WO2015110099A1 - Electrolytic bath - Google Patents

Electrolytic bath Download PDF

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Publication number
WO2015110099A1
WO2015110099A1 PCT/DE2014/100412 DE2014100412W WO2015110099A1 WO 2015110099 A1 WO2015110099 A1 WO 2015110099A1 DE 2014100412 W DE2014100412 W DE 2014100412W WO 2015110099 A1 WO2015110099 A1 WO 2015110099A1
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WO
WIPO (PCT)
Prior art keywords
electrolytic bath
silver
nickel
content
bath according
Prior art date
Application number
PCT/DE2014/100412
Other languages
German (de)
French (fr)
Inventor
Alexander Meyerovich
Frank Brode
Original Assignee
Harting Kgaa
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 Harting Kgaa filed Critical Harting Kgaa
Priority to EP14825092.1A priority Critical patent/EP3099847A1/en
Publication of WO2015110099A1 publication Critical patent/WO2015110099A1/en

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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
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • 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
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver

Definitions

  • the invention relates to an electrolytic bath according to the preamble of independent claim 1.
  • Such electrolytic baths are used for surface coating of metallic workpieces, in particular for
  • SU 66 23 23 A1 shows an electrolytic bath, for the deposition of a silver-nickel alloy on substrates.
  • US 2005/0035843 A1 describes an electrolytic deposition of a silver-nickel alloy on a metallic surface with a nickel content of up to 4% by weight (weight percent). This one
  • deposited silver-nickel layer has a low
  • the object of the invention is to generate an electrolytic bath for the deposition of thermostable silver-nickel alloys with high abrasion resistance and a low electrical resistance.
  • the electrolytic bath proposed herein is intended for depositing bright silver-nickel alloy coatings.
  • the electrolytic bath consists essentially of an aqueous solution of 15 to 30 grams per liter (g / L) of silver in the form of
  • Potassium silver cyanide 3 - 15 g / L nickel in the form of tetracyanonickelate, and 10 to 20 g / L potassium carbonate.
  • the electrolytic bath contains 220 g / L of potassium cyanate.
  • the electrolytic bath contains 220 g / L of potassium cyanate.
  • the electrolytic bath contains surfactants from the
  • Suitable surfactants are, for example:
  • Anionic surfactants such as sodium pasminate,
  • Nonionic surfactants for example partial fatty acid esters, polyhydric alcohols, for example glyceryl monostearate, partial fatty acid esters of sorbitan such as sorbitan monostearate or monooleate, sorbitan sesquioleate, esters of polyethylene glycol sorbitan such as monolaurate, onostearate or
  • Monooleate Also suitable are polyhydroxyethylene fatty alcohol ethers, polyhydroxyethylene fatty acid esters, ethylene oxide-propylene oxide block copolymers or ethoxylated triglycerides.
  • Amphoteric tenisde such as betaines and sulfobetaines of the general formula
  • Turkish red oil is basically an anionic surfactant which is used as wetting agent in dyeing plants (emulsifier, foaming agent). In electroplating this surfactant has not been used before.
  • the electrolytic bath of the present invention provides excellent glossy silver-nickel alloy coatings on metallic ones
  • the deposited alloy layer from the bath which is subject to a low tarnish insensitivity. This effect is particularly advantageous for the practical application of the proposed electrolytic bath.

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  • 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

The invention relates to an electrolytic bath for the deposition of glossy silver-nickel alloys onto substrates, consisting of an aqueous solution containing an ionic compound having a silver content of 15 to 30 g/l, preferably potassium silver cyanide, a nickel complex having a nickel content of 3 to 15 g/l, preferably tetracyanonickelate, and 10 to 20 g/l of potassium carbonate.

