which is preferably between the working area of the composition and the area in which nickel hydrolysis begins, i.e. mainly in a pH range between 3 and 7 5 to 7.
- the leveling performance of the composition is comparable to that of boric acid.
- the degree of gloss of the nickel layer that can be achieved is comparable to that of boric acid.
- composition according to the invention also enables the nickel layers produced to be pore-free. So-called burns in the high current density range due to the formation of hydrogen and nickel hydroxide are avoided.
- the additional source of sulfoxylate ions can, for example, be a sulfonic acid compound and the sulfoxylate ions (anions) can be, for example, sulfonates.
- the additional source of carboxylate ions comprises a salicylic acid compound.
- an additional source of carboxylate ions may also include, but is not limited to, an acetic acid compound, formic acid compound, malic acid compound, tartaric acid compound, gluconic acid compound, benzoic acid compound, 3-sulfobenzoic acid compound, propionic acid compound or adibic acid compound, for example. Mixtures of the aforementioned acid compounds are also conceivable.
- the carboxylate ions (anions) of the present invention can be mono-, di-, tri- or tetracarboxylate ions, preferably of C 1 to C 30 carbon atoms, preferably mono- or dicarboxylate ions of C 1 to C 10 carbon atoms.
- the carboxylate ions can be present, for example, as acetates, formates, malates, tartrates, gluconates, benzoates, 3-sulfobenzoates, propionates, adibates, salicylates or mixtures thereof.
- Other salts and / or esters are also conceivable.
- the salicylic acid compound is particularly advantageously a 5-sulfosalicylic acid (II).
- 5-sulfosalicylic acid pK 1 2.75, pK 2 12.38
- Ni 2+ ions pK 1 2.75, pK 2 12.38
- 5-sulfosalicylic acid prefers the formation of an intramolecular hydrogen bond which is so strong that complex formation with divalent nickel only becomes significant above a pH value of 5.5. This behavior is practically identical to that between Ni 2+ ions and boric acid or borate.
- a composition which comprises hydroquinone and 5-sulfosalicylic acid is therefore particularly advantageous.
- the mono-, di- or tri-hydroxybenzene compound preferably the hydroquinone compound, or its salts or mixtures thereof is advantageously present in amounts of 5-30 g / l, preferably 10-20 g / l, preferably 15 g / l .
- the additional source of sulfoxylate ions and / or the additional source of carboxylate ions are advantageously present in amounts of 5-40 g / l, preferably 5-25 g / l, preferably 10 g / l in front.
- a nickel layer is deposited on the substrate, which has the properties described above.
- the applied electrical current preferably has a strength of 0.5 to 4 A, preferably 1.5 to 3.5 A, preferably 3 A.
- the solution is made up to 1500 ml with deionized water.
- the pH value is determined electrochemically using a pH measuring chain on a pH meter (Metrohm 744 pH meter).
- the device is calibrated with appropriate commercial solutions (CertiPUR Buffer Solution for pH values 1, 4 and 7 from Merck) before the measurement.
- a calibrated fluke is used to measure the current 175 True RMS multimeter used.
- the measured pH is 5.
- Solid anodes made of solid nickel material (1 cm thick) with casings are used as anodes.
- the pH of the electrolyte is also measured using the method described above.
- the measured pH is 5.1.
- a homogeneous, high-gloss layer was found from 0.05 A / dm 2 to the upper edge of the Hull cell sheet, with at least as good a leveling as that in the comparative example with boric acid (45 g / l instead of hydroquinone and 5 -Sulfosalicylic acid) is the case.
- hydroquinone and 5-sulfosalicylic acid thus has a strong inhibiting effect on the layer growth in the high current density range, with an extremely homogeneous layer thickness distribution being achieved without the evolution of hydrogen being visible.
- Examples 2 to 4 are carried out and evaluated analogously to Example 1. What all the examples have in common is that they produce high-gloss, highly leveling and ductile layers.
