U.S. patent number 3,630,792 [Application Number 04/819,930] was granted by the patent office on 1971-12-28 for process for the production of colored coatings.
This patent grant is currently assigned to Cominco Ltd.. Invention is credited to Gerald Perley Lewis, Robert William Smyth.
United States Patent |
3,630,792 |
Smyth , et al. |
* December 28, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS FOR THE PRODUCTION OF COLORED COATINGS
Abstract
A process for the production of colored surfaces on zinc, tin
and lead-tin coatings by the provision of oxide films having light
interference effects; zinc, tin and lead-tin alloys for use in the
process; and alloy coating compositions and colored articles
produced thereby. A molten alloy of zinc, tin or lead-tin with a
minor amount of an oxygen-avid element such as titanium, manganese
or vanadium is oxidized by exposure to a free oxygen-containing gas
under controlled time and temperature conditions for the provision
of a surface film of an oxide of the oxygen-avid addition element
having light interference color characteristics.
Inventors: |
Smyth; Robert William
(Oakville, Ontario, CA), Lewis; Gerald Perley
(Streetsville, Ontario, CA) |
Assignee: |
Cominco Ltd. (Montreal, Quebec,
CA)
|
[*] Notice: |
The portion of the term of this patent
subsequent to September 22, 1987 has been disclaimed. |
Family
ID: |
25229470 |
Appl.
No.: |
04/819,930 |
Filed: |
April 28, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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574684 |
Aug 24, 1966 |
3530023 |
|
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Current U.S.
Class: |
428/629; 148/281;
148/282; 148/284; 148/285; 427/433; 428/336; 428/472.1 |
Current CPC
Class: |
C22C
18/00 (20130101); C23C 2/06 (20130101); C22C
20/00 (20130101); Y10T 428/265 (20150115); Y10T
428/1259 (20150115) |
Current International
Class: |
C23C
2/06 (20060101); C22C 20/00 (20060101); C22C
18/00 (20060101); C23f 007/02 () |
Field of
Search: |
;148/6.3 ;75/178.1
;117/114A,114B |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
International Lead Zinc Research Organization Digest -12 pp. 39-40
Oct. 1, 1963.
|
Primary Examiner: Kendall; Ralph S.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application, Ser. No.
574,684, filed Aug. 24, 1966 now U.S. Pat. No. 3,530,013.
Claims
What we claim as new and desire to protect by Letters Patent of the
United States is:
1. A process for the production of a colored surface which
comprises melting a metal selected from the group consisting of
zinc, tin and lead-tin having an oxygen-avid element effective to
produce an oxide film having discernible light interference color
effects alloyed therewith to form a molten surface, the alloy so
formed having less than about 0.002 percent by weight aluminum and
less than about 0.006 percent by weight magnesium, contacting said
molten metal surface with a free-oxygen-containing gas for a time
sufficient to provide thereon an oxide film and a reflective
surface intermediate said oxide film and said alloy having said
color effects, and solidifying said molten surface provided with
said oxide film and said reflective surface.
2. A process for the production of a colored surface as claimed in
claim 1 comprising the steps of applying a metal selected from said
group consisting of zinc, tin and lead-tin having a said
oxygen-avid element alloyed therewith to an article to form a
molten coating thereon, and contacting said molten coating with a
free-oxygen-containing gas for a time sufficient to provide an
oxide film and a reflective surface intermediate said oxide film
and the alloy having said color effects, and solidifying said
molten coating provided with said oxide film and said reflective
surface.
3. In a process as claimed in claim 2, said oxygen-avid element
being selected from the group consisting of titanium, manganese and
vanadium.
4. A process for the production of a colored coating on a surface
comprising the steps of applying zinc having an oxygen-avid
element, selected from the group consisting of titanium, manganese,
vanadium, columbium, zirconium, thorium, mischmetal, cadmium,
arsenic, copper, lead and chromium and effective to produce an
oxide film having discernible light interference color effects,
alloyed therewith to said surface to form an adherent molten
coating thereon, the alloy so formed having less than about 0.002
percent by weight aluminum and less than about 0.006 percent by
weight magnesium, reacting said molten coating with an
oxygen-containing atmosphere for a time sufficient to form thereon
a film of an oxide of said alloying element and a reflective
surface intermediate said oxide film and the alloy having said
color effects, and solidifying said molten coating provided with
said oxide film and said reflective surface.
5. A process for the production of a colored coating as claimed in
claim 4 in which said surface is a metal surface.
6. A process for the production of a colored coating as claimed in
claim 4 on a surface comprising the steps of forming a bath of said
zinc alloy and applying the zinc alloy to said surface by immersing
the surface in said bath to form an adherent molten coating
thereon.
7. In a process as claimed in claim 5, said oxygen-avid element
being selected from the group consisting of titanium, manganese,
vanadium, columbium, zirconium, thorium and mischmetal.
8. In a process as claimed in claim 6, said oxygen-avid element
being selected from the group consisting of titanium, manganese,
vanadium, columbium, zirconium, thorium and mischmetal.
9. In a process as claimed in claim 7, contacting the molten zinc
alloy coating with air for the provision of a film of an oxide of
said alloying element.
10. In a process as claimed in claim 8, contacting the molten zinc
alloy coating with air for the provision of a film of an oxide of
said alloying element.
11. In a process as claimed in claim 7, cooling the molten zinc
alloy coating in air for the provision of a film of an oxide of
said alloying element.
