US2243429A - Electroplating of nonconductive surfaces - Google Patents

Electroplating of nonconductive surfaces Download PDF

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Publication number
US2243429A
US2243429A US184392A US18439238A US2243429A US 2243429 A US2243429 A US 2243429A US 184392 A US184392 A US 184392A US 18439238 A US18439238 A US 18439238A US 2243429 A US2243429 A US 2243429A
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Prior art keywords
copper
metal
coating
deposit
solution
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Expired - Lifetime
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US184392A
Inventor
Laux Rudolf
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Langbein Pfanhauser Werke AG
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Langbein Pfanhauser Werke AG
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating

Definitions

  • metal coating metal mirror
  • a copper layer is then usually first electrolytically deposited from alkali cyanide or acid copper galvanoplastic baths, and finally a further electrolytic deposit of another metal is produced.
  • the present invention refers particularly to those processes in which the first conductive surface coating on the object consists of an exceedingly thin metal coating, e. g. a silver mirror or a copper mirror which is deposited from a corresponding metallic salt solution by chemical v reduction. It has been proved that, when the object is suspended in those galvanic baths which usually serve for the electrolytic separation of copper, namely acid galvanoplastic copper baths or also alkali cyanide copper baths, an exceedingly thin metal coating of this kind is attacked by these baths in a manner which causes solution, so that considerable wastage occurs because the galvanoplastic copper deposits then turn out irregular or incomplete.
  • an exceedingly thin metal coating e. g. a silver mirror or a copper mirror which is deposited from a corresponding metallic salt solution by chemical v reduction.
  • the purpose of th invention is to remove these drawbacks.
  • the object which is provided for instance with a silver mirror, is treated cathodically for some time in an aqueous copper sulphate solution before suspension in one of the usual galvanic copper baths, the pH value of the copper. sulphate solution amounting to about 3.4 to 1.8.
  • This corresponds to aqueous solutions of copper sulphate which contain only up to about 2.5 gms. of free sulphuric acid per litre.
  • the concentration of the copper sulphate preferably amounts to only about 40 to 100 gms. per litre.
  • the further thickening of the copper deposit can be effected in one of the usual galvanic copper baths, for instance in one of the acid copper baths, usual in galvanoplastics, containing about 200 to 300 gms. of copper sulphate and about 15 to 40 gms. of free'sulphuric acid per litre and of which the pH value amounts to about 1.1 to0.9.
  • Process for .the production of a conductive coating on an object having a nonconductive surface which comprises reducing a solution of a copper salt while in contact with said surface, thereby producing a thin copper deposit thereon, then electrolytically depositing further copper on said copper deposit from solution containing copper sulphate and some free sulphuric acid and having a pH value of from about 3.4 to about 1.8, and finally building up the copper coating by electrolytic deposition from a solution containing a higher concentration of copper sulphate and of free acid than said last mentioned solution.
  • Process for the production of a conductive coating on an object having a nonconductive surface which comprises providing a thin metal deposit on said surface and then electrolytically depositing copper on said metal deposit from an aqueous solution containing copper sulphate and some free sulphuric acid and having a pH value from about 3.4 .-to about 1.8 and.finally building up the copper coating by electrolytic deposition from a solution containing about 200 grams to about 300 grams of copper sulphate and about 15 grams to about 40 grams of free sulphuric acid per litre.
  • Process for the electrolytic production of'a metal coating on an object having a noncondu'ctive surface which comprises providing a thin metal deposit on said surface, then electrolytically depositing copper on said metal deposit from an aqueous solution containing copper sulphate and some free sulphuric acid and having a pH value of from about 3.4 to about 1.8, and finally electrolytically depositing metal on the copper coating, from a solution containing a higher confrom an aqueous centration of metal salt and of free acid than said last-mentioned solution.
  • Process for the electrolytic production of a metal coating on an object having a nonconductive surface which comprises providing a thin silver deposit on said surface and then electrolytically depositing copper on said silver deposit solution containing copper sulphate and some free sulphuric acid and having a pH value of from about 3.4 to about 1.8 and finally depositing metal on the copper coating tion of a salt 01 a metal while in contact with p said surface thereby producing a thin metal deposit thereon then electrolytically depositing copper on said metal deposit from an aqueous solution conteiningcoppcr sulphate and some free sulphuric acid and having a pH value of irom about 3.4 to about 1.8 and. finally electrolytically depositing metal on said copper coating, from a solution containing a higher concentration of metal salt and of free acid than said last-mentioned solution.