Description

Elektrolvtisch.es Bad  Elektrolvtisch.es bath
Beschreibung description
Die Erfindung betrifft ein elektrolytisches Bad nach dem Oberbegriff des unabhängigen Anspruchs 1 .  The invention relates to an electrolytic bath according to the preamble of independent claim 1.
Derartige elektrolytische Bäder werden zur Oberflächenbeschichtung von metallischen Werkstücken, insbesondere zur Such electrolytic baths are used for surface coating of metallic workpieces, in particular for
Oberflächenbeschichtung von Kontaktelementen für Steckverbinder eingesetzt. Surface coating of contact elements used for connectors.
Stand der Technik State of the art
Die SU 66 23 23 A1 zeigt ein elektrolytisches Bad, zur Abscheidung einer Silber-Nickel-Legierung auf Substraten.  SU 66 23 23 A1 shows an electrolytic bath, for the deposition of a silver-nickel alloy on substrates.
US 2005/0035843 A1 beschreibt eine elektrolytische Abscheidung einer Silber-Nickel-Legierung auf einer metallischen Oberfläche mit einem Nickelgehalt bis zu 4 Gew.% (Gewichtsprozent). Die hier US 2005/0035843 A1 describes an electrolytic deposition of a silver-nickel alloy on a metallic surface with a nickel content of up to 4% by weight (weight percent). This one
abgeschiedene Silber-Nickel-Schicht hat eine niedrige deposited silver-nickel layer has a low
Korrosionsbeständigkeit und einen relativ hohen elektrischen Corrosion resistance and a relatively high electrical
Widerstand und ist daher für die Verwendung von elektrischen Resistance and is therefore for the use of electrical
Kontaktelementen stark begrenzt. Contact elements strongly limited.
Aufgabenstellung task
Die Aufgabe der Erfindung besteht darin, ein elektrolytisches Bad zur Abscheidung von thermostabilen Silber-Nickel-Legierungen mit hoher Abriebfestigkeit und einem niedrigen elektrischen Widerstand zu generieren.  The object of the invention is to generate an electrolytic bath for the deposition of thermostable silver-nickel alloys with high abrasion resistance and a low electrical resistance.
Die Aufgabe wird durch die kennzeichnenden Merkmale des The task is characterized by the characterizing features of
unabhängigen Anspruchs 1 gelöst. Vorteilhafte Ausgestaltungen der Erfindung sind in den independent claim 1 solved. Advantageous embodiments of the invention are in the
Unteransprüchen angegeben. Subclaims specified.
Das hier vorgeschlagene elektrolytische Bad ist zum Abscheiden von glänzenden Silber-Nickel-Legierungsüberzügen vorgesehen. Das elektrolytische Bad besteht im Wesentlichen aus einer wässrigen Lösung mit 15 bis 30 Gramm pro Liter (g/L) Silber in Form von The electrolytic bath proposed herein is intended for depositing bright silver-nickel alloy coatings. The electrolytic bath consists essentially of an aqueous solution of 15 to 30 grams per liter (g / L) of silver in the form of
Kaliumsilbercyanid, 3 - 15 g/L Nickel in Form von Tetracyanonickelat, und 10 bis 20 g/L Kaliumcarbonat. Potassium silver cyanide, 3 - 15 g / L nickel in the form of tetracyanonickelate, and 10 to 20 g / L potassium carbonate.
Vorzugsweise enthält das elektrolytische Bad 220 g/L Kaliumcyanat. Dadurch wird eine Härteerhöhung sowie eine Erhöhung des Preferably, the electrolytic bath contains 220 g / L of potassium cyanate. As a result, a hardness increase and an increase in the
Schichtglanzes der abgeschiedenen Oberfläche und eine höhere Stromausbeute beim elektrolytischen Bad erreicht. Die Härteprüfung erfolgt nach Vickers und nach der DIN EN ISO 6507. Layer gloss achieved the deposited surface and a higher current efficiency in the electrolytic bath. The hardness test is carried out according to Vickers and according to DIN EN ISO 6507.
Vorteilhafterweise enthält das elektrolytische Bad Tenside aus derAdvantageously, the electrolytic bath contains surfactants from the
Gruppe der anionischen Tenside, der nicht-ionischen Tenside, der amphoteren Tenside oder eine Mischungen der vorgenannten Tenside. Als Tenside kommen beispielsweise in Frage: Group of anionic surfactants, nonionic surfactants, amphoteric surfactants or a mixture of the aforementioned surfactants. Suitable surfactants are, for example:
