Patented Mar.

9, 1948 2,437,474

UNITED STATES PATENT of FICE

2,437,474
METHOD OF ANODIC CLEANING
Gilbert H. Orozco, Euclid, Ohio, assignor to Gi
bert H. Orozco and Roland A. Whitbeck, part
hers, doing business as Giron Products Con
pany, Cleveland, Ohio
No Drawing. Application March 24, 1944,
Serial No. 527,956
4 Claims. (C. 204-41)
1. 2
This application is a continuation-in-part of When films Such as discussed above are Sub
my prior application Serial No. 383,982, filed jected to so-called hot or vapor degreasing treat
March 18, 1941, and abandoned subsequent to the ment in a cleaning bath containing chlorinated
filing of the present application. solvents such as trichloroethylene and dichloro
The invention relates to a method of cleaning ethylene only the oily and greasy Substances and
rinetal articles and particularly articles made light metal soaps are usually removed. Such
froin carbon Steel, preparatory to plating and to treatment because it will not remove heavy metal
a Composition for use in connection with the soap films is not therefore fully effective or de
niethod. pendable as a means for preparing articles for
Most articles Which are to be plated are sub O plating and particularly articles made from high
jected to certain manufacturing operations dur carbon steel. Similarly the degreasing proceSS
ing which they become coated with oils, greases, mentioned and others discussed above are not
WaXes and Stearic acids, the stearic acids and completely effective in removing colioidal clayS
waxes being present in buffing and polishing com and the like used in manufacturing processes.
pounds which are applied to the articles during 5 Those leave light pigment films Which although
buffing, polishing and like operations. practically imperceptible interfere with subse
It is common practice to remove such films by quent plating.
electrolysis of the articles in certain hot aque Most metals, and particularly high carbon Steel,
ous aikaline cleaning baths. cleaned by the prior methods, although appar
The alkaline cleaning baths, while effective for 20 ently very clean, are found upon handling to have
removing the greater portion of such films from very light films and surface deposits of foreign
the articles do not entirely remove the illins. This matter, commonly referred to as 'smut films'
is because the Water commonly used in cleaning and in the case of carbon steel "graphitic films'
baths usually contains calcium and magnesium and “carbon Smut', all of which are detrimental
Which, in the presence of alkaline cleaning agents, 25 in subsequent plating processes.
combine with the oil, grease, and wax films to One of the objects of the present invention is
form deposits of Very light calcium and magne to remove all of the films and deposits such as
sium colloidal Soap films or eimulsions on the air hereinbefore described from the surface of metal
ticles. Calcium and magnesium are often pres articles by dissolving the films chemically while
ent in the buffing and drawing compounds so that 30 concurrently subjecting the articles anodically to
they are introduced into the cleaning bath even electrolytic cleaning at a high current density.
though the Water used is originally free from such Another object is to prepare the Sulface of the
materials. articles by subjecting the articles to an aqueous
The colloidal filfins thus formed are insoluble in Solution which either prevents the formation of
water, have a high affinity for the metal and ad 35 the colloidal films and other films originally, or
here tightly thereto, the tenacity of the soap films removes them after formation, or so conditions
increasing in a rather direct proportional rea them that they are removed in the usual rinsing
tionship to the increase in the pH of the alkaline and acid dipping Which precedes the actual plat
bath. ing operation.
Alkaline cleaning baths and electrolytic proc 40 Other objects and advantages Will become aipu
esses heretofore used do not remove these films parent from the following specification wherein
in their entirety but leave a very slight but tena a preferred embodiment of the present invention
cious in which renders the Surfaces of the air is disclosed for purposes of illustration.
ticles unsuitable for subsequent plating. These The present method has to do essentially with
slight fins are customarily removed by the rela 45 the cleaning operation which precedes the usual
tively expensive steps of brushing, Scrubbing, highwater rinse and acid dip Which are commonly
pressure Spraying, and other mechanical opera employed subsequent to cleaning in the plating
tions after Subjection of the articles to electro art, and would not in most cases displace the
lytic cleaning. Due to the very high affinity for water rinse and/or acid dip in those instances
metal of the colloidal or Soapy films and particu 50 in which such are generally required.