Description

this is brought about Patented May l'2' 7, 1941 ELECTROPLATING F NONCONDUCTI-VE SURFACES Rudolf Laux, Leipzig, Germany, assignor to Langbein Pfanhauser Leipzig, Germany N 0 Drawing.
rial No.
Claims.
Various processes are known for producing metal coatings electrolytically on objects of insulating material or on objects with a nonconducting surface. For carrying out such electroplating processes, the insulating surface of the object must first be made conductive, e. g. by graphiting or by depositing an exceedingly thin Werke Aktiengesellschaft,
Application January 11, 1938, Se- 184,392. In Germany January 13,
metal coating (metal mirror) from a reducible metal salt solution. on to this first conductive surface coating, a copper layer is then usually first electrolytically deposited from alkali cyanide or acid copper galvanoplastic baths, and finally a further electrolytic deposit of another metal is produced.
The present invention refers particularly to those processes in which the first conductive surface coating on the object consists of an exceedingly thin metal coating, e. g. a silver mirror or a copper mirror which is deposited from a corresponding metallic salt solution by chemical v reduction. It has been proved that, when the object is suspended in those galvanic baths which usually serve for the electrolytic separation of copper, namely acid galvanoplastic copper baths or also alkali cyanide copper baths, an exceedingly thin metal coating of this kind is attacked by these baths in a manner which causes solution, so that considerable wastage occurs because the galvanoplastic copper deposits then turn out irregular or incomplete.
The purpose of th invention is to remove these drawbacks. According'to the invention, owing to the fact that the object, which is provided for instance with a silver mirror, is treated cathodically for some time in an aqueous copper sulphate solution before suspension in one of the usual galvanic copper baths, the pH value of the copper. sulphate solution amounting to about 3.4 to 1.8. This corresponds to aqueous solutions of copper sulphate which contain only up to about 2.5 gms. of free sulphuric acid per litre. In so doing, the concentration of the copper sulphate preferably amounts to only about 40 to 100 gms. per litre. In baths of .this kind, a satisfactory electrolytic coppering of the exceedingly thin metal surface is obtained without risk of its partial solution 'or injury in any other manner during suspension. Objects with an exceedingly thin silver layer can even be suspended in the copper sulphate solution for several hours without current.
After the metal surface is well covered with copper in the copper bath constructed according to the invention, the further thickening of the copper deposit can be effected in one of the usual galvanic copper baths, for instance in one of the acid copper baths, usual in galvanoplastics, containing about 200 to 300 gms. of copper sulphate and about 15 to 40 gms. of free'sulphuric acid per litre and of which the pH value amounts to about 1.1 to0.9.
I claim:
1. Process for .the production of a conductive coating on an object having a nonconductive surface, which comprises reducing a solution of a copper salt while in contact with said surface, thereby producing a thin copper deposit thereon, then electrolytically depositing further copper on said copper deposit from solution containing copper sulphate and some free sulphuric acid and having a pH value of from about 3.4 to about 1.8, and finally building up the copper coating by electrolytic deposition from a solution containing a higher concentration of copper sulphate and of free acid than said last mentioned solution.
2. Process for the production of a conductive coating on an object having a nonconductive surface, which comprises providing a thin metal deposit on said surface and then electrolytically depositing copper on said metal deposit from an aqueous solution containing copper sulphate and some free sulphuric acid and having a pH value from about 3.4 .-to about 1.8 and.finally building up the copper coating by electrolytic deposition from a solution containing about 200 grams to about 300 grams of copper sulphate and about 15 grams to about 40 grams of free sulphuric acid per litre.