12. In a process as claimed in claim 8, cooling the molten zinc
alloy coating in air for the provision of a film of an oxide of
said alloying element.
13. In a process as claimed in claim 5, said oxygen-avid element
being selected from the group consisting of cadmium, arsenic,
copper, lead and chromium.
14. In a process as claimed in claim 13, contacting the molten zinc
alloy coating with air for the provision of a film of an oxide of
said alloying element.
15. In a process as claimed in claim 13, cooling the molten zinc
alloy coating in air for the provision of a film of an oxide of
said alloying element.
16. In a process as claimed in claim 6, said oxygen-avid element
being selected from the group consisting of cadmium, arsenic,
copper, lead and chromium.
17. In a process as claimed in claim 16, contacting the molten zinc
alloy coating with air for the provision of a film of an oxide of
said alloying element.
18. In a process as claimed in claim 16, cooling the molten zinc
alloy coating in air for the provision of a film of an oxide of
said alloying element.
19. In a process for the production of a colored coating on a
surface as claimed in claim 4, said zinc alloy consisting
essentially of zinc with at least about 0.02 percent by weight
manganese, and said molten coating being contacted with a
free-oxygen-containing gas for the formation of a manganese oxide
film thereon having light-interference color effects.
20. In a process as claimed in claim 19, forming a bath of said
zinc alloy and applying the zinc alloy to said surface by dipping
said surface in said bath.
21. In a process as claimed in claim 20, said bath having at least
about 0.07 percent by weight manganese.
22. In a process for the production of a colored coating on a
surface as claimed in claim 4, said zinc alloy consisting
essentially of zinc with at least about 0.001 percent by weight
titanium, and said molten coating being contacted with a
free-oxygen-containing gas for the formation of a titanium oxide
film thereon having light-interference color effects.
23. In a process as claimed in claim 22, forming a bath of said
zinc alloy and applying said zinc alloy to the surface by dipping
said surface therein.
24. In a process as claimed in claim 23, said bath having at least
about 0.008 percent by weight titanium.
25. In a process for the production of a colored coating on a
surface as claimed in claim 4, said zinc alloy consisting
essentially of zinc with at least about 0.001 percent by weight
vanadium, and said molten coating being contacted with a
free-oxygen-containing gas for the formation of a vanadium oxide
film thereon having light-interference color effects.
26. In a process as claimed in claim 25, forming a bath of said
zinc alloy and applying the molten zinc alloy to the surface by
dipping said surface in said bath.
27. In a process as claimed in claim 26, said bath having at least
about 0.075 percent by weight vanadium.
28. In a process as claimed in claim 5, said oxygen-avid element
being selected from the group consisting of manganese, titanium and
vanadium in amount of from about 0.1 percent by weight to about the
respective eutectic composition.
29. In a process as claimed in claim 5, said oxygen-avid element
being selected from the group consisting of manganese, titanium and
vanadium in amount of from about 0.1 percent by weight to about the
solubility limit of the respective element at the bath
temperature.
30. In a process as claimed in claim 19, contacting said molten
coating with air and concurrently cooling said coating at a
controlled rate for obtaining a desired oxide film color.
31. In a process as claimed in claim 22, contacting said molten
coating with air and concurrently cooling said coating at a
controlled rate for obtaining a desired oxide film color.
32. In a process as claimed in claim 25, contacting said molten
coating with air and concurrently cooling said coating at a
controlled rate for obtaining a desired oxide film color.
33. In a process as claimed in claim 30, said surface being
steel.
34. In a process as claimed in claim 31, said surface being
steel.
35. In a process as claimed in claim 32, said surface being
steel.
36. A composition of matter in the form of a coating on an article,
said coating having a colored surface, said composition consisting
essentially of an alloy of zinc and an element selected from the
group consisting of titanium, manganese, vanadium, columbium,
zirconium, thorium, and mischmetal, a film of an oxide of said
alloying element formed on the surface of said alloy and a
reflective surface formed on said alloy intermediate said oxide
film and said alloy, said alloy having less than about 0.002
percent by weight aluminum and less than about 0.006 percent by
weight magnesium.
37. A composition of matter as claimed in claim 36 having less than
0.0005 percent by weight aluminum.
38. A composition of matter in the form of a coating on an article,
said coating having a colored surface, said composition consisting
essentially of a zinc base alloy formed from a melt of zinc
containing from about 0.0001 percent to about 0.45 percent by
weight titanium, a titanium oxide film formed on a surface of the
said zinc base alloy, and a reflective surface formed on said alloy
intermediate said oxide film and said alloy, said zinc base alloy
having less than about 0.002 percent and weight aluminum and less
than about 0.006 percent by weight magnesium.
39. In a composition of matter as claimed in claim 38, said zinc
base alloy and oxide film together having not less than 0.008
percent by weight titanium and having less than 0.0005 percent by
weight aluminum.
40. In a composition of matter as claimed in claim 39, a titanium
oxide being essentially in the form of rutile.
41. In a composition of matter as claimed in claim 39, a titanium
oxide being essentially in the form of anatase.
42. A composition of matter in the form of a coating on an article,
said coating having a colored surface, said composition consisting
essentially of a zinc base alloy formed from a melt of zinc
containing from about 0.02 percent to about 0.45 percent by weight
manganese, a manganese oxide film formed on a surface of the said
zinc base alloy, and a reflective surface formed on said alloy
intermediate said oxide film and said alloy, said alloy having less
than about 0.002 percent by weight aluminum and less than about
0.006 percent by weight magnesium.
