U.S. patent number 3,772,165 [Application Number 05/216,450] was granted by the patent office on 1973-11-13 for method of treating surfaces of steel products.
This patent grant is currently assigned to Nippon Kokan Kabushiki Kaisha. Invention is credited to Naoki Gunji, Hidehisa Yamagishi.
United States Patent |
3,772,165 |
Yamagishi , et al. |
November 13, 1973 |
METHOD OF TREATING SURFACES OF STEEL PRODUCTS
Abstract
Method of treating the surfaces of metal products to provide
protection against corrossive attack, comprising the steps of
treating such metal products anodically in an aqueous electrolyte
consisting of hexavalent chromium ions and borate ions and
thereafter treating said metal products cathodically in an aqueous
electrolyte consisting of hexavalent chromium ions and borate
ions.
Inventors: |
Yamagishi; Hidehisa (Yokohama,
JA), Gunji; Naoki (Tokyo, JA) |
Assignee: |
Nippon Kokan Kabushiki Kaisha
(Tokyo, JA)
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Family
ID: |
13556567 |
Appl.
No.: |
05/216,450 |
Filed: |
January 10, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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775802 |
Nov 14, 1968 |
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Foreign Application Priority Data
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Nov 22, 1967 [JA] |
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42/74761 |
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Current U.S.
Class: |
205/140; 205/141;
205/142; 205/147; 205/217; 205/319 |
Current CPC
Class: |
C25D
11/38 (20130101) |
Current International
Class: |
C25D
11/38 (20060101); C25D 11/00 (20060101); C23b
005/58 (); C23b 011/00 () |
Field of
Search: |
;204/33-34,32,29,141,56,58,41,51,56R,28 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Modern Electroplating by F. A. Lowenheim, 2nd Ed., John Wiley &
Sons Inc., 1963, p. 105..
|
Primary Examiner: Mack; John H.
Assistant Examiner: Andrews; Richard L.
Parent Case Text
This application is a continuation-in-part of application Ser. No.
775,802, filed Nov. 14, 1968 and now abandoned.
Claims
We claim:
1. A method of applying a corrosion-resistant coating to a metal
article which comprises the steps of immersing the article in an
aqueous electrolyte bath consisting essentially of a mixture of
hexavalent chromium ions in a concentration between 3 and 50 grams
per liter and borate ions in a concentration between 5 and 50 grams
per liter, the said electrolyte being maintained at a pH value
between 0 and 6.0, electrolyzing the said article immersed in the
said electrolyte first anodically until the current applied is
between 0.1 and 30 coulombs per square decimeter and then
cathodically until the desired corrosion-resistant coating is
formed.
2. A method of treating metal products as described in claim 1
wherein the hexavalent chromium ions are present in said
electrolyte in a concentration of 3 to 50 g/l.
3. A method of treating metal products as described in claim 1
wherein the concentration range of borate compounds which provide
borate ions in said aqueous electrolyte is between 5 and 50
g/l.
4. A method as defined in claim 1 in which the metal article
consists of a metal strip and the strip is electrolyzed in the bath
by being passed between two counter electrodes that are immersed in
the bath, the first of which serves as an anode and the second of
which serves as a cathode with respect to the strip.
5. A method as defined in claim 1 in which the electrolyte is
maintained at a temperature between 30.degree. and 80.degree.
C.
6. A method of treating metal products according to claim 1 wherein
the electrolyte is maintained at a pH value of from zero to
six.
7. A method as defined in claim 1 in which the current applied
during the cathodic electrolysis is between 1 and 300 coulombs per
square decimeter.
8. A method of treating metal products as described in claim 1,
wherein said metal products are treated anodically by the passage
of between 0.1 and 30 coul/dm.sup.2 and subsequently treated
cathodically by passage of between 1 and 300 coul/dm.sup.2.
9. A method as defined in claim 1 in which the electrolytic bath
contains 20 grams per liter of sodium dichromate (Na.sub.2 Cr.sub.2
O.sub.7.sup.. 2H.sub.2 O) and 25 grams per liter of boric acid
(H.sub.3 BO.sub.3).
10. A process as defined in claim 4 in which the metal article is a
tin-plated steel sheet material.
Description
The present invention relates to a method for treating the surfaces
of steel products, metal plated steel products and non-ferrous
metal products to improve the corrosion resistance properties
thereof in a shorter treatment period.
The method of this invention is of the so-called electrolytic
chromate treatment type of process. A number of patents have been
issued directed to the conventional electrolytic chromate treating
procedures utilizing chromic acid and boric acid including U.S.
Pat. Nos. 2,733,199 and 2,370,592 and Japanese Pat. No.
268,837.