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)
Abstract
Die Erfindung betrifft eine Zusammensetzung zur elektrolytischen Vernickelung. Um eine verbesserte Zusammensetzung bereitzustellen, wird vorgeschlagen, dass diese eine oder mehrere Nickelionenquellen und eine Mono-, Di- oder Tri-Hydroxybenzolverbindung, vorzugsweise eine Hydrochinonverbindung, oder deren Salze oder Mischungen davon umfasst.The invention relates to a composition for electrolytic nickel plating. In order to provide an improved composition, it is suggested that it comprise one or more nickel ion sources and a mono-, di- or tri-hydroxybenzene compound, preferably a hydroquinone compound, or their salts or mixtures thereof.
Description
Die Erfindung betrifft eine Zusammensetzung gemäß dem Oberbegriff von Anspruch 1 sowie ein Verfahren zur elektrolytischen Vernickelung gemäß dem Oberbegriff von Anspruch 8.The invention relates to a composition according to the preamble of claim 1 and a method for electrolytic nickel plating according to the preamble of claim 8.
Klassische Nickelbäder bestehen aus einem Gemisch aus Nickelsulfat, Nickelchlorid, Na-Saccharin oder -Allylsulfonat (sogenannten primären Glanzträgern), sekundären Glanzträgern, welche im Allgemeinen eine Alkingruppe als Funktionalität aufweisen, sowie Borsäure als sogenanntes Leitsalz beziehungsweise Puffersubstanz. Der Anwendungsbereich solcher Nickelbäder liegt in einem pH-Bereich von 3,5 bis 4,8.Classic nickel baths consist of a mixture of nickel sulfate, nickel chloride, sodium saccharine or allyl sulfonate (so-called primary gloss carriers), secondary gloss carriers, which generally have an alkyne group as functionality, and boric acid as a so-called conductive salt or buffer substance. The application range of such nickel baths is in a pH range from 3.5 to 4.8.
Aufgrund immer wiederkehrender Bedenken bezüglich der mutagenen Eigenschaften von Borsäure bei entsprechend hoher Exposition sowie durch die starke Einschränkung mittels Gesetzgebung (vgl. CLP Verordnung 1272/2008/EG; SVHC-Kandidatenliste nach Art. 57 bzw. 59 REACh Verordnung), werden vermehrt borsäurefreie Zusammensetzungen zur elektrolytischen Vernickelung angeboten und verwendet. Diese Zusammensetzungen haben jedoch im Allgemeinen den Nachteil, dass die daraus abgeschiedenen Nickelschichten weniger glänzend und insbesondere weniger eingeebnet sind.Due to recurring concerns about the mutagenic properties of boric acid at correspondingly high exposure as well as due to the severe restrictions imposed by legislation (cf. CLP regulation 1272/2008 / EC; SVHC candidate list according to Art. 57 or 59 REACh regulation), boric acid-free compositions are increasing offered and used for electrolytic nickel plating. However, these compositions generally have the disadvantage that the nickel layers deposited therefrom are less shiny and, in particular, less leveled.
Aus der
Der Erfindung liegt die Aufgabe zugrunde, eine Zusammensetzung zur elektrolytischen Vernickelung bereitzustellen, welche Eigenschaften der auf dem Substrat erzeugten Nickelschicht ermöglicht, die gleich oder besser sind als solche, die mit einer borsäurehaltigen Zusammensetzung erreicht werden können. Zudem liegt der Erfindung die Aufgabe zugrunde, ein entsprechendes Verfahren zur elektrolytischen Vernickelung unter Verwendung einer solchen Zusammensetzung bereitzustellen.The invention is based on the object of providing a composition for electrolytic nickel plating which has properties on the Substrate generated nickel layer enables the same or better than those that can be achieved with a boric acid-containing composition. In addition, the invention is based on the object of providing a corresponding method for electrolytic nickel plating using such a composition.
Diese Aufgabe wird durch eine Zusammensetzung mit den Merkmalen des Anspruchs 1 sowie ein Verfahren zur elektrolytischen Vernickelung mit den Merkmalen des Anspruchs 8 gelöst. In den abhängigen Ansprüchen 2 bis 7 und 9 sind vorteilhafte Ausgestaltungen der Erfindung angegeben.This object is achieved by a composition with the features of claim 1 and a method for electrolytic nickel plating with the features of claim 8. In the dependent claims 2 to 7 and 9, advantageous embodiments of the invention are specified.