larly those formed by heavy metal soaps, even In accordance with the present invention, the
these mechanical steps are not as effective as could article to be cleaned, without presoaking, is Sub
be desired. jected anodically to a bath containing sodium or
 2,487,474
3
potassium acetate, or a combination thereof, and,
in addition thereto, an alkaline salt which in Preferred Range
parts to the bath a pH greater than . The
bath is purposely maintained free from silicates Parts Parts
and borates such, for example, as metasilicate, 12 Sodium acetate (anhydrous)-------------
Sodium hydroxide-----------------------
15
45
5 to 50
10 to 55
waterglass, orthosilicate, borates, and other wa 34 Sodium carbonate-----------------------
An alkaline (e.g. potassium or sodium)
29 10 to 40
ter soluble calcium precipitants. Borates or sili phosphate salt having the properties
cates have been used in alkaline cleaning baths of disintegrating magnesium or calcium
heretofore because of their detergent properties, soaps, such for example, as one or more
of the group comprising tetrasodium
but I have found that the borates or silicates 10 pyrophosphate, sodium, metaphos
phate, potassium pyrophosphate or
themselves are hard to rinse off and produce det potassium hexametaphosphate.--------- 10 5 to 55
rimental micro-films. 5. A wetting agent, if desired about.-------- 1 1 to 2
The piece is immersed in the bath in a tank
which is a cathode, the piece itself being Sup In the event, in either Example I or II, a
ported on a suitable rack which is the anode of a 15 formulation is chosen that uses the upper range
high current density plating circuit, as distin of either the acetate or phosphate components of
guished from the method generally used in plat the cleaner, the increase would be balanced by
ing wherein the piece forms the cathode.and the employing the indicated lower percentages of
tank the anode and a low current density Cir sodium carbonate in the mixture.
cuit is employed. A current density of at least 20 The sodium acetate is extremely effective for
35 amperes per square foot of surface Of the piece removal of graphitic films from steel Such as tend
to be cleaned is preferred and the term "high to form particularly on high carbon steels of the
current density' as used hereinafter signifies at type commonly used, for example, as automobile
least 35 amperes per square foot of surface. With bumper stock. Sodium acetate or potassium ac
this high density current anodically applied to 25 etate, one or the other or an equivalent thereof
the article while the article is in the bath de or mixture of the two are essential ingredients in
scribed, complete cleaning in about 30 to 60 sec the bath particularly in that they augment the
Onds in the case of non-ferrous metals and 1 to 5 action of the phosphates of the bath in rendering
minutes in the case of ferrous metals is obtained. the surfaces of the articles uniformly clean and
By subjecting the piece to the current anodi 30 free from smut and superficial films. The pH
cally the so-called "hydrogen effect' on the metal of a sodium acetate solution is below about 9 and
piece or article and which results in cathodic therefore is not in the pH range of optimum de
cleaning by release of hydrogen at the piece is tergency. Hence the Sodium acetate must be
eliminated. Instead the oxygen is released at the augmented by stronger alkaline salts when used
piece or anode and, therefore, there is no "hydro 35 in a cleaning bath. In practicing the present in
gen effect' on the piece. The so-called "hydro vention the pH of the bath is maintained above
gen effect' on the surface of an article to be 9 at all times, and the acetate should not be be
plated is such that after plating the article, there low 5% of the solute.
is a tendency for the plating to peel after ex The sodium or potassium hydroxide impart
posure in air for lack of proper bond to the piece 40 electrical conductivity to the solution. Since the
and appears to be due to the hydrogen inclusion hydroxyl anion has about twice the equivalent
or the plating out of metallic impurities in the conductivity of any other anion, it is apparent
bath. - - - - that an addition of caustic Soda or caustic potash
Eacdmaple I will impart twice the conductivity of any other
alkaline salt that could be added.
