U.S. patent number 3,860,438 [Application Number 05/449,805] was granted by the patent office on 1975-01-14 for flux and method of coating ferrous article.
This patent grant is currently assigned to Bethlehem Steel Corporation. Invention is credited to Carlyle E. Shoemaker.
United States Patent |
3,860,438 |
Shoemaker |
January 14, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
FLUX AND METHOD OF COATING FERROUS ARTICLE
Abstract
This invention relates to the process of coating ferrous
articles by the molten metal immersion method, more particularly to
the provision of an aqueous flux applied to said article prior to
the metal coating thereof. Specifically, the process includes
cleaning the ferrous article, wetting the surfaces with an aqueous
flux consisting essentially of potassium fluosilicate, hydrofluoric
acid, potassium fluoride and optionally zinc chloride, drying said
flux on the surface, immersing said article in a molten metal bath
consisting essentially of at least 25% by weight aluminum, balance
essentially zinc, and after removal from the bath, shaking off
excess metal and cooling to yield a ferrous article having a
continuous, adherent and uniform layer of said aluminum-zinc
alloy.
Inventors: |
Shoemaker; Carlyle E.
(Bethlehem, PA) |
Assignee: |
Bethlehem Steel Corporation
(Bethlehem, PA)
|
Family
ID: |
23785563 |
Appl.
No.: |
05/449,805 |
Filed: |
March 11, 1974 |
Current U.S.
Class: |
427/310; 148/23;
427/433; 427/321 |
Current CPC
Class: |
C23C
2/30 (20130101); C23C 2/06 (20130101); C23C
2/12 (20130101) |
Current International
Class: |
C23C
2/04 (20060101); C23C 2/06 (20060101); C23C
2/12 (20060101); C23C 2/30 (20060101); C23c
001/08 (); C23f 017/00 () |
Field of
Search: |
;117/50,51,114A,114C,52
;148/23 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weiffenbach; Cameron K.
Assistant Examiner: Smith; John D.
Attorney, Agent or Firm: Noll; William B. O'Keefe; Joseph
J.
Claims
I claim:
1. A method of forming a continuous alloy coating consisting of
from 25% to about 70%, by weight aluminum, balance essentially
zinc, on a ferrous article, comprising the steps of cleaning said
ferrous article to remove grease and oxides from the surfaces
thereof to be coated, immersing said article in an aqueous flux
consisting essentially of potassium fluosilicate, potassium
fluoride, zinc chloride, and an acid selected from the group
consisting of hydrofluoric acid and a mixture of hydrofluoric acid
and hydrochloric acid, removing said article from the aqueous flux,
drying said article by heating to a low temperature, and immersing
the article in a molten bath containing said aluminum - zinc
coating alloy.
2. The method according to claim 1 wherein said aqueous flux, per
100 mls, comprises 3 to 40 gms. potassium fluosilicate, 2.6 to 9.0
gms. potassium fluoride, 3 to 50 mls. hydrofluoric acid, up to 5
gms. zinc chloride, balance water.
3. The method according to claim 2 wherein said acid is a mixture
of hydrochloric acid and hydrofluoric acid, the quantity of the
hydrochloric acid does not exceed 30% of the hydrofluoric acid.
4. The method according to claim 2 wherein said aqueous flux, per
100 mls., comprises 7 to 13 gms. potassium fluosilicate, 3 to 7
gms. potassium fluoride, 5 to 11 mls. hydrofluoric acid, 1 to 3
gms. zinc chloride, balance water.
5. The method according to claim 4 wherein said acid is a mixture
of hydrochloric acid and hydrofluoric acid, the quantity of the
hydrochloric acid does not exceed 30% of the hydrofluoric acid.
6. The method according to claim 1 wherein said aqueous flux, per
100 mls, comprises 7 to 13 gms. potassium fluosilicate, 3 to 7 gms.
potassium fluoride, 5 to 11 mls. hydrofluoric acid, balance
water.
