US3929595A - Electrolytic burnished gold bath with higher rate of deposition - Google Patents

Electrolytic burnished gold bath with higher rate of deposition Download PDF

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Publication number
US3929595A
US3929595A US520844A US52084474A US3929595A US 3929595 A US3929595 A US 3929595A US 520844 A US520844 A US 520844A US 52084474 A US52084474 A US 52084474A US 3929595 A US3929595 A US 3929595A
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US
United States
Prior art keywords
bath
sulfonic acid
acid
article
gold
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.)
Expired - Lifetime
Application number
US520844A
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English (en)
Inventor
Peter Biberbach
Werner Dietschmann
Hans-Joachim Lubke
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Evonik Operations GmbH
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Degussa GmbH
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Publication date
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Publication of US3929595A publication Critical patent/US3929595A/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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold

Definitions

  • ABSTRACT There is provided an electrolytic gold bath for the deposition of thicker, bright gold coatings at high rates of deposition.
  • the bath contains a heterocyclic azohydrocarbon sulfonic acid or salt thereof, e.g. pyridine sulfonic acid.
  • the invention is directed to an electrolytic gold bath for the deposition of thick, bright gold coatings at higher rates of deposition which contain sulfonic acids of heterocyclic nitrogen containing hydrocarbons, i.e. heterocyclic azohydrocarbons.
  • N-heterocyclic hydrocarbon sulfonic acids i.e., the compounds consist of carbon, hydrogen, the hetero-N-atom and the sulfonic acid group
  • salts of such N-heterocyclic sulfonic acids i.e., the compounds consist of carbon, hydrogen, the hetero-N-atom and the sulfonic acid group
  • pyridine sulfonic acid e.g. pyridine-3-sulfonic acid, pyridine-4-sulfonic acid and pyridine-2-sulfonic acid and/or their salts, e.g. water solubles such as salts with alkali metals or ammonium, e.g. the sodium or potassium salts, e.g. the sodium salt of pyridine-3-sulfonic acid and the potassium salt of pyridine-3-sulfonic'acid and/or their simple ring alkyl derivatives, as for example the picoline sulfonic acids, e.g. 2-methylpyridine-3-sulfonic acid, 2-methylpyridine-4-sulfonic acid, 3-methylpyridine-2-sulfonic acid, 3-methylpyridine-4-sulfonic acid and 4-methylpyridine-3-sulfonic acid.
  • picoline sulfonic acids e.g. 2-methylpyridine-3-sulfonic acid, 2-methylpyridine-4-sulf
  • the sulfonic acid derivatives of nitrogen containing heterocyclic also considerably increases the rate of deposition of the gold layer since the baths can be operated at higher current yields at higher current densities.
  • the current density can range from 0.5 to 12 A/dm preferably from 2 to 6 Aldm
  • pyridine sulfonic acids and picoline sulfonic acid there can also be added the sulfonic acids of other substituted nitrogen containing heterocyclics, as for example quinoline sulfonic acid, e.g. quinoline sulfonic acids such as quinoline-5 -sulfonic acid and quinoline-8- sulfonic acid.
  • quinoline sulfonic acid e.g. quinoline sulfonic acids such as quinoline-5 -sulfonic acid and quinoline-8- sulfonic acid.
  • pyridine sulfonic acids, especially pyridine-3-sulfonic acid has proven best.
  • the pyridine sulfonic acid or salt and/or derivative is employed in weakly acid gold baths, e.g., pH 3 to 5.5.
  • weakly acid gold baths e.g., pH 3 to 5.5.
  • gold baths according to the invention for example, have the following composition.
  • alkali gold cyanide e.g. sodium gold cyanide or potassium gold cyanide or ammonium gold cyanide.
  • a weak organic acid preferably citric acid or tartaric acid
  • hydroxide e.g. sodium hydroxide or potassium hydroxide or ammonium hydroxide to adjust the pH to between 3.5 and 5.0 or 5.5.
  • Additional suitable weak organic acids include formic acid, lactic acid, kojic acid, itaconic acid, citraconic acid, gluconic acid, glutaric acid, glycolic acid, acetic acid and propionic acid.
  • pyridine sulfonic acid 1-20 g/l of pyridine sulfonic acid, preferably 1-10 g/l.
  • the buffering action of the weak organic acids added can also be produced by addition of or the use of only other buffers known to be usable in the named pH range as for example phosphates and borates, e.g. dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium metaborate and potassium metaborate.
  • buffers known to be usable in the named pH range as for example phosphates and borates, e.g. dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium metaborate and potassium metaborate.
