US2871173A - Method of making ductile copper platings - Google Patents

Method of making ductile copper platings Download PDF

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Publication number
US2871173A
US2871173A US713104A US71310458A US2871173A US 2871173 A US2871173 A US 2871173A US 713104 A US713104 A US 713104A US 71310458 A US71310458 A US 71310458A US 2871173 A US2871173 A US 2871173A
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copper
per liter
grams per
acid
plating
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US713104A
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Eugene N Castellano
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Seymour Manufacturing Co
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Seymour Manufacturing Co
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Priority to US713104A priority Critical patent/US2871173A/en
Priority to GB43/59A priority patent/GB848387A/en
Priority to DES61291A priority patent/DE1086508B/en
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    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • This invention relates as indicated to electrodeposition of metals and, more specifically, to a process of and materials for use in the process of electrodepositing copper characterized in that the resulting copper plate as deposited, displays exceptional ductility, smoothness and throwing power. More particularly, the present invention has to do with new addition agents for producing the above-named desirable characteristics in the copper plate and which may be used with acid copper baths of usual composition operating under usual conditions.
  • Electrolytic copper plating baths including such proposed additives do not have the required degree of throwing power which is demanded for many specialized applications.
  • throwing power is meant the ability of the copper plate to form smooth and adherent coatings of copper-on base metals having apertures, pits and other surface irregularities.
  • the main object of the present invention is not to produce bright copper deposits, but rather to substantially increase the stability of the resulting copper plate and to provide an essentially permanent copper plate which has the qualities of ductility, smoothness and throwing power to an exceptional degree of thickness.
  • the only known additives for this purpose have been dextrin, glue, molasses and the like which are subject to the objection that over a period of time as the bath is aging, they will break down and contaminate the solution. deposit is extremely brittle. Moreover, this break down necessitates the periodic purification of the electrolyte for the removal and elimination of these break down impurities.
  • the electrolytic solutions of the present invention form copper plate which is free of brittleness and retains the desirable characteristics enumerated above indefinitely.
  • the additives which are discovered to substantially enhance these qualities of electrolytic copper solutions possess a high degree of solubility in the plating baths as distinguished particularly from the colloidal additives heretofore suggested in the prior art.
  • the base metals to which the copper plating baths of the present invention are applicable include the various types of steel, zinc, nickel, tin, alloys of these metals as well as other metals and their alloys.
  • the preferred additives for producing the indicated are selected from the class consisting of those having the formula SIOaH NHz m-Aminobenzenesulfonic acid, sodium salt, also called sodium metanilate m-Aminobenzenesulfonic acid 3-amino-4-methoxybenzenesulfonic acid 3-amino-4-chlorobenzenesulfonic acid 3-amino-o-chlorobenzenesulfonic acid
  • These compounds are preferably used in the form of their soluble salts.
  • the first compound of the above list is preferred because of its exceptionally high solubility as compared with the second and third compounds of the list.
  • Compounds 4 and 5 of the above list are characterized by high solubility similar to the first compound but the chloride substituent reduces the solubility of the resulting compound to a certain degree.
  • composition of the bath exclusive of the novel addition agents is of standard character.
  • aqueous solutions containing from 187.5 to 262.5 of copper sulfate (CuSO .5H O) 60 to grams per liter of sulfuric acid (7 and the remainder water are conventional and appropriate for the practice of the invention.
  • Other well-known copper salts and corresponding acids such as aqueous solutions of copper fluoborate and fluoboric acid may be used with equal facility with the addition agents of the present invention to produce ductile platings of high throw power.
  • a typically optimum plating bath for purposes of the present invention contains approximately 240 grams per liter copper sulfate, 75 grams per liter sulfuric acid operated at a temperature of aproximately F. and at a current density of from 10 to 100 amperes per square foot.
  • the additives may be employed in the proportion range and concentration of from one-tenth gram per liter to 100 grams per liter and above.
  • the optimum concentration is approximately 5 to 20 grams per liter with excellent results being accomplished at approximately 10 grams per liter.
  • the baths listed below are generally operated under condition normally used in industry as above indicated.
  • the proportions given in the examples are in grams per liter and during the plating process the work is made the cathode.
  • Example I There is provided a copper sulfate plating bath contamlng sodium m-aminobenzenesulfonate and having the following compositions:
  • Nickel flashed steel plate was made the cathode in an electrolytic bath having the above composition, and a current density of 100 amperes per square foot, direct current was applied to the solution. The plating proceeded for approximately two hours whereupon a smooth ductile copper plate of 0012 had occurred. This ductile copper plate was, nevertheless, hard with a dense grain structure. The general appearance of the plate showed an exceptional smooth ductile copper deposit.
  • Example II A cooper plating bath is prepared having the following composition:
  • Copper fiuoborate 200 Fluoboric acid to within the range of to 2.0 pH.
  • Example 111 A copper plating bath was prepared according to the specifications indicated in Example I but using 3-arnino- 4-methoxybenzenesulfonic acid instead of sodium metanilate. While a current density of 100 amperes per square foot was applied to the solution a smooth ductile copper plate of superior characteristics and having a thickness of about 0.012 was obtained in approximately two hours.
  • Example IV An aqueous copper fiuoborate plating bath was prepared having the same composition as the plating bath of Example II but employing 3-amino-6-chlorobenzene sulfonic acid as the addition agent instead of sodium metanilate. An exceptionally smooth ductile plating of copper having a thickness of approximately 0.018 inch was obtained in a period of three hours at a current density of 100 amperes per square foot.
  • An electrolytic bath comprising an aqueous acid solution of a, copper salt and from one-tenth to 100 grams per liter of a compound selected from the class consisting.
  • An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of sodium metanilate.
  • An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of metanilic acid.
  • An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of 3-amino-4-chlorobenzenesulfonic acid.
  • An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of 3-amino-6-chlorobenzenesulfonic acid.
  • An electrolytic bath comprising from 187.5 to 262.5 grams per liter of copper sulfate, to grams per liter of sulfuric acid, 5 to 20 grams per liter of a compound selected from the class consisting of compounds having the formula slOsH References Cited in the file of this patent UNITED STATES PATENTS Gray et a1. Aug. 6, 1929 Phillips et al. Nov. 29, 1949

