EP0163944A2 - Electrolytes aqueux, acides contenant des ions de nickel et cobalt pour le dépôt galvanique de couches d'alliage dures, stables à la coloration et blanches brillantes - Google Patents

Electrolytes aqueux, acides contenant des ions de nickel et cobalt pour le dépôt galvanique de couches d'alliage dures, stables à la coloration et blanches brillantes Download PDF

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Publication number
EP0163944A2
EP0163944A2 EP85105345A EP85105345A EP0163944A2 EP 0163944 A2 EP0163944 A2 EP 0163944A2 EP 85105345 A EP85105345 A EP 85105345A EP 85105345 A EP85105345 A EP 85105345A EP 0163944 A2 EP0163944 A2 EP 0163944A2
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EP
European Patent Office
Prior art keywords
nickel
cobalt
ions
solutions
boric acid
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.)
Withdrawn
Application number
EP85105345A
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German (de)
English (en)
Other versions
EP0163944A3 (fr
Inventor
Heinz Dr. Wagner
Klaus Scharwächter
Monika Nee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gerhard Collardin GmbH
Original Assignee
Gerhard Collardin GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gerhard Collardin GmbH filed Critical Gerhard Collardin GmbH
Publication of EP0163944A2 publication Critical patent/EP0163944A2/fr
Publication of EP0163944A3 publication Critical patent/EP0163944A3/fr
Withdrawn legal-status Critical Current

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    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Definitions