a. Anionische Tenside wie beispielsweise Natriumpa!minat, a. Anionic surfactants such as sodium pasminate,
Natriumstearat, Natriumoleat, Triethanoiaminstearat, Natriumsalze von Fettalkoholsulfaten wie Natriumlaurylsulfat, Natriumcetylstrearylsulfat, Sulfonsuccinate. Sodium stearate, sodium oleate, triethanolamine stearate, sodium salts of fatty alcohol sulfates such as sodium lauryl sulfate, sodium cetyl strearyl sulfate, sulfone succinates.
b. Nichtionische Tenside, beispielsweise partielle Fettsäureester, mehrwertige Alkohole, beispielsweise Giycerinmonostearat, partielle Fettsäureester des Sorbitans wie Sorbitanmonostearat oder - monooleat, Sorbitansesquioleat, Ester von Polyethylenglykoisorbitan wie beispielsweise das Monolaureat, das onostearat oder das b. Nonionic surfactants, for example partial fatty acid esters, polyhydric alcohols, for example glyceryl monostearate, partial fatty acid esters of sorbitan such as sorbitan monostearate or monooleate, sorbitan sesquioleate, esters of polyethylene glycol sorbitan such as monolaurate, onostearate or
Monooleat. Weiterhin kommen Polyhydroxyethylen-Fettalkoholether, Polyhydroxyethylen-Fettsäureester, Ethyienoxid-Propyienoxid- Blockcopolmyere oder Ethoxylierte Triglyceride in Betracht. c. Amphotere Tenisde wie Betaine und Sulfobetaine der allgemeinen Formel
Figure imgf000004_0001
Monooleate. Also suitable are polyhydroxyethylene fatty alcohol ethers, polyhydroxyethylene fatty acid esters, ethylene oxide-propylene oxide block copolymers or ethoxylated triglycerides. c. Amphoteric tenisde such as betaines and sulfobetaines of the general formula
Figure imgf000004_0001
wobei n = 8 bis 18.  where n = 8 to 18.
Besonders vorteilhaft ist es als Tensid das Türkischrotöl, auch It is particularly advantageous as a surfactant Turkish red oil, too
Tournantöl genannt, im elektrolytischen Bad zu verwenden. Das Türkischrotöl ist grundsätzlich ein anionisches Tensid, welches als Netzmittel in Färbereien (Emulgator, Schaumbildner) verwendet wird. In der Galvanik wurde dieses Tensid vorher noch nicht benutzt. Called Tournant oil to use in the electrolytic bath. Turkish red oil is basically an anionic surfactant which is used as wetting agent in dyeing plants (emulsifier, foaming agent). In electroplating this surfactant has not been used before.
Das erfindungsgemäße elektrolytische Bad liefert hervorragend glänzende Silber-Nickel-Legierungsüberzüge auf metallischen The electrolytic bath of the present invention provides excellent glossy silver-nickel alloy coatings on metallic ones
Oberflächen, die sich nicht nur durch ihren Glanz auszeichnen, sondern auch durch ihre Duktilität, hohe Härte und hohe Abriebfestigkeit. Surfaces that are not only distinguished by their gloss, but also by their ductility, high hardness and high abrasion resistance.
Die abgeschiedene Legierungsschicht aus dem Bad die unterliegt einer geringen Anlaufunempfindlichkeit. Dieser Effekt ist vor allem für die praktische Anwendung des vorgeschlagenen elektrolytischen Bades von Vorteil. The deposited alloy layer from the bath which is subject to a low tarnish insensitivity. This effect is particularly advantageous for the practical application of the proposed electrolytic bath.
Außerdem wird durch die oben genannten Zusatzstoffe die In addition, by the above additives, the
Abhängigkeit der Silber-Nickel-Legierungszusammensetzung von den Arbeitsparametern des Bades, wie Stromdichte, Badtemperatur und Metallgehalte abgeschwächt. Mit dem vorgeschlagenen elektrolytischen Bad erhält man in breiteren Arbeitsbereichen eine gleichmäßige Legierungszusammensetzung. Dadurch ist das elektrolytische Bad besonders für die industrielle Produktion geeignet. Dependence of the silver-nickel alloy composition on the operating parameters of the bath, such as current density, bath temperature and metal contents weakened. With the proposed electrolytic bath, a uniform alloy composition is obtained in wider work areas. As a result, the electrolytic bath is particularly suitable for industrial production.