Erfindungsgemäß wird eine verbesserte Zusammensetzung zur elektrolytischen Vernickelung dadurch geschaffen, dass diese eine oder mehrere Nickelionenquellen und eine Mono-, Di- oder Tri-Hydroxybenzolverbindung, vorzugsweise eine Hydrochinonverbindung, oder deren Salze oder Mischungen davon umfasst.According to the invention, an improved composition for electrolytic nickel plating is created in that it comprises one or more sources of nickel ions and a mono-, di- or tri-hydroxybenzene compound, preferably a hydroquinone compound, or their salts or mixtures thereof.
Hiermit werden ohne Borsäure sehr gute Nickelschichten mit vergleichbarer Einebnung, vergleichbarem Glanzgrad und vergleichbarer Porenfreiheit erhalten.With this, very good nickel layers with comparable leveling, a comparable degree of gloss and a comparable freedom from pores are obtained without boric acid.
Eine Zusammensetzung zur elektrolytischen Vernickelung im Rahmen dieser Erfindung bedeutet ein Nickelbad, welches zur galvanischen Abscheidung einer Nickelschicht auf einem Substrat verwendet wird, wobei die Nickelionenquelle Nickelsulfat, Nickelchlorid und/oder Nickelsulfamat ist.A composition for electrolytic nickel plating in the context of this invention means a nickel bath which is used for the galvanic deposition of a nickel layer on a substrate, the nickel ion source being nickel sulfate, nickel chloride and / or nickel sulfamate.
Die Mono-, Di- oder Tri-Hydroxybenzolverbindung weist vorzugsweise einen pKs-Wert zwischen 6,5 und 12,5 auf.The mono-, di- or tri-hydroxybenzene compound preferably has a pKa value between 6.5 and 12.5.
Eine Mono-Hydroxybenzolverbindung kann beispielsweise Phenolsulfonsäure, eine Di-Hydroxybenzolverbindung beispielsweise Brenzcatechin, Resorcin oder Hydrochinon, eine Tri-Hydroxybenzolverbindung beispielsweise Pyrogallol, Phloroglucin oder Hydroxyhydrochinon sein, diese sind aber nicht hierauf beschränkt.A monohydroxybenzene compound can be, for example, phenolsulfonic acid, a di-hydroxybenzene compound, for example pyrocatechol, resorcinol or hydroquinone, a tri-hydroxybenzene compound, for example, pyrogallol, phloroglucinol or hydroxyhydroquinone, but these are not restricted to this.
Aus der Reihe der Di- Hydroxybenzolverbindungen ist Hydrochinon (I) oder dessen Salze ganz besonders bevorzugt.
In besonders vorteilhafter Weise ist vorgesehen, dass die Zusammensetzung eine zusätzliche Sulfoxylationenquelle und/oder eine zusätzliche Carboxylationenquelle umfasst.In a particularly advantageous manner, it is provided that the composition comprises an additional source of sulfoxyl ions and / or an additional source of carboxylate ions.
Die zusätzliche Sulfoxylationenquelle beziehungsweise die zusätzliche Carboxylationenquelle wird als schwacher Komplexbildner verwendet und dient zusammen mit der Mono-, Di- oder Tri-Hydroxybenzolverbindung als Puffersubstanz. Die Sulfoxylationenquelle beziehungsweise die Carboxylationenquelle weist ebenfalls einen pKs-Wert im Bereich von 6,5 bis 12,5 und/oder <3 auf.The additional source of sulfoxylate ions or the additional source of carboxylate ions is used as a weak complexing agent and, together with the mono-, di- or tri-hydroxybenzene compound, serves as a buffer substance. The source of sulfoxylate ions or the source of carboxylate ions likewise has a pKa value in the range from 6.5 to 12.5 and / or <3.
Hierdurch kann ein pH-Wert der Zusammensetzung von 3 bis 9 erreicht werden. Werden Sulfoxylat- beziehungsweise Carboxylationenquellen eingesetzt, die pKs-Werte zwischen 3 und 6,5 besitzen, so dürfen diese eine Konzentration von mehr als 1 g/l nicht überschreiten.In this way, a pH of the composition of 3 to 9 can be achieved. If sulfoxylate or carboxylate sources with pKa values between 3 and 6.5 are used, these must not exceed a concentration of more than 1 g / l.
