U.S. patent number 3,771,972 [Application Number 05/208,653] was granted by the patent office on 1973-11-13 for coated article.
This patent grant is currently assigned to Battelle Development Corporation. Invention is credited to William H. Safranek, Glenn R. Schaer.
United States Patent |
3,771,972 |
Schaer , et al. |
November 13, 1973 |
COATED ARTICLE
Abstract
An article comprising a metallic substrate and a mechanically
deformable corrosion-protective coating thereon comprising a layer
on the substrate of ductile bright nickel containing less than
about 0.005 percent sulfur and about 0.2 to 2 mils thick, and a
layer thereon of chromium at least about 0.01 mil thick and having
cracks substantially uniformly distributed therein at an average
spacing of not more than about 3 mils, the coating having been
maintained at about 350.degree. to 450.degree.F for at least about
one minute. The bright nickel layer typically is electroplated from
an aqueous solution comprising nickel sulfate, nickel chloride or
fluroborate, boric acid, and coumarin or a derivative or analog
thereof. A layer of ductile bright copper not more than about 1 mil
thick may be provided between the substrate and the layer of bright
nickel, and a layer of ductile semibright nickel not more than
about 2 mils thick may be provided between the copper layer and the
bright nickel layer.
Inventors: |
Schaer; Glenn R. (Columbus,
OH), Safranek; William H. (Columbus, OH) |
Assignee: |
Battelle Development
Corporation (Columbus, OH)
|
Family
ID: |
22775452 |
Appl.
No.: |
05/208,653 |
Filed: |
December 16, 1971 |
Current U.S.
Class: |
428/613; 205/113;
205/227; 428/667; 428/675; 428/935; 205/180; 428/636; 428/926 |
Current CPC
Class: |
C25D
5/627 (20200801); C25D 5/14 (20130101); C25D
5/50 (20130101); C25D 5/625 (20200801); Y10T
428/1291 (20150115); Y10T 428/12854 (20150115); Y10T
428/12639 (20150115); Y10T 428/12479 (20150115); Y10S
428/935 (20130101); Y10S 428/926 (20130101) |
Current International
Class: |
C25D
5/14 (20060101); C25D 5/10 (20060101); C25D
5/50 (20060101); C25D 5/48 (20060101); C23b
005/06 (); C23b 005/08 (); C23b 005/50 () |
Field of
Search: |
;29/196.6 ;204/37R
;148/127,34 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Stallard; W. W.
Claims
We claim:
1. An article comprising a metallic substrate and a mechanically
deformable corrosion-protective coating thereon comprising a layer
on the substrate consisting essentially of ductile bright nickel
substantially free of sulfur and a layer thereon consisting
essentially of chromium having cracks substantially uniformly
distributed therein at an average spacing of not more than about 3
mils, the protective coating having been maintained at about
350.degree. to 450.degree.F for at least about 1 minute.
2. An article as in claim 1, wherein the bright nickel layer has a
ductility factor of about 100 percent as measured by micrometer
bend test.
3. An article as in claim 1, wherein the bright nickel layer has a
ductility equivalent to at least about 0.15 percent elongation for
a thickness of 2 mils.
4. An article as in claim 1, wherein the bright nickel layer
contains less than about 0.005 percent sulfur.
5. An article as in claim 4, wherein the bright nickel layer is
about 0.2 to 2 mils thick.
6. An article as in claim 1, wherein the chromium layer is at least
about 0.01 mil thick.
7. An article as in claim 1, comprising also a layer consisting
essentially of ductile bright copper between the substrate and the
layer of bright nickel.
8. An article as in claim 7, wherein the copper layer is not more
than about 1 mil thick.
9. An article as in claim 8, wherein the bright nickel layer is not
more than about 2 mils thick.
10. An article as in claim 7, comprising also a layer consisting
essentially of ductile semi-bright nickel between the copper layer
and the bright nickel layer.
11. An article as in claim 10, wherein the bright nickel layer is
substantially free of sulfur and about 0.2 to 2 mils thick.
12. An article as in claim 11, wherein the semi-bright nickel layer
is not more than about 2 mils thick.
13. A method of providing an article as in claim 1 that comprises
electroplating on the substrate a layer of ductile bright nickel
from an aqueous solution consisting essentially of nickel sulfate,
nickel chloride or fluoborate, boric acid, and coumarin or a
derivative or analog thereof, electroplating, on the bright nickel
layer a layer of microcracked chromium, and maintaining the
protective coating at about 350 to 450.degree.F for about one to 60
minutes.