43. In a composition of matter as claimed in claim 42, said zinc
base alloy and oxide film together having not less than 0.07
percent by weight manganese and having less than 0.0005 percent by
weight aluminum.
44. A composition of matter in the form of a coating on an article,
said coating having a colored surface, said composition consisting
essentially of a zinc base alloy formed from a melt of zinc
containing from about 0.001 percent to about 0.15 percent by weight
vanadium, a vanadium oxide film formed on a surface of the said
zinc base alloy, and a reflective surface formed on said alloy
intermediate said oxide film and said alloy, said alloy having less
than about 0.002 percent by weight aluminum and less than about
0.006 percent by weight magnesium.
45. In a composition of matter as claimed in claim 44, said zinc
base alloy and oxide film together having not less than 0.075
percent by weight vanadium and having less than 0.0005 percent by
weight aluminum.
46. A composition of matter in the form of a coating on an article,
said coating having a colored surface, said composition consisting
essentially of a zinc-base alloy formed from a melt of zinc
containing not less than 0.1 percent by weight of an element
selected from the group consisting of titanium, manganese and
vanadium, an oxide film of said element formed on a surface of the
said zinc base alloy, and a reflective surface formed on said alloy
intermediate said oxide film and said alloy, said alloy having less
than about 0.002 percent by weight aluminum and less than about
0.006 percent by weight magnesium.
47. A composition of matter as claimed in claim 46 having less than
0.005 percent by weight aluminum.
48. In a composition of matter as claimed in claim 46, said oxide
film having a substantially uniform thickness within the range of
from about 120 A. to about 3,100 A.
49. A composition of matter as claimed in claim 46, said oxide film
having a smooth reflecting inner surface formed by the
solidification of molten alloy.
50. An article of manufacture having a metallic coating with a
colored surface, said coating being integrally bonded to a surface
of said article, said coating consisting essentially of a zinc base
alloy formed from a melt having not less than 0.1 percent by weight
of an element selected from the group consisting of titanium,
manganese and vanadium, an oxide film of said element formed on a
surface of the said zinc base alloy, and a reflective surface
formed on said alloy intermediate said oxide film and said alloy,
said alloy having less than about 0.002 percent by weight aluminum
and less than about 0.006 percent by weight magnesium.
51. In an article as claimed in claim 50, said oxide film having a
substantially uniform thickness within the range of from about 120
A. to about 3,100 A.
52. An article as claimed in claim 50, said oxide film having a
smooth reflecting inner surface formed by the solidification of
molten alloy.
53. In an article as claimed in claim 50, said article being formed
of a metal.
54. In a metal article according to claim 53, said metal being
steel and said coating bonded to said steel by a layer of zinc-iron
alloy.
55. An alloy formed as an adherent colored coating on a sheet steel
substrate, said alloy consisting essentially of zinc and from about
0.001 percent to about 0.45 percent by weight titanium and having
less than about 0.002 percent by weight aluminum and less than
about 0.006 percent by weight magnesium.
56. An alloy formed as an adherent colored coating on a sheet steel
substrate, said alloy consisting essentially of zinc and from about
0.02 percent to about 0.45 percent by weight manganese and having
less than about 0.002 percent by weight aluminum and less than
about 0.004 percent by weight magnesium.
57. An alloy formed as an adherent colored coating on a sheet steel
substrate, said alloy consisting essentially of zinc and from about
0.001 percent to about 0.15 percent by weight vanadium and having
less than about 0.002 percent by weight aluminum and less than
about 0.006 percent by weight magnesium.
58. A composition of matter in the form of a coating of an article,
said coating having a colored surface, said composition consisting
essentially of an alloy of tin and an element selected from the
group consisting of titanium, manganese and vanadium, a film of an
oxide of said alloying element formed on the surface of said alloy,
and a reflective surface formed on said alloy intermediate said
oxide film and said alloy, said alloy having less than about 0.002
percent by weight aluminum and less than about 0.006 percent by
weight magnesium.
59. A composition of matter in the form of a coating on an article,
said coating having a colored surface, said composition consisting
essentially of an alloy of lead-tin and an element selected from
the group consisting of titanium, manganese and vanadium, a film of
an oxide of said alloying element formed on the surface of said
alloy, and a reflective surface formed on said alloy intermediate
said oxide film and said alloy, said alloy having less than about
0.002 percent by weight aluminum and less than about 0.006 percent
by weight magnesium.
60. An article of manufacture having a metallic coating with a
colored surface, said coating being integrally bonded to the
surface of said article, said coating consisting essentially of a
tin base alloy formed from a melt having not less than 0.02 percent
by weight of an element selected from the group consisting of
titanium, manganese and vanadium, an oxide film of said element
formed on a surface of the said tin base alloy, and a reflective
surface formed on said alloy intermediate said oxide film and said
alloy, said alloy having less than about 0.002 percent by weight
aluminum and less than about 0.006 percent by weight magnesium.
61. An article of manufacture having a metallic coating with a
colored surface, said coating being integrally bonded to a surface
of said article, said coating consisting essentially of a lead-tin
base alloy formed from a melt having not less than 0.02 percent by
weight of an element selected from the group consisting of
titanium, manganese and vanadium, an oxide film of said element
formed on a surface of the said lead-tin alloy, and a reflective
surface formed on said alloy intermediate said oxide film and said
alloy, said alloy having less than about 0.002 percent by weight
aluminum and less than about 0.006 percent by weight magnesium.
