U.S. patent number 3,627,654 [Application Number 04/878,197] was granted by the patent office on 1971-12-14 for electrolytic process for cleaning high-carbon steels.
Invention is credited to George S. Petit, Ralph R. Wright.
United States Patent |
3,627,654 |
Petit , et al. |
December 14, 1971 |
ELECTROLYTIC PROCESS FOR CLEANING HIGH-CARBON STEELS
Abstract
A single-step process for uniformly etching a high-carbon-steel
surface, including its crystal boundaries, and for continuously
removing from the surface the carbon exposed by etching. The steel
surface is made anodic in an aqueous solution of orthophosphoric
acid containing fluoride ion and a wetting agent. The applied
voltage is selected to provide an overvoltage condition at the
anode so that copious amounts of oxygen are liberated at the anodic
surface to sweep exposed carbon therefrom. High-carbon-steel
surfaces so processed form a chemical bond with subsequently
deposited metal coatings, such as nickel platings.
Inventors: |
Petit; George S. (Oak Ridge,
TN), Wright; Ralph R. (Oak Ridge, TN) |
Assignee: |
|
Family
ID: |
25371571 |
Appl.
No.: |
04/878,197 |
Filed: |
November 19, 1969 |
Current U.S.
Class: |
205/671; 205/680;
205/682 |
Current CPC
Class: |
C25F
3/06 (20130101) |
Current International
Class: |
C25F
3/06 (20060101); C25F 3/00 (20060101); C23b
001/04 (); C23b 001/00 () |
Field of
Search: |
;204/145R,140.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Tufariello; Thomas
Claims
What is claimed is:
1. The process of uniformly etching a high-carbon-steel surface and
concurrently removing therefrom carbon exposed by said etching,
comprising making a high-carbon-steel surface anodic in an
electrolyte consisting essentially of an aqueous solution of
orthophosphoric acid containing a small but effective amount,
sufficient to effect etching rather than polishing of said surface,
of a water-soluble fluoride, and establishing an overvoltage
condition at the anodic surface to liberate oxygen at said surface
during etching.
2. The process of claim 1 wherein said aqueous solution is from
about 20 to 70 percent by volume orthophosphoric acid and contains
from about 0.03 to 10 g./l. of said fluoride.
3. The process of claim 1 wherein said aqueous solution is from
about 32 to 52 percent by volume orthophosphoric acid and contains
about 0.06 to 0.2 g./l. of said fluoride.
4. The process of claim 1 wherein said electrolyte contains an
anionic wetting agent.
5. The process of claim 1 wherein said water-soluble fluoride is a
metal fluoride.
6. The process of claim 1 wherein said water-soluble fluoride is
hydrogen fluoride.
7. The process of claim 1 wherein said water-soluble fluoride is
ammonium hydrogen fluoride.
8. The process of claim 1 wherein said electrolyte is maintained at
a temperature of about 20.degree.-35.degree. C.
9. The process of claim 1 wherein said electrolyte is agitated
during etching.
Description
BACKGROUND OF THE INVENTION
This invention was made in the course of, or under, a contract with
the United States Atomic Energy Commission.
Our invention relates to a method for cleaning metal surfaces, and
more specifically to a method for cleaning high-carbon-steel
surfaces. The term high-carbon steel is used herein to refer to
steels containing about 0.3 percent carbon or above.
To obtain a strong, tenacious bond between high-carbon-steel
surfaces and metal coatings deposited thereon, it is necessary to
uniformly etch the steel surfaces and then remove the carbon smut
exposed but not removed by the etching operation. Various
treatments, both electrolytic and nonelectrolytic, have been
employed to etch and clean such surfaces before plating, but these
treatments share the disadvantage of including a final mechanical
scouring step for removal of the carbon smut. The scouring often is
done manually and in any event is both tedious and time-consuming.
More important, such scouring is largely ineffective in removing
smut from small bores, inside corners, dimples, and the like.
SUMMARY OF THE INVENTION
It is, therefore, an object of this invention to provide a method
for the uniform etching of surfaces composed of high-carbon
steel.
It is another object of this invention to provide a method for
effectively removing carbon smut from etched high-carbon-steel
surfaces, including surfaces not amenable to mechanical
scouring.
It is another object to provide a single-step method for uniformly
etching carbon-containing steel surfaces and removing carbon smut
therefrom during the etching operation.
Other objects will become apparent from an examination of the
following description.
DESCRIPTION OF THE INVENTION
In carrying out our invention, the high-carbon-steel surface to be
coated with metal is made anodic in a special acidic solution under
conditions designed to provide a carbon-free etched surface. The
treatment is designed to produce a steel surface which consists
predominantly of undistorted, unbroken crystals. Electropolishing
does not produce a suitably active surface, nor does simple
chemical etching. To provide the desired surface, one which will
form a chemical bond with the metal coating to be deposited, we
etch the entire steel surface, including its crystal boundaries. In
addition, we continually remove from the surface the carbon exposed
during etching. Removal of the carbon promotes uniform etching and
provides a clean etched surface amenable to bonding.
EXAMPLE I
A machined rectangular workpiece composed of SAE-4340 steel (carbon
content, 0.43 percent) and formed with a bore having a diameter of
0.25 inch and a length of 2.5 inches was degreased by immersion in
technical-grade chromic acid solution for 1 minute. After
degreasing, the workpiece was immersed for 5 minutes in a 20
percent-HCl solution to remove rust and scale. The workpiece then
was rinsed thoroughly in tap water.