14. A method of providing an article as in claim 1 that comprises
electroplating on the substrate a layer of ductile bright nickel
from an aqueous solution consisting essentially of about 150 to 400
grams per liter of nickel sulfate, about 5 to 25 grams per liter of
nickel fluoborate, about 20 to 40 grams per liter of boric acid,
and about 1 to 3 grams per liter of coumarin or a derivative or
analog thereof, with a pH of about 5 to 5.5, at a temperature of
about 110.degree. to 140.degree.F and a current density of about 10
to 60 amperes per square foot, for about 2 to 10 minutes,
electroplating on the bright nickel layer a layer of microcracked
chromium, and maintaining the protective coating at about
350.degree. to 450.degree.F for about one to 60 minutes.
Description
BACKGROUND OF THE INVENTION
This invention relates to a metallic article having a bright
ductile chromium coating system where a bright nickel with
ductility higher than conventional bright, sulfur-containing nickel
is used with microcracked chromium. During bending the deformation
takes place by expansion of the cracks already in the microcracked
chromium system. Cracks do not penetrate a significant distance
into the sulfur-free ductile nickel layer.
This system is useful for plating flat steel sheets which are later
formed to the desired shape. By plating flat sheets, cost savings
are realized because less metal is deposited, and smaller plating
equipment is used to plate sheet materials.
SUMMARY OF THE INVENTION
A typical article according to the present invention comprises a
metallic substrate and a mechanically deformable
corrosion-protective coating thereon comprising a layer on the
substrate consisting essentially of ductile bright nickel and a
layer thereon consisting essentially of chromium having cracks
substantially uniformly distributed therein at an average spacing
of not more than about 3 mils, the protective coating having been
maintained at about 350.degree. to 450.degree.F for at least about
one minute. The bright nickel layer typically has a ductility
factor of about 100 percent as measured by micrometer bend test,
and a ductility equivalent to at least about 0.15 percent
elongation for a thickness of 2 mils.
The bright nickel layer preferably is substantially free of sulfur.
It typically contains less than about 0.005 percent sulfur and is
about 0.2 to 2 mils thick. The chromium layer typically is at least
about 0.01 mil thick. The bright nickel layer typically is
electroplated from an aqueous solution comprising essentially
nickel sulfate, nickel chloride or fluoroborate, boric acid, and
coumarin or a derivative or analog thereof.
The article may comprise also a layer consisting essentially of
ductile bright copper between the substrate and the layer of bright
nickel. The copper layer typically is not more than about 1 mil
thick, and the bright nickel layer typically is not more than 2
mils thick.
The article may comprise still another layer consisting essentially
of ductile semibright nickel between the copper layer and the
bright nickel layer. The bright nickel layer preferably is
substantially free of sulfur and about 0.2 to 2 mils thick, and the
semibright nickel layer typically is not more than about 2 mils
thick.
A typical method of providing the article comprises electroplating
on the substrate a layer of ductile bright nickel from an aqueous
solution consisting essentially of nickel sulfate, nickel chloride
or fluoborate, boric acid, and coumarin or a derivative or analog
thereof, (typical solutions consist essentially of about 150 to 400
grams per liter of nickel sulfate, about 5 to 25 grams per liter of
nickel fluoborate, about 20 to 40 grams per liter of boric acid,
and about 1 to 3 grams per liter of coumarin or a derivative or
analog thereof); typically with a pH of about 5 to 5.5, at a
temperature of about 110.degree. to 140.degree.F and a current
density of about 10 to 60 amperes per square foot, for about 2 to
10 minutes; electroplating on the bright nickel layer a layer of
microcracked chromium, and maintaining the protective coating at
about 350.degree. to 450.degree.F for about 1 to 60 minutes.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a photomicrograph at 150 power of the surface of an
article comprising a steel substrate coated with a layer of
conventional bright nickel (containing sulfur) and an outer layer
of microcracked chromium, showing an area that was bent to an angle
of about 90.degree. around a one-fourth inch radius and exposed to
16 hours of copper accelerated salt spray (CASS).
FIG. 2 is a photomicrograph at 500 power of a cross section of the
area shown in FIG. 1 (two layers, prior art).
FIG. 3 is a photomicrograph as in FIG. 1 of a similar article
except that the layer of bright nickel comprises ductile bright
nickel (sulfur free) in accordance with the present invention.
FIG. 4 is a photomicrograph similar to FIG. 2 of a cross section of
the area shown in FIG. 3 (two layers, this invention).
