[go: up one dir, main page]

US3475292A - Gold plating bath and process - Google Patents

Gold plating bath and process Download PDF

Info

Publication number
US3475292A
US3475292A US526385A US3475292DA US3475292A US 3475292 A US3475292 A US 3475292A US 526385 A US526385 A US 526385A US 3475292D A US3475292D A US 3475292DA US 3475292 A US3475292 A US 3475292A
Authority
US
United States
Prior art keywords
gold
per liter
sulfite
sodium
potassium
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
US526385A
Inventor
Hrant H Shoushanian
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.)
Technic Inc
Original Assignee
Technic Inc
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 Technic Inc filed Critical Technic Inc
Application granted granted Critical
Publication of US3475292A publication Critical patent/US3475292A/en
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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • 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

  • Gold has been reported electrodeposited from sodium gold sulfite solutions as early as 1842, Dinglers Journal 97, pp. 429-446 (1845), and British Patent No. 9,431, issued Aug. 1, 1842. Such solutions were apparently used for a period of approximately ten years.
  • the gold deposits produced were porous and the physical properties were inferior to deposits obtained from cyanide-containing gold plating baths, resulting in the abandonment of the sulfite baths in favor of the cyanide baths.
  • One aspect of the present invention contemplates electrodepositing gold and gold alloys from an alkaline aqueous bath containing (i) Between 1 and 30 grams per liter and preferably between 5 and 15 grams per liter of gold as sulfite selected from the group consisting of potassium gold sul fite and sodium gold sulfite;
  • a buffering and conducting salt selected from soluble phosphate, sulfate, acetate, and citrate salts of the alkali metals and the alkaline earth metals, in an amount between 5 and 150 grams per liter and preferably between 10 and 100 grams per liter;
  • At least one brightening and/or alloying additive selected from (a) Between about 5 and 500 milligrams per liter of a base metal in the form of a soluble salt or a soluble complex,
  • the base metals effective as brighteners are cadmium, titanium, molybdenum, tungsten, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese, and vanadium.
  • the semimetals effective as brighteners are arsenic, antimony, selenium, and tell-urium. Lead, copper, arsenic and cobalt are the preferred brighteners.
  • the base metals and semimetals effective as alloying agents are cadimum, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese and antimony. Cobalt, antimony and nickel are the preferred alloying agents.
  • the soluble salts may vary widely in their degree of solubility in the electrolyte. With the relatively small amounts of the metals required, salts having even limited solubility may be utilized. Advantage may be taken of this limited solubility to provide control of the additive level by maintaining an undissolved excess of the salt in the bath.
  • salts of the metals and semimetals which are suitable sources of the metal or semimetal respectively: cadmium sulfate, cadmium acetate, lead acetate, lead nitrate, zinc sulfate, zinc acetate, iron sulfate, iron acetate, nickel sulfate, nickel nitrate, cobalt sulfate, cobalt acetate, indium sulfate, indium nitrate, copper sulfate, copper acetate, manganese sulfate, and manganese acetate.
  • Compounds in which the metal or semimetal is in the anionic moiety may also be used, e.g., potassium titanate, ammonium titanate, sodium molybdate, potassium molybdate, sodium tungstate, potassium tungstate, sodium stannate, potassium stannate, sodium vanadate, ammonium vanadate, potassium arsenite, ammonium arsenite, potassium antimony tartrate, sodium .antimonite, sodium selenate, potassium selenate, potassium tellurate, and sodium tellurate.
  • anions could also be introduced into solution in the form of any soluble salt with the following cationic moieties: cesium, lithium, quaternary ammonium salts and other organic cationic moieties.
  • the base metals and semimetals may also be added to the bath in the form of a soluble complex, sometimes also referred to as a chelate, with a compound selected from the group consisting of aminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, iminodiacetic acid, etc.; acetylacetonates; and hydroxyorganic acid moieties such as citric acid, lactic acid, and tartaric acid.
  • aminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid
  • the buffering and conducting salts are selected from the soluble phosphate, sulfate, carbonate, acetate, citrate, and tartrate salts of the alkali metals and the alkaline earth metals.
  • Such salts as dipotassium phosphate, disodium phosphate, dipotassium ethylenediarninediacetate, disodium ethylenediamine diacetate, disodium ethylenediamine tetraacetate, dipotassium ethylenediaminetetraacetate, tripotassium phosphate, trisodium phosphate, sodium tetraphosphate, potassium tetraphosphate, sodium metaphosphate, potassium metaphosphate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium citrate, potassium citrate, sodium tartrate, potassium tartrate, sodium hexametaphosphate, and potassium hexametaphosphate are illustrative of operative buffering and conducting salts.
  • the bath is operated at a pH more alkaline than 8, to an alkalinity in excess of 12.