Mit der erfindungsgemäßen Zusammensetzung wird in Verbindung mit Ni2+-Ionen die Ausbildung eines neuen Pufferbereichs ermöglicht, welcher zwischen dem Arbeitsbereich der Zusammensetzung und dem Bereich, in welchem Nickel-Hydrolyse einsetzt, also vorwiegend in einem pH-Bereich zwischen 3 und 7, vorzugsweise 5 bis 7, liegt.With the composition according to the invention, in connection with Ni 2+ ions, the formation of a new buffer area is made possible, which is preferably between the working area of the composition and the area in which nickel hydrolysis begins, i.e. mainly in a pH range between 3 and 7 5 to 7.
Es wird angenommen, dass - analog zur Borsäure - die Ni2+-Ionen nicht koordinativ gesättigt werden und damit für die acetylenartigen Glanzträger zugänglich bleiben. Diese Zugänglichkeit ist Voraussetzung dafür, dass die Glanzträger als Elektronenmangel-Verbindungen ihre π-Rückbindungs-Eigenschaften entfalten können und so Übergangszustände tiefer Oxidationsstufen von Nickel stabilisieren können, was mit zur Inhibition der Elektrokristallisation und der damit verbundenen Einebnung führt.It is assumed that - analogously to boric acid - the Ni 2+ ions are not saturated by coordination and thus remain accessible to the acetylene-like glossy substrates. This accessibility is a prerequisite for the gloss carriers, as electron deficiency compounds, to be able to develop their π-rebonding properties and thus to stabilize transition states of deep oxidation states of nickel, which leads to the inhibition of electrocrystallization and the associated leveling.
Die Einebnungsleistung der Zusammensetzung ist vergleichbar mit derjenigen der Borsäure. Zudem ist der Glanzgrad der erzielbaren Nickelschicht vergleichbar mit demjenigen der Borsäure.The leveling performance of the composition is comparable to that of boric acid. In addition, the degree of gloss of the nickel layer that can be achieved is comparable to that of boric acid.
Auch eine Porenfreiheit der hergestellten Nickelschichten wird mit der erfindungsgemäßen Zusammensetzung weitestgehend ermöglicht. Sogenannte Anbrennungen im hohen Stromdichtebereich aufgrund von Wasserstoff- und Nickelhydroxid-Bildung werden vermieden.The composition according to the invention also enables the nickel layers produced to be pore-free. So-called burns in the high current density range due to the formation of hydrogen and nickel hydroxide are avoided.
Die zusätzliche Sulfoxylationenquelle kann beispielsweise eine Sulfonsäureverbindung und die Sulfoxylationen (Anionen) können beispielsweise Sulfonate sein.The additional source of sulfoxylate ions can, for example, be a sulfonic acid compound and the sulfoxylate ions (anions) can be, for example, sulfonates.
Besonders vorteilhaft ist vorgesehen, dass die zusätzliche Carboxylationenquelle eine Salicylsäureverbindung umfasst.It is particularly advantageously provided that the additional source of carboxylate ions comprises a salicylic acid compound.
Eine zusätzliche Carboxylationenquelle kann jedoch auch beispielsweise eine Essigsäureverbindung, Ameisensäureverbindung, Äpfelsäureverbindung, Weinsäureverbindung, Gluconsäureverbindung, Benzoesäureverbindung, 3-Sulfobenzoesäureverbindung, Propionsäureverbindung oder Adibinsäureverbindung umfassen, ist aber nicht hierauf beschränkt. Auch Mischungen aus den vorgenannten Säurenverbindungen sind denkbar.However, an additional source of carboxylate ions may also include, but is not limited to, an acetic acid compound, formic acid compound, malic acid compound, tartaric acid compound, gluconic acid compound, benzoic acid compound, 3-sulfobenzoic acid compound, propionic acid compound or adibic acid compound, for example. Mixtures of the aforementioned acid compounds are also conceivable.
Die Carboxylationen (Anionen) der vorliegenden Erfindung können Mono-, Di-, Tri- oder Tetracarboxylationen sein, vorzugsweise von C 1 bis C 30-Kohlenstoffatomen, vorzugsweise Mono- oder Dicarboxylationen von C 1 bis C 10-Kohlenstoffatomen.The carboxylate ions (anions) of the present invention can be mono-, di-, tri- or tetracarboxylate ions, preferably of C 1 to C 30 carbon atoms, preferably mono- or dicarboxylate ions of C 1 to C 10 carbon atoms.