Claims

Elektrolytisches Bad  Electrolytic bath
Ansprüche claims
Elektrolytisches Bad, zur Abscheidung von glänzenden Silber- Nickel-Legierungen auf Substraten, bestehend aus einer wässrigen Lösung beinhaltend Electrolytic bath, for depositing shiny silver-nickel alloys on substrates, consisting of an aqueous solution
• eine ionische Verbindung mit 15 bis 30 g/L Silberanteil,  An ionic compound with 15 to 30 g / L silver content,
vorzugsweise Kaliumsilbercyanid,  preferably potassium silver cyanide,
• einen Nickelkomplex mit 3-15 g/L Nickelanteil, vorzugsweise Tetracyanonickelat und  A nickel complex with 3-15 g / L nickel content, preferably tetracyanonickelate and
• 10 bis 20 g/L Kaliumkarbonat  • 10 to 20 g / L potassium carbonate
• Tenside, aus der Gruppe der anionischen und/oder der nichtionischen und/oder der amphoteren Tenside, oder eine Mischungen der vorgenannten Tenside, wobei der Gehalt der Tenside im Bereich von 0,05 bis 2,0 Gew.-%, vorzugsweise im Bereich von 0, 1 bis 0,8 Gew.-% liegt.  Surfactants, from the group of anionic and / or nonionic and / or amphoteric surfactants, or a mixture of the aforementioned surfactants, wherein the content of the surfactants in the range of 0.05 to 2.0 wt .-%, preferably in the range from 0.1 to 0.8% by weight.
Elektrolytisches Bad nach Anspruch 1 Electrolytic bath according to claim 1
dadurch gekennzeichnet, dass characterized in that
das elektrolytische Bad weiterhin 180 bis 220 g/L Kaliumcyanat enthält. the electrolytic bath further contains 180 to 220 g / L of potassium cyanate.
Elektrolytisches Bad nach einem der vorstehenden Ansprüche dadurch gekennzeichnet, dass Electrolytic bath according to one of the preceding claims, characterized in that
das der pH-Wert des elektrolytischen Bades zwischen 8,5 bis 9,5 liegt. the pH of the electrolytic bath is between 8.5 to 9.5.
Elektrolytisches Bad nach einem der vorstehenden Ansprüche dadurch gekennzeichnet, dass Electrolytic bath according to one of the preceding claims, characterized in that
das Bad bei den Temperaturen von 20 bis 40°C, vorzugsweise zwischen 20 bis 25°C betrieben wird. the bath at the temperatures of 20 to 40 ° C, preferably is operated between 20 to 25 ° C.
5. Elektrolytisches Bad nach einem der vorstehenden Ansprüche 5. Electrolytic bath according to one of the preceding claims
dadurch gekennzeichnet, dass  characterized in that
das Bad anorganische oder/und organische Glanzzusätze enthält.  the bath contains inorganic or / and organic brighteners.
6. Elektrolytisches Bad nach vorstehendem Anspruch 6. Electrolytic bath according to the preceding claim
dadurch gekennzeichnet, dass  characterized in that
der Gehalt der Glanzzusätze in einem Bereich zwischen 30 mg/L bis 8 g/L, vorzugsweise zwischen 100 bis 500 mg/L, liegt.  the content of the brightener additives is in a range between 30 mg / L and 8 g / L, preferably between 100 and 500 mg / L.
7. Werkstück, dessen Oberfläche in einem elektrolytischen Bad nach Anspruch 1 beschichtet ist 7. workpiece whose surface is coated in an electrolytic bath according to claim 1
dadurch gekennzeichnet, dass  characterized in that
die Oberfläche aus einer Silber-Nickelschicht (AgNi-Schicht) mit einem Anteil von 0, 1 bis 0,5% Nickel besteht.  the surface consists of a silver-nickel layer (AgNi layer) in a proportion of 0, 1 to 0.5% nickel.
8. Werkstück, dessen Oberfläche in einem elektrolytischen Bad nach vorstehendem Anspruch 8. workpiece whose surface in an electrolytic bath according to the preceding claim
dadurch gekennzeichnet, dass  characterized in that
die abgeschiedene Silber-Nickelschicht (AgNi-Schicht) eine Härte von 130 bis 160 HV besitzt.  the deposited silver-nickel layer (AgNi layer) has a hardness of 130 to 160 HV.
PCT/DE2014/100412 2014-01-27 2014-11-24 Electrolytic bath WO2015110099A1 (en)