FIG. 5 is a photomicrograph as in FIG. 1 of a similar article
except that the coating includes also a layer of conventional
bright copper between the steel substrate and the bright nickel
layer.
FIG. 6 is a photomicrograph similar to FIG. 2 of a cross section of
the area shown in FIG. 5 (three layers, prior art).
FIG. 7 is a photomicrograph as in FIG. 5 of a similar article
except that the layer of bright nickel comprises ductile bright
nickel (sulfur free) in accordance with the present invention.
FIG. 8 is a photomicrograph similar to FIG. 6 of a cross section of
the area shown in FIG. 7 (three layers, this invention).
FIG. 9 is a photomicrograph as in FIG. 5 of a similar article
except that the coating includes also a layer of semibright nickel
between the copper layer and the bright nickel layer.
FIG. 10 is a photomicrograph similar to FIG. 6 of a cross section
of the area shown in FIG. 9 (four layers, prior art).
FIG. 11 is a photomicrograph as in FIG. 9 of a similar article
except that the layer of bright nickel comprises ductile bright
nickel (sulfur free) in accordance with the present invention.
FIG. 12 is a photomicrograph similar to FIG. 10 of a cross section
of the area shown in FIG. 11 (four layers, this invention).
DESCRIPTION OF PREFERRED EMBODIMENTS
Preferred operating limits have been identified for depositing
decorative ductile bright nickel-chromium composites on sheet steel
for forming after plating. One of the best of several ductile
composites consists of a four coat system as follows: leveling acid
copper, ductile semi-bright nickel and bright nickel deposited
without current interruption in the same sulfur-free nickel bath,
and a microcracked chromium system applied by a post-nickel-strike
(PNS) and a conventional chromium plate. The microcracks prevent
the macrocrack formation that is widely encountered with prior
procedures. Macrocracks commonly extend through the plated coatings
to the basis metal. A short heat treatment of the plated sheet
before forming improves ductility. Corrosion, metallographic,
ductility, and percent elongation studies have confirmed the
benefits of this invention over prior procedures of plating.
When steel panels 0.025-inch thick plated with the preferred
ductile composite coating system were bent up to 180.degree. around
a 1/8-inch-diameter mandrel, the cracks intentionally introduced in
the microcracked chromium propagated less than one-fourth the
thickness of the coating. In comparison, cracks propagated all the
way through the coating system applied by prior techniques, on
similar panels subjected to similar bends. Thus, the new system
offers superior corrosion protection to the steel substrate. The
decorative appearance (brightness) of the coating was retained on
the bent areas. No orange peel was seen at the bends.
TYPICAL PROCEDURES FOR PLATING DUCTILE NICKEL-CHROMIUM COMPOSITES
ON STEEL PANELS
A. preliminary (all systems)
1. Degrease if necessary
2. Electroclean
3. Acid dip in 10 percent hydrochloric acid for about 30
seconds.
4. Rinse in tap water
B. copper (3 and 4 coat systems only)
5. Copper strike in a cyanide copper bath, to protect the basis
metal
6. Rinse in tap water
7. Acid dip in 5 percent sulfuric acid
8. Rinse in tap water
9. Copper plate in a conventional bright acid copper bath
containing copper sulfate, sulfuric acid, and proprietary organic
brighteners (Dayton Bright Copper Co., Cuflex Brighteners)
C. semibright Nickel (4 coat system only)
10. Immerse in a semibright watts type nickel bath containing
coumarin addition agent within the ranges listed in U.S. Pat. No.
2,635,076, DuRose, and plate to a thickness of about 0.5 mil; or
((10) alternative) Immerse in a bath as in (11) below, and with the
following operating conditions
Range Preferred pH 5.0 to 5.5 5.2 Current density 60 to 150 75
amp/sq ft Temperature, F 110 to 140 135 Agitation Mild air Anodes
Sulfur de- polarized nickel (International Nickel Company)
Filtration Continuous
10.5. plate to a thickness of about 0.5 mil
D. ductile Bright Nickel (all systems)
11. Immerse in a sulfur-free nickel bath with the following
composition
Range Preferred Nickel sulfate, NiSo.sub.4.sup.. 6H.sub.2 O, 150 to
400 225 g/l Nickel fluoborate, NiBF.sub.4, 10 to 50 20 mil/l Boric
acid, H.sub.3 BO.sub.3, g/l 20 to 40 30 Conventional anti-pit
agent, 0 to 0.5 0.3 such as Harshaw AG4, per- cent by volume
Brightener, coumarin, g/l 0.5 to 3.0 3.0
and the following operating conditions
Range Preferred pH 5.0 to 5.5 5.2 Current density 10 to 60 50
amp/sq ft Temperature, F 110 to 140 135 Agitation Vigorous air
Anodes Sulfur depolarized nickel (International Nickel Company)
Filtration COntinuous
12. Plate to a thickness of about 0.2 to 2 mils
13. Rinse in cold tap water E. Microcracked Chromium (all
systems)