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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)

Description

United States Patent METHOD OF MAKING DUCTILE COPPER PLATINGS Eugene N. Castellano, Seymour, 'Conn., assignor to The Seymour Manufacturing Company, Seymour, -Conn., a corporation of Connecticut No Drawing. Application February 4, 1958 Serial No. 713,104
7 Claims. (Cl. 204-52) This invention relates as indicated to electrodeposition of metals and, more specifically, to a process of and materials for use in the process of electrodepositing copper characterized in that the resulting copper plate as deposited, displays exceptional ductility, smoothness and throwing power. More particularly, the present invention has to do with new addition agents for producing the above-named desirable characteristics in the copper plate and which may be used with acid copper baths of usual composition operating under usual conditions.
Heretofore, various additives have been proposed for electrolytic copper plating baths to improve the ultimate quality of the copper plate. Some of the proposed addition agents are colloidal aliphatic and aromatic sulphides which are intended to produce smooth and ductible deposits of copper from the electrolyte. Electrolytic copper plating baths including such proposed additives do not have the required degree of throwing power which is demanded for many specialized applications. By throwing power is meant the ability of the copper plate to form smooth and adherent coatings of copper-on base metals having apertures, pits and other surface irregularities.
Various aliphatic and aromatic sulfonated additives have been proposed for producing bright copper platings. However, the main object of the present invention is not to produce bright copper deposits, but rather to substantially increase the stability of the resulting copper plate and to provide an essentially permanent copper plate which has the qualities of ductility, smoothness and throwing power to an exceptional degree of thickness. The only known additives for this purpose have been dextrin, glue, molasses and the like which are subject to the objection that over a period of time as the bath is aging, they will break down and contaminate the solution. deposit is extremely brittle. Moreover, this break down necessitates the periodic purification of the electrolyte for the removal and elimination of these break down impurities.
It is, accordingly, a primary object of the present invention to produce electrodepositable solutions of cop per which are characterized by an exceptionally high degree of smoothness, ductility and throwing power wherein the additives are stable and free of break down products. The electrolytic solutions of the present invention, accordingly, form copper plate which is free of brittleness and retains the desirable characteristics enumerated above indefinitely. The additives which are discovered to substantially enhance these qualities of electrolytic copper solutions possess a high degree of solubility in the plating baths as distinguished particularly from the colloidal additives heretofore suggested in the prior art. The base metals to which the copper plating baths of the present invention are applicable include the various types of steel, zinc, nickel, tin, alloys of these metals as well as other metals and their alloys.
According to the present invention, it has been found that the preferred additives for producing the indicated The result of this break down is that the copper I characteristics in copper plating baths are selected from the class consisting of those having the formula SIOaH NHz m-Aminobenzenesulfonic acid, sodium salt, also called sodium metanilate m-Aminobenzenesulfonic acid 3-amino-4-methoxybenzenesulfonic acid 3-amino-4-chlorobenzenesulfonic acid 3-amino-o-chlorobenzenesulfonic acid These compounds are preferably used in the form of their soluble salts. The first compound of the above list is preferred because of its exceptionally high solubility as compared with the second and third compounds of the list. Compounds 4 and 5 of the above list are characterized by high solubility similar to the first compound but the chloride substituent reduces the solubility of the resulting compound to a certain degree.
The composition of the bath exclusive of the novel addition agents is of standard character. For example, aqueous solutions containing from 187.5 to 262.5 of copper sulfate (CuSO .5H O) 60 to grams per liter of sulfuric acid (7 and the remainder water are conventional and appropriate for the practice of the invention. Other well-known copper salts and corresponding acids such as aqueous solutions of copper fluoborate and fluoboric acid may be used with equal facility with the addition agents of the present invention to produce ductile platings of high throw power. A typically optimum plating bath for purposes of the present invention contains approximately 240 grams per liter copper sulfate, 75 grams per liter sulfuric acid operated at a temperature of aproximately F. and at a current density of from 10 to 100 amperes per square foot.