  • the preferred operating range is between 9 and 11.
  • the bath is generally adjusted to the desired pH range by the addition of an alkali metal or alkaline earth metal hydroxide, preferably sodium or potassium hydroxide. If by chance the pH of the bath is above the desired operating range, the necessary adjustment may be made by addition of an acid, preferably a sulfur acid such as sulphuric acid.
  • the baths may be operated, dependent on the desired rate of electrodeposition and the amount of agitation, over a wide range of current densities. A range of between about 1 and 50 amperes per square foot is preferred with moderate agitation. Agitation enhances brightness and uniformity of the deposit, and also permits a wider current density operating range.
  • the bath may be operated from about room temperature up to about 180 F., with a preferred range between about 110 F. and 140 F.
  • Hardness is 320 Knoop hardness number.
  • Similar sound gold and gold alloy deposits are obtained following the procedure of the examples and utilizing baths having compositions within the ranges specified and containing cadmium, iron, zinc, titanium, tin, antimony, selenium, or tellurium, as the metal or semimetal additive.
  • the deposits have a Knoop hardness of between about 85 and 350.
  • the deposits of the present invention may be electrodeposited on a variety of basis metals.
  • the basis metal should be a conductor and preferably a metal having a clean, smooth surface.
  • the gold and gold alloy electrodeposits may be obtained on the wide variety of basis metals which are known as conductors and may also be obtained on nonconducting materials by first making the surface conductive, utilizing the techniques conventional for this purpose.
  • the gold electrodeposits and gold alloy electrodeposits obtained using the baths and processes of this invention are sound deposits which may be formed in relatively thick deposits.
  • the deposits have good physical proper-- ties. They are hard and have superior wearing characteristics. They are also bright, being categorized as bright deposits on two grounds: they are visually bright and they are brighter than the surface upon which they are deposited. They have high luster and specular reflection. Alloy deposits of various shades of yellow having a pleasing appearance may be obtained using metal alloying additives.
  • the baths have excellent characteristics for electroplating purposes permitting electrodeposition over a relatively wide range of process conditions. Good throwing power is obtained.
  • An important economic advantage of utilizing the baths of the present invention rather than the currently widely used gold cyanide electroplating baths results from the savings in not having to construct and operate elaborate facilities for processing waste cyanide solutions.
  • An alkaline aqueous bath for electroplating gold and gold alloys consisting essentially of (i) between 1 and 30 grams per liter of gold as sulfite selected from the group consisting of potassium gold sulfite and sodium gold sulfite;
  • a buffering and conducting salt selected from the group consisting of the soluble phosphate, sulfate, carbonate, acetate, citrate, and tartrate salts of the alkali metals and the alkaline earth metals;
  • At least one additive selected from the group consisting of (a) a brightening metal additive selected from the group consisting of cadmium, titanium, molybdenum, tungsten, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese, and vanadium, in an amount between 5 and 500 milligrams per liter, as a soluble salt of said meal or as a soluble complex of said metal,
  • a brightening metal additive selected from the group consisting of cadmium, titanium, molybdenum, tungsten, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese, and vanadium, in an amount between 5 and 500 milligrams per liter, as a soluble salt of said meal or as a soluble complex of said metal
  • a brightening semimetallic additive selected from the group consisting of antimony, arsenic, selenium and tellurium in an amount between 1 and 400 milligrams per liter as a soluble salt or a soluble complex of said semimetal, and
  • an alloying element selected from the group consisting of cadmium, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese, and antimony as a soluble salt or soluble complex, when in the form of a salt in an amount between 0.5 and 5 grams per liter, and when in the form of a complex in an amount between 0.5 and grams per liter; and
  • the bath of claim 1 having a pH between 9 and 11, and containing between about 5 grams per liter and grams per liter of gold, between about 40 grams per liter and 120 grams per liter of said alkali metal sulfites, and between about 10 grams per liter and 100 grams per liter of said buffering and conducting salt.
  • said buffering and conducting salt is selected from the group consisting of dipotassium phosphate, disodium phosphate, disodium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, disodium ethylenediaminediacetate, and dipotassium ethylenediamine diacetate.
  • said brightening additive is selected from the group consisting of cobalt, lead, copper, and arsenic.
  • alloying additive is selected from the group consisting of cobalt and nickel.
  • the process of plating gold comprising electrodepositing gold on a cathode from the aqueous bath of claim 1 at a temperature between room temperature and 180 F.