14. Immerse in a post nickel strike bath as in U.S. Pat. No.
3,563,864, DuRose (PNS- Harshaw Chemical Company) for 2.5 minutes
at 80 amp/sq ft and a temperature of 80.degree.F
15. Rinse in cold water
16. Immerse in a conventional 33 oz/gal chromic acid bath
containing fluosilicic and sulfuric acids as catalysts
17. Plate for 2.5 minutes
This outer layer develops about 800 to 1,000 continuous cracks per
linear inch. or (E. alternative)
14 alt. Immerse in a conventional 33 oz/gal chromic
acid bath containing fluosilicic and sulfuric
acids as catalysts
15 alt. Plate for 3.5 minutes
16 alt. Without rinsing, transfer to, and immerse in, a bath as in
(14 alt.) but containing also about 18 mg of sodium selenate
17 alt. Plate for 3.5 minutes
The outer layer deposited by this alternative procedure develops
about 3,300 cracks per linear inch.
F. heating (all systems)
18. Heat at 400.degree.F for one to 30 minutes
EXAMPLES
A. two-Coat System
Panels were coated in accordance with Parts A, D, E, and F of the
above Typical Procedures.
In this system 0.8 to 1.2 mil of ductile bright nickel was
deposited directly on steel in the sulfur-free nickel bath. The
nickel plated steel was then plated with 0.1-mil PNS nickel, in
accordance with U.S. Pat. No. 3,563,864, DuRose, and 0.01 mil of
conventional chromium, and heated at 400.degree.F for 1 to 30
minutes before bending.
FIGS. 3 and 4 illustrate the effectiveness of this system by
comparison with FIGS. 1 and 2 of the prior art. A microcracked
chromium system is essential. Microcracked chromium developed by
the two different procedures (E and E alternative) produced the
same good corrosion resistance. The microcracks must be not more
than about 3 mils apart. When they are farther apart the cracks
propagate deeper and are likely to penetrate through the bright
nickel layer and into the substrate of steel. In corrosive
environments this can result in rusting, especially in any areas of
the coated article that are subjected to bending or other
strain.
B. three-Coat System
Panels were coated in accordance with Parts A, B, D, E, and F of
the above Typical Procedures.
In the three-coat system, (1) copper, (2) ductile bright nickel,
and (3) microcracked chromium were applied. About 0.5 to 1.0 mil of
leveling bright copper was applied to the steel after a cyanide
copper strike. These steps involve conventional techniques. The
nickel plate of 0.2 to 1.0 mil applied on the copper is the
ductile, sulfur-free bright nickel. Over the ductile bright nickel,
a microcracked chromium system was applied by either the two-layer
chromium (E alternative) or the PNS nickel and conventional
chromium system (E). The advantage of the three-coat system over
the two-coat system is that more deformation can be tolerated
because the copper uniformily distributes the bending forces in the
ductile nickel coating.
FIGS. 7 and 8 illustrate the effectiveness of this system by
comparison with FIGS. 5 and 6 of the prior art.
C. four-Coat System
Panels were coated in accordance with all parts of the above
Typical Procedures.
In the four-coat system, (1) copper, (2) semibright nickel sulfur
free, (3) bright nickel sulfur free, and (4) microcracked chromium
were deposited. The advantage of the four-coat system over the
three-coat system is that sharper bends can be sustained without
causing cracks to penetrate to the steel substrate, Cracks which
penetrate through the coating to the steel are corrosion sites.
FIGS. 11 and 12 illustrate the effectiveness of this system by
comparison with FIGS. 9 and 10 of the prior art.
The sulfur-free, bright nickel plating process, which is an
important part of the invention, deposits full bright metal
according to accepted standards. However, maximum ductility is not
achieved until the deposit is backed. Minimum time and temperature
for obtaining 100 percent ductility as measured by the bend test
are approximately:
Temperature Time, minutes 280.degree.F 15 340.degree.F 8
400.degree.F 1
ductility was determined by two methods. In the first one, 1-mil
thick foils were electroformed, heated, cooled, and bent between
the jaws of a micrometer. The jaws were closed until cracking of
the foil occurred or the jaws were closed to give a reading equal
to twice the thickness of the foil. When no cracking occurs,
ductility equals 100 percent, which is the limit of this measuring
procedure, ASTM Designation B-490-68. Ductility of the sulfur-free,
bright nickel deposit after heating was consistantly 100 percent
whereas the ductility of conventional bright nickel foils measured
by the same foil test ranged from 2 to 22 percent. All the nickel
foils containing sulfur decreased in ductility when heated. This
change is typical of sulfur-containing nickel.