7. A flux for the treatment of a ferrous article prior to its
immersion in a molten bath containing an aluminum-zinc alloy,
comprising an aqueous acidic solution consisting essentially of
potassium fluosilicate, potassium fluoride, fluoride chloride, and
an acid selected from the group consisting of hydrofluoric acid and
a mixture of hydrofluoric acid and hydrochloric acid.
8. The flux according to claim 7 wherein said aqueous acidic
solution, per 100 mls, comprises 3 to 40 gms. potassium
fluosilicate, 2.6 to 9.0 gms. potassium fluoride, 3 to 50 mls.
hydrofluoric acid, up to 5 jms. zinc chloride, balance water.
9. The flux according to claim 8 wherein said acid is a mixture of
hydrochloric acid and hydrofluoric acid, the quantity of the
hydrochloric acid does not exceed 30% of the hydrofluoric acid.
10. The flux according to claim 8 wherein said aqueous acidic
solution, per 100 mls, comprises 7 to 13 gms. potassium
fluosilicate, 3 to 7 gms. potassium fluoride, 5 to 11 mls.
hydrofluoric acid, 1 to 3 gms. zinc chloride, balance water.
11. The flux according to claim 10 wherein said acid is a mixture
of hydrochloric acid and hydrofluoric acid, the quantity of the
hydrochloric acid does not exceed 30% of the hydrofluoric acid.
12. The flux according to claim 14 wherein said aqueous acidic
solution, per 100 mls, comprises 7 to 13 gms. potassium
fluosilicate, 3 to 17 gms. potassium fluoride, 5 to 11 mls.
hydrofluoric acid, balance water.
13. A method of forming a continuous alloy coating consisting of
from 25% to about 70%, by weight aluminum, balance essentially
zinc, on a ferrous aritcle, comprising the steps of cleaning said
ferrous article to remove grease and oxides from the surfaces
thereof to be coated, immersing said article in an aqueous flux
consisting essentially of potassium fluosilicate, potassium
fluoride and an acid selected from the group consisting of
hydrofluoric acid and a mixture of hydrofluoric acid and
hydrochloric acid removing said article from the aqueous flux,
drying said article by heating to a low temperature, and immersing
the article in a molten bath containing said aluminum-zinc coating
alloy.
14. A flux for the treatment of a ferrous article prior to its
immersion in a molten bath containing an aluminum-zinc alloy,
comprising an aqueous acidic solution consisting essentially of
potassium fluosilicate potassium fluoride and an acid selected from
the group consisting of hydrofluoric acid and a mixture of
hydrofluoric acid and hydrochloric acid.
Description
CROSS-REFERENCES TO RELATED APPLICATION
This application is related to and represents an improvement over
the invention disclosed and claimed in copending application, Ser.
No. 275,610, now U.S. Pat. No. 3,806,356 by the inventor herein and
assigned to the same assignee.
BACKGROUND OF THE INVENTION
This invention is directed to the concept of coating ferrous metal
articles, by the hot metal immersion method, to enhance the
article's appearance and resistance to corrosion. To effect such
results, a continuous, adherent and uniform layer of a corrosion
resistant material on the ferrous article is essential. The prior
art using various combinations of salts and acid has met with
reasonable success in galvanizing and aluminumizing processes.
Typically, the ferrous article to be coated has to be cleaned of
grease and scale (oxides of iron) prior to the application of the
metallic coating. In a continuous strand operation, i.e., strip or
wire, the material preferably is cleaned and then bathed in an
oxide reducing atmosphere, and without exposing it to the
atmosphere is immediately immersed in a molten metal bath
containing the coating metal. For batch operations, particularly
for large structural members, atmospheric exclusion is virtually
impossible. Accordingly, fluxes for protecting the cleaned surfaces
had to be found. Generally, the procedure is to apply a thin flux
coating following the cleaning, and then, after drying, to immerse
the flux coated ferrous article into the molten metal bath.
Naturally, the nature of the fluxing composition is important to
its effect on the ferrous base, for its ability to provide a proper
surface for the reception of a metal coating, which is both
continuous and adherent. Thus there is a relationship between the
flux and coating metal.