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)

Description

United States Patent OJ 3,475,292 GOLD PLATING BATH AND PROCESS Hrant H. Shoushanian, Cranston, R.I., assignor t Technic, Inc., Cranston, RI. N0 Drawing. Filed Feb. 10, 1966, Ser. No. 526,385 Int. Cl. C23b /46, 5/42, 5/28 U.S. Cl. 204-44 Claims ABSTRACT OF THE DISCLOSURE The present invention is directed to a process for electrodepositing gold and gold alloys and to improved complex gold sulfite baths used in such processes.
Gold has been reported electrodeposited from sodium gold sulfite solutions as early as 1842, Dinglers Journal 97, pp. 429-446 (1845), and British Patent No. 9,431, issued Aug. 1, 1842. Such solutions were apparently used for a period of approximately ten years. The gold deposits produced were porous and the physical properties were inferior to deposits obtained from cyanide-containing gold plating baths, resulting in the abandonment of the sulfite baths in favor of the cyanide baths.
It is an object of the present invention to provide improved processes for preparing gold electrodeposits, including 24 karat gold, having superior physical properties including high luster and specular reflection.
It is another object of the present invention to provide improved sulfite electroplating baths suitable for use in said processes.
It is a further object of the invention to provide improved processes for electrodepositing superior alloy gold deposits having improved brightness and hardness; said processes being capable of yielding deposits of various shades of yellow.
It is also an object of this invention to provide improved sulfite electroplating baths for plating gold alloy deposits.
Other objects and advantages of this invention will in part be obvious and will in part become apparent from the following specification.
One aspect of the present invention contemplates electrodepositing gold and gold alloys from an alkaline aqueous bath containing (i) Between 1 and 30 grams per liter and preferably between 5 and 15 grams per liter of gold as sulfite selected from the group consisting of potassium gold sul fite and sodium gold sulfite;
(ii) Potassium sulfite or sodium sulfite in an amount between 40 and 150 grams per liter and preferably between 40 and 120 grams per liter;
(iii) A buffering and conducting salt selected from soluble phosphate, sulfate, acetate, and citrate salts of the alkali metals and the alkaline earth metals, in an amount between 5 and 150 grams per liter and preferably between 10 and 100 grams per liter;
(iv) At least one brightening and/or alloying additive selected from (a) Between about 5 and 500 milligrams per liter of a base metal in the form of a soluble salt or a soluble complex,
3,475,292 Patented Oct. 28, 1969 (b) Between 1 and 400 milligrams per liter of a semimetal in the form of a soluble salt complex, and
(c) An alloying metal or semimetal in the form of a soluble salt or soluble complex, when in the form of a salt in the amount between 0.5 and 5 grams per liter,
and when in the form of a complex in an amount between 0.5 and 10 grams per liter; and
(v) Sufficient of an acid or alkali to adjust the pH to a value in excess of 8 and preferably between about 9 and 11.
The base metals effective as brighteners are cadmium, titanium, molybdenum, tungsten, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese, and vanadium.
The semimetals effective as brighteners are arsenic, antimony, selenium, and tell-urium. Lead, copper, arsenic and cobalt are the preferred brighteners.
The base metals and semimetals effective as alloying agents are cadimum, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese and antimony. Cobalt, antimony and nickel are the preferred alloying agents.
The soluble salts may vary widely in their degree of solubility in the electrolyte. With the relatively small amounts of the metals required, salts having even limited solubility may be utilized. Advantage may be taken of this limited solubility to provide control of the additive level by maintaining an undissolved excess of the salt in the bath. The following list of specific salts that may be used is illustrative of the many salts of the metals and semimetals which are suitable sources of the metal or semimetal respectively: cadmium sulfate, cadmium acetate, lead acetate, lead nitrate, zinc sulfate, zinc acetate, iron sulfate, iron acetate, nickel sulfate, nickel nitrate, cobalt sulfate, cobalt acetate, indium sulfate, indium nitrate, copper sulfate, copper acetate, manganese sulfate, and manganese acetate. The foregoing cations could also be introduced into solution in the form of any soluble salt with the following anionic moieties: acetates, sulfates, chlorides, nitrates, bromides, borates, borofluorides, oxalates, formates, sulfamates, and similar weak organic acids. Compounds in which the metal or semimetal is in the anionic moiety may also be used, e.g., potassium titanate, ammonium titanate, sodium molybdate, potassium molybdate, sodium tungstate, potassium tungstate, sodium stannate, potassium stannate, sodium vanadate, ammonium vanadate, potassium arsenite, ammonium arsenite, potassium antimony tartrate, sodium .antimonite, sodium selenate, potassium selenate, potassium tellurate, and sodium tellurate. The
' foregoing anions could also be introduced into solution in the form of any soluble salt with the following cationic moieties: cesium, lithium, quaternary ammonium salts and other organic cationic moieties.
The base metals and semimetals may also be added to the bath in the form of a soluble complex, sometimes also referred to as a chelate, with a compound selected from the group consisting of aminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, iminodiacetic acid, etc.; acetylacetonates; and hydroxyorganic acid moieties such as citric acid, lactic acid, and tartaric acid.