Priority Applications (1)

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DE102014100862.6A DE102014100862B4 (en) 2014-01-27 2014-01-27 Electrolytic bath
DE102014100862.6 2014-01-27

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807576A (en) * 1955-01-18 1957-09-24 Hanson Van Winkle Munning Co Bright silver plating
SU662623A1 (en) * 1976-07-26 1979-05-15 Вильнюсский Ордена Трудового Красного Знамени Государственный Университет Им.В.Капсукаса Electrolyte for depositing silver-nickel alloy
SU662323A1 (en) 1973-07-16 1979-05-15 Всесоюзный Научно-Исследовательский Инструментальный Институт Grinding method
US20050035843A1 (en) 2003-04-03 2005-02-17 Ronald Dedert Fuel tank resistor card having improved corrosion resistance
KR100888015B1 (en) * 2008-09-26 2009-03-09 주식회사 네오스코 Electroplating solution for ag-ni alloy and ag-ni alloy plated by the same
US7628903B1 (en) * 2000-05-02 2009-12-08 Ishihara Chemical Co., Ltd. Silver and silver alloy plating bath
CN102242382A (en) * 2010-05-11 2011-11-16 铜陵金力铜材有限公司 Production method of silver-plated conductor for producing highly sophisticated products for aviation and aerospace

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4728571B2 (en) * 2003-10-31 2011-07-20 古河電気工業株式会社 Manufacturing method of silver-coated stainless steel strip for movable contacts

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807576A (en) * 1955-01-18 1957-09-24 Hanson Van Winkle Munning Co Bright silver plating
SU662323A1 (en) 1973-07-16 1979-05-15 Всесоюзный Научно-Исследовательский Инструментальный Институт Grinding method
SU662623A1 (en) * 1976-07-26 1979-05-15 Вильнюсский Ордена Трудового Красного Знамени Государственный Университет Им.В.Капсукаса Electrolyte for depositing silver-nickel alloy
US7628903B1 (en) * 2000-05-02 2009-12-08 Ishihara Chemical Co., Ltd. Silver and silver alloy plating bath
US20050035843A1 (en) 2003-04-03 2005-02-17 Ronald Dedert Fuel tank resistor card having improved corrosion resistance
KR100888015B1 (en) * 2008-09-26 2009-03-09 주식회사 네오스코 Electroplating solution for ag-ni alloy and ag-ni alloy plated by the same
CN102242382A (en) * 2010-05-11 2011-11-16 铜陵金力铜材有限公司 Production method of silver-plated conductor for producing highly sophisticated products for aviation and aerospace

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198005, Derwent World Patents Index; AN 1980-08772C, XP002736992 *
DATABASE WPI Week 200929, Derwent World Patents Index; AN 2009-G73458, XP002736994 *
DATABASE WPI Week 201208, Derwent World Patents Index; AN 2011-Q79009, XP002736993 *
See also references of EP3099847A1 *

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EP3099847A1 (en) 2016-12-07
DE102014100862B4 (en) 2018-02-08

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