3. Process for the electrolytic production of'a metal coating on an object having a noncondu'ctive surface which comprises providing a thin metal deposit on said surface, then electrolytically depositing copper on said metal deposit from an aqueous solution containing copper sulphate and some free sulphuric acid and having a pH value of from about 3.4 to about 1.8, and finally electrolytically depositing metal on the copper coating, from a solution containing a higher confrom an aqueous centration of metal salt and of free acid than said last-mentioned solution.
4. Process for the electrolytic production of a metal coating on an object having a nonconductive surface which comprises providing a thin silver deposit on said surface and then electrolytically depositing copper on said silver deposit solution containing copper sulphate and some free sulphuric acid and having a pH value of from about 3.4 to about 1.8 and finally depositing metal on the copper coating tion of a salt 01 a metal while in contact with p said surface thereby producing a thin metal deposit thereon then electrolytically depositing copper on said metal deposit from an aqueous solution conteiningcoppcr sulphate and some free sulphuric acid and having a pH value of irom about 3.4 to about 1.8 and. finally electrolytically depositing metal on said copper coating, from a solution containing a higher concentration of metal salt and of free acid than said last-mentioned solution. v
RUDOLF LAUX.
US184392A 1937-01-13 1938-01-11 Electroplating of nonconductive surfaces Expired - Lifetime US2243429A (en)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2481718A1 (en) * 1980-05-01 1981-11-06 Hooker Chemicals Plastics Corp METHOD FOR PRETREATING SUBSTANTIALLY NON-CONDUCTIVE SUBSTRATES TO MAKE THEM RECEPTIVE TO ELECTROLYTIC COATINGS
US4619741A (en) * 1985-04-11 1986-10-28 Olin Hunt Specialty Products Inc. Process for preparing a non-conductive substrate for electroplating
US4622108A (en) * 1986-05-05 1986-11-11 Olin Hunt Specialty Products, Inc. Process for preparing the through hole walls of a printed wiring board for electroplating
US4622107A (en) * 1986-05-05 1986-11-11 Olin Hunt Specialty Products Inc. Process for preparing the through hole walls of a printed wiring board for electroplating
US4631117A (en) * 1985-05-06 1986-12-23 Olin Hunt Specialty Products Inc. Electroless plating process
US4684560A (en) * 1985-11-29 1987-08-04 Olin Hunt Specialty Products, Inc. Printed wiring board having carbon black-coated through holes
US4718993A (en) * 1987-05-29 1988-01-12 Olin Hunt Specialty Products Inc. Process for preparing the through hole walls of a printed wiring board for electroplating
US4724005A (en) * 1985-11-29 1988-02-09 Olin Hunt Specialty Products Inc. Liquid carbon black dispersion
US4964959A (en) * 1990-04-12 1990-10-23 Olin Hunt Specialty Products Inc. Process for preparing a nonconductive substrate for electroplating
US4969979A (en) * 1989-05-08 1990-11-13 International Business Machines Corporation Direct electroplating of through holes
US4994153A (en) * 1990-06-28 1991-02-19 Olin Corporation Process for preparing nonconductive substrates
US5106537A (en) * 1990-04-12 1992-04-21 Olin Hunt Sub Iii Corp. Liquid dispersion for enhancing the electroplating of a non-conductive surface
US5139642A (en) * 1991-05-01 1992-08-18 Olin Corporation Process for preparing a nonconductive substrate for electroplating
US5476580A (en) * 1993-05-17 1995-12-19 Electrochemicals Inc. Processes for preparing a non-conductive substrate for electroplating
US5674372A (en) * 1996-09-24 1997-10-07 Mac Dermid, Incorporated Process for preparing a non-conductive substrate for electroplating
US5690805A (en) * 1993-05-17 1997-11-25 Electrochemicals Inc. Direct metallization process
US5725807A (en) * 1993-05-17 1998-03-10 Electrochemicals Inc. Carbon containing composition for electroplating
US6171468B1 (en) 1993-05-17 2001-01-09 Electrochemicals Inc. Direct metallization process
US6303181B1 (en) 1993-05-17 2001-10-16 Electrochemicals Inc. Direct metallization process employing a cationic conditioner and a binder
US6710259B2 (en) 1993-05-17 2004-03-23 Electrochemicals, Inc. Printed wiring boards and methods for making them