  • the bright range of the burnished gold baths of the invention in regard to working parameters such as concentration, temperature, pH-value or current density can be widened considerably by small additions of non-noble metals such as iron, cobalt, nickel, chromium, cadmium, copper, zinc, tin, indium and/or antimony in an amount of 3 to mg/l, preferably 10 to 50 mg/l.
  • non-noble metals such as iron, cobalt, nickel, chromium, cadmium, copper, zinc, tin, indium and/or antimony in an amount of 3 to mg/l, preferably 10 to 50 mg/l.
  • non-noble metals are normally added in the form of soluble salts, e.g. as salts of the acids set forth above such as citric acid and tartaric acid for example.
  • the amounts of foreign metals used in the baths of the invention are considerably below the amounts necessary to produce brightness in the known baths.
  • compositions can comprise, consist of'or consist essentially of the materials set forth.
  • potassium gold cyanide employed was potassium gold (I) cyanide (potassium cyanoaurite).
  • potassium gold (I) cyanide potassium gold (I) cyanide
  • sodium cyanoaurite potassium gold (I) cyanide
  • alkali gold cyanides such as sodium gold (I) cyanide
  • bathtemperatures of 45C were used in the working examples, this can be varied as is conventional in the art, e.g. 30 to 50C.
  • EXAMPLE 3 acid resulted only in dirty brown coatings. An improvement also was not produced by variation of the current density, pH-value and temperature which showed the decisive influence of the pyridine sulfonic acid in the baths of the invention.
  • EXAMPLE 5 The bath composition and temperature were the same as in Example 4 but at an article motion of 25 cm/sec.
  • EXAMPLE 6 The bath composition and temperature were the same as in Example 4 but at an article motion of 25 cm/sec. and simultaneous vibration movement of the bath.
  • an aqueous, acidic alkali gold cyanide bath suitable for the electrolytic deposition of gold comprising including in the bath a heterocyclic sulfonic acid selected from the group consisting of pyridine sulfonic acid, picoline sulfonic acid and quinoline sulfonic acid or a water soluble salt of such heterocyclic sulfonic acid in an amount sufficient to provide improved bright gold deposition from the bath.
  • a heterocyclic sulfonic acid selected from the group consisting of pyridine sulfonic acid, picoline sulfonic acid and quinoline sulfonic acid or a water soluble salt of such heterocyclic sulfonic acid in an amount sufficient to provide improved bright gold deposition from the bath.
  • heterocyclic sulfonic acid is pyridine sulfonic acid or quinoline sulfonic acid.
  • a bath according to claim 2 wherein the heterocyclic sulfonic acid is pyridine sulfonic acid.
  • a bath according to claim 4 containing 2-15 g/l gold as alkali gold cyanide, 30-200 g/l of a weak organic acid and 1-20 g/l of a pyridine sulfonic acid, said bath having a pH of 3.5 to 5.5.
  • a bath according to claim 5 including a buffer capable of maintaining the pH within the range 3.5 to 5.5.
  • a bath according to claim 5 also including 5-100 mg/l of iron, cobalt, nickel, chromium, cadmium, copper, zinc, tin, indium or antimony in the form ofa water soluble salt thereof.
  • a bath according to claim 7 containing 10-50 mg/l of iron.
  • a bath according to claim 5 wherein the weak organic acid is an alka'noic acid or a hydroxyalkanoic acid.
  • a bath according to claim 10 wherein the acid is a hydroxyalkanoic acid.
  • a bath according to claim 11 wherein the acid is citric acid or tartaric acid.
  • a bath according to claim 1 containing 1 to 20 g/l of the heterocyclic sulfonic acid.
  • a process of electrolytically depositing a glossy gold coating on an article comprising placing the article in the bath of claim 1 and passing a current therethrough at a current density of 0.5 to 12 A/dm 15.
  • a process of electrolytically depositing a glossy gold coating on an article comprising placing the article in the bath of claim 1 and passing a current therethrough at a current density of 2 to 6 A/dm 16.
  • a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 5 and passing a current therethrough at a current density of 0.5 to 12 A/dm 17.
  • a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 5 and passing a current therethrough at a current density of 2 to 6 Aldm 18.
  • a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 7 and passing a current therethrough at a current density of 0.5 to 12 A/dm.
  • a process of electrolytically depositing a bright gold coating on an article comprising placing the article in the bath of claim 7 and passing a current therethrough at a current density of 2 to 6 A/dm

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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)
US520844A 1973-11-07 1974-11-04 Electrolytic burnished gold bath with higher rate of deposition Expired - Lifetime US3929595A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2355581A DE2355581C3 (de) 1973-11-07 1973-11-07 Galvanisches Glanzgoldbad mit hoher Abscheidungsgeschwindigkeit