  • the invention relates to aqueous, acidic, nickel and cobalt ions and boric acid and, as a gloss additive, to electrolytes containing an aliphatic aldehyde and an aromatic carbonyl compound for the galvanic deposition of hard, tarnish-resistant, shiny white alloy coatings.
  • Nickel-cobalt alloys have proven themselves in numerous technological areas because they are not only characterized by good physical properties, but can also be easily galvanically deposited in any desired composition. Electroplating baths are used to form nickel-cobalt alloy layers which contain suitable nickel and cobalt salts, e.g. Chlorides, sulfates or sulfamates, boric acid and other additives that influence the electrical conductivity of the bath and the anode solubility.
  • suitable nickel and cobalt salts e.g. Chlorides, sulfates or sulfamates, boric acid and other additives that influence the electrical conductivity of the bath and the anode solubility.
  • aqueous, acid baths for the electrodeposition of nickel coatings which, in addition to nickel salts and boric acid, also contain a so-called gloss additive, which consists of an aliphatic, 1 to 4 carbon atom and a aromatic compound having a carbonyl group.
  • Such nickel layers have the disadvantage that they have a bright, but yellowish shimmering, touch-sensitive surface that tends to tarnish, which can be used for subsequent treatment, e.g. chrome plating, required.
  • the hardness of the electrodeposited coating layer does not always meet the requirements.
  • the baths used for the process according to the invention are suitable for the production of hard, tarnish-resistant, metallic white shiny alloy coatings.
  • Preferred baths contain, for example, nickel ions in an amount of 36.0 to 93.3 g. 1 -1 , cobalt ions in an amount of 1.7 to 11.5 g. 1 -1, g chloride ion in an amount of 8.0 to 12, the 0th 1 and boric acid in an amount of 30 g. 1 -1 .
  • These contents of the individual components can be adjusted in a manner known per se, for example by adding 150 to 400 g. 1 -1 nickel sulfate heptahydrate, 20 to 40 g. 1 -1 nickel chloride hexahydrate, 8 to 55 g. 1 -1 cobalt sulfate heptahydrate and 30 g. 1-1 boric acid.
  • They have a pH in the range from 3.6 to 4.8, preferably from 4.0 to 4.4.
  • the acidic electroplating baths can optionally be used as additional components.
  • Wetting agents such as alkyl sulfates or alkyl ether sulfates with 8 to 18 carbon atoms and 2 to 6 alkylene oxide groups are particularly suitable. Isononyl sulfate and sodium lauryl ether sulfate are preferred as optionally added wetting agents.
  • the wetting agents are used in amounts of 0.1 to 20 g. 1 -1 bath solution used.
  • the galvanic deposition is carried out at a temperature of 40 to 60 ° C., preferably from 50 to 55 ° C.
  • the cathodic current density can fluctuate within wide limits, low cathodic current densities being required for drum electroplating and higher cathodic current densities being used for frame galvanizing.
  • the baths can have current densities of up to 7 A. dm -2 are charged.
  • Pieces of nickel and cobalt are used as anode materials in a weight ratio of 5: 1 to 10: 1 in titanium baskets with anode bags. Any material that can also be used for galvanic nickel plating can be used as the nickel anode.
  • cobalt metal for the anodes has to meet the highest purity requirements, as this has a decisive influence on the quality of the white nickel deposits. Only metallic cobalt with a purity of at least 99.9% can be used. Contamination may only occur in the ppm range.
  • cobalt can be used as anode material, its arsenic content is 1 ppm, copper 10 ppm, iron 15 ppm, lead 3 ppm, zinc 2 ppm, nickel 0.07%, carbon 20 ppm, hydrogen 2 ppm, oxygen 30 ppm, nitrogen 2 ppm and sulfur is 2 ppm.
  • the nickel salts used must at least comply with the DIN 50970 standard; Boric acid suitable for the method according to the invention must have galvanic quality, that is to say it must be suitable for use in high-performance galvanic nickel baths.
  • Aliphatic aldehydes suitable for use as a constituent in the gloss additive are, for example, formaldehyde including paraformaldehyde, acetaldehyde, propionaldehyde and butyraldehyde.
  • o-benzoyl sulfimide as the aromatic carbonyl compound is expediently used in the form of the alkali metal salts, preferably in the form of the sodium salt, for the addition of gloss.
  • o-benzoyl sulfimide N-acetyl-o-benzoyl sulfimide can also be used.
  • the two organic components mentioned for the addition of gloss are mixed in a molar ratio of 20: 1 to 50: 1 and stored in the form of an aqueous solution.
  • this solution is added to the electrolyte-containing aqueous solutions in such an amount that the aliphatic aldehyde content is 0.1 to 1.0 g. 1 -1 and the content of aromatic carbonyl compound 0.005 to 0.05 g. Is 1 -1 .
  • layers containing nickel and cobalt are electrodeposited on suitable surfaces.
  • the depletion of the solution of nickel and cobalt ions caused by the deposition is compensated for by the fact that the metallic nickel and cobalt ions gradually dissolve.
  • a constant content of nickel and cobalt ions in the baths is established with the other parameters of the process remaining the same.
  • the ratio of nickel to cobalt ions in the solution is in the range from 8: 1 to 20: 1.
  • a variation of the process control is also possible in that only nickel anodes are used.
  • the proportion of cobalt consumed in the electrodeposition must be supplemented by adding cobalt sulfate heptahydrate. Amounts of approximately 12 kg CoSo 4 . 7 H 2 0 per 10,000 Ah can be added.
  • the gloss additive solutions which can be used for the process according to the invention are consumed in the course of the electroplating process. Therefore, their content in the bathroom solutions must be continuously checked and if necessary. can be adjusted to the specified values by re-sharpening with additional gloss solutions.
  • nickel and cobalt containing layers are obtained on metallic surfaces or on plastic parts pretreated according to methods known per se.
  • the composition of the electrodeposited, shiny white alloy layers is essentially dependent on the applied cathodic current density and on the ratio of the nickel and cobalt ions in the electrolyte.
  • Layers with a composition of 60 to 84% by weight of nickel and 16 to 40% by weight of cobalt are obtained.
  • Relatively low cobalt and high nickel contents preferably occur at high current densities and relatively high cobalt and low nickel contents at low current densities. 1 shows the dependence of the layer composition on the cathodic current density.
  • the metal layers obtained by the process according to the invention are distinguished by a high tarnish resistance and an excellent corrosion protection effect. Due to the presence of cobalt, these layers are harder than galvanically deposited bright nickel layers. They also show a good gloss and an excellent spread of gloss depth. Because of these outstanding properties, the method according to the invention is used wherever decorative or decorative-functional coatings are required as the final layer in the galvanic finishing, for example as a replacement for gloss chrome after galvanic nickel plating, as a final layer for double or trinickel deposits or the galvanization of bulk articles. The method is also used to achieve special surface effects, such as imitation of a polished aluminum surface on plastic parts.
  • the cathodic current yields are of the same order of magnitude as in known semi-gloss and bright nickel baths.
  • Electroplating baths were produced which contained the components given in Table 1 in the amounts indicated.
  • Polished brass sheets which were moved mechanically in the electroplating bath, were used as cathode sheets for the subsequent electroplating process.
  • the Anode consisted of metallic nickel and metallic cobalt of high purity in titanium baskets with anode bags.
  • the brass sheets were electroplated at a temperature of 55 to 60 ° C for 10 minutes using methods known per se.
  • Electroplating baths were produced which contained the components indicated in Table 1 in the respective amounts. A solution was added to these electroplating baths as a gloss additive in the amounts given in Table 1, which had the following composition:
  • Polished brass sheets were used as cathode sheets, which (in the case of Examples 7 and V5) were moved mechanically back and forth; in the case of Examples 8, 9, the electrolyte bath was moved by blowing in air.
  • the brass sheets were galvanized at a temperature of 55 to 60 ° C for 10 minutes at a current density given in Table 1 according to methods known per se.
EP85105345A 1984-05-09 1985-05-02 Electrolytes aqueux, acides contenant des ions de nickel et cobalt pour le dépôt galvanique de couches d'alliage dures, stables à la coloration et blanches brillantes Withdrawn EP0163944A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843416993 DE3416993A1 (de) 1984-05-09 1984-05-09 Waessrige, saure, nickel- und cobalt-ionen enthaltende elektrolyte zur galvanischen abscheidung von harten, anlaufbestaendigen, weiss glaenzenden legierungsueberzuegen
DE3416993 1984-05-09