In connection with conventional plating solutions of the indicated character, current densities of from 0 to 300 amperes per square foot and temperatures within the range of from room temperatures to F. may be employed depending upon the thickness and quality of the coating desired.
The additives may be employed in the proportion range and concentration of from one-tenth gram per liter to 100 grams per liter and above. The optimum concentration, however, is approximately 5 to 20 grams per liter with excellent results being accomplished at approximately 10 grams per liter.
The following are specific examples of the operation of the invention. The baths listed below are generally operated under condition normally used in industry as above indicated. The proportions given in the examples are in grams per liter and during the plating process the work is made the cathode.
Example I There is provided a copper sulfate plating bath contamlng sodium m-aminobenzenesulfonate and having the following compositions:
Copper sulfate 240 Sulfuric acid 75 Sodium m-aminobenzenesulfonate 10 Nickel flashed steel plate was made the cathode in an electrolytic bath having the above composition, and a current density of 100 amperes per square foot, direct current was applied to the solution. The plating proceeded for approximately two hours whereupon a smooth ductile copper plate of 0012 had occurred. This ductile copper plate was, nevertheless, hard with a dense grain structure. The general appearance of the plate showed an exceptional smooth ductile copper deposit.
Example II A cooper plating bath is prepared having the following composition:
Copper fiuoborate 200 Fluoboric acid to within the range of to 2.0 pH.
Sodium rn-amino-benzenesulfonate The temperature of the bath was maintained at 100 F. and a current density of 75 amp'eres per square foot applied to the solution for approximately one and onehalf hours. A superior copper plate of 0.007 thickness was found to have occurred having the characteristics indicated in the preceding example.
Example 111 A copper plating bath was prepared according to the specifications indicated in Example I but using 3-arnino- 4-methoxybenzenesulfonic acid instead of sodium metanilate. While a current density of 100 amperes per square foot was applied to the solution a smooth ductile copper plate of superior characteristics and having a thickness of about 0.012 was obtained in approximately two hours.
Example IV An aqueous copper fiuoborate plating bath was prepared having the same composition as the plating bath of Example II but employing 3-amino-6-chlorobenzene sulfonic acid as the addition agent instead of sodium metanilate. An exceptionally smooth ductile plating of copper having a thickness of approximately 0.018 inch was obtained in a period of three hours at a current density of 100 amperes per square foot.
Other examples illustrate the general applicability of the novel addition agents involving the plating of other base metals such as zinc, nickel and tin with correspondingly superior results over methods heretofore employed.
While preferred embodiments of the invention have been specifically described herein for illustrative purposes, it will be understood that changes in modification may be made without departing from the spiritand scope of the invention as defined by the accompanying claims.
What I claim is:
1. An electrolytic bath comprising an aqueous acid solution of a, copper salt and from one-tenth to 100 grams per liter of a compound selected from the class consisting.
of compounds having the formula SOzH 2. An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of sodium metanilate.
3. An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of metanilic acid.
4. An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of 3-amino-4-chlorobenzenesulfonic acid.
5. An electrolytic bath comprising an aqueous acid solution of a copper salt and from one-tenth to 100 grams per liter of 3-amino-6-chlorobenzenesulfonic acid.
6. An electrolytic bath comprising from 187.5 to 262.5 grams per liter of copper sulfate, to grams per liter of sulfuric acid, 5 to 20 grams per liter of a compound selected from the class consisting of compounds having the formula slOsH References Cited in the file of this patent UNITED STATES PATENTS Gray et a1. Aug. 6, 1929 Phillips et al. Nov. 29, 1949