While the prior art has made significant contributions in the area
of galvanizing and aluminizing, the previous fluxes have not been
totally satisfactory for preparing ferrous surfaces for the
reception of an aluminum-zinc coating. It was not until the
development of the fluosilicic acid containing fluxes, the subject
matter of said copending application, that an effective means was
found to prepare the surface of a ferrous article for subsequent
coating by an aluminum-zinc alloy.
The potassium fluosilicate containing flux of the present invention
represents an improvement over said fluosilicic acid flux, which
improvements will be detailed in the discussion to follow.
SUMMARY OF THE INVENTION
This invention relates to the process of coating ferrous articles
by the molten metal immersion method, more particularly to the
provision of a suitable aqueous flux consisting essentially of
potassium fluosilicate, hydrofluoric acid, potassium fluoride and
optionally zinc chloride, for applying to the surfaces of the
ferrous article prior to the metal coating thereon. In its
preferred embodiment, said process includes cleaning the ferrous
surfaces to remove grease, etc., pickling to remove scale, dipping
directly into a flux bath consisting essentially of 3 to 40 gms/100
mls. potassium fluosilicate, 2.6 to 9.0 gms/100 mls. potassium
fluoride, 3 to 50 mls/100 mls. (50%) hydrofluoric acid, and up to 5
gms/100 mls. zinc chloride, drying the flux in situ, and immersing
the flux coated ferrous article in a molten metal bath of at least
25% by weight aluminum, balance essentially zinc. Upon withdrawal
from the molten bath, and removal of excess metal, such as by
bumping, the metallic coating solidifies to produce a ferrous
article having a continuous, adherent and uniform coating of an
aluminum-zinc alloy.
BRIEF DESCRIPTION OF DRAWING
FIG. 1 is a flow sheet illustrating the preferred sequence of steps
followed in carrying out the process of this invention.
FIG. 2 is a plot of the amount of flux deposited on a cleaned and
oxide-free ferrous article, at various withdrawal rates from two
different fluxes, where the flux solutions are a fluosilicic acid
flux and the flux of this invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
Turning now to a more detailed review of the invention, as set
forth in the illustrated flow sheet of FIG. 1, it will be seen that
the present invention provides an improved hot metal immersion
coating procedure yielding a ferrous article having a continuous,
adherent and more uniform coating of an aluminum-zinc alloy
thereon.
The coating method generally comprising wetting the cleaned
scale-free ferrous article with an aqueous solution consisting
essentially of potassium fluosilicate, hydrofluoric acid, potassium
fluoride and optionally zinc chloride.
A preferred and optimum range for each of the flux ingredients is
listed below; however, it is contemplated that the preferred range
may be modified to the extent as shown in the optimum range, by one
or more of the components listed:
Preferred Range Optimum Range per 100 mls. per 100 mls.
______________________________________ K.sub.2 SiF.sub.6 3-40 gms.
7-13 gms. KF 2.60-9.0 gms. 3-7 gms. HF(50%) 3-50 mls. 5-11 mls.
ZnCl.sub.2 0-5 gms. 1-3 gms. Water Bal. Bal.
______________________________________
Following the wetting of the ferrous article to be coated, such as
by dipping or immersion in the aqueous flux, the ferrous article is
dried such as by heating to a low temperature of up to about
400.degree. F. to remove all signs of dampness. This is important,
especially from a safety standpoint, to avoid splashing during
immersion of the flux coated ferrous article into the molten
coating metal. At this juncture note the date illustrated in FIG.
2. Such data indicate one of the advantages of the fluxx of this
invention over that disclosed in said copending application.
The function of the flux is to protect the surface of the ferrous
article to be coated and to prepare it for the reception of the
molten metal coating. However, retention of too much flux on the
surface of the ferrous article may result in the appearance of
drain lines showing through the metal coating. This is caused by
irregular drainage of the flux. Another problem may arise when
relatively large amounts of a flux are applied from a thickened
flux solution. Excessive surface scum may develop on the surface of
the bath and coated part. These were the types of problems observed
with the fluosilicic acid fluxes of said copending application.
These difficulties have now been overcome with the flux of the
present invention.