62. A process for the production of a colored coating on a surface
comprising the steps of applying zinc having an oxygen-avid element
selected from the group consisting of titanium, manganese,
vanadium, columbium, zirconium, thorium, mischmetal, cadmium,
arsenic, copper, lead and chromium alloyed therewith to said
surface to form a molten adherent coating thereon, said alloy
having less than about 0.002 percent by weight aluminum and less
than about 0.006 percent by weight magnesium, reacting said molten
coating with an oxygen-containing atmosphere for a time sufficient
to form on the zinc alloy a film of an oxide of said alloying
element having said color effects, and solidifying said molten
coating provided with said oxide film to provide a reflective
surface on the zinc alloy intermediate said oxide film and said
zinc alloy.
63. A process for the production of a colored coating on a surface
as claimed in claim 62 comprising the steps of forming a bath of
said zinc alloy and applying the zinc alloy to said surface by
immersing the surface in said bath to form an adherent molten
coating thereon.
64. In a process as claimed in claim 62, said oxygen-avid element
being selected from the group consisting of titanium, manganese,
aluminum, columbium, zirconium, thorium and mischmetal.
65. In a process as claimed in claim 62, said oxygen-avid element
being selected from the group consisting of cadmium, arsenic,
copper, lead and chromium.
66. A colored foil comprising a thin sheet of a zinc base alloy
formed from melt having not less than 0.1 percent by weight of an
element selected from the group consisting of titanium, manganese
and vanadium, an oxide film of said element formed on said alloy,
and a reflective surface formed on said alloy intermediate said
oxide film and said alloy, said alloy having less than about 0.002
percent by weight aluminum and less than about 0.006 percent by
weight magnesium.
67. In a process as claimed in claim 6, said bath having a
temperature in the range of 420.degree. to 700.degree. C.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process for the production of colored
surfaces and is particularly directed to a process for the
production of colored zinc, tin and lead-tin coatings and to alloy
coating compositions therefor.
The phenomenon of colored metal surfaces produced by oxidation of a
metal is known as, for example, in the tempering of steels to
increase toughness, the degree of tempering being characterized by
specific surface colors. The tempering process, and attendant color
which is a measure of the degree of tempering, can be arrested as
desired by quenching.
The formation on ferrous bodies of an oxide film having a thickness
characterized by a color ranging from light yellow to purple and
gray for subsequent reconversion to the parent metal by reduction
is taught in Sendzimir U.S. Pat. No. 2,197,622.
It is also known to color metal surfaces, particularly iron or
nickel, by forming a layer of less than 2 microns thickness on the
surface of the metal by electrodepositing lead oxide thereon, as is
taught in British Pat. No. 1,010,065.
And, it is known to oxidize articles of titanium and titanium
alloys containing more than 20 percent titanium by anodic treatment
of said articles in an aqueous electrolyte to impart surface
coloring and improved corrosion resistance thereto, as described in
British Pat. No. 1,046,929. Commercial anodizing processes
necessitate costly surface preparation to provide a substrate which
is receptive to an oxide film and which will provide maximum
reflectivity.
It is not known, however, how to color surfaces in a predictable
and facile manner by the use of molten zinc alloyed with an
oxygen-avid addition agent whereby the zinc functions as a carrier
of the addition agent for the formation of a film of an oxide of
said addition agent having light interference properties. Such
colored coatings are not formed under normal galvanizing
conditions.
SUMMARY OF THE INVENTION
We have found that the addition of a minor amount of certain
oxygen-avid addition agents to zinc, tin or lead-tin and oxidation
of the resulting alloys surprisingly results in the production of
surface films of oxides of the addition agents, substantially free
of host metals, having light interference color characteristics to
produce coatings or surfaces having attractive and predictable
surface colors and textures. More particularly, we have discovered
a novel process for the production of colored zinc surfaces and of
colored zinc coatings on articles comprising, in general, the steps
of forming an alloy of zinc and an oxygen-avid element selected
from the group consisting of titanium, manganese, vanadium,
columbium, zirconium, thorium and mischmetal, applying the alloy
composition to a surface or to a surface of the article such as by
dipping said article in a melt of the alloy or flowing the molten
alloy onto the article surface, and contacting the resulting molten
coating with a free-oxygen-containing gas under controlled time and
temperature conditions to permit reaction of the molten alloy
composition with oxygen for the provision of a thin oxide film
having desirable light interference color characteristics and
effects.
We have also discovered that the alloying of cadmium, arsenic,
copper, lead or chromium with zinc and oxidation of the resulting
alloy at elevated temperatures of at least about 625.degree. C.
results in the production of colored coatings when applied to
surfaces.
It is a principal object of the present invention, therefore, to
provide a process for the production of colored zinc, tin and
lead-tin alloy coatings.
It is another object of the present invention to provide colored
coatings on the surfaces of workpieces in a manner adaptable for
use with galvanizing techniques, with optimum control and
consistency of color.
It is another object of the present invention to provide a process
for the production of colored metal oxide coatings using zinc as an
inexpensive and convenient carrier of the metal from which the
color is derived.