Die Carboxylationen können beispielsweise als Acetate, Formiate, Malate, Tartrate, Gluconate, Benzoate, 3-Sulfobenzoate, Propionate, Adibate, Salicylate oder Mischungen davon vorliegen. Auch andere Salze und/oder Ester sind denkbar.The carboxylate ions can be present, for example, as acetates, formates, malates, tartrates, gluconates, benzoates, 3-sulfobenzoates, propionates, adibates, salicylates or mixtures thereof. Other salts and / or esters are also conceivable.
In besonders vorteilhafterweise ist die Salicylsäureverbindung eine 5-Sulfosalicylsäure (II).
Es wird angenommen, dass bei pH-Werten von 3 bis 5 keine oder eine nur sehr geringfügige Reaktion zwischen 5-Sulfosalicylsäure (pK1 2,75, pK2 12,38) und Ni2+-Ionen stattfindet. Die 5-Sulfosalicylsäure bevorzugt nach Deprotonierung die Ausbildung einer intramolekularen Wasserstoffbrücke, welche so stark ausgebildet ist, dass eine Komplexbildung mit divalentem Nickel erst oberhalb von einem pH-Wert von 5,5 signifikant wird. Dieses Verhalten ist praktisch identisch mit demjenigen zwischen Ni2+-Ionen und Borsäure beziehungsweise Borat.It is assumed that at pH values of 3 to 5 there is little or no reaction between 5-sulfosalicylic acid (pK 1 2.75, pK 2 12.38) and Ni 2+ ions. After deprotonation, 5-sulfosalicylic acid prefers the formation of an intramolecular hydrogen bond which is so strong that complex formation with divalent nickel only becomes significant above a pH value of 5.5. This behavior is practically identical to that between Ni 2+ ions and boric acid or borate.
Besonders vorteilhaft ist also eine Zusammensetzung, die Hydrochinon und 5-Sulfosalicylsäure umfasst.A composition which comprises hydroquinone and 5-sulfosalicylic acid is therefore particularly advantageous.
In vorteilhafter Weise liegt die Mono-, Di- oder Tri-Hydroxybenzolverbindung, vorzugsweise die Hydrochinonverbindung, oder deren Salze oder Mischungen davon in Mengen von 5-30 g/l, vorzugsweise 10-20 g/l, vorzugsweise 15 g/l, vor.The mono-, di- or tri-hydroxybenzene compound, preferably the hydroquinone compound, or its salts or mixtures thereof is advantageously present in amounts of 5-30 g / l, preferably 10-20 g / l, preferably 15 g / l .
In vorteilhafter Weise liegen die zusätzliche Sulfoxylationenquelle und/oder die zusätzliche Carboxylationenquelle, vorzugsweise die Salicylsäureverbindung, vorzugsweise die 5-Sulfosalicylsäure, oder Mischungen davon in Mengen von 5-40 g/l, vorzugsweise 5-25 g/l, vorzugsweise 10 g/l vor.The additional source of sulfoxylate ions and / or the additional source of carboxylate ions, preferably the salicylic acid compound, preferably 5-sulfosalicylic acid, or mixtures thereof are advantageously present in amounts of 5-40 g / l, preferably 5-25 g / l, preferably 10 g / l in front.
Erfindungsgemäß umfasst das Verfahren zur elektrolytischen Vernickelung auf einem Substrat:
- das Bereitstellen des Substrats;
- das Kontaktieren des Substrats mit einer der vorgenannten Zusammensetzungen; und
- das Anlegen eines elektrischen Stroms an die Zusammensetzung und das Substrat.
- providing the substrate;
- contacting the substrate with one of the aforementioned compositions; and
- applying an electrical current to the composition and the substrate.
Hierdurch wird eine Nickelschicht auf dem Substrat abgeschieden, welche die oben beschriebenen Eigenschaften aufweist.As a result, a nickel layer is deposited on the substrate, which has the properties described above.
Vorzugsweise weist hierzu der angelegte elektrische Strom eine Stärke von 0,5 bis 4 A, vorzugsweise von 1,5 bis 3,5 A, vorzugsweise 3 A, auf.For this purpose, the applied electrical current preferably has a strength of 0.5 to 4 A, preferably 1.5 to 3.5 A, preferably 3 A.