In any case, with the flux coated ferrous article sufficiently
drained and dried, it is then immersed for from 1-5 minutes
depending on the thickness of the piece being coated and the
coating weight desired, in a molten metal bath containing at least
25% by weight, aluminum, preferably up to about 70%, balance
essentially zinc. After removal, excess coating metal is removed,
such as bumping or agitating the coated ferrous article, where it
may be cooled by air or water quenching. The resulting product
exhibits a continuous, adherent and uniform alloy coating on the
processed ferrous article, which article is free of flux drain
lines.
At this juncture, it should be made clear that as used herein, the
term "article" is intended to include strip and wire (treated in a
continuous manner), and shapes, such as structural members treated
in a batch process. Actually, the greatest benefits from this
invention are realized in the batch treatment of ferrous shapes,
such as large structural steel members used in the construction
industry. Though not limiting, the further description and
exemplary showings shall be directed to batch operations.
By way of a specific embodiment, a low-alloy steel was cleaned to
reveal a surface free of oxide and grease. Said steel was then
immersed for about one-half second in an aqueous flux whose
formulation is as follows:
Ingredient per 100 mls. % by weight
______________________________________ K.sub.2 SiF.sub.6 10 gms.
9.1 KF 5 gms. 4.55 HF(50%) 8 mls. 4.2 ZnCl.sub.2 2 gms. 1.8 Water
bal. bal. ______________________________________
After drainage and drying, the steel had a thin smooth flux coating
on the order of 0.004 gms/in.sup.2 or 0.062 gms/dm.sup.2. The dry
flux coated steel was then immersed in a molten metal bath
consisting essentially of, by weight, 55% aluminum, 1.5% silicon,
balance zinc, for approximately 21/2 minutes. After withdrawal and
bumping to remove excessive coating metal, the aluminum-zinc coated
steel was cooled in air exhibiting a product having a relatively
smooth, continuous and adherent alloy coating. Further, the product
was free of a flux drain line pattern.
As indicated previously, one of the most important advantages of
the flux of this invention is that it is not as thick as the
fluosilicic acid containing flux of said copending application. As
a consequence, smaller amounts are deposited and retained on the
surface of the ferrous article at comparable withdrawal rates. The
difference is even more significant at faster withdrawal rates, see
FIG. 2. The respective formulations for the two fluxes illustrated
in FIG. 2 are given below in quantity/100 msl.
______________________________________ H.sub.2 SiF.sub.6 Flux
Invention Flux ______________________________________ H.sub.2
SiF.sub.6 15 mls. K.sub.2 SiF.sub.6 9.4 gms HF(50%) 7 mls. HF 12
mls. KF 10 gms. KF 5.2 gms. ZnCl.sub.2 2 gms. ZnCl.sub.2 2 gms.
Specific Specific Gravity 1.12 Gravity 1.1
______________________________________
Since the foregoing formulations and the composition ranges noted
earlier represent only preferred embodiments of this invention, it
is contemplated that variations may be effected herein by those
skilled in the art, particularly after reading these
specifications. For example, it may be desirable from a cost
standpoint to further minimize the amount of potassium fluoride as
this is the most expensive ingredient. Further, the potassium
fluoride should be present in an amount less than the potassium
fluosilicate to minimize bare spots.
Part of the hydrofluoric acid can be replaced by hydrochloric acid
but at some sacrifice in quality, i.e., coverage. Thus, it is
preferred that HCl be present in an amount no greater than 30% of
the HF. Finally, some attention should be given to the K.sub.2
SiF.sub.6 as it represents the key ingredient in the successful use
of the flux of this invention. Since K.sub.2 SiF.sub.6 is only
partially soluble, it must be kept suspended by stirring or
agitation of the flux solution. Any attempt to substitute or
replace the key ingredient with another alkali metal fluosilicate,
such as Na.sub.2 SiF.sub.6 which is much less soluble then K.sub.2
SiF6would result in an unsuitable flux solution. That is, the more
insoluble components that are present in the solution, the greater
the problems. Thus, as changes or variations are readily
contemplated, no limitation is intended to be imposed herein except
as set forth in the appended claims.
* * * * *