The rinsed workpiece was made anodic in a solution formed of equal
parts by volume of water and 85 percent orthophosphoric acid,
containing 0.1 gram/liter ammonium bifluoride and 1
milliliter/liter anionic wetting agent. A nickel block having an
area approximately equal to that of the workpiece was immersed in
the solution as the cathode. A DC voltage of approximately 6 volts
was impressed across the electrodes to establish a current density
of approximately 50 amperes per square inch for 2 minutes. During
this treatment period the solution was maintained at a temperature
of 27.degree. C. .+-.5 and was agitated by sparging with air.
Throughout the treatment copious bubbling was observed at the
surface of the steel anode. This was the result of oxygen being
liberated at the anode, the voltage impressed across the electrodes
having been preselected to ensure an overvoltage condition. The
observable surfaces of the anode remained clean throughout the
treatment.
Examination of the workpiece after removal from the electrolyte
established that its surfaces-- including the wall of the
above-mentioned bore--were free of smut. The steel surfaces and
their crystal boundaries were smoothly etched but not polished
(brightened).
The etched workpiece was chemically plated with an amorphous
nickel-phosphorous alloy by immersion in a standard bath for the
autocatalytic reduction of nickel cations by means of hypophosphite
anions in aqueous solution. Examination established that the
resulting plating (thickness, 0.25 mil.) was uniformly
adherent.
Referring to the electrolyte used in our process, we have found
that if a selected proportion of fluoride ion is maintained in the
phosphoric acid solution, the usual polishing action of this acid
is modified so that the entire surface of the metal is etched
uniformly, including its crystal boundaries. As indicated above, we
have also found that it is necessary to maintain an overvoltage
condition at the anode to ensure copious liberation of oxygen so
that exposed carbon is continually swept away from the surface
thereof.
We prefer to use an aqueous etching solution comprising about 32 to
52 percent phosphoric acid, by volume, and containing a
water-soluble fluoride in the amount of about 0.06 to 0.2 g./l. and
an anionic wetting agent in the amount of about 0.5 to 4 ml./l.
Such electrolytes not only provide the desired kind of etching (as
opposed to polishing) but also have a desirably high electrical
conductivity, thus reducing the time required for etching. If high
electrical conductivity is not considered essential, etching can be
accomplished with electrolytes having a broader range of
concentrations--for example, electrolytes containing from about 20
to 70 percent phosphoric acid and about 0.03 to 10 g./l.
water-soluble fluoride.
In our opinion orthophosphoric acid is the only acid which will
accomplish the purposes of this invention. For convenience, we
prefer to use commercial-grade phosphoric acid. If desired, of
course, the orthophosphoric acid can be prepared by hydrolyzing
metaphosphoric or pyrophosphoric acid in hot water.
The inclusion of fluoride in our electrolyte is essential because,
for reasons not well understood, the fluoride ion promotes
preferential attack of the crystal boundaries of the metal. Any
water-soluble fluoride may be incorporated in the electrolyte to
provide the fluoride ion. The following are examples of a few such
fluorides: NH.sub.4 HF.sub.2, AgF, LiF, NiF, FeF.sub.2, NaF, HF,
BeF.sub.2, and Ag.sub.2 SiF.sub.6 .sup.. 4H.sub.2 0. During use of
the electrolyte, replenishment of the fluoride may be necessary.
The need for additional fluoride can be determined by observation
of the steel surface being treated, additional fluoride being
needed if there is a trend toward polishing (brightening) of the
anode.
The incorporation of an anionic wetting agent in the electrolyte
promotes wetting of the steel surface, as well as fast escape of
liberated gases. Any of a variety of commercially available wetting
agents can be used, and the concentration thereof is not highly
critical.
As mentioned, it is essential to maintain an overvoltage at the
anode to ensure removal of carbon smut during etching and thus to
provide a clean and uniformly etched surface for the deposition of
metal. In example I, above, an overvoltage condition was provided
by impressing a DC voltage of 6 volts across the electrodes. An
overvoltage condition is characterized by abundant bubbling at the
anode. Loss of the overvoltage condition is evidenced by loss of
bubbling, darkening of the anode, and, eventually, by the formation
of a velvetlike smut on the anode.
The composition of the cathode is not critical. Various inert
conductors, such as carbon, can be used. Preferably, the surface
area of the cathode approximates that of the surface being treated.
For highly uniform treatment of the anode surfaces it may be
preferred to dispose several cathodes about the anode. The time of
treatment does not vary greatly with the size of the part.
Preferably, the electrolyte is agitated continually in the vicinity
of the anode.
Preferably, our treatment is conducted at a temperature in the
range of about 20.degree. to 35.degree. C., but this is not highly
critical.
High-carbon steels tend to absorb hydrogen, and hydrogen
embrittlement impairs bonding of the steel to a metal coating. In
our process, such embrittlement is minimized or eliminated, since
oxygen is liberated at the anode throughout the treatment.
We have found our invention to be effective for the cleaning of
various types of high-carbon steels, such as those commonly used in
the fabrication of cutting tools, threaded fasteners, drill bits,
and the like. Although our invention has been illustrated above in
terms of preparing a high-carbon-steel surface suitable for forming
a chemical bond with a chemically deposited nickel-phosphorous
alloy, the surfaces so treated will form chemical bonds with other
metal coatings deposited by other techniques, as by
electroplating.
The foregoing description is intended to be illustrative of this
invention, and it is to be understood that this invention is not to
be limited except as indicated in the appended claims.
* * * * *