The buffering and conducting salts are selected from the soluble phosphate, sulfate, carbonate, acetate, citrate, and tartrate salts of the alkali metals and the alkaline earth metals. Such salts as dipotassium phosphate, disodium phosphate, dipotassium ethylenediarninediacetate, disodium ethylenediamine diacetate, disodium ethylenediamine tetraacetate, dipotassium ethylenediaminetetraacetate, tripotassium phosphate, trisodium phosphate, sodium tetraphosphate, potassium tetraphosphate, sodium metaphosphate, potassium metaphosphate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium citrate, potassium citrate, sodium tartrate, potassium tartrate, sodium hexametaphosphate, and potassium hexametaphosphate are illustrative of operative buffering and conducting salts.
The bath is operated at a pH more alkaline than 8, to an alkalinity in excess of 12. The preferred operating range is between 9 and 11. The bath is generally adjusted to the desired pH range by the addition of an alkali metal or alkaline earth metal hydroxide, preferably sodium or potassium hydroxide. If by chance the pH of the bath is above the desired operating range, the necessary adjustment may be made by addition of an acid, preferably a sulfur acid such as sulphuric acid.
The baths may be operated, dependent on the desired rate of electrodeposition and the amount of agitation, over a wide range of current densities. A range of between about 1 and 50 amperes per square foot is preferred with moderate agitation. Agitation enhances brightness and uniformity of the deposit, and also permits a wider current density operating range. The bath may be operated from about room temperature up to about 180 F., with a preferred range between about 110 F. and 140 F.
The following examples further illustrate the invention to those skilled in the art. All parts and percentages are by Weight. The baths were adjusted to the specified pH by addition of sodium or potassium hydroxide.
EXAMPLE 1. 24 KARAT GOLD DEPOSITION Into an amount of water suflicient to form one liter of solution is dissolved:
6 grams of gold in the form of potassium gold sulfite,
90 grams of potassium sulfite,
15 grams of dipotassium phosphate, and
200 milliagrams of cobalt as cobalt ethylenediaminetetraacetic acid.
At a pH of 9.5, 120 F. and about 6 amperes per square foot, smooth, pore-free deposits of about 96 Knoop hardness number are obtained.
EXAMPLE II.24 GARAT GOLD DEPOSITION Into an amount of water sufiicient to form one liter of solution is dissolved:
12 grams of gold in the form of potassium gold sulfite,
120 grams of sodium sulfite,
30 grams of dipotassium ethylenediaminediacetate, and
15 milligrams of lead as lead acetate.
At a pH of 10.0, 140 F. and amperes per square foot, bright deposits are obtained.
EXAMPLE III.-HARD ALLOY GOLD DEPOSITION Into an amount of water suflicient to form one liter of solution is dissolved:
10 grams of gold in the form of sodium gold sulfite,
90 grams of sodium sulfite,
30 grams of dipotassium phosphate, and
0.50 gram of nickel as nickel imminodiacetate.
At a pH of 10.0, 120 F. and 6 amperes per square foot, bright deposits are obtained. Hardness is 320 Knoop hardness number.
EXAMPLE IV.24 KARAT GOLD DEPOSITION Into an amount of water sufiicient to form one liter of solution is dissolved:
10 grams of gold in the form of sodium gold sulfite,
90 grams of sodium sulfite,
30 grams of disodium ethylenediaminetetraacetate,
4 milligrams of arsenic as arsenic trioxide.
At a pH of 10.0, 130 F. and 8 amperes per square foot, bright deposits are obtained.
EXAMPLE V.-HARD ALLOY GOLD DEPOSITION Into an amount of water suflicient to form one liter of solution is dissolved:
6 grams of gold in the form of potassium gold sulfite, 75 grams of potassium sulfite,
30 grams of ethylenediaminetetraacetic acid, and
6 grams of nickel as nickel nitrilotriacetate.
At a pH of 10.0, 140 F. and 5 amperes per square foot, bright deposits are obtained.
EXAMPLE VI.HARD ALLOY GOLD DEPOSITION Into an amount of water sufiicient to form one liter of solution is dissolved:
10 grams of gold in the form of sodium gold sulfite,
grams of sodium sulfite,
30 grams of dipotassium phosphate, and
1.0 gram of antimony in the form of potassium antimony tartrate.
At a pH of 10, F. and about 7 amperes per square foot, bright deposits are obtained having a very pale yellow color. The hardness of the deposit is 200 Knoop hardness number.
Similar sound gold and gold alloy deposits are obtained following the procedure of the examples and utilizing baths having compositions within the ranges specified and containing cadmium, iron, zinc, titanium, tin, antimony, selenium, or tellurium, as the metal or semimetal additive. The deposits have a Knoop hardness of between about 85 and 350. The use of other salts and complexes within the definition of the specification in place of those exemplified, similarly results in the production of sound gold and gold alloy electrodeposits.
The deposits of the present invention may be electrodeposited on a variety of basis metals. As is usual in electroplating metals, the basis metal should be a conductor and preferably a metal having a clean, smooth surface. The gold and gold alloy electrodeposits may be obtained on the wide variety of basis metals which are known as conductors and may also be obtained on nonconducting materials by first making the surface conductive, utilizing the techniques conventional for this purpose.