Publications (1)

Publication Number Publication Date
US3929595A true US3929595A (en) 1975-12-30

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US520844A Expired - Lifetime US3929595A (en) 1973-11-07 1974-11-04 Electrolytic burnished gold bath with higher rate of deposition

Country Status (12)

Country Link
US (1) US3929595A (xx)
JP (1) JPS5615472B2 (xx)
BE (1) BE821923A (xx)
BR (1) BR7409243A (xx)
CH (1) CH603825A5 (xx)
DE (1) DE2355581C3 (xx)
ES (1) ES430054A1 (xx)
FR (1) FR2249979B1 (xx)
GB (1) GB1426849A (xx)
IT (1) IT1020940B (xx)
NL (1) NL186825C (xx)
SE (1) SE7413961L (xx)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150439A1 (en) * 1983-12-22 1985-08-07 LeaRonal (UK) plc An acid bath for electrodeposition of gold or gold alloys, an electroplating method and the use of said bath
US4670107A (en) * 1986-03-05 1987-06-02 Vanguard Research Associates, Inc. Electrolyte solution and process for high speed gold plating
US4744871A (en) * 1986-09-25 1988-05-17 Vanguard Research Associates, Inc. Electrolyte solution and process for gold electroplating
US4755264A (en) * 1987-05-29 1988-07-05 Vanguard Research Associates, Inc. Electrolyte solution and process for gold electroplating
US4767507A (en) * 1986-05-21 1988-08-30 Engelhard Corporation Gold electroplating bath
DE4040526A1 (de) * 1989-12-19 1991-06-20 H E Finishing Sa Bad zur galvanischen abscheidung von goldlegierungen
DE4105272A1 (de) * 1990-02-20 1991-08-22 Enthone Omi Inc Zusammensetzung und verfahren zur herstellung eines galvanischen ueberzuges
US6165342A (en) * 1996-07-23 2000-12-26 Degussa Huls Aktiengesellschaft Cyanide-free electroplating bath for the deposition of gold and gold alloys
US6336962B1 (en) * 1997-10-08 2002-01-08 Atotech Deutschland Gmbh Method and solution for producing gold coating
US6576114B1 (en) 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
EP1403401A2 (en) * 2002-09-24 2004-03-31 Northrop Grumman Corporation Precious alloyed metal solder plating process
US6814850B1 (en) 1999-06-17 2004-11-09 Umicore Galvanotechnik Gmbh Acid bath for electrodeposition of glossy gold and gold alloy layers and a gloss additive for same
US20050205425A1 (en) * 2002-06-25 2005-09-22 Integran Technologies Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents
CN103397356A (zh) * 2013-07-15 2013-11-20 苏州苏凯路化学科技有限公司 一种无毒镀金用金盐及其合成方法
US10570525B2 (en) * 2015-01-16 2020-02-25 Hutchinson Technology Incorporated Gold electroplating solution and method

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8501245D0 (en) * 1985-01-18 1985-02-20 Engelhard Corp Gold electroplating bath
JPS61276992A (ja) * 1985-05-30 1986-12-06 Shinko Electric Ind Co Ltd 電解金めつき液
JPS61276990A (ja) * 1985-05-30 1986-12-06 Shinko Electric Ind Co Ltd 電解金めつき液
JPS637390A (ja) * 1986-06-26 1988-01-13 Nippon Engeruharudo Kk 金−コバルト合金めつき液
GB9522591D0 (en) * 1995-11-03 1996-01-03 Enthone Omi Suisse S A Electroplating processes compositions and deposits
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
DE102011114931B4 (de) 2011-10-06 2013-09-05 Umicore Galvanotechnik Gmbh Verfahren zur selektiveren, elektrolytischen Abscheidung von Gold oder einer Goldlegierung
DE102012004348B4 (de) 2012-03-07 2014-01-09 Umicore Galvanotechnik Gmbh Verwendung von organischen Thioharnstoffverbindungen zur Erhöhung der galvanischen Abscheiderate von Gold und Goldlegierungen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2905601A (en) * 1957-08-13 1959-09-22 Sel Rex Corp Electroplating bright gold
US2967135A (en) * 1960-06-08 1961-01-03 Barnet D Ostrow Electroplating baths for hard bright gold deposits
US2986498A (en) * 1954-03-13 1961-05-30 Dehydag Gmbh Process for the production of metal electrodeposits
US3023150A (en) * 1954-03-22 1962-02-27 Dehydag Gmbh Bath for the production of metal electroplates
US3149058A (en) * 1959-12-31 1964-09-15 Technic Bright gold plating process

