EP1192297A1 - Bain acide pour deposer par voie electrolytique des couches d'or ou d'alliage d'or brillantes, et agent de brillantage prevu a cet effet - Google Patents

Bain acide pour deposer par voie electrolytique des couches d'or ou d'alliage d'or brillantes, et agent de brillantage prevu a cet effet

Info

Publication number
EP1192297A1
EP1192297A1 EP00929491A EP00929491A EP1192297A1 EP 1192297 A1 EP1192297 A1 EP 1192297A1 EP 00929491 A EP00929491 A EP 00929491A EP 00929491 A EP00929491 A EP 00929491A EP 1192297 A1 EP1192297 A1 EP 1192297A1
Authority
EP
European Patent Office
Prior art keywords
gold
atoms
sulfonate
sulfate
branched
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
Application number
EP00929491A
Other languages
German (de)
English (en)
Other versions
EP1192297B1 (fr
Inventor
Uwe Manz
Klaus Bronder
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.)
Umicore Galvanotechnik GmbH
Original Assignee
Degussa Galvanotechnik 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
Priority claimed from DE10007325A external-priority patent/DE10007325A1/de
Application filed by Degussa Galvanotechnik GmbH filed Critical Degussa Galvanotechnik GmbH
Publication of EP1192297A1 publication Critical patent/EP1192297A1/fr
Application granted granted Critical
Publication of EP1192297B1 publication Critical patent/EP1192297B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the invention relates to an acid bath for the galvanic deposition of shiny gold and gold alloy layers and a gloss additive therefor.
  • Galvanic gold baths usually contain gold and optionally one or more alloy elements in dissolved form.
  • Such electrolytes are mainly based on gold cyanide complexes. It is necessary to adjust these electrolytes to a weak to moderately acidic pH using inorganic and / or organic acids and buffer salts.
  • shiny gold or gold alloy layers are deposited from such baths, they usually contain certain inorganic or organic compounds as so-called “gloss additives”.
  • a typical, very frequently used gloss additive is, as described for example in DE 23 55 581, the compound pyridine-3-sulfonic acid.
  • Such additives shift or expand the working range, that is the range of applicable current density, in which a shiny gold plating is deposited, in the direction of high current densities.
  • the use of higher current densities in turn allows deposition at a higher speed.
  • the working range of such gold baths also depends on the pH of the electrolyte. It applies here that the working range (applicable current density range) is narrowed at a higher pH value, but at the same time the current yield and thus the separation speed is increased.
  • the invention thus relates to an acidic bath for the electrodeposition of shiny gold and gold alloy layers, containing gold and optionally one or more alloy elements in dissolved form and at least one organic compound as an additive, characterized in that the bath as at least one compound of the additive general formula R - SO m -H (I)
  • the gloss additives according to formula I are selected compounds from the classes of the alkyl sulfonates and the alkyl, aryl or heteroaryl sulfates.
  • R means a straight or branched chain or cyclic alkyl group with up to 20 C atoms. If m stands for the number 4, then R can also be an aryl or heteroaryl group with up to 10 C atoms, it being possible for these to be substituted one or more times with straight-chain or branched-chain alkyl groups with 1 to 14 C atoms .
  • Preferred gloss additives are compounds of the formula I in which R represents straight-chain or branched-chain or cyclic alkyl groups having 5 to 12 carbon atoms and in particular branched-chain alkyl groups having 6 to 10 carbon atoms.
  • Typical gloss additives according to the invention are
  • Branched-chain and short-chain connections are particularly suitable due to their lower tendency to foam, especially in processes and systems in which strong foam formation interferes, e.g. in air-moving electrolytes where
  • Drum processing in systems for high-speed separation (spraying systems) and in systems for selective separation, e.g. Diving cells.
  • the use of the further gloss additive according to the invention in acid baths for the electrodeposition of shiny gold and gold alloy layers is advantageously carried out in a concentration range from 0.01 to 10 g / l.
  • Baths according to the invention which contain the gloss additive according to formula I in a concentration of 0.1 to 5 g / l are particularly advantageous.
  • the compounds of the formula I according to the invention as a further gloss additive in galvanic gold baths of otherwise customary composition the applicable current density working range is expanded in an unexpected manner and at the same time the current yield and the separation efficiency are drastically increased in part.
  • the galvanic gold baths according to the invention typically contain approximately
  • alloy metals such as iron, cobalt, nickel, indium, silver, copper, cadmium, tin, zinc, bismuth, arsenic, antimony as salt or complex salt
  • a low gold content can be used with the same separation performance.
  • the advantages are the lower carry-over due to electrolytes adhering to the goods and the lower capital commitment.
  • a maximum current density of 3 A / dm 2 is reached on pre-nickel-plated sheets of size 25 x 40 mm (experimental setup: 1 liter beaker, platinum-coated titanium anode, bath movement 200 rpm using a magnetic stirring bar 60 mm, movement of goods 5 cm / s).
  • the cathodic current yield at 3 A / dm 2 is 52% and the deposition rate is 1.0 ⁇ m / min.
  • a maximum current density of 5 A / dm 2 is achieved on sheets of size 25 x 40 mm (conditions see example 2).
  • the cathodic current yield is 31% and the deposition rate is 1.0 ⁇ m / min.
  • the maximum applicable current density is increased to over 6 A / dm 2 .
  • the current yield is still 30%; the separation rate increases to 1.16 ⁇ m / min. This corresponds to a speed increase of 16%.
  • a working range of up to 5 A / dm 2 is achieved in a Hull cell (test conditions: platinum-plated titanium anode, temperature 50 ° C., duration 2 min, movement 500 rpm by means of a magnetic stirring bar 25 mm) with a cell current of 2 A.
  • the current yield at 5 A / dm 2 is 26%; the separation speed is 0.83 ⁇ m / min.
  • the maximum applicable current density is increased to over 8 A / dm 2 .
  • the current yield is still 19%; the separation rate increases to 1.0 ⁇ m / min.
  • the maximum applicable current density is increased to over 5 A / dm 2 by the addition of 1 g / 1 hexyl sulfonate.
  • the current yield is 35.1%, the separation efficiency increases to 1.13 ⁇ m / min. This corresponds to a speed increase of 15%.
  • the maximum applicable current density is increased to over 7 A / dm 2 by the addition of 1 g / 1 octyl sulfonate.
  • the current yield is 26.2%, the separation efficiency increases to 1.18 ⁇ r ⁇ / min. This corresponds to a 20% increase in speed.