Die folgenden Beispiele dienen der Erläuterung der Erfindung.The following examples serve to illustrate the invention.
Um die Einebnungsleistung zu beurteilen, werden handelsübliche Messingbleche (Hullzellbleche, Fa. Ossian) mittels elektrolytischer Vernickelung beschichtet und anschließend am unteren Rand für 10 Minuten mit einer 40 °C warmen wässrigen Lösung, welche Natriumperoxodisulfat in einer Menge von 200 g/l enthält, angeätzt.To assess the leveling performance, commercially available brass sheets (Hullzellbleche, Fa. Ossian) are coated with electrolytic nickel plating and then etched on the lower edge for 10 minutes with a 40 ° C aqueous solution containing sodium peroxodisulfate in an amount of 200 g / l .
Zur Herstellung der Zusammensetzung werden in einem 2 I Becherglas (der Fa. VWR) 1000 ml vollentsalztes Wasser vorgelegt und auf 55 °C temperiert. Unter Rühren werden die folgenden Verbindungen hinzugeben:To prepare the composition, 1000 ml of deionized water are placed in a 2 l beaker (from VWR) and heated to 55 ° C. The following compounds are added while stirring:
Die Lösung wird auf 1500 ml mit vollentsalztem Wasser aufgefüllt.The solution is made up to 1500 ml with deionized water.
Die pH-Wert Bestimmung erfolgt elektrochemisch mittels pH-Messkette an einem pH-Meter (Metrohm 744 pH-Meter). Das Gerät wird mit entsprechenden kommerziellen Lösungen (CertiPUR Buffer Solution für die pH-Werte 1, 4 und 7 der Fa. Merck) vor der Messung kalibriert. Zur Strommessung wird ein kalibriertes Fluke 175 True RMS Multimeter verwendet. Der gemessene pH-Wert beträgt 5.The pH value is determined electrochemically using a pH measuring chain on a pH meter (Metrohm 744 pH meter). The device is calibrated with appropriate commercial solutions (CertiPUR Buffer Solution for pH values 1, 4 and 7 from Merck) before the measurement. A calibrated fluke is used to measure the current 175 True RMS multimeter used. The measured pH is 5.
Als Anoden werden massive Anoden aus Nickelvollmaterial (1 cm Stärke) mit Umhüllungen verwendet.Solid anodes made of solid nickel material (1 cm thick) with casings are used as anodes.
Es werden handelsübliche Messingbleche (Hullzellbleche, Fa. Ossian) nach üblicher Vorbehandlung (Entfettung, Spülen, Aktivieren, Spülen) mit 3 A für 780 min bei 55 °C beschichtet. Als Elektrolytbewegung wird ein Magnetrührkern mit 100 Umdrehungen pro Minute verwendet.Commercially available brass sheets (Hullzellbleche, Ossian) are coated with 3 A for 780 min at 55 ° C. after the usual pretreatment (degreasing, rinsing, activating, rinsing). A magnetic stirrer with 100 revolutions per minute is used to move the electrolyte.
Nach der Beschichtung wird der pH-Wert des Elektrolyts ebenfalls mittels des oben beschriebenen Verfahrens gemessen. Der gemessene pH-Wert beträgt 5,1.After the coating, the pH of the electrolyte is also measured using the method described above. The measured pH is 5.1.
Im Rahmen der Untersuchung der Einebnungsleistung zeigte sich von 0.05 A/dm2 bis an die obere Kante des Hullzellbleches eine homogene, hochglänzende Schicht, mit einer mindestens so guten Einebnung, wie das beim Vergleichsbeispiel mit Borsäure (45 g/l anstelle von Hydrochinon und 5-Sulfosalicylsäure) der Fall ist.As part of the investigation of the leveling performance, a homogeneous, high-gloss layer was found from 0.05 A / dm 2 to the upper edge of the Hull cell sheet, with at least as good a leveling as that in the comparative example with boric acid (45 g / l instead of hydroquinone and 5 -Sulfosalicylic acid) is the case.