It is another object of the invention to provide highly reflective
inner surfaces for colored coatings on workpieces in a manner that
obviates the need for elaborate polishing of the article being
coated.
DESCRIPTION OF THE DRAWINGS
Additional objects and the manner in which they can be attained
will become readily apparent to one skilled in the art from the
following detailed description of the invention, reference being
had to the following drawings, in which:
FIG. 1 is a graph illustrating the effect of bath temperature and
composition on yellow color formation for a Zn--Mn alloy;
FIG. 2 is a graph illustrating the effect of bath temperature and
cooling rate on variable color formation for a Zn--Mn alloy;
FIG. 3 is a graph illustrating the effect of bath temperature and
cooling rate on variable color formation for a Zn--Ti alloy;
and
FIG. 4 is a graph illustrating the effect of bath temperature and
cooling rate on variable color formation for a Zn--V alloy.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the process of the present invention and with
particular reference now to zinc coatings, colored coatings can be
produced on surfaces of various metals such as iron, steel, copper,
nickel, zinc and other metals, and on surfaces of nonmetallic
materials such as graphite by applying to said surfaces a coating
of zinc having alloyed therewith an oxygen-avid addition agent such
as manganese, titanium and vanadium in amount sufficient to form on
the coating, upon reaction of the surface of said coating with
oxygen, an oxide film derived from the addition agent, said film
having light interference colors. Any material which is amenable to
receiving a coating of the zinc alloy, under suitable temperature
conditions and other operating conditions discussed hereinbelow,
can be color coated according to the process of the invention.
The colors formed on the surfaces of zinc coatings containing
alloying elements are due to light interference effects that are
dependent on the thickness of thin oxide films. Transmission of a
portion of an incident beam and subsequent reflection from the
inner surface of the film can result in the reinforcement of one
color and the interference with and dimming of other colors in the
part of the incident beam that is reflected at the outer
surface.
The characteristics of the interference colors are dependent on the
index of refraction and absorbing power of the film, as well as on
the reflectivity of the surfaces. Hence, differing color shades and
intensities and to some extent, different color sequences, result
from interference effects on films of different materials.
It will be understood that the term "oxygen-avid element (or
addition agent)" refers to an element that forms a stable oxide
film of suitable thickness for the production of light interference
color effects. Elements such as sodium and potassium that will not
form stable oxide films, and aluminum and magnesium that will not
form a film of suitable thickness, do not provide light
interference color effects and are not included in this term for
the operation of the process of the invention.
Table 1 records observations of sequences of colors that were
obtained by progressively increasing the thickness of the oxide
film on a zinc titanium alloy bath, which is generally
representative of the color sequence obtained with the various
alloys of the invention. Beyond the fourth order, the coloring
effects decrease and disappear.
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TABLE
I First Order yellow (gold) red blue silver Second Order yellow red
blue green Third Order yellow red green Fourth Order yellow (narrow
range) red green Fifth Order red
__________________________________________________________________________
The films are believed to consist of oxides of the alloying metals
which appear to react preferentially with oxygen. The thin films,
generally having a thickness within the range of from about 120 A.
to about 3,100 A., are formed in layers with an increasing oxygen
to metal ratio towards the surface of the film. For example, in the
case of titanium alloyed with zinc, we have found that the film on
the coating is substantially zinc-free and consists of an oxide or
oxides of titanium with rutile (TiO.sub.2) formed on the surface
(or anatase [TiO.sub.2 ] with a layer of rutile below the anatase)
and a layer of Ti.sub.2 O.sub.3 below the rutile. Adjacent to the
Ti.sub.2 O.sub.3 is zinc-titanium alloy depleted of titanium in
accordance with the amount of oxide formed. In an extreme case, it
is conceivable that the metal in contact with the Ti.sub.2 O.sub.3
would be zinc substantially completely depleted of titanium. With a
steel substrate, the coating is bonded to the steel by transition
layers of zinc-iron alloys.
Similarly, films formed on zinc-manganese coatings have been found
to be substantially free of zinc and are believed to consist of
oxides of manganese with MnO.sub.2 at the surface, and Mn.sub.2
O.sub.3, Mn.sub.3 O.sub.4, and MnO between the MnO.sub.2 and the
zinc-manganese alloy (or zinc, if the manganese has been completely
depleted). With a steel substrate, there are transition layers of
zinc-iron alloys.
The films formed on zinc-vanadium coatings also are substantially
free of zinc, and the oxide film is believed to consist of V.sub.2
O.sub.5 at the surface, underlain by V.sub.2 O.sub.4, V.sub.2
O.sub.3, VO, depleted zinc base alloy (or zinc) and, with a steel
substrate, transition layers of zinc-iron alloys.
In FIGS. 2-4, color sequences, which can be obtained reproducibly,
are shown for manganese, titanium and vanadium alloyed with zinc.
The different alloying elements produce differing color shades and
intensities, e.g., soft pastel shades from the titanium alloy
system and more intense colors from the vanadium system. Color
brilliance, a quality of the process, is believed to be due to the
smooth interface between the film and the zinc alloy, a protected
reflecting surface being formed as the molten alloy solidifies.