A suitable dry mix, by weight, for forming an The sodium carbonate, which is formed in
effective bath to be used in connection with the sodium hydroxide solutions exposed to air, is
high current density anodic cleaning of metals likewise a conducting salt. Its properties in Sof
such as copper or low carbon steel may comprise tening hard or temporarily hard water high in
the following: .. . . .. . . . . . . calcium or magnesium bicarbonates are well
known.
Preferred - Range As an illustration of the value of electrical
conductivity in the present cleaner, it was found
Sodium (anhydrous) or potassium ace- Per cent | Parts that a prior art cleaner containing twelve ounces
tate about----------------------------- -- - 10 5 to 50 55 per gallon of a proprietary material produced an
2 Sodium or potassium hydroxide about.-- 16.5 - 0 to 55 average anode current density of 35 to 45 am
3 Sodium carbonate about---------------- 20 - 10 to 40 peres per Square foot at 200' F. at a pressure of
4 Alkaline phosphate salt, such as tetra
sodium pyrophosphate or sodium or six volts. Using the identical cleaner tank but
potassium metaphosphate about.------- 28 } 5 to 55
Trisodium phosphate, about.-------------
A wetting agent (e.g. a sodium salt of an
25 substituting twelve ounces per gallon of the pre
alcohol Sulphuric acid) about.---------- 60 ferred composition in Example II for the prior
art material, an average anode current density
The dry mixture is dissolved in water in the of 60 to 90 amperes per square foot was obtained
ratio of about eight Ounces of the dry mix for at an identical voltage and temperature. Since
each gallon of water. A current density of 80 to commercial plating generators are made at 6, 9,
100 amperes per square foot of Surface of the 65 or 12 volts it can be seen that the optimum range
metal article to be cleaned is used and With the of high anode current density can only be ob
Work constituting the anode. tained for a given spacing of the electrodes by a
cleaner of high conductivity. - .
Eacample II The alkaline phosphate salts, for example
70 tetra-sodium pyrophosphate, hexametaphosphate
A bath which is particularly useful in connec or the like, are varied in amount depending upon
tion with the cleaning of high carbon steel may the condition of the water and of the articles.
comprise the following dry mix, by weight, mixed They effectively prevent the formation of mag
with water in about the concentration above re nesium and calcium Soaps and are an effective
cited: - v. -- - - w -
75 conditioner of the bath. While the pyro and
 2,487,474
5 6
metaphosphates are the preferred materials in and said bath being substantially free from sili
this invention because of their Superior sequester cates and borates.
ing action, it should be pointed out that the ortho 3. The method of cleaning and preparing metal
phosphates are also effective. It is well known articles for plating, which comprises removing
that aqueous solutions of both the pyro and meta carbonaceous film by subjecting the article anodi
phosphates tend to hydrolize or revert to the cally to a current While immersed in an aqueous
orthophosphate under heating in the presence alkaline cleaning bath consisting essentially of
of free alkali-hydroxides. I have found, how water as a solvent and a dry solute of ingredients
ever, that such hydrolysis does not interfere ma as follows, by weight:
terially with the operation of the present cleaner 10 PartS
composition or at least render it inoperative. A substance selected from the group
The concentration of the Solution is preferably consisting of sodium acetate and po
increased in the case of extremely hard water tassium acetate--------------------- 5 to 50
and decreased toward the lower limit in the case Sodium hydroxide-------------------- 10 to 55
of Softer Water. 5 Sodium carbonate-------------------- 10 to 40
By maintaining the bath free from water sol and Said bath being substantially free from sili
uble silicates or borates, micro-films which would cates and borates,
be caused by the silicates or borates are elim 4. The method of cleaning and preparing metal