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

L'invention concerne un bain acide pour déposer par voie électrolytique des couches d'or ou d'alliage d'or brillantes, ainsi qu'un agent de brillantage prévu à cet effet. L'utilisation de composés de formule (I) : R - SOm-H, comme agent de brillantage supplémentaire, permet d'élargir la plage de travail de densité de courant, avec une faible influence négative due aux variations de pH, et d'accroître le rendement en courant et le rendement de dépôt. Dans la formule (I), m vaut 3 ou 4 ; R représente un groupe cyclique alkyle ou à chaîne linéaire ou ramifiée comportant jusqu'à 20 atomes de C, et lorsque m = 4, également un groupe aryle ou hétéroaryle comportant jusqu'à 10 atomes de C, pouvant être éventuellement substitué une ou plusieurs fois par des groupes alkyle à chaîne linéaire ou ramifiée comportant 1 à 14 atomes de C.
EP00929491A 1999-06-17 2000-05-04 Bain acide pour deposer par voie electrolytique des couches d'or ou d'alliage d'or brillantes, et agent de brillantage prevu a cet effet Expired - Lifetime EP1192297B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19927642 1999-06-17
DE19927642 1999-06-17
DE10007325 2000-02-17
DE10007325A DE10007325A1 (de) 1999-06-17 2000-02-17 Saures Bad zur galvanischen Abscheidung von glänzenden Gold- und Goldlegierungsschichten und Glanzzusatz hierfür
PCT/EP2000/003993 WO2000079031A1 (fr) 1999-06-17 2000-05-04 Bain acide pour deposer par voie electrolytique des couches d'or ou d'alliage d'or brillantes, et agent de brillantage prevu a cet effet

Publications (2)

Publication Number Publication Date
EP1192297A1 true EP1192297A1 (fr) 2002-04-03
EP1192297B1 EP1192297B1 (fr) 2007-01-10

