Method of stripping silver from a printed circuit board

Etching a substrate: processes – Nongaseous phase etching of substrate – Etching inorganic substrate

Reexamination Certificate

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C216S013000, C252S079500, C427S307000, C174S250000

Reexamination Certificate

active

06783690

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a method of treating a printed circuit board to chemically remove plated silver from a printed circuit board without the use of harmful chemicals or the application of external current.
BACKGROUND OF THE INVENTION
In the manufacture of electronic equipment utilizing printed circuits, connections of electronic components to the printed circuits are made by soldering of the leads of the components to the through-holes, surrounding pads, lands, and other points of connections.
To facilitate this soldering operation, the printed circuit fabricator is required to arrange that the through-holes, pads, lands, and other points of connection are receptive to the subsequent soldering processes. Thus, these surfaces must be readily wettable by the solder and permit an integral conductive connection with the leads or surfaces of the electronic components. Because of these needs, printed circuit fabricators have devised various methods of preserving and enhancing the solderability of surfaces.
Soldering directly to copper surfaces has been difficult and inconsistent. These problems are due mainly to the inability of keeping the copper surfaces clean and free of oxidation throughout the soldering operation. Immersion silver deposits have been found to provide excellent solderability preservatives, which are particularly useful in the fabrication of printed circuit boards. The soluble source of silver ions can be derived from a variety of silver compounds. An example of a silver immersion plating process can be found in U.S. Pat. No. 6,200,451, to Redline et al., the subject matter of which is hereby incorporated by reference. The immersion silver solution is used to plate a thin layer of silver onto the surface to be soldered. The resultant silver coating is generally between 1 and 100 micro-inches in thickness for effective enhancement and preservation of the solderability of the surface.
In general, an immersion plating process results from a replacement reaction whereby the surface being plated dissolves into solution and at the same time the metal being plated deposits from the plating solution onto the surface. The immersion plating initiates without prior activation of the surfaces. The metal to be plated is generally more noble that the surface metal. Thus, immersion plating is usually significantly easier to control and significantly more cost effective than electroless plating, which requires sophisticated auto catalytic plating solutions and processes for activation of the surfaces prior to plating.
In the course of fabricating a printed circuit board, it may also be necessary to afterwards strip the silver from all or selected copper, or other metal, surfaces over which it was deposited. This need arises, for example, where it is necessary to plate another metal, such as nickel or gold, directly over the copper at certain portions of the board, or where it is desired to apply a solder mask over certain bare copper surfaces. It also may be necessary to strip silver from the copper layer in the course of treating a reject piece in order to recover and reuse the underlying copper material.
It is well known in the art of stripping silver to use chemicals such as cyanides, chromates, and strong acid solutions to facilitate the removal of silver from the surface of a substrate. In addition it is well known to use an anodic current to facilitate the removal of silver, with or without the use of such chemicals.
Examples of useful silver strippers are inhibited acid or cyanide solutions. The acids include sulfuric and sulfonic acids and other mineral acids useful in metal stripping compositions. The cyanide stripper compositions include alkali or alkaline earth metals or ammonium cyanide stripping compositions known to those in the art. The inhibited compositions typically are inhibited by nitrocompounds. Examples of useful inhibiting compounds include nitrobenzenes, nitrobenzoic acids, nitrobenzaldehydes, nitroparafins, and nitroalkanes.
While these methods do facilitate the removal of plated silver, these methods are unacceptable due to environmental concerns relating to the use of cyanide or chromate. The chemicals used in the prior art also have a tendency to attack the underlying solder mask or substrate. In addition, there may be an inability, when using an anodic current, to apply current across the entirety of the printed circuit board.
U.S. Statutory Invention Registration H1,136, to Janikowski, the subject matter of which is hereby incorporated by reference, discloses a method for electroplating silver which comprises a plating solution and/or stripping solution of an alkali hydroxide and ethylenediamine. While the plating and/or stripping solution does not contain cyanide, the process of the invention does require an anodic current.
Likewise, U.S. Pat. No. 5,002,649, to Smith, the subject matter of which is hereby incorporated by reference, discloses an apparatus for electrolytically or chemically stripping plating material, including silver plating, from a selected surface. The apparatus requires anodic current, although the stripping can be accomplished either electrolytically or chemically. In addition, the chemical stripping solution may contain cyanide.
The method of the present invention provides a new stripping solution for removing silver that does not contain any of the more toxic chemicals of prior art stripping solutions or require the use of an anodic current to facilitate removal of the plated silver. In addition, the silver stripping solution of the present invention does not attack either the base metal to which the silver is plated or the solder mask. The method provides an inventive stripping solution to chemically remove plated silver from printed circuit boards without the problems inherently found in the prior art.
SUMMARY OF THE INVENTION
The present invention relates to a method of stripping silver from a printed circuit board without attacking the underlying base metal. Another benefit of the method of the present invention is its ability to selectively remove silver without attacking the solder mask.
The present invention comprises a method for removing plated silver from a printed circuit board comprising the steps of:
(a) contacting said printed circuit board with a stripping solution comprising an oxidizing agent, an alkaline pH adjuster, and a silver solubilizing agent; and
(b) neutralizing said printed circuit board with a neutralization solution.


REFERENCES:
patent: 3615950 (1971-10-01), Lacal
patent: 3860423 (1975-01-01), Okamoto
patent: 4204013 (1980-05-01), Arcilesi et al.
patent: 4448637 (1984-05-01), Hiraishi et al.
patent: 4960490 (1990-10-01), Berg et al.
patent: 5002649 (1991-03-01), Smith
patent: H1136 (1993-02-01), Janikowski
patent: 5245111 (1993-09-01), Betz
patent: 5611905 (1997-03-01), Florio et al.
patent: 6126720 (2000-10-01), Okada et al.
patent: 6200451 (2001-03-01), Redline et al.
patent: 6221520 (2001-04-01), Takaki et al.
patent: 6238592 (2001-05-01), Hardy et al.
patent: 407316845 (1995-12-01), None

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