Elongation of nickel foils was measured by making tensile specimens
from about 2.4 to 3.5 mil thick foils. Elongation values were 0.17
to 0.35 percent for the sulfur-free bright nickel. By contrast, the
sulfur containing bright nickel had elongation values of 0.04
percent, only about 10 to 25 percent of the values for the
sulfur-free bright nickel.
The article shown in FIGS. 11 and 12 was prepared in accordance
with the Typical Procedures, comprising all of the Parts A-F for
preparing the four-coat system according to the present invention.
The article shown in FIGS. 9 and 10 was made in the same way except
that the ductile bright nickel layer of the present invention (Part
D) was replaced by a bright nickel layer as in conventional
commercial practice (containing sulfur).
The article shown in FIGS. 7 and 8 was prepared in the same manner
as that of FIGS. 11 and 12 except that the deposition of the
semi-bright nickel layer (Part C) was omitted, and the thickness of
the ductile bright nickel layer was increased by the thickness of
the omitted layer. The article shown in FIGS. 5 and 6 was made in
the same way as the article in FIGS. 9 and 10 except that the
semi-bright nickel layer was omitted and the thickness of the
conventional bright nickel layer increased by the thickness of the
omitted layer.
The article shown in FIGS. 3 and 4 was made in the same way as the
article in FIGS. 7 and 8 except that the layer of copper (Part B)
was omitted. The article shown in FIGS. 1 and 2 was made in the
same way as the article in FIGS. 5 and 6 except that the copper
layer was omitted.
A typical procedure for depositing the conventional bright nickel
layer in the examples of the prior art, FIGS. 1, 2, 5, 6, 9, and
10, (upper half of the drawings) comprises the preferred commercial
practices developed over many years using a modified Watts bath
composition containing organic brighteners, which contribute sulfur
to the deposit. The procedure is described below in more
detail.
G. typical Procedure for Plating a Conventional Bright Nickel
Layer
19. Immerse in a Watts-type bath with the following
composition:
Range Preferred Nickel sulfate 225-450 g/l 260 Nickel chloride
37.5-60 g/l 45 Boric acid 45-49 g/l 45 Addition agents P-1* 7-14
ml/l 10 Addition agents P-224* 0.7-1.25 ml/l 0.75 Addition agents
P-4* 3-5 ml/l 4 *Harshaw Perglow Bright Nickel Plating Process The
Harshaw Chemical Company
and the following operating conditions
Range Preferred pH 3.3-4.4 4.0 Current density, 20-100 50 amp/sq ft
Temperature, F. 125-160 140 Agitation Vigorous air Filtration
Continuous
20. Plate to a thickness of about 0.2 to 2 mils
21. Rinse in cold tap water
Referring back to the brief description of the drawings as well as
to the upper half of the drawings themselves, it is apparent that
with the articles made in accordance with the best available prior
art, bending of the articles caused a relatively few of the
microcracks in the outer chromium layer to expand and that some of
these cracks propagated further so as to penetrate through the
conventional bright nickel layer (containing sulfur) which is
fairly brittle. In contrast, as shown in the lower half of the
drawings, depicting articles made in accordance with the present
invention, bending caused a substantially uniform expansion of most
of the microcracks in the outer chromium layer, and thus the
expansion of each crack was much less than in the articles made
according to the best prior art. Moreover the more evenly
distributed cracking of the chromium layer exposed more nickel from
the contiguous layer of ductile bright nickel. This increased the
ratio of nickel to chromium in the cracked regions, providing
increased protection against electrolytic erosion (such as is
commonly encountered on bumpers and other automotive hardware) and
thus minimizing such corrosion.
It is apparent therefore that the present invention provides much
greater protection against corrosion of the substrate, while
providing also a bright, decorative, and pleasing appearance to the
articles coated in accordance therewith.
While the forms of the invention herein disclosed constitute
presently preferred embodiments, many others are possible. It is
not intended herein to mention all of the possible equivalent forms
or ramifications of the invention. It is to be understood that the
terms used herein are merely descriptive rather than limiting, and
that various changes may be made without departing from the spirit
or scope of the invention.
* * * * *