The first two described procedures require more than 10 seconds for
the treatment time making it very difficult to treat metal articles
continuously and quickly for imparting corrosion resistance
thereto. According to the last method, a coating of crystalline
phosphate and gel-like chromate is deposited on a metal surface by
cathodic electrolytic treatment. This coating is converted easily
into a chalk-like film so that it is then very hard to form a
hydrated homogeneous chromium oxide film from the electrolyte
containing phosphoric acid. This has the result that the corrosion
resistance provided by the coating is very poor.
This invention has as its object avoiding the above mentioned
disadvantages.
Another object of this invention is to provide a method for
improving corrosion resistance properties of metal surfaces adapted
to be carried out continuously and rapidly.
These and other objects and advantages of the invention will become
apparent from a consideration of the following disclosure.
In accordance with the invention it has now been found that if a
metal product is anodically treated in an aqueous electrolyte
containing hexavalent chromium ions and borate ions and thereafter
treated cathodically in an aqueous electrolyte containing
hexavalent chromium and borate ions, a stable film is formed on the
metal surface in a shorter treatment time.
A complete understanding of the invention may be had from the
following detailed description and explanation which refer to the
accompanying drawing illustrating the preferred practice. The
drawing shows diagrammatically an apparatus for carrying out the
surface treatment process of the invention.
Illustrative of the preferred hexavalent chromium compounds which
can be used in accordance with the invention, there may be
mentioned chromic acid, alkali metal chromate, ammonium chromate,
alkali metal dichromate, ammonium dichromate and the like.
Among the preferred borate compounds which may be used are boric
acid, boric anhydride, alkali metal borate, ammonium borate and the
like.
The concentration of the hexavalent chromium ions in the
electrolyte can vary within the range of from 3 to 50 g/l. When the
concentration of the hexavalent chromium ions is less than 3 g/l,
the improved and desired properties in the coating film which is
obtained will not be realized. When the concentration exceeds 50
g/l, the hydrated chromium compounds deposited on the metal surface
dissolve easily and a stable and uniform coating does not result.
The concentration of the compound which is converted into borate
ions in the electrolyte may range from 5 to 50 g/l. When the
concentration of the borate compound is less than 5 g/l, the
depositing power for effecting coating of the resultant electrolyte
is poor and the properties of the coating are unsatisfactory.
Further, when the concentration of the borate compound exceeds 50
g/l, the borate compound does not dissolve easily in the
electrolyte and is easily separated out therefrom.
A further important aspect of the process of the invention is that
the metal surface is first subjected to treatment anodically in the
electrolyte containing the hexavalent chromium and borate ion and
thereafter is cathodically treated in the same electrolyte. If the
metal surface is treated using only one of the steps, i.e., anodic
or cathodic treatment steps or if the metal surface is subjected to
cathodic treatment first, that is if the anodic treatment is
carried out following the cathodic treatment, the improved
properties resulting from the high coating power, high current
efficiency and high corrosion resistance are not obtained.
Moreover, it has been found by experiment that only by a process in
which the metal surface is treated cathodically directly after the
anodic treatment is there obtained a clear coating on the metal
surface. More particularly the experiments have established that
the anodic treatment step removes oxide and any other contaminants
from the metal surface being treated and only then is the improved
coating formed by the cathodic treatment step. Further it has been
found from the experimental data that a coating formed from the
electrolyte at about room temperature tends to be non-uniform and
is only poorly structured so that it is necessary to heat the
electrolyte in order to avoid such difficulties. However, if the
electrolyte is heated to a temperature in excess of 80.degree. C,
the loss of electrolyte by evaporation becomes quite marked and is
not desirable from an economical point of view. Generally speaking
in the electrolytic chromate treatment with the use of increasing
temperatures, the electrical current efficiency of the electrolyte
and the corrosion resistance properties of the coating are
decreased. It has been found that the temperature of the treating
electrolyte is most advantageously maintained at about 30.degree.
to 80.degree. C and preferably at between 40.degree. and 50.degree.
C.
The pH range to be maintained in the electrolyte varies according
to the type of metal to be treated. Generally a pH of from zero to
six is used. In the case of steel surfaces, pH values at the lower
end of the range and desirable. However, in the case of aluminum,
zinc and tin surfaces, if the pH of the electrolyte as used is too
low, the metal surface will undergo dissolution and there is the
danger of resultant impairment of the properties of the surface, so
that in this instance, higher pH values are desirable. The pH value
of the electrolyte can be regulated and maintained by addition of
an alkali metal hydroxide or chromic acid as indicated.