The gold electrodeposits and gold alloy electrodeposits obtained using the baths and processes of this invention are sound deposits which may be formed in relatively thick deposits. The deposits have good physical proper-- ties. They are hard and have superior wearing characteristics. They are also bright, being categorized as bright deposits on two grounds: they are visually bright and they are brighter than the surface upon which they are deposited. They have high luster and specular reflection. Alloy deposits of various shades of yellow having a pleasing appearance may be obtained using metal alloying additives. The baths have excellent characteristics for electroplating purposes permitting electrodeposition over a relatively wide range of process conditions. Good throwing power is obtained. An important economic advantage of utilizing the baths of the present invention rather than the currently widely used gold cyanide electroplating baths results from the savings in not having to construct and operate elaborate facilities for processing waste cyanide solutions.
What is claimed is:
1. An alkaline aqueous bath for electroplating gold and gold alloys consisting essentially of (i) between 1 and 30 grams per liter of gold as sulfite selected from the group consisting of potassium gold sulfite and sodium gold sulfite;
(ii) between 40 and grams per liter of an alkali metal sulfite selected from the group consisting of sodium sulfite and potassium sulfite;
(iii) between 5 and 150 grams per liter of a buffering and conducting salt selected from the group consisting of the soluble phosphate, sulfate, carbonate, acetate, citrate, and tartrate salts of the alkali metals and the alkaline earth metals;
(iv) at least one additive selected from the group consisting of (a) a brightening metal additive selected from the group consisting of cadmium, titanium, molybdenum, tungsten, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese, and vanadium, in an amount between 5 and 500 milligrams per liter, as a soluble salt of said meal or as a soluble complex of said metal,
(b) a brightening semimetallic additive selected from the group consisting of antimony, arsenic, selenium and tellurium in an amount between 1 and 400 milligrams per liter as a soluble salt or a soluble complex of said semimetal, and
(c) an alloying element selected from the group consisting of cadmium, lead, zinc, iron, nickel, cobalt, tin, indium, copper, manganese, and antimony as a soluble salt or soluble complex, when in the form of a salt in an amount between 0.5 and 5 grams per liter, and when in the form of a complex in an amount between 0.5 and grams per liter; and
(v) sufiicient of an acid or alkali to adjust the pH to a value in excess of 8.
2. The bath of claim 1 having a pH between 9 and 11, and containing between about 5 grams per liter and grams per liter of gold, between about 40 grams per liter and 120 grams per liter of said alkali metal sulfites, and between about 10 grams per liter and 100 grams per liter of said buffering and conducting salt.
3. The bath of claim 2 wherein said additive is at least one of said brightening metal additives.
4. The bath of claim 2 wherein said additive is at least one of said brightening semimetallic additives.
5. The bath of claim 2 wherein said additive is at least one of said alloying elements.
6. The bath of claim 2 wherein said buffering and conducting salt is selected from the group consisting of dipotassium phosphate, disodium phosphate, disodium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, disodium ethylenediaminediacetate, and dipotassium ethylenediamine diacetate.
7. The bath of claim 6 wherein said brightening additive is selected from the group consisting of cobalt, lead, copper, and arsenic.
8. The bath of claim 6 wherein said alloying additive is selected from the group consisting of cobalt and nickel.
9. The bath of claim 1 containing 6 grams per liter of gold as potassium gold sulfite,
90 grams per liter of potassium sulfite,
15 grams per liter of dipotassium phosphate, and
200 milligrams per liter of cobalt as cobalt ethylenediaminetetraacetic acid.
10. The bath of claim 1 containing 12 grams per liter of gold as potassium gold sulfite,
120 grams per liter of sodium sulfite,
30 grams per liter of dipotassium ethylenediamineacetate, and
15 milligrams per liter of lead as lead acetate.
11. The bath of claim 1 containing 10 grams per liter of gold as sodium gold sulfite,
90 grams per liter of sodium sulfite,
30 grams per liter of dipotassium phosphate,
0.5 gram per liter of nickel as nickel imminodiacetate.
12. The bath of claim 1 containing 10 grams per liter of gold as sodium gold sulfite,
90 grams per liter of sodium sulfite,
30 grams per liter of disodium ethylenediaminetetraacetate,
4 milligrams per liter of arsenic as arsenic trioxide.
13. The bath of claim 1 containing 6 grams per liter of gold as potassium gold sulfite,
grams per liter of potassium sulfite,
30 grams per liter of ethylenediaminetetraacetic acid,
6 grams per liter of nickel as nickel nitrilotriacetate.
14. The bath of claim 1 containing 10 grams per liter of gold as sodium gold sulfite,
grams per liter of sodium sulfite,
30 grams per liter of dipotassium phosphate,
1.0 gram per liter of antimony as potassium antimony tartrate.
15. The process of plating gold comprising electrodepositing gold on a cathode from the aqueous bath of claim 1 at a temperature between room temperature and 180 F.
References Cited UNITED STATES PATENTS 2,800,439 7/1957 Fischer et a1. 20446 XR 923,864 6/1909 Levy 20446 XR 2,812,299 11/1957 VOlk 20446 XR 2,905,601 9/1959 Rinker et al. 20446 XR 2,967,135 1/1961 Ostrow et al. 204-46 XR 3,020,217 2/1962 Rinker 20 4-43 3,057,789 10/ 1962 Smith 20446 3,149,057 9/ 1964 Parker 20443 XR FOREIGN PATENTS 78,438 11/1954 Denmark.
9,431 1842 Great Britain.
OTHER REFERENCES Brenner, Abner, Electrodeposition of Alloys, vol. 2, pp. 496-497, 1963.
Frary, Francis C., Electrodeposition of Gold and Silver, Transactions of the Electrochemical Soc., vol. 23, pp. 49-59, 1913.
Fischer, Johannes, et al., Precious Metal Plating, pp. -111, 1964.
JOHN H. MACK, Primary Examiner G. L. KAPLAN, Assistant Examiner U.S. c1. X.R. 204 43, 46
US526385A 1966-02-10 1966-02-10 Gold plating bath and process Expired - Lifetime US3475292A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US52638566A 1966-02-10 1966-02-10