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL273924A (xx) * 1961-01-24
USB373094I5 (xx) * 1964-08-26

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2986498A (en) * 1954-03-13 1961-05-30 Dehydag Gmbh Process for the production of metal electrodeposits
US3023150A (en) * 1954-03-22 1962-02-27 Dehydag Gmbh Bath for the production of metal electroplates
US2905601A (en) * 1957-08-13 1959-09-22 Sel Rex Corp Electroplating bright gold
US3149058A (en) * 1959-12-31 1964-09-15 Technic Bright gold plating process
US2967135A (en) * 1960-06-08 1961-01-03 Barnet D Ostrow Electroplating baths for hard bright gold deposits

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150439A1 (en) * 1983-12-22 1985-08-07 LeaRonal (UK) plc An acid bath for electrodeposition of gold or gold alloys, an electroplating method and the use of said bath
US4591415A (en) * 1983-12-22 1986-05-27 Learonal, Inc. Plating baths and methods for electro-deposition of gold or gold alloys
US4670107A (en) * 1986-03-05 1987-06-02 Vanguard Research Associates, Inc. Electrolyte solution and process for high speed gold plating
US4767507A (en) * 1986-05-21 1988-08-30 Engelhard Corporation Gold electroplating bath
US4744871A (en) * 1986-09-25 1988-05-17 Vanguard Research Associates, Inc. Electrolyte solution and process for gold electroplating
US4755264A (en) * 1987-05-29 1988-07-05 Vanguard Research Associates, Inc. Electrolyte solution and process for gold electroplating
WO1988009401A1 (en) * 1987-05-29 1988-12-01 Vanguard Research Associates, Inc. Electrolyte solution and process for gold electroplating
WO1988009834A1 (en) * 1987-06-01 1988-12-15 Vanguard Research Associates, Inc. Electrolyte solution and process for gold electroplating
DE4040526A1 (de) * 1989-12-19 1991-06-20 H E Finishing Sa Bad zur galvanischen abscheidung von goldlegierungen
DE4040526C3 (de) * 1989-12-19 1998-05-20 H E Finishing Sa Bad zur galvanischen Abscheidung von Goldlegierungen
US5169514A (en) * 1990-02-20 1992-12-08 Enthone-Omi, Inc. Plating compositions and processes
DE4105272A1 (de) * 1990-02-20 1991-08-22 Enthone Omi Inc Zusammensetzung und verfahren zur herstellung eines galvanischen ueberzuges
US6576114B1 (en) 1995-11-03 2003-06-10 Enthone Inc. Electroplating composition bath
US6165342A (en) * 1996-07-23 2000-12-26 Degussa Huls Aktiengesellschaft Cyanide-free electroplating bath for the deposition of gold and gold alloys
US6336962B1 (en) * 1997-10-08 2002-01-08 Atotech Deutschland Gmbh Method and solution for producing gold coating
US6814850B1 (en) 1999-06-17 2004-11-09 Umicore Galvanotechnik Gmbh Acid bath for electrodeposition of glossy gold and gold alloy layers and a gloss additive for same
US20050205425A1 (en) * 2002-06-25 2005-09-22 Integran Technologies Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents
EP1403401A2 (en) * 2002-09-24 2004-03-31 Northrop Grumman Corporation Precious alloyed metal solder plating process
EP1403401A3 (en) * 2002-09-24 2005-09-28 Northrop Grumman Corporation Precious alloyed metal solder plating process
CN103397356A (zh) * 2013-07-15 2013-11-20 苏州苏凯路化学科技有限公司 一种无毒镀金用金盐及其合成方法
CN103397356B (zh) * 2013-07-15 2017-04-19 苏州苏凯路化学科技有限公司 一种无毒镀金用金盐及其合成方法
US10570525B2 (en) * 2015-01-16 2020-02-25 Hutchinson Technology Incorporated Gold electroplating solution and method

Also Published As

Publication number Publication date
FR2249979A1 (xx) 1975-05-30
DE2355581A1 (de) 1975-05-28
DE2355581C3 (de) 1979-07-12
NL186825C (nl) 1991-03-01
CH603825A5 (xx) 1978-08-31
GB1426849A (en) 1976-03-03
ES430054A1 (es) 1976-10-16
JPS5615472B2 (xx) 1981-04-10
NL7413010A (nl) 1975-05-12
BR7409243A (pt) 1976-05-18
DE2355581B2 (xx) 1978-11-16
IT1020940B (it) 1977-12-30
FR2249979B1 (xx) 1976-10-22
BE821923A (fr) 1975-05-06
SE7413961L (xx) 1975-05-09
JPS5075531A (xx) 1975-06-20

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