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2481718A1 (en) * 1980-05-01 1981-11-06 Hooker Chemicals Plastics Corp METHOD FOR PRETREATING SUBSTANTIALLY NON-CONDUCTIVE SUBSTRATES TO MAKE THEM RECEPTIVE TO ELECTROLYTIC COATINGS
US4619741A (en) * 1985-04-11 1986-10-28 Olin Hunt Specialty Products Inc. Process for preparing a non-conductive substrate for electroplating
US4631117A (en) * 1985-05-06 1986-12-23 Olin Hunt Specialty Products Inc. Electroless plating process
US4684560A (en) * 1985-11-29 1987-08-04 Olin Hunt Specialty Products, Inc. Printed wiring board having carbon black-coated through holes
US4724005A (en) * 1985-11-29 1988-02-09 Olin Hunt Specialty Products Inc. Liquid carbon black dispersion
US4622108A (en) * 1986-05-05 1986-11-11 Olin Hunt Specialty Products, Inc. Process for preparing the through hole walls of a printed wiring board for electroplating
US4622107A (en) * 1986-05-05 1986-11-11 Olin Hunt Specialty Products Inc. Process for preparing the through hole walls of a printed wiring board for electroplating
US4718993A (en) * 1987-05-29 1988-01-12 Olin Hunt Specialty Products Inc. Process for preparing the through hole walls of a printed wiring board for electroplating
US4969979A (en) * 1989-05-08 1990-11-13 International Business Machines Corporation Direct electroplating of through holes
US5106537A (en) * 1990-04-12 1992-04-21 Olin Hunt Sub Iii Corp. Liquid dispersion for enhancing the electroplating of a non-conductive surface
US4964959A (en) * 1990-04-12 1990-10-23 Olin Hunt Specialty Products Inc. Process for preparing a nonconductive substrate for electroplating
US4994153A (en) * 1990-06-28 1991-02-19 Olin Corporation Process for preparing nonconductive substrates
US5139642A (en) * 1991-05-01 1992-08-18 Olin Corporation Process for preparing a nonconductive substrate for electroplating
USRE37765E1 (en) 1991-05-01 2002-06-25 Macdermid, Incorporated Process for preparing a nonconductive substrate for electroplating
US5476580A (en) * 1993-05-17 1995-12-19 Electrochemicals Inc. Processes for preparing a non-conductive substrate for electroplating
US5690805A (en) * 1993-05-17 1997-11-25 Electrochemicals Inc. Direct metallization process
US5725807A (en) * 1993-05-17 1998-03-10 Electrochemicals Inc. Carbon containing composition for electroplating
US6171468B1 (en) 1993-05-17 2001-01-09 Electrochemicals Inc. Direct metallization process
US6303181B1 (en) 1993-05-17 2001-10-16 Electrochemicals Inc. Direct metallization process employing a cationic conditioner and a binder
US6710259B2 (en) 1993-05-17 2004-03-23 Electrochemicals, Inc. Printed wiring boards and methods for making them
US20040084321A1 (en) * 1993-05-17 2004-05-06 Thorn Charles Edwin Printed wiring boards and methods for making them
US5674372A (en) * 1996-09-24 1997-10-07 Mac Dermid, Incorporated Process for preparing a non-conductive substrate for electroplating

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Publication number Publication date
GB493485A (en) 1938-10-10

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