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US2677654A - Copper electroplating and compositions therefor - Google Patents

Copper electroplating and compositions therefor Download PDF

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Publication number
US2677654A
US2677654A US225672A US22567251A US2677654A US 2677654 A US2677654 A US 2677654A US 225672 A US225672 A US 225672A US 22567251 A US22567251 A US 22567251A US 2677654 A US2677654 A US 2677654A
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US
United States
Prior art keywords
copper
bath
cyanide
ounces
dithiobiuret
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
US225672A
Inventor
Allan E Chester
Joseph T Irwin
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.)
Brent Chemicals Corp
Poor and Co
Original Assignee
Poor and Co
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 Poor and Co filed Critical Poor and Co
Priority to US225672A priority Critical patent/US2677654A/en
Application granted granted Critical
Publication of US2677654A publication Critical patent/US2677654A/en
Priority claimed from US583943A external-priority patent/US2871171A/en
Anticipated expiration legal-status Critical
Assigned to BRENT CHEMICALS CORPORATION, A CORP. OF DE. reassignment BRENT CHEMICALS CORPORATION, A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: STAUFFER CHEMICAL COMPANY
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • C25D3/40Electroplating: Baths therefor from solutions of copper from cyanide baths, e.g. with Cu+
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • C25D5/36Pretreatment of metallic surfaces to be electroplated of iron or steel
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • This invention relates to new and useful electroplating compositions, and to a new and improved method for the electrodeposition of copper.
  • Gne of the objects of the invention is to prepare new and useful cyanide copper plating baths.
  • Another object of the invention is to prepare new and useful cyanide copper plating baths which produce improved brightening efiects.
  • Still another object of th invention is to pro vide a method of electroplating copper whereby a bright copper plate is obtained on polished steel over which chromium can be plated without bufilng the copper.
  • Another object of the invention is to provide a method of electrodepositing copper which operates efficiently in temperature ranges that are lower than those used in most cyanide copper plating baths. Other objects will appear hereinafter.
  • Dithiobiuret has the following formula The dithiobiuret is employed in an amount which is sufficient to enhance the brightness of the electrodeposited copper plate.
  • Example An electrolyte was prepared by mixing the following ingredients:
  • Antarox B-201 polyethylene glycol esterether
  • Polished steel sheets were plated in this electrolyte at a temperature of 130 F. and at at current density of 20 amperes per square foot.
  • cyanide copper plating baths can be used in the practice of the invention.
  • any of the copper cyanide plating baths described in Metal Finishing, 1949 edition, page 229 can be employed by substituting dithiobiuret for the brightener addition agents used in said baths. The same plating conditions can also be used.
  • the Antarox 33-201 is a non-ionic wetting agent.
  • the wetting agent functions in the electroplating bath to prevent pitting due to hydrogen bubbles that stick to the surface of the plate unless made more readily removable by agitation or lower surface tension resulting from the use of a wetting agent. It will be understood that any bath stable wetting agent can be used and even such use is optional.
  • the quantity of the dithiobiuret added to the copper plating bath may be varied. However, an increase in the quantity over that given in the illustrated example does not substantially increase the brightness of the resultant plate and a decrease in the quantity tends to reduce the brightness of the plate. In general it is preferable to employ a quantity of dithiobiuret within the range of about 0.4 to 1 gram per gallon of a cyanide copper plating bath.
  • the current densities employed in plating copper from electroplating baths prepared in accordance with the invention and the tempera.- tures used may be substantially the same as those now employed in the art for plating copper from alkaline cyanide solutions. Most copper plating baths are operated at current densities of 15 to 20 amperes per square foot. In some instances the current densities can be as low as 5 amperes per square foot and higher current densities above 20 amperes per square foot can also be employed.
  • the temperature used is preferably within the range of to 140 F., the optimum temperature being around F, whereas the temperatures customarily employed in the art for most bright copper cyanide plating baths are at least F. and usually somewhat higher.
  • the quantity of copper in the copper plating bath described in the example is around 5 ounces of copper per gallon of bath. In general, it is preferable that the bath contain 3 to 8 ounces of copper in dissolved form per gallon of bath where direct current is used. Where pulsating direct current is used the bath can contain higher concentrations of copper as, for example, around 12 ounces of copper per gallon of bath. A concentration of copper around 5 ounces per gallon of plating solution is preferred.
  • the electroplating bath contains 0.5 to 1.15 ounces per gallon of free sodium cyanide over and above the amount required to form the complex sodium copper cyanide NazCu(CN)s.
  • the quantity of free alkali usually corresponds to 1 to '7 ounces of alkali metal hydroxide, preferably 3 to 4 ounces of sodium hydroxide.
  • Sodium carbonate may be present in the bath either as an impurity or as a makeup agent.
  • An alkaline copper cyanide plating bath comprising copper in a soluble form dissolved in an alkaline cyanide aqueous liquid containing dithiobiuret dissolved in said path, the quantity of dithiobiuret being sufficient to produce a bright plate when copper is electrodeposited from said bath.
  • An alkaline cyanide copper plating bath comprising essentially 3 to 8 ounces per gallon of metallic copper dissolved in the form of a complex alkaline copper cyanide salt in water containing 0.4 to 1 ounce per gallon of dithiobiuret.
  • An alkaline copper cyanide plating bath comprising essentially copper in the form of the complex salt Na2C11(CN)3 dissolved in water in proportions such that the quantity of copper is within the range of 3 to 12 ounces per gallon, free cyanide in proportions within the range of 0.5 to 1.75 ounces per gallon, free sodium hydroxide in proportions within the range of l to '7 ounces per gallon and dithiobiur'et in proportions within the range of 0.4 to 1 gram per gallon together with sufiicient water to make a gallon of electrolyte.
  • a method of copper plating which comprises electrodepositing copper from an alkaline aqueous cyanide bath containing copper in a soluble form in proportions within the range of 3 to 8 ounces of copper as metal per gallon of bath and a suflicient quantity of dithiobiuret to brighten the resultant copper plate.
  • a method of copper plating which comprises electrodepositing copper at a temperature within the range from to F. from an alkaline aqueous cyanide plating bath containingcopper in a soluble form in proportions within the range of about 3 ounces to 8 ounces of copper as metal 'per gallon of bath and dithiobiuret'in proportions within the range of about 0.4 to 1 gram per gallon of bath.
  • a method of copper plating which comprises electrodepositing copper from an alkailne aque ous cyanide plating bath onto polished steel, said bath containing 3 ounces to 8 ounces per gallon of copper as metal dissolved in the form of a complex sodium copper cyanide, 0.5 ounces to 1.75 ounces per gallon of cyanide, as NaCN, 3 to 4 ounces per gallon of NaOI-I and sufficient dithiobiuret to increase the brightness of the copper electrodeposited from said bath.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (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