Publications (2)

Publication Number Publication Date
EP0163944A2 true EP0163944A2 (fr) 1985-12-11
EP0163944A3 EP0163944A3 (fr) 1986-05-21

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EP85105345A Withdrawn EP0163944A3 (fr) 1984-05-09 1985-05-02 Electrolytes aqueux, acides contenant des ions de nickel et cobalt pour le dépôt galvanique de couches d'alliage dures, stables à la coloration et blanches brillantes

Country Status (4)

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US (1) US4565611A (fr)
EP (1) EP0163944A3 (fr)
JP (1) JPS60251298A (fr)
DE (1) DE3416993A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111074308A (zh) * 2019-12-30 2020-04-28 福建南平南孚电池有限公司 在钢壳的表面上电镀镍钴合金镀层的方法和装置

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0765228B2 (ja) * 1989-04-28 1995-07-12 松下電器産業株式会社 高磁束密度４元系合金電着薄膜の製造方法
US9926641B2 (en) * 2012-10-15 2018-03-27 Toyo Kohan Co., Ltd Method of manufacturing metal sheet having alloy plated layer
JP6960363B2 (ja) * 2018-03-28 2021-11-05 Ｊｘ金属株式会社 Ｃｏアノード、Ｃｏアノードを用いた電気Ｃｏめっき方法及びＣｏアノードの評価方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB461126A (en) * 1935-05-10 1937-02-10 Otto Hinrichsen Improvements in the production of bright electro-deposits of nickel-cobalt alloys
DE2450527A1 (de) * 1974-10-24 1976-05-06 Henkel & Cie Gmbh Saures bad fuer die herstellung von halbglaenzenden nickelueberzuegen
US3972786A (en) * 1974-06-28 1976-08-03 Ampex Corporation Mechanically enhanced magnetic memory
JPS52147535A (en) * 1976-06-04 1977-12-08 Hitachi Ltd Alloy plated articles to be welded
JPS5521579A (en) * 1978-08-04 1980-02-15 Toshiba Corp Method of electrodepositing nickel cobalt alloy
GB2078258A (en) * 1980-06-17 1982-01-06 Rockwell International Corp Electrodeposition of ni- co alloys

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2026718A (en) * 1935-03-30 1936-01-07 Weisberg & Greenwald Inc Electrodeposition of metals
US3093557A (en) * 1961-08-25 1963-06-11 Westinghouse Electric Corp Methods and electrolytes for depositing nickel and cobalt
US4069112A (en) * 1976-06-18 1978-01-17 M & T Chemicals Inc. Electroplating of nickel, cobalt, mutual alloys thereof or ternary alloys thereof with iron

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB461126A (en) * 1935-05-10 1937-02-10 Otto Hinrichsen Improvements in the production of bright electro-deposits of nickel-cobalt alloys
US3972786A (en) * 1974-06-28 1976-08-03 Ampex Corporation Mechanically enhanced magnetic memory
DE2450527A1 (de) * 1974-10-24 1976-05-06 Henkel & Cie Gmbh Saures bad fuer die herstellung von halbglaenzenden nickelueberzuegen
JPS52147535A (en) * 1976-06-04 1977-12-08 Hitachi Ltd Alloy plated articles to be welded
JPS5521579A (en) * 1978-08-04 1980-02-15 Toshiba Corp Method of electrodepositing nickel cobalt alloy
GB2078258A (en) * 1980-06-17 1982-01-06 Rockwell International Corp Electrodeposition of ni- co alloys

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 88, Nr. 20, 15. Mai 1978, Seite 473, Zusammenfassung Nr. 143486r, Columbus, Ohio, US; & JP - A - 77 147 535 (HITACHI LTD.), 08-12-1977 *
CHEMICAL ABSTRACTS, Band 93,Nr. 2, Juli 1980, Seite 483, Zusammenfassung Nr. 33952k, Columbus, Ohio, US; & JP - A - 80 21 579 (TOKIYO SHIBAURA ELECTRIC CO. LTD.), 15-02-1980 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111074308A (zh) * 2019-12-30 2020-04-28 福建南平南孚电池有限公司 在钢壳的表面上电镀镍钴合金镀层的方法和装置
CN111074308B (zh) * 2019-12-30 2021-03-12 福建南平南孚电池有限公司 在钢壳的表面上电镀镍钴合金镀层的方法和装置

Also Published As

Publication number Publication date
US4565611A (en) 1986-01-21
DE3416993A1 (de) 1985-11-21
EP0163944A3 (fr) 1986-05-21
JPS60251298A (ja) 1985-12-11

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