The zinc alloy coating can be applied to surfaces of substrates by
spraying the alloy in molten form onto said surfaces, by pouring
molten alloy said surfaces, or by immersing or dipping said
surfaces into a bath of the molten alloy. The thus-coated surfaces
are contacted with a free oxygen-containing gas such as air, with
or without further heating, and then cooled to form a solid coating
with a thin oxide film derived from the addition agent and
producing the desired color. The thickness of the oxide film, and
hence the final color, is dependent upon the alloy composition,
alloy temperature, and the period of time the coating, at an
elevated temperature, is permitted to react with oxygen.
Although the description will not principally proceed with
particular reference to binary alloys of zinc with manganese,
titanium, or vanadium, it will be understood that the invention is
intended to include binary, ternary, quaternary and the like alloys
of the said addition agents with zinc as well as the
above-mentioned addition agents of the group consisting of
columbium, zirconium, thorium and mischmetal, and the group
consisting of cadmium, arsenic, copper, lead and chromium.
With reference now to FIG. 1, the effect of bath or initial coating
temperature and composition of zinc-manganese baths is shown
relative to time of contact with the oxygen in air for the
occurrences of first, second and third orders of the color yellow
on the melt surface, the manganese content of the zinc bath being
controlled at levels of 0.04 percent, 0.07 percent, 0.11 percent
and 0.33 percent by weight. It will be evident from the graph that
the occurrence of first order yellow at manganese concentration of
0.11 percent and 0.33 percent was almost instantaneous at all
temperature above about 419.degree. C., i.e., the melting point of
the alloy. At manganese concentrations of 0.07 percent and below,
however, considerable time was necessary for the occurrence of
first order yellow even at bath temperatures up to about
480.degree. C. and 500.degree. C.; the occurrence of first order
yellow for a 0.04 percent manganese content occurring only at a
temperature above 520.degree. C. after 50 seconds of exposure to
oxygen. Thus, a range of manganese contents above 0.07 percent by
weight in the zinc is desirable, the practical lower limit being
about 0.1 percent concentration above which increases in the
manganese content do not appreciably increase the rate of color
formation. The upper practical limit is determined by the
solubility of the manganese in the zinc at the operating
temperatures since manganese in excess of its solubility would be
present in elemental or intermetallic compound form. Excessive
amounts of manganese may be added to compensate for additive losses
through bath oxidation or the like losses. The presence of
manganese exceeding the solubility limit will not prevent the
formation of colored coatings.
Comparable tests conducted on zinc-vanadium alloy baths established
the occurrence of the first order yellow at a bath temperature of
500.degree. C. at 8 seconds for a 0.018 percent by weight vanadium
content, 15 seconds for a 0.011 percent by weight vanadium content,
and 19 seconds for a 0.009 percent by weight vanadium content. The
first order yellow appeared at 3 seconds at vanadium concentrations
in the zinc of 0.076 percent and 0.46 percent by weight at an alloy
bath temperature of 500.degree. C. The color occurrence was
therefore relatively consistent at vanadium contents by weight in
the zinc at and above about 0.075 percent, the practical lower
limit being about 0.1 percent by weight. The upper practical limit
is determined by the solubility of vanadium in zinc at the
operating temperatures, amounts of vanadium in excess of the
solubility limit and present in elemental or intermetallic compound
form not preventing the formation of colored coatings.
Tests conducted on zinc-titanium alloy baths established the
occurrence of first order yellow at a temperature of 500.degree. C.
at 7 seconds for titanium contents in the zinc of 0.09 percent and
0.16 percent by weight. Color occurrence was relatively consistent
at titanium concentrations down to 0.008 percent by weight, and at
concentrations below 0.008 percent by weight the rate of coloration
decreased rapidly. The lower practical limit is 0.1 percent by
weight titanium in zinc and the upper practical limit is determined
by the solubility of titanium in zinc at the operating
temperatures. Amounts of titanium in excess of the solubility limit
and present in elemental or intermetallic compound form do not
prevent the formation of colored coatings.
The foregoing alloy composition ranges and limits of manganese,
vanadium and titanium with zinc were established by color
occurrence on the respective alloy bath surfaces. Color occurrences
were noted for each alloy composition at concentrations as low as
0.0001 percent by weight. Color occurrences on dipped articles were
noted at manganese, vanadium and titanium concentrations by weight
in zinc of 0.02 percent, 0.001 percent and 0.001 percent
respectively at alloy bath temperatures of 600.degree. C.,
650.degree. C. and 650.degree. C. respectively, as will be evident
from the following example. It will be understood that although the
preferred and practical composition ranges and limits were
determined by color formation on bath surfaces, the parameters
apply equally to dipped articles, only the time of color formation
being changed because of the effect of cooling of the article by
exposure to air. Prolonged retention of dipped articles at elevated
temperatures in a free-oxygen-containing environment such as air
can be controlled to approximate bath temperature conditions and
hence rate and extent of color formation can also be
controlled.
The preferred lower limit for manganese, vanadium and titanium of
0.1 percent by weight in the zinc permits compensation for loss of
the alloying element in the bath. The upper practical limit for
alloys of manganese, vanadium and titanium with zinc can be
determined by their respective solubility limits at the operating
temperatures or by their respective eutectic compositions if it is
desired to avoid precipitation of the addition agents from the
solutions upon temperature variations of the bath. The eutectic
compositions for the above alloys of manganese and titanium with
zinc, about 0.45 percent Mn or about 0.45 percent Ti, were obtained
from pages 1,243 and 964 respectively of "The Constitution of
Binary Alloys," Second Edition 1958, M. Hansen, McGraw-Hill Book
Company, Ltd. The eutectic composition for the alloys of vanadium
with zinc, about 0.15 percent V, was obtained from Transactions of
the Metallurgical Society of AIME, Vol. 227, page 485, 1953. The
preferred range for the alloy compositions of manganese, vanadium
and titanium with zinc to avoid precipitation is therefore from
about 0.1 percent by weight to about the eutectic composition of
the respective alloying element in zinc, that is, from about 0.1
percent to about 0.45 percent for manganese and titanium, and from
0.1 percent to about 0.15 percent for vanadium.