?af:ented May 4, 1954 UNITED STATES PATENT OFFICE COPPER ELEo'rnOrLATING AND COMPOSITIONS THEREFOR Ware No Drawing. Application May 10, 1951, Serial No. 225,672
6 Claims. 1
This invention relates to new and useful electroplating compositions, and to a new and improved method for the electrodeposition of copper.
Gne of the objects of the invention is to prepare new and useful cyanide copper plating baths.
Another object of the invention is to prepare new and useful cyanide copper plating baths which produce improved brightening efiects.
Still another object of th invention is to pro vide a method of electroplating copper whereby a bright copper plate is obtained on polished steel over which chromium can be plated without bufilng the copper.
Another object of the invention is to provide a method of electrodepositing copper which operates efficiently in temperature ranges that are lower than those used in most cyanide copper plating baths. Other objects will appear hereinafter.
These objects are accomplished in accordance with this invention by preparing an alkaline aqueous cyanide copper electroplating bath containing dithiobiuret and electrodepositing copper therefrom.
Dithiobiuret has the following formula The dithiobiuret is employed in an amount which is sufficient to enhance the brightness of the electrodeposited copper plate.
The invention will be further illustrated by the following example:
Example An electrolyte was prepared by mixing the following ingredients:
9 ounces sodium cyanide 7 ounces copper cyanide 3-4 ounces sodium hydroxide 0.4 gram dithiobiuret a co. Antarox B-201 (polyethylene glycol esterether) Water sufficient to make a gallon of solution.
Polished steel sheets were plated in this electrolyte at a temperature of 130 F. and at at current density of 20 amperes per square foot.
An extremely bright copper plate was produced over which chromium could be plated without bufilng the copper.
Other cyanide copper plating baths can be used in the practice of the invention. For ex" ample, any of the copper cyanide plating baths described in Metal Finishing, 1949 edition, page 229 can be employed by substituting dithiobiuret for the brightener addition agents used in said baths. The same plating conditions can also be used.
In the foregoing example the Antarox 33-201 is a non-ionic wetting agent. The wetting agent functions in the electroplating bath to prevent pitting due to hydrogen bubbles that stick to the surface of the plate unless made more readily removable by agitation or lower surface tension resulting from the use of a wetting agent. It will be understood that any bath stable wetting agent can be used and even such use is optional.
The quantity of the dithiobiuret added to the copper plating bath may be varied. However, an increase in the quantity over that given in the illustrated example does not substantially increase the brightness of the resultant plate and a decrease in the quantity tends to reduce the brightness of the plate. In general it is preferable to employ a quantity of dithiobiuret within the range of about 0.4 to 1 gram per gallon of a cyanide copper plating bath.
The current densities employed in plating copper from electroplating baths prepared in accordance with the invention and the tempera.- tures used may be substantially the same as those now employed in the art for plating copper from alkaline cyanide solutions. Most copper plating baths are operated at current densities of 15 to 20 amperes per square foot. In some instances the current densities can be as low as 5 amperes per square foot and higher current densities above 20 amperes per square foot can also be employed. The temperature used is preferably within the range of to 140 F., the optimum temperature being around F, whereas the temperatures customarily employed in the art for most bright copper cyanide plating baths are at least F. and usually somewhat higher.