inated. articles for plating, which comprises removing
The current density of the work is dependent 20 carbonaceous film by subjecting the article anodi
upon the conductivity of the solution which in cally to a current While immersed in an aqueous
turnis proportional to the concentration and tem alkaline cleaning bath consisting essentially of
perature of the cleaning bath. I have found that water as a solvent and a dry solute of ingredients
the higher concentrations and temperatures are as follows, by weight:
to be preferred. The method is practiced prefer 25 Parts
ably with a bath temperature about 150 F. up A substance selected from the group
to the boiling point of the particular bath. consisting of sodium acetate and po- -
The combination of anodic application of cur tassium acetate--------------------- 5 to 50
lent of high density to an article while the article Sodium hydroxide-------------------- 10 to 55
is in an alkaline cleaning bath of a character de Sodium carbonate-------------------- 10 to 40
scribed, effectively cleans the article and removes An alkaline phosphate Salt from the class
any and all films and foreign matter so that the Consisting of tetrasodium pyrophoS
article is made ready for plating in all instances phate, Sodium metaphosphate, potas
by the simple Subsequent step of Water rinse and Sium pyrophOSphate, potassium hexa
acid dip, metaphosphate -------------------- 5 to 55
I claim:
1. The method of cleaning and preparing metal and Said bath being substantially free from sili
articles for plating, which comprises removing cates and borates.
carbonaceous film by subjecting the articles GILBER. H. OROZ.CO.
anodically to a current density greater than 35 40
amperes per square foot of surface of the article REFERENCES CITED
While the article is immersed in an aqueous alka The following references are of record in the
line cleaning bath consisting essentially of water file of this patent:
as a Solvent and a dry Solute of ingredients as UNITED STATES PATENTS
follows, by Weight;
PartS Number Name Date
A substance selected from the group - Re. 19,719 Hall ---------------- Oct. 8, 1935
Consisting of Sodium acetate and po 1334,092 Harmeling --------- Mar. 16, 1920
tassium acetate--------------------- 5 to 50 1954,473 Dunn ------------- Apr. 10, 1934
Sodium hydroxide-------------------- 10 to 55 50 2,314,285 Morgan ------------ Mar. 16, 1943
Sodium carbonate-------------------- 10 to 40 2,346,562 Long -------------- Apr. 11, 1944
and said bath being substantially free from sili FOREIGN PATENTS
cates and borates. Number Country date
2. The method of cleaning and preparing metal 55 297,508 Great Britain ------ Sept. 27, 1928
articles for plating, which comprises removing 436,332 Great Britain ------ Oct. 9, 1935
carbonaceous film by Subjecting the article 584,477 Germany ---------- Sept. 20, 1933
anodically to a current density greater than 35
amperes per square foot of surface of the article OTHER REFERENCES
While the article is immersed in an aqueous alka 60 Mitchell-'The Cleaning of Metal,' copyright
line cleaning bath consisting essentially of water 1930 by the Magnus Chemical Co., pages 23, 24,
as a solvent and a dry solute of ingredients as 29, 30, 31, 38, and 44.
follows, by weight: Mitchell-articles in Metal Cleaning and Fin
Parts ishing, Dec. 1931, pages 945-949; Oct. 1932, pages
A substance selected from the group 65 541-546.
consisting of Sodium acetate and po Rogers-Transactions of the Electrochemical
tassium acetate--------------------- 5 to 50 Society, vol. 65, pages 357-360 (1934).
Sodium hydroxide.-------------------- 10 to 55 Promisel-article in Monthly Review of the
Sodium carbonate-------------------- 10 to 40 American Electroplaters' Society, June 1935,
An alkaline phosphate Salt from the class
Consisting of tetrasodium pyrophOS 70 pages 4-19.
Cobbs-article in Soap, Nov. 1938, pages 24,
phate, Sodium metaphosphate, potas 25, 26, and 26A.
sium pyrophosphate, potassium hexa Metal Finishing-Feb. 1944, page 85.
metaphosphate ------------------- 5 to 55