Die Kombination von Hydrochinon und 5-Sulfosalicylsäure wirkt sich also im hohen Stromdichtebereich stark inhibierend auf das Schichtwachstum aus, wobei eine äußerst homogene Schichtdickenverteilung erzielt wird, ohne dass dabei eine Wasserstoff-Entwicklung sichtbar ist.The combination of hydroquinone and 5-sulfosalicylic acid thus has a strong inhibiting effect on the layer growth in the high current density range, with an extremely homogeneous layer thickness distribution being achieved without the evolution of hydrogen being visible.
Die Beispiele 2 bis 4 werden analog Beispiel 1 durchgeführt und bewertet. Allen Beispielen ist gemeinsam, dass sie hochglänzende, hocheinebnende und duktile Schichten erzeugen.Examples 2 to 4 are carried out and evaluated analogously to Example 1. What all the examples have in common is that they produce high-gloss, highly leveling and ductile layers.
Des Weiteren kann bereits bei alleiniger Verwendung der 4-Phenolsulfonsäure eine entsprechende Schicht erzeugt werden, die allen Anforderungen einer Schicht eines Glanznickelbades entspricht mit der Ausnahme einer geringen, in der Praxis meist nicht relevanten Anbrennung im hohen Stromdichtebereich. Diese Beschränkung bei hohen Stromdichten kann sehr effizient mit der Zugabe der in den Beispielen angegebenen Zweitsubstanzen korrigiert werden, womit der anwendbare Stromdichtebereich deutlich größer als bei entsprechenden Borsäure-Verfahren wird unter Beibehaltung aller sonstigen Aspekte einer Glanznickelschicht.Furthermore, even with the sole use of 4-phenolsulphonic acid, a corresponding layer can be generated which meets all the requirements of a layer of a bright nickel bath with the exception of a slight, in practice mostly irrelevant burn in the high current density range. This limitation in the case of high current densities can be corrected very efficiently by adding the secondary substances specified in the examples, which means that the applicable current density range is significantly larger than with corresponding boric acid processes while maintaining all other aspects of a bright nickel layer.
Es wird angenommen, dass diese Erweiterung des Stromdichtebereichs maßgeblich den komplexierenden Eigenschaften der zusätzlich eingebrachten, phenolischen Verbindungen zu verdanken ist, welche genau im pH-Bereich der Nickelhydroxid-Bildung wirksam sind.It is assumed that this expansion of the current density range is largely due to the complexing properties of the additionally introduced phenolic compounds, which are effective precisely in the pH range of nickel hydroxide formation.
Claims (9)
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DE2054221B2 (en) * | 1970-11-04 | 1973-11-08 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Stabilized aqueous solutions of unsaturated aliphatic sulfonic acids or their salts |
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JP6046406B2 (en) * | 2011-07-26 | 2016-12-14 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | High temperature resistant silver coated substrate |
CN109137008A (en) * | 2018-10-25 | 2019-01-04 | 扬州祥龙电镀有限公司 | A kind of handware electroplate liquid |
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2019
- 2019-03-22 DE DE102019107416.9A patent/DE102019107416A1/en not_active Withdrawn
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GB244167A (en) | 1924-09-11 | 1925-12-11 | Madsenell Corp | Means and methods for electrodepositing nickel, cobalt or nickel alloys |
DE865695C (en) | 1951-02-02 | 1953-02-05 | Metallic Industry Nv | Process for electrolytic high-gloss nickel plating of metals |
GB892904A (en) * | 1960-09-20 | 1962-04-04 | Guy Villette | Process for obtaining bright ductile nickel deposits |
US4129482A (en) * | 1977-06-24 | 1978-12-12 | M&T Chemicals Inc. | Electroplating iron group metal alloys |
KR100971555B1 (en) * | 2010-02-25 | 2010-07-21 | 주식회사 유니테크 | High concentration ni-flash plating composition for pre-treatment of cold-rolled steel sheet in electrolytic galvanized iron plating process |
EP3431634A1 (en) | 2017-06-15 | 2019-01-23 | Rohm and Haas Electronic Materials LLC | Environmentally friendly nickel electroplating compositions and methods |
CN107829114A (en) * | 2017-11-28 | 2018-03-23 | 江苏澳光电子有限公司 | A kind of terminal surfaces electroplate liquid and its application |
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EP3712302B1 (en) | 2023-09-20 |
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