The following example, results of which are shown in table II,
describes concentration effects at lower composition levels on
color occurrences on dipped samples coated with compositions of
manganese, titanium and vanadium alloyed with zinc. Tests were
conducted in which specimens of galvanized sheet steel of three
thicknesses, 30-, 24- and 16-gauge, were dipped in baths of
zinc-manganese alloy within the temperature range of 500.degree. C.
to 600.degree. C. and zinc-titanium and zinc-vanadium alloys within
the temperature range of 500.degree. C. to 650.degree. C. All
specimens were allowed to reach the bath temperature before
withdrawal for exposure to ambient air conditions for coating
solidification.
Initial tests were conducted wherein the bath temperatures were
maintained constant and the alloying agents were diluted until no
coloration was observed on dipped samples. The bath temperatures
were then raised in steps, maintaining the alloy composition, until
color was again produced on the dipped samples. This procedure of
diluting the alloying agents to first eliminate color and then
raising the bath temperature to produce color at the same alloy
composition was continued until no coloration on dipped samples
occurred at the established upper temperature limits. Assay samples
were taken for each dilution step and, together with color
observations, were tabulated as shown in table II. The first three
zinc-manganese bath compositions represent calculated values and
the remaining compositions in table II represent wet analysis
results. ##SPC1##
The following example illustrates the effect of regulating the
length of effective time of reaction of oxygen with the zinc alloy.
A series of 16-, 24- and 30-gauge pregalvanized panels and one-half
inch diameter rods were dipped into melts of zinc containing 0.1
percent manganese, zinc containing 0.15 percent titanium and zinc
containing 0.15 percent vanadium. The panel immersion time and bath
temperature were varied and the freezing time of the coating and
final color were noted. At each temperature level, the melt surface
was skimmed and color formation was also timed. Results plotted on
the graphs in FIGS. 2, 3 and 4 show the effect of cooling rate and
bath temperature on the formation of colors on the surface of
dipped articles. With reference to the graphs, the areas bounded by
fine solid lines are the colors observed on the surface of the
melt, representing a zero-cooling rate, and the areas bounded by
heavy solid lines are the final colors that are formed on the
surface of dipped articles, both upon exposure to air. The areas
defined by both groups of solid lines indicate the actual colors
observed. The broken lines represent the coating freezing times for
30-, 24- and 16-gauge sheet specimens, air cooled at room
temperature of 20.degree. C. and the heavy solid-lined areas
intersected indicate the final colors that form on the specimen
surfaces when dipped at particular temperatures.
The observations tabulated in table III may be made from the graphs
of FIGS. 2-4; in each case immersion times being sufficient for the
specimens to attain bath temperature and the coatings subsequently
air cooled at room temperature (20.degree. C.).
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TABLE III
Bath Bath Final Analysis Temperature Material Coating Figure (by
weight) (.degree.C.) Gauge Color
__________________________________________________________________________
2 Zn-0.1% Mn 475 24 yellow 2 Zn-0.1% Mn 475 16 blue 3 Zn-0.15% Ti
500 30 yellow 3 Zn-0.15% Ti 500 16 red 4 Zn-0.15% V 500 30 red 4
Zn-0.15% V 500 16 blue
__________________________________________________________________________
The foregoing examples relate to colors achieved where the dipped
article was allowed to air cool from the bath temperature. By
quenching the article with cold air blasts, a color appearing
earlier in the color sequence is formed. Immersion times
insufficient to attain the bath temperature also form colors
appearing earlier in the sequence. By decreasing the cooling rate
or increasing bath temperature, a color appearing later in the
color sequence can be formed, as for example, where an article is
dipped, held at the bath temperature (zero-cooling rate) for a
prolonged time, and then rapidly cooled by quenching when the
desired color had formed. If desired, the article can also be
heated after dipping, and subsequently cooled or quenched, or a
finished article can be reheated for further color change by means
of, for example, induction heating.
The graphs indicate that the effect of cooling rate on color
formation is more pronounced on the zinc-manganese (Zn-0.1 percent
Mn) alloy than on either the zinc-titanium (Zn-0.15 percent Ti) or
zinc-vanadium (Zn-0.15 percent V) alloys.
Immersion times when dipping articles in molten baths are not
critical when coating nonreactive materials, provided, of course,
that a suitable temperature is reached for the desired color if no
post heating is provided. However, with a reactive substrate such
as low alloy steel or the usual mild steel sheet used in
conventional galvanizing operations, and particularly for
continuous operation an immersion time of less than 1 minute is
preferred. We have found immersion times of from about one up to
about 20 seconds satisfactory for the application of a uniform
layer of the zinc alloy, provided the coating is post heated after
short immersions to ensure uniform thickness and adequate oxidation
of the coating surface for formation of the oxide film of desired
thickness and resulting color. Post heating can be accomplished by
means of, for example, induction heating.
