Method and apparatus for electrochemical processing

Electrolysis: processes – compositions used therein – and methods – Electrolytic coating – Contacting coating as it forms with solid member or material...

Reexamination Certificate

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C205S138000, C204S207000

Reexamination Certificate

active

06800186

ABSTRACT:

BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to the deposition of metallic coatings from plating solutions as well as anodizing of metals. More particularly, this invention relates to wiping the cathodic coating surface of sheet and strip and during continuous electroplating as well as continuous anodizing and more particularly still to the use of a substantially solid wiper blade during such electroplating or anodizing.
(2) Prior Art
As detailed more particularly in U.S. application Ser. No. 08/316,530 filed Sep. 30, 1994, the disclosure of which is hereby expressly incorporated in and made a part of the present application, a number of coatings are deposited from so-called plating baths subjected to an imposed electrical potential basically enhancing an already naturally occurring tendency for metal ions in the solution to plate out.
Since the coating of a cathodic workpiece is largely merely the acceleration of a naturally occurring process or phenomena, fairly small changes in technique and apparatus accentuating those conditions that favor deposition and de-emphasizing these conditions that disfavor deposition, may have rather large effects upon the final coating obtained. The history of improvements in the field, therefore, is largely one of progressive small improvements and adjustments to improve the conditions for deposition of various coating metals on a metallic substrate temporarily included as the cathode in a plating circuit.
It has been found, for example, by the present inventors as well as others that it is conducive to good coating results to remove the hydrogen bubbles which are produced at the cathodic work surface by transfer of electrons not only to the positive ions of the coating metal in the solution, but also to positive hydrogen ions in the electrolytic solution. The initial cathodic film is believed to be a combination or mixture of both hydrogen ions and atomic or molecular hydrogen. This film initially is only one atom thick. It interferes to some extent with good coating in that it may tend to hold the larger metallic coating ions away from the surface to be coated. However, the hydrogen atoms are small and the layer of hydrogen is initially discontinuous so that their initial interference with coating is not too serious.
If nothing is done to remove the hydrogen from the surface coating during the coating process, coating will usually continue, even though it may be seriously interfered with by the increasing hydrogen present as the thickness of the hydrogen layer increases the interference with efficient plating out of metal atoms upon the substrate surface. Such hydrogen, as it accumulates, however, tends to coalesce into larger local accumulations resulting in small bubbles and then larger and larger bubbles until such bubbles have sufficient volume and buoyancy to overcome their initial attraction for or adhesion to the substrate surface and float upwardly in the solution to the surface where they are finally dissipated into the surrounding atmosphere or local environment. Consequently, the hindrance to coating caused by the presence of hydrogen gas at the surface of a cathodic workpiece does not tend to progress to the limit where it would cut off electrolytic plating completely. However, hydrogen is still a very significant hindrance to rapid coating or plating and the larger bubbles clinging to the surface of a workpiece may even lead to macroscopic pits and other defects in an electrolytic coating.
A second significant problem which has been long recognized in electrolytic coating baths is depletion of the electrolytic solution as coating progresses. In many cases, the only result is that the coating rate slows down as there are progressively less coating metal ions in the solution to plate out. This decreasing coating rate has been counteracted by pumping in fresh coating solution, throwing in chunks of soluble coating metal for solution to “beef up” the electrolyte as well as other expedients. The trend has been for closer and closer control of the electrolyte composition during coating. Sometimes this has been implemented by continuous testing or analysis of the electrolytic bath as coating progresses. In addition, the coating solution baths have been mixed by impellers or the like, force circulated and re-circulated as well as frequently tested to hold them to a desired composition.
It has also been recognized that the coating bath next to a workpiece being coated may become locally depleted of coating metal ions and that such depletion may compromise efficient coating. Some installations have adopted the expedient of forced circulation of electrolyte past the point of coating or through a restricted coating area to increase the efficiency of coating. If the forced circulation is rapid enough, such circulation in itself also tends to detach bubbles of hydrogen from the cathodic coating surface, in effect, “killing two birds with one stone”. However, the use of forced circulation of this type by pumps, jets and the like is not only unwieldy and expensive, but is believed by some to possibly have detrimental effects upon the coating itself because of the generalized rapidity of movement between the coating solution and cathodic workpiece, which macroscopically, at least, may interfere with efficient plating out of the metallic ions upon such work surface. Among the processes which have made use of rapid forced circulation is the so-called gap coating process in which a small coating gap between a coating anode and a cathodic workpiece is created and electrolytic solution is forced rapidly through such gap or opening.
Depletion of the coating solution has recently been found by one of the present inventors to be particularly serious in chrome plating solutions in which insoluble electrodes are used. It has been found that unless the chromium plating operation is maintained substantially continuous and at a fairly uniform rate that hard chrome is difficult to efficiently plate out in a brush-type coating operation, or, for that matter, in semi-brush type operations.
While various efforts to remove hydrogen bubbles from the coating surface in an electrolytic coating bath at the point of deposition have been tried, none has provided the ultimate quality of coating and efficiency of the coating operation which has been desired. Likewise, the ultimate in practical prevention of localized depletion in a coating bath has also not been attained.
A further problem in the continuous coating of a flexible material such as sheet, strip and wire products is that the efficiency of electroplating usually increases as the spacing between the electrodes, one of which is the material to be coated, decreases. In other words, the efficiency of coating is usually inversely related to the spacing between the electrodes one of which is the workpiece. However, due to the flexibility of the material being coated, it must, as a practical matter, be held away from the opposing electrode a sufficient distance to prevent arcing between the cathodic work material and the coating electrodes or anodes. The longer the unsupported run of material past the coating electrodes, the more deviation of the flexible material from its intended path is likely to occur, while closer spacing of supporting rolls or the like decreases the area available for coating and interferes with continuous coating. Very close spacing of the coating electrodes and the material being coated has been effected by the so-called jet coating process alluded to previously, but such process is complicated and sensitive to minor changes, making it suitable only for highly sophisticated coating lines.
There has been a need, therefore, for a means for removing hydrogen bubbles and cathodic film from a cathodic coating surf ace, preventing localized depletion of the coating bath with respect to coating material as well as allowing closer spacing of the coating electrodes and material being coated. The present applicants have found that a very effective means for accomplish

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