The quantity of copper in the copper plating bath described in the example is around 5 ounces of copper per gallon of bath. In general, it is preferable that the bath contain 3 to 8 ounces of copper in dissolved form per gallon of bath where direct current is used. Where pulsating direct current is used the bath can contain higher concentrations of copper as, for example, around 12 ounces of copper per gallon of bath. A concentration of copper around 5 ounces per gallon of plating solution is preferred.
Although the invention does not reside in the specific proportions of cyanide and free hydroxide present in the bath, it is preferable that the electroplating bath contain 0.5 to 1.15 ounces per gallon of free sodium cyanide over and above the amount required to form the complex sodium copper cyanide NazCu(CN)s. The quantity of free alkali usually corresponds to 1 to '7 ounces of alkali metal hydroxide, preferably 3 to 4 ounces of sodium hydroxide. Sodium carbonate may be present in the bath either as an impurity or as a makeup agent.
An ordinary alkaline cyanide copper bath containing 5 ounces per gallon of copper gives a frosty or burned copper plate when copper is electrodeposited therefrom at a temperature of 130 F. at a current density of amperes per square foot. The same bath containing a small quantity of dithiobiuret when electroplated under the same conditions gives a brilliant copper plate so bright that it can be electrodeposited on polished steel-and chromium can be plated therecver without buffing the copper. It will therefore be apparent that the present invention provides anew and useful contribution to the art of bright copper plating. The electrolytes provided in ac cordance with the invention also have excellent throwing power even in the lower temperature ranges of 120 to 140 F.
The invention is hereby claimed as follows:
1. An alkaline copper cyanide plating bath comprising copper in a soluble form dissolved in an alkaline cyanide aqueous liquid containing dithiobiuret dissolved in said path, the quantity of dithiobiuret being sufficient to produce a bright plate when copper is electrodeposited from said bath.
2. An alkaline cyanide copper plating bath comprising essentially 3 to 8 ounces per gallon of metallic copper dissolved in the form of a complex alkaline copper cyanide salt in water containing 0.4 to 1 ounce per gallon of dithiobiuret.
3. An alkaline copper cyanide plating bath comprising essentially copper in the form of the complex salt Na2C11(CN)3 dissolved in water in proportions such that the quantity of copper is within the range of 3 to 12 ounces per gallon, free cyanide in proportions within the range of 0.5 to 1.75 ounces per gallon, free sodium hydroxide in proportions within the range of l to '7 ounces per gallon and dithiobiur'et in proportions within the range of 0.4 to 1 gram per gallon together with sufiicient water to make a gallon of electrolyte.
4. A method of copper plating which comprises electrodepositing copper from an alkaline aqueous cyanide bath containing copper in a soluble form in proportions within the range of 3 to 8 ounces of copper as metal per gallon of bath and a suflicient quantity of dithiobiuret to brighten the resultant copper plate.
5. A method of copper plating which comprises electrodepositing copper at a temperature within the range from to F. from an alkaline aqueous cyanide plating bath containingcopper in a soluble form in proportions within the range of about 3 ounces to 8 ounces of copper as metal 'per gallon of bath and dithiobiuret'in proportions within the range of about 0.4 to 1 gram per gallon of bath.
6. A method of copper plating which comprises electrodepositing copper from an alkailne aque ous cyanide plating bath onto polished steel, said bath containing 3 ounces to 8 ounces per gallon of copper as metal dissolved in the form of a complex sodium copper cyanide, 0.5 ounces to 1.75 ounces per gallon of cyanide, as NaCN, 3 to 4 ounces per gallon of NaOI-I and sufficient dithiobiuret to increase the brightness of the copper electrodeposited from said bath.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,903,860 Gockel Apr. 18, 1933 2,391,289 Beaver Dec. 18, 1945 2,489,538 Phillips 'et al Nov. 29, 199 2,495,658 Wills'on et a1 Jan. 24, 1950 2,563,360 Phillips et a1 Aug. 7, 1951