The current density and treating period are interrelated both being
dependent one on the other. Thus when a metal surface is treated at
high speed, a high current density and a shorter treating period
should be utilized. In treating a metal surface by the method of
this invention, it is easy to select proper current densities by
considering the treatment period involved. The preferred anode
treating current amounts to between 0.1 coul/dm.sup.2 and 30
coul/dm.sup.2. It is advantageous to select a suitable current
density according to the type of metal and the other treating
conditions. The cathodic treatment follows the anodic treatment
step and the cathodic current density in the second step amounts to
between 1 coul/dm.sup.2 and 300 coul/dm.sup.2. The current density
selected should take into consideration the type of metal involved,
the anodic treating current which has been used and the other
treatment conditions. The treatment times for the aforesaid current
ranges generally amounts to between 0.2 seconds and 10 seconds for
each treatment step, although of course in selecting the treatment
time, consideration must be given to the speed at which the metal
article is moving through the apparatus.
In order to show the criticality of the two treatment steps and
namely a preliminary anodic treatment step followed by a cathodic
treatment step, samples of tin-plates steel were subjected to
cathodic treatment alone and to a combination of both anodic and
cathodic treatments. The results and details of such treatment are
set out in the Table which follows:
Comparing electrochemical coating of tin plated steel in one and
two steps ##SPC1##
A tin plated steel was heated in air at a temperature of
200+3.degree. C for one hour, the tin oxide formed in such a time
cathodically electrolyzed for reduction in an HBr aqueous solution,
and the amount of the oxidized film determined.
B tin plated steel was immersed in 5 percent Na.sub.2 S.9H.sub.2 O
at a temperature of 40.degree. C for one hour and the sulfide
staining discoloration evaluated as falling into one of 11 classes
of from zero (no staining) to 10 (heavy staining).
Comparison of the results set out in the Table shows that much
better corrosion resistance is achieved when an anodic treatment
preceeds the cathodic treatment. Moreover, the comparison clearly
establishes that the addition of boric acid to the chromate
solution is by itself not sufficient to produce a satisfactory film
and that for full protection, the preceeding anodic treatment is
required. Although the entries would appear to indicate that some
degree of protection can be obtained without the use of boric acid
it should be noted that the film produced by the treatment without
using the same was more than four times as thick as that produced
in the treatment in accordance with the invention where the same
was used.
In order to further emphasize the importance of the presence of the
borate ions in the electrolyte in the process of the invention a
further series of Experiments was carried out.
A basic electrolyte solution containing only chromate ions was
prepared which was modified as hereinafter indicated and tin plated
steel strips then subjected to both anodic and cathodic treatment
as follows:
Main agent : Na.sub.2 Cr.sub.2 O.sub.7.sup.. 2H.sub.2 O 20 g/l Bath
temperature : 50.degree.C Cathodic current density : 4.0A/dm.sup.2
Anodic current density : 0.2A/dm.sup.2 Cathodic treating time : 1
sec. Anodic treating time : 1 sec.
The data and results can be seen from the Table set out on the
following page: ##SPC2##
The above Table clearly shows that when both an anodic and cathodic
treatment was carried out, the appearance was not markedly affected
by the presence or absence of the borate ions. However, when both
steps and the sequence thereof were followed, the presence of the
borate ions had a considerable effect on the resistance to sulfur
staining and oxidation.
A more complete understanding of the invention may be obtained from
the following detailed description and explanation which refer to
the accompanying Drawing illustrating the preferred practice. The
Drawing shows diagrammatically the two steps of the invention and
apparatus used for performing it.
Referring in detail to the Drawing, the reference numeral 1
designates an electrolytic cell containing electrolyte 2. The cell
is fitted with conductor rolls 3 mounted above deflector rolls 4
for guiding the steel strip 5 which is fed in the direction shown
by the arrow. The conductor rolls 3 lead the strip to the deflector
rolls 4 and into the cell 1, drawing it off therefrom. At the point
where the strip 5 is dipped into the electrolyte 2, insoluble
electrode plates 6 are installed as counter electrodes. On the down
pass side, the counter electrodes are made the cathode with respect
to the strip 5 which then serves as the anode and on the up pass
side, the counter electrodes constitute the anode with respect to
the strip 5 which now serves as the cathode. The counter electrodes
therefore serve as cathode and anode with respect to the strip 5
and are arranged respectively on both sides of the strip in the
electrolyte so that the strip passes therebetween and is treated
first anodically and then cathodically in a continuous manner. The
periods of anodic treatment and cathodic treatment may be freely
regulated by shortening or lengthening the length of the counter
electrodes and by use of auxiliary cells arranged prior to or after
the cell 1.
The following Examples serve to illustrate the invention but are in
nowise to be construed as limiting the scope thereof.
Example 1
A previously degreased and pickled steel strip was treated under
the following conditions:
Chromic acid 50 g/l Borax 30 g/l Treating temperature 50 .degree.C
Anodic treating current density 10 A/dm .sup.2 Anodic treating time
1 sec. Cathodic treating current density 20 A/dm .sup.2 Cathodic
treating time 4 sec.