Publications (1)

Publication Number Publication Date
US3475292A true US3475292A (en) 1969-10-28

Family

ID=24097129

Family Applications (1)

Application Number Title Priority Date Filing Date
US526385A Expired - Lifetime US3475292A (en) 1966-02-10 1966-02-10 Gold plating bath and process

Country Status (4)

Country Link
US (1) US3475292A (en)
BE (1) BE741892A (en)
DE (1) DE1621180C3 (en)
GB (1) GB1134615A (en)

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3669852A (en) * 1969-10-23 1972-06-13 Bell Telephone Labor Inc Electroplating gold
FR2211539A1 (en) * 1972-12-22 1974-07-19 Western Electric Co
US3883409A (en) * 1972-07-10 1975-05-13 Degussa Gold alloy electroplating bath
US3904493A (en) * 1972-08-10 1975-09-09 Oxy Metal Industries Corp Gold sulfite baths containing organophosphorus compounds
US3910774A (en) * 1970-08-13 1975-10-07 Gen Dynamics Corp Solid film lubricant and method for lubricating cycling low-high temperature friction surfaces
US3981782A (en) * 1972-07-28 1976-09-21 Johnson Matthey & Co., Limited Electroplating of gold and gold compounds therefor
US3990954A (en) * 1973-12-17 1976-11-09 Oxy Metal Industries Corporation Sulfite gold plating bath and process
US4012294A (en) * 1972-08-10 1977-03-15 Oxy Metal Industries Corporation Gold sulfite baths containing organophosphorous compounds
US4076598A (en) * 1976-11-17 1978-02-28 Amp Incorporated Method, electrolyte and additive for electroplating a cobalt brightened gold alloy
US4199416A (en) * 1977-05-03 1980-04-22 Johnson, Matthey & Co., Limited Composition for the electroplating of gold
US4212708A (en) * 1979-06-05 1980-07-15 Belikin Alexandr V Gold-plating electrolyte
US4366035A (en) * 1979-04-24 1982-12-28 Engelhard Corporation Electrodeposition of gold alloys
US4374006A (en) * 1980-04-03 1983-02-15 Degussa Aktiengesellschaft Electrolytic bath for the deposition of high gloss white gold coatings
US4435253A (en) 1983-01-28 1984-03-06 Omi International Corporation Gold sulphite electroplating solutions and methods
US4465564A (en) * 1983-06-27 1984-08-14 American Chemical & Refining Company, Inc. Gold plating bath containing tartrate and carbonate salts
EP0119424A1 (en) * 1983-03-16 1984-09-26 Degussa Aktiengesellschaft Process for the deposition of low carat brilliant gold-silver alloy coatings
US5024733A (en) * 1989-08-29 1991-06-18 At&T Bell Laboratories Palladium alloy electroplating process
EP0525890A1 (en) * 1991-07-31 1993-02-03 Calgon Corporation Method for solubilizing tellurium using organic acids
US5575900A (en) * 1995-07-03 1996-11-19 Antelman Technologies Ltd. Gold plating solutions
US20050092616A1 (en) * 2003-11-03 2005-05-05 Semitool, Inc. Baths, methods, and tools for superconformal deposition of conductive materials other than copper
JP2007002310A (en) * 2005-06-24 2007-01-11 Asahi Pretec Corp Gold recovery method and apparatus
US20090283414A1 (en) * 2008-05-19 2009-11-19 Jiaxiong Wang Electroplating methods and chemistries for deposition of group iiib-group via thin films
WO2010009225A1 (en) * 2008-07-15 2010-01-21 Enthone Inc. Cyanide free electrolyte composition for the galvanic deposition of a copper layer
US20100024930A1 (en) * 2006-10-03 2010-02-04 The Swatch Group Research And Development Ltd. Electroforming method and part or layer obtained via the method
ITMI20081610A1 (en) * 2008-09-09 2010-03-10 Giuseppe Antognazzi BATHROOM FOR ELECTRIC ELECTROPOSITION.
US20100140101A1 (en) * 2008-05-19 2010-06-10 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films
US20100206739A1 (en) * 2007-09-21 2010-08-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US20110089040A1 (en) * 2009-10-15 2011-04-21 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
CN103755738A (en) * 2014-01-13 2014-04-30 孙松华 Complexing agent and preparation method and use thereof
ITFI20130057A1 (en) * 2013-03-18 2014-09-19 Bluclad S R L SOLUTION FOR THE ELECTRODEPTITION OF A GOLDEN LEAGUE AND THE LEAGUE THEREOF DERIVING.
US11255021B2 (en) * 2019-03-04 2022-02-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Aqueous formulation for creating a layer of gold and silver
CN114934302A (en) * 2022-04-27 2022-08-23 深圳市联合蓝海黄金材料科技股份有限公司 Cyanide-free electrogilding liquid and application thereof
WO2023041972A1 (en) * 2021-09-16 2023-03-23 Galvasols P & S High-speed pure gold electroforming/electroplating bath