Claims (1)

1. AN ALKALINE COPPER CYANIDE PLATING BATH COMPRISING COPPER IN A SOLUBLE FORM DISSOLVED IN AN ALKALINE CYANIDE AQUEOUS LIQUID CONTAINING DITHIOBIURET DISSOLVED IN SAID BATH, THE QUANTITY OF DITHIOBIURET BEING SUFFICIENT TO PRODUCE A BRIGHT PLATE WHEN COPPER IS ELECTRODEPOSITED FROM SAID BATH.
US225672A 1951-05-10 1951-05-10 Copper electroplating and compositions therefor Expired - Lifetime US2677654A (en)

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Application Number Priority Date Filing Date Title
US225672A US2677654A (en) 1951-05-10 1951-05-10 Copper electroplating and compositions therefor
US583943A US2871171A (en) 1956-05-10 1956-05-10 Method of electroplating copper on aluminum

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2828252A (en) * 1953-04-28 1958-03-25 Degussa Electrodeposition of bright zinc, copper, or nickel
US2841542A (en) * 1955-12-19 1958-07-01 Udylite Res Corp Electrodeposition of copper
US3021266A (en) * 1957-08-12 1962-02-13 Barnet D Ostrow Additive for copper plating bath
US20050211561A1 (en) * 1999-08-06 2005-09-29 Ibiden Co., Ltd. Electroplating solution, method for manufacturing multilayer printed circuit board using the same solution, and multilayer printed circuit board

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1903860A (en) * 1930-04-25 1933-04-18 Ig Farbenindustrie Ag Preparation of metallic coatings
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
US2489538A (en) * 1941-05-24 1949-11-29 Gen Motors Corp Electrodeposition of copper
US2495668A (en) * 1946-12-21 1950-01-24 Harshaw Chem Corp Electrodeposition of copper
US2563360A (en) * 1941-05-24 1951-08-07 Gen Motors Corp Electrodeposition of copper

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1903860A (en) * 1930-04-25 1933-04-18 Ig Farbenindustrie Ag Preparation of metallic coatings
US2489538A (en) * 1941-05-24 1949-11-29 Gen Motors Corp Electrodeposition of copper
US2563360A (en) * 1941-05-24 1951-08-07 Gen Motors Corp Electrodeposition of copper
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
US2495668A (en) * 1946-12-21 1950-01-24 Harshaw Chem Corp Electrodeposition of copper

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2828252A (en) * 1953-04-28 1958-03-25 Degussa Electrodeposition of bright zinc, copper, or nickel
US2841542A (en) * 1955-12-19 1958-07-01 Udylite Res Corp Electrodeposition of copper
US3021266A (en) * 1957-08-12 1962-02-13 Barnet D Ostrow Additive for copper plating bath
US20050211561A1 (en) * 1999-08-06 2005-09-29 Ibiden Co., Ltd. Electroplating solution, method for manufacturing multilayer printed circuit board using the same solution, and multilayer printed circuit board
US20080230263A1 (en) * 1999-08-06 2008-09-25 Ibiden Co., Ltd. Electroplating solution, method for manufacturing multilayer printed circuit board using the same solution, and multilayer printed circuit board
US7812262B2 (en) 1999-08-06 2010-10-12 Ibiden Co., Ltd. Multilayer printed circuit board
US7993510B2 (en) * 1999-08-06 2011-08-09 Ibiden Co., Ltd. Electroplating solution, method for manufacturing multilayer printed circuit board using the same solution, and multilayer printed circuit board

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AS Assignment

Owner name: BRENT CHEMICALS CORPORATION, A CORP. OF DE.

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:STAUFFER CHEMICAL COMPANY;REEL/FRAME:003837/0384

Effective date: 19810202