The coating film obtained was blue-yellow in color. The thusly
treated steel was exposed for 6 hours to the conditions of the JIS
Z-2371 salt spray test. On examination, it was found that the steel
sheet was free of ferric rust while an untreated steel sheet
exposed to the same conditions showed ferric rust over
substantially the entire surface thereof after 5 minutes of
exposure. Phosphate treated steel evidenced ferric rust formation
after only about 30 minutes of exposure. A previously degreased and
pickled steel strip was then treated in the same electrolyte under
the following conditions:
Cathodic current density 20 A/dm .sup.2 Treating time 4 sec.
The coating film thereby obtained, i.e., by cathodic treatment
alone was blue-yellow and showed evidence of ferric rust after only
3 hours of exposure.
Example 2
An aluminum plated steel strip was treated under the following
conditions:
Chromic acid 50 g/l Boric acid 40 g/l Treating temperature 40
.degree.C Anodic treating current density 0.5 A/dm .sup.2 Anodic
treating time 1 sec. Cathodic treating current density 20 A/dm
.sup.2 Cathodic treating time 6 sec.
The coated film thusly obtained was grey-white and after exposure
for 120 hours to salt spray in accordance with the test procedure
of JIS Z-2371 did not show any white rust formation while an
untreated aluminum plated sheet showed white rust after only 2
hours of exposure.
Example 3
A galvanized sheet strip was treated under the following
conditions:
Sodium dichromate 20 g/l Borax 20 g/l pH adjusted to 4.0 by adding
chromic acid Anodic treating current density 0.2 A/dm .sup.2 Anodic
treating time 1 sec. Cathodic treating current density 6 A/dm
.sup.2 Cathodic treating time 2 sec.
The coated film which was obtained was clear and after treatment
and exposure for 24 hours to salt spray (JIS Z-2371) still did not
show any white rust while an untreated galvanized sheet showed
white rust after only 1 hour of exposure.
Example 4
A tin plated strip (No. 25) was treated under the following
conditions:
Sodium chromate 20 g/l pH adjusted to 2.5 by adding of chromic acid
Anodic treating current density 0.7 A/dm .sup.2 Anodic treating
time 1 sec. Cathodic treating current density 4 A/dm .sup.2
Cathodic treating time 1 sec.
The coated film thereby obtained was colorless and clear. After the
treated tin plate had been exposed for 6 hours in a humidity
cabinet under conditions of 100 percent relative humidity and a
temperature of 50.degree. C, it did not show any evidence of ferric
rusting while an untreated tin plate (No. 25) showed ferric rust
after only 30 minutes of exposure.
As has been set out above, according to the instant invention,
highly corrosion resistant tin plate is obtained. Moreover, the tin
plate as treated in accordance with the invention is highly
resistant to oxidation and sulfide staining. The oxidation
resistant properties are evidenced in that a tin plate treated in
the foregoing process has an oxide film value of about 0.1
mcoul/cm.sup.2 when the oxide value is determined after 3 months of
storage at room temperature and measured by a coulometric reduction
procedure while a conventionally treated tin plate has a value of 3
mcoul/cm.sup.2 under the same conditions.
Cans manufactured in the conventional manner from the tin plate
produced in accordance with the above Example were packed with
boiled mackeral and stored at approximately 50.degree. C. After one
month's storage the cans did not show any sulfide staining and the
rating number for the staining amounted to zero when measured under
a scale of discoloration calculated on the basis of 11 stages, zero
representing no staining and 10 heavy staining. Cans manufactured
from the conventional tin plate had rating values of seven under
the same conditions.
The tin plate strip was also treated in the same electrolyte under
the following conditions:
Cathodic current density 4 A/dm .sup.2 Treating time 1 sec.
The coated films thereby obtained using cathodic treatment alone
was colorless and clear and the treated tin plate showed ferric
rust after 2 hours in the humidity cabinet test under conditions of
100 percent humidity and a temperature of 50.degree. C. the sheets
had an oxide film value of 2.5 mcoul/cm.sup.2 after 3 months of
storage at room temperature. Cans prepared from this cathodic
treated tin plate had a rating of six in the sulfur staining test
after one month of storage under the conditions as set out
above.
According to the invention the metal surface treatment is carried
out in a very short period of time and results in uniform hydrated
chromium films whereby there is realized a markedly improved
corrosion resistance. It is further evident that the oxidation
resistance properties and sulfide staining discoloration resistance
properties which are required in connection with plate used as
canning materials are substantially improved making the instant
invention for treating metal surfaces a considerable contribution
to the industry.
* * * * *