Claims (1)

1. AN ELECTROLYTIC BATH COMPRISING AN AQUEOUS ACID SOLUTION OF A COPPER SALT AND FROM ONE-TEETH TO 100 GRAMS PER LITER OF A COMPOUND SELECTED FROM THE CLASS CONSISTING OF COMPOUNDS HAVING THE FORMULA
US713104A 1958-02-04 1958-02-04 Method of making ductile copper platings Expired - Lifetime US2871173A (en)

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US713104A US2871173A (en) 1958-02-04 1958-02-04 Method of making ductile copper platings
GB43/59A GB848387A (en) 1958-02-04 1959-01-01 An electrolytic bath mixture
DES61291A DE1086508B (en) 1958-02-04 1959-01-12 Acid galvanic copper bath

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3027415A (en) * 1958-03-19 1962-03-27 Production of unsaturated hydrocarbons
EP1197586A2 (en) * 2000-10-13 2002-04-17 Shipley Company LLC Electrolyte
US20020053519A1 (en) * 2000-11-02 2002-05-09 Shipley Company, L.L.C. Seed layer repair
US6679983B2 (en) 2000-10-13 2004-01-20 Shipley Company, L.L.C. Method of electrodepositing copper

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1723277A (en) * 1924-04-05 1929-08-06 Oneida Community Ltd Aluminum-plated article and process for producing the same
US2489538A (en) * 1941-05-24 1949-11-29 Gen Motors Corp Electrodeposition of copper

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1723277A (en) * 1924-04-05 1929-08-06 Oneida Community Ltd Aluminum-plated article and process for producing the same
US2489538A (en) * 1941-05-24 1949-11-29 Gen Motors Corp Electrodeposition of copper

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3027415A (en) * 1958-03-19 1962-03-27 Production of unsaturated hydrocarbons
EP1197586A2 (en) * 2000-10-13 2002-04-17 Shipley Company LLC Electrolyte
EP1197586A3 (en) * 2000-10-13 2002-09-25 Shipley Company LLC Electrolyte
US6679983B2 (en) 2000-10-13 2004-01-20 Shipley Company, L.L.C. Method of electrodepositing copper
US20020053519A1 (en) * 2000-11-02 2002-05-09 Shipley Company, L.L.C. Seed layer repair
US6797146B2 (en) 2000-11-02 2004-09-28 Shipley Company, L.L.C. Seed layer repair

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GB848387A (en) 1960-09-14

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