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH530473A (en) * 1969-08-19 1972-11-15 Sel Rex Corp Process for the electrolytic deposition of brilliant gold and electrolytic bath for the implementation of this process
JPS5324898B2 (en) * 1972-11-13 1978-07-24
DE3341233A1 (en) * 1983-11-15 1985-05-30 Robert Bosch Gmbh, 7000 Stuttgart Acidic electroplating bath for depositing fine soft-gold patterns and process for depositing such patterns
GB2323853B (en) * 1997-03-25 2002-04-24 Enthone Omi Electroplating processes compositions and deposits
CN104233384A (en) * 2014-09-17 2014-12-24 朱忠良 Cyanide-free gold electroplating solution and electroplating process using same
CN110699713A (en) * 2019-11-21 2020-01-17 长春黄金研究院有限公司 Cyanide-free gold alloy electroforming solution and using method thereof
CN119530899A (en) * 2024-12-02 2025-02-28 北京金百镀科技有限公司 A kind of sulfite electroforming gold liquid and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US923864A (en) * 1908-02-03 1909-06-08 Alfred Levy Process for the electric dissociation of metals by the wet method.
US2800439A (en) * 1954-06-26 1957-07-23 Degussa Bright metal plating
US2812299A (en) * 1949-05-05 1957-11-05 Birle & Co K G Electrolytic deposition of gold and gold alloys
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
US3020217A (en) * 1956-10-19 1962-02-06 Sel Rex Precious Metals Inc Mirror bright gold alloy electroplating
US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
US3149057A (en) * 1959-04-27 1964-09-15 Technic Acid gold plating

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US923864A (en) * 1908-02-03 1909-06-08 Alfred Levy Process for the electric dissociation of metals by the wet method.
US2812299A (en) * 1949-05-05 1957-11-05 Birle & Co K G Electrolytic deposition of gold and gold alloys
US2800439A (en) * 1954-06-26 1957-07-23 Degussa Bright metal plating
US3020217A (en) * 1956-10-19 1962-02-06 Sel Rex Precious Metals Inc Mirror bright gold alloy electroplating
US2905601A (en) * 1957-08-13 1959-09-22 Sel Rex Corp Electroplating bright gold
US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
US3149057A (en) * 1959-04-27 1964-09-15 Technic Acid gold plating
US2967135A (en) * 1960-06-08 1961-01-03 Barnet D Ostrow Electroplating baths for hard bright gold deposits