The foregoing Sendzimir patent, illustrative of the disclosures of
the prior art, teaches that the presence of from 0.001 percent to
0.35 percent aluminum in zinc is necessary for effective bath
control in the continuous galvanizing of metal surfaces with zinc.
In general, small additions of aluminum in amount of about 0.003
percent normally are made to zinc baths for control of surface
dross in the galvanizing of structural shapes and fabricated
articles. We have found that the presence of about 0.002 percent to
about 0.005 percent by weight aluminum in the zinc alloy bath
precludes formation of a desirable oxide film having light
interference effects. The presence of as little as 0.0005 percent
by weight aluminum, while not sufficient to prevent coloration,
does decrease the rate of color formation sufficiently to impede
the operation of the process of the present invention.
Although it will be understood the invention is free from
hypothetical considerations, it is believed that the presence of
the aluminum in amounts of 0.005 percent and more results in the
aluminum preferentially oxidizing to form a protective film of
Al.sub.2 O.sub.3 which prevents the formation of, for example,
TiO.sub.2, V.sub.2 O.sub.5 or MnO.sub.2 oxide films. In that the
Al.sub.2 O.sub.3 layer is extremely thin, no light interference
colors are obtained.
The following example, conducted to establish deleterious aluminum
concentrations, describes tests conducted in which the aluminum
content of zinc alloy baths was increased from 0 to 0.005 percent
by weight.
Melts of commercial Special High Grade zinc (99.99+ percent) with
titanium (Zn-0.15 percent Ti), manganese (Zn-0.15 percent Mn) and
vanadium (Zn-0.15 percent V) were held at a constant temperature,
and aluminum, in the form of a zinc aluminum alloy (Zn-1.0 percent
al. was added to each melt to increase the concentration of
aluminum by increments by weight of 0.0005 percent. The rate of
color formation on the surface of the melt and the color formed on
the dipped panel were noted after each addition of aluminum. The
results are listed in table IV. ##SPC2##
The foregoing tests were made with commercial Special High Grade
zinc. Other commercial grades of zinc, e.g., Prime Western which
contains up to 1.5 percent Pb, can be used provided that the
foregoing limitations regarding aluminum content (preferably below
0.002 percent) are observed.
The effect of magnesium is similar to that of aluminum, small
amounts (0.004-0.006 percent by weight) having been found to
prevent the formation of color.
Table V below lists the results of coating specimen panels
according to the process of the invention with zinc containing
alloying elements from the group columbium, zirconium, thorium, and
mischmetal and the group cadmium, arsenic, copper, lead and
chromium.
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TABLE V
Bath Analysis Bath Color Sequence (by weight) Temperature
__________________________________________________________________________
Zn-0.1% Cb 500.degree.-650.degree. C. Gold light shades Purple
light shades Blue light shades Zn-0.1% Zr 550.degree.-650.degree.
C. Gold light shades Purple light shades Blue light shades Zn-2.0%
Th 450.degree.-600.degree. C. Yellow light shades Purple light
shades Blue light shades Zn-0.5% mischmetal 500.degree.-600.degree.
C. Yellow Purple Blue Purple (deep) Zn-5.0-10% Cd 650.degree. C.
Yellow light shades Blue light shades Zn-1.5% As 650.degree. C.
Yellow Zn-2.7% Cu 650.degree.-700.degree. C. Light Gold Zn-1.0% Pb
700.degree. C. Light Gold Zn-1.0% Cr 625.degree.-700.degree. C.
Gold
__________________________________________________________________________
Alloy compositions of zinc and titanium, manganese, vanadium,
columbium, zirconium, thorium or mischmetal provide colored
coatings on steel and pregalvanized materials at temperatures
within the range of from about 419.degree. C., i.e., the melting
point of the alloy composition, to about 600.degree. C. and above.
Alloy composition of zinc and cadmium, arsenic, copper, lead or
chromium provide colored coatings on said substrates at
temperatures of at least 625.degree. C.
We have also found that the presence of titanium, manganese, or
vanadium in amounts of 0.02 percent to about 1 percent by weight in
molten tin or in lead-tin alloys containing at least 5 percent tin,
permits production of colored coatings by the process of the
present invention. With tin, a wide range of attractive colors is
produced at temperatures from 280.degree. C. to 520.degree. C., and
with lead-tin alloys a suitable temperature range is 320.degree. C.
to 500.degree. C. It will be understood that although the
description of the process has proceeded with reference to the use
of zinc alloys for the provision of colored surfaces, the process
of the invention can be used in like manner for the provision of
colored surfaces on tin and lead-tin alloys.
The present invention provides a number of advantages. Colors
produced by the process and compositions of the invention are
reproducible, and can readily be controlled by varying one or more
of the following: alloy composition, alloy temperature, temperature
of molten alloy surface in a free-oxygen-containing atmosphere, and
the time during which the alloy coating remains in its molten and
relatively reactive state. Variegated colors, patterns and textures
can be produced that provide, in combination, aesthetic effects and
corrosion resistant properties. The coatings can be applied to or
formed on nonmetallic and metallic substrates, such as ceramics and
various metals, particularly steel in the form of sheet, wire and
formed articles such as expanded mesh, extruded or cast pipe and
structural members. If desired, colored films or foil can be
removed from the surface of an alloy bath or the coating can be
formed on and removed from a substrate such as graphite to provide
thin sheets for decorative uses.
* * * * *