Family

ID=26004396

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00929491A Expired - Lifetime EP1192297B1 (fr) 1999-06-17 2000-05-04 Bain acide pour deposer par voie electrolytique des couches d'or ou d'alliage d'or brillantes, et agent de brillantage prevu a cet effet

Country Status (8)

Country Link
US (1) US6814850B1 (fr)
EP (1) EP1192297B1 (fr)
JP (1) JP3933930B2 (fr)
CN (1) CN1205360C (fr)
DE (1) DE50013952D1 (fr)
HK (1) HK1047773B (fr)
TW (1) TWI234591B (fr)
WO (1) WO2000079031A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6736954B2 (en) * 2001-10-02 2004-05-18 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
JP4868116B2 (ja) * 2005-09-30 2012-02-01 学校法人早稲田大学 金−コバルト系アモルファス合金めっき皮膜、電気めっき液及び電気めっき方法
JP4868121B2 (ja) * 2005-12-21 2012-02-01 学校法人早稲田大学 アモルファス金−ニッケル系合金めっき皮膜形成用電気めっき液及び電気めっき方法
JP4945193B2 (ja) * 2006-08-21 2012-06-06 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． 硬質金合金めっき液
CH714243B1 (fr) * 2006-10-03 2019-04-15 Swatch Group Res & Dev Ltd Procédé d'électroformage et pièce ou couche obtenue par ce procédé.
CH710184B1 (fr) 2007-09-21 2016-03-31 Aliprandini Laboratoires G Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques.
JP5471276B2 (ja) * 2009-10-15 2014-04-16 上村工業株式会社 電気銅めっき浴及び電気銅めっき方法
EP2312021B1 (fr) * 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques
JP2011122192A (ja) * 2009-12-09 2011-06-23 Ne Chemcat Corp 電解硬質金めっき液及びこれを用いるめっき方法
JP5854727B2 (ja) * 2010-09-21 2016-02-09 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 シアン化物を含まない銀電気めっき液
JP2013177654A (ja) * 2012-02-28 2013-09-09 Matex Japan Co Ltd 電解硬質金めっき液、めっき方法、及び、金−鉄合金被膜の製造方法
CN105401180A (zh) * 2015-12-23 2016-03-16 苏州市金星工艺镀饰有限公司 一种耐磨镀金膜的电镀液及其电镀方法
CN105463530A (zh) * 2015-12-23 2016-04-06 苏州市金星工艺镀饰有限公司 一种装饰性镍铜金三元合金电镀液

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2355581C3 (de) 1973-11-07 1979-07-12 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Galvanisches Glanzgoldbad mit hoher Abscheidungsgeschwindigkeit
CH629258A5 (en) 1978-02-23 1982-04-15 Systemes Traitements Surfaces Bath for electrolytic deposition of white gold alloy
DE3032469A1 (de) * 1980-08-28 1982-04-01 Siemens AG, 1000 Berlin und 8000 München Cyanidische goldbaeder und verfahren zur galvanischen abscheidung von feststoffschmiermittel-haltigen gold-dispersionsueberzuegen und seine anwendung
JPS604920B2 (ja) 1981-03-30 1985-02-07 日本鉱業株式会社 耐摩耗性良好な黒色ロジウムメッキ被覆物品の製造方法
US4402802A (en) 1981-01-03 1983-09-06 Dequssa Aktiengesellschaft Electrolytic bath for the deposition of rhodium coatings
CH680370A5 (fr) * 1989-12-19 1992-08-14 H E Finishing Sa
JPH1150295A (ja) 1997-07-28 1999-02-23 Daiwa Kasei Kenkyusho:Kk めっき浴

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0079031A1 *

Also Published As

Publication number Publication date
DE50013952D1 (de) 2007-02-22
CN1205360C (zh) 2005-06-08
US6814850B1 (en) 2004-11-09
HK1047773A1 (en) 2003-03-07
WO2000079031A1 (fr) 2000-12-28
TWI234591B (en) 2005-06-21
JP2003502513A (ja) 2003-01-21
JP3933930B2 (ja) 2007-06-20
HK1047773B (zh) 2006-01-27
EP1192297B1 (fr) 2007-01-10
CN1357060A (zh) 2002-07-03

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