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3669852A (en) * 1969-10-23 1972-06-13 Bell Telephone Labor Inc Electroplating gold
US3910774A (en) * 1970-08-13 1975-10-07 Gen Dynamics Corp Solid film lubricant and method for lubricating cycling low-high temperature friction surfaces
US3883409A (en) * 1972-07-10 1975-05-13 Degussa Gold alloy electroplating bath
US3981782A (en) * 1972-07-28 1976-09-21 Johnson Matthey & Co., Limited Electroplating of gold and gold compounds therefor
US4012294A (en) * 1972-08-10 1977-03-15 Oxy Metal Industries Corporation Gold sulfite baths containing organophosphorous compounds
US3904493A (en) * 1972-08-10 1975-09-09 Oxy Metal Industries Corp Gold sulfite baths containing organophosphorus compounds
US3833487A (en) * 1972-12-22 1974-09-03 Bell Telephone Labor Inc Electrolytic soft gold plating
FR2211539A1 (en) * 1972-12-22 1974-07-19 Western Electric Co
US3990954A (en) * 1973-12-17 1976-11-09 Oxy Metal Industries Corporation Sulfite gold plating bath and process
US4076598A (en) * 1976-11-17 1978-02-28 Amp Incorporated Method, electrolyte and additive for electroplating a cobalt brightened gold alloy
US4199416A (en) * 1977-05-03 1980-04-22 Johnson, Matthey & Co., Limited Composition for the electroplating of gold
US4366035A (en) * 1979-04-24 1982-12-28 Engelhard Corporation Electrodeposition of gold alloys
US4212708A (en) * 1979-06-05 1980-07-15 Belikin Alexandr V Gold-plating electrolyte
US4374006A (en) * 1980-04-03 1983-02-15 Degussa Aktiengesellschaft Electrolytic bath for the deposition of high gloss white gold coatings
US4435253A (en) 1983-01-28 1984-03-06 Omi International Corporation Gold sulphite electroplating solutions and methods
EP0119424A1 (en) * 1983-03-16 1984-09-26 Degussa Aktiengesellschaft Process for the deposition of low carat brilliant gold-silver alloy coatings
US4465564A (en) * 1983-06-27 1984-08-14 American Chemical & Refining Company, Inc. Gold plating bath containing tartrate and carbonate salts
JPS6021391A (en) * 1983-06-27 1985-02-02 アメリカン・ケミカル・アンド・リフアイニング・カンパニ−，インコ−ポレ−テツド Aqueous gold plating bath
US5024733A (en) * 1989-08-29 1991-06-18 At&T Bell Laboratories Palladium alloy electroplating process
EP0525890A1 (en) * 1991-07-31 1993-02-03 Calgon Corporation Method for solubilizing tellurium using organic acids
US5575900A (en) * 1995-07-03 1996-11-19 Antelman Technologies Ltd. Gold plating solutions
US20050092616A1 (en) * 2003-11-03 2005-05-05 Semitool, Inc. Baths, methods, and tools for superconformal deposition of conductive materials other than copper
JP2007002310A (en) * 2005-06-24 2007-01-11 Asahi Pretec Corp Gold recovery method and apparatus
US20100024930A1 (en) * 2006-10-03 2010-02-04 The Swatch Group Research And Development Ltd. Electroforming method and part or layer obtained via the method
US10233555B2 (en) * 2007-09-21 2019-03-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US9683303B2 (en) 2007-09-21 2017-06-20 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US10619260B2 (en) * 2007-09-21 2020-04-14 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
KR101280675B1 (en) * 2007-09-21 2013-07-01 더 스와치 그룹 리서치 앤 디벨롭먼트 엘티디 Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids
US20100206739A1 (en) * 2007-09-21 2010-08-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
JP2010539335A (en) * 2007-09-21 2010-12-16 ジイ・アリプランディーニ Method for obtaining yellow gold alloy deposits by electroplating without using toxic or semi-metals
US20190153608A1 (en) * 2007-09-21 2019-05-23 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US20090283414A1 (en) * 2008-05-19 2009-11-19 Jiaxiong Wang Electroplating methods and chemistries for deposition of group iiib-group via thin films
US8066865B2 (en) * 2008-05-19 2011-11-29 Solopower, Inc. Electroplating methods and chemistries for deposition of group IIIA-group via thin films
US8425753B2 (en) 2008-05-19 2013-04-23 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films
US8444842B2 (en) * 2008-05-19 2013-05-21 Solopower, Inc. Electroplating methods and chemistries for deposition of group IIIA-group via thin films
US20100140101A1 (en) * 2008-05-19 2010-06-10 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films
WO2010009225A1 (en) * 2008-07-15 2010-01-21 Enthone Inc. Cyanide free electrolyte composition for the galvanic deposition of a copper layer
US8808525B2 (en) 2008-07-15 2014-08-19 Enthone Inc. Cyanide free electrolyte composition for the galvanic deposition of a copper layer
US20110180415A1 (en) * 2008-07-15 2011-07-28 Enthone Inc. Cyanide free electrolyte composition for the galvanic deposition of a copper layer
ITMI20081610A1 (en) * 2008-09-09 2010-03-10 Giuseppe Antognazzi BATHROOM FOR ELECTRIC ELECTROPOSITION.
US9567684B2 (en) 2009-10-15 2017-02-14 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US20110089040A1 (en) * 2009-10-15 2011-04-21 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
ITFI20130057A1 (en) * 2013-03-18 2014-09-19 Bluclad S R L SOLUTION FOR THE ELECTRODEPTITION OF A GOLDEN LEAGUE AND THE LEAGUE THEREOF DERIVING.
EP2781629A1 (en) * 2013-03-18 2014-09-24 Bluclad S.R.L. Solution for the electrodeposition of a gold alloy and the alloy derived therefrom
CN103755738A (en) * 2014-01-13 2014-04-30 孙松华 Complexing agent and preparation method and use thereof
US11255021B2 (en) * 2019-03-04 2022-02-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Aqueous formulation for creating a layer of gold and silver
WO2023041972A1 (en) * 2021-09-16 2023-03-23 Galvasols P & S High-speed pure gold electroforming/electroplating bath
CN114934302A (en) * 2022-04-27 2022-08-23 深圳市联合蓝海黄金材料科技股份有限公司 Cyanide-free electrogilding liquid and application thereof

Also Published As

Publication number Publication date
DE1621180A1 (en) 1971-05-19
DE1621180C3 (en) 1978-08-24
GB1134615A (en) 1968-11-27
BE741892A (en) 1970-05-04
DE1621180B2 (en) 1976-09-02

Similar Documents

Publication Publication Date Title
US3475292A (en) Gold plating bath and process
US4428802A (en) Palladium-nickel alloy electroplating and solutions therefor
US5514261A (en) Electroplating bath for the electrodeposition of silver-tin alloys
US2830014A (en) Electroplating process
US3580820A (en) Palladium-nickel alloy plating bath
US3666640A (en) Gold plating bath and process
US3980531A (en) Bath and process for the electrolytic separation of rare metal alloys
US3458409A (en) Method and electrolyte for thick,brilliant plating of palladium
US5256275A (en) Electroplated gold-copper-silver alloys
US3902977A (en) Gold plating solutions and method
GB718574A (en) Bath for the deposit of gold alloys by electroplating
KR910004972B1 (en) Manufacturing method of tin-cobalt, tin-nickel, tin-lead binary alloy electroplating bath and electroplating bath manufactured by this method
US3380898A (en) Electrolyte and method for electrodepositing a pink gold alloy
US3637474A (en) Electrodeposition of palladium
US3764489A (en) Electrodeposition of gold alloys
US2198365A (en) Electroplating
US3620936A (en) Electroplating a decorative chromium-plating resistant to corrosion
GB1272536A (en) Electroplating solutions and process for electroplating using such solutions
US3149057A (en) Acid gold plating
US3174918A (en) Bright gold electroplating
US4048023A (en) Electrodeposition of gold-palladium alloys
US2770587A (en) Bath for plating bright copper
US3776822A (en) Gold plating electrolyte
US3440151A (en) Electrodeposition of copper-tin alloys
US4265715A (en) Silver electrodeposition process