U.S. patent number 3,907,608 [Application Number 05/370,437] was granted by the patent office on 1975-09-23 for coated metal and method.
This patent grant is currently assigned to Diamond Shamrock Corporation. Invention is credited to Leo Donald Barrett, Irving Malkin.
United States Patent |
3,907,608 |
Barrett , et al. |
September 23, 1975 |
Coated metal and method
Abstract
A coating on a metal substrate of CrO.sub.3 and pulverulent
metal in aqueous medium and containing particular organic liquid
provides a corrosion and alkali resistant coating to the metal. The
pulverulent metal, of which metal flake is of special interest, the
liquids and the CrO.sub.3, typically all supplied by chromic acid,
are mixed and applied to the metal substrate. The resulting coated
substrates have electroconductivity, e.g., for application of
electrocoating primer, after the application and baking of the
coating composition on a substrate.
Inventors: |
Barrett; Leo Donald (Cleveland
Heights, OH), Malkin; Irving (University Heights, OH) |
Assignee: |
Diamond Shamrock Corporation
(Cleveland, OH)
|
Family
ID: |
26868924 |
Appl.
No.: |
05/370,437 |
Filed: |
June 15, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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173243 |
Aug 19, 1971 |
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Current U.S.
Class: |
428/552; 148/248;
148/268; 428/341 |
Current CPC
Class: |
B23K
35/226 (20130101); C23C 22/74 (20130101); C09D
5/10 (20130101); Y10T 428/12056 (20150115); Y10T
428/273 (20150115) |
Current International
Class: |
C09D
5/10 (20060101); C23C 22/74 (20060101); C23C
22/73 (20060101); B23K 35/22 (20060101); C23F
007/26 () |
Field of
Search: |
;148/6.2,6.16 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kendall; Ralph S.
Assistant Examiner: Wolfe, Jr.; Charles R.
Attorney, Agent or Firm: Freer; John J.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. pending
application Ser. No. 173,243, filed Aug. 19, 1971 and now
abandoned.
Claims
We claim:
1. An aqueous coating composition for application to, and curing
on, a metal substrate, thereby preparing an adherent water
insoluble, alkali and corrosion resistant as well as substantially
resinfree coating on said substrate, which composition before
curing comprises an intimate mixture in aqueous liquid medium
of:
A. a hexavalent-chromium-providing substance, supplied by about 80
to 100 weight percent chromic acid and providing above 5 but below
about 100 grams per liter of chromium, expressed as CrO.sub.3 ;
B. above 50 but below about 500 grams per liter of liquid medium of
pulverulent metal selected from the group consisting of zinc,
aluminum, mixtures thereof and alloys of same, said composition
having a weight ratio of chromium, expressed as CrO.sub.3, to
pulverulent metal of between about 1:1 and 1:15;
C. below about 50 volume percent but substantially above 15 volume
percent, based on the volume of the total liquid of the aqueous
liquid medium, of water soluble organic liquid substance that
maintains liquidity above 100.degree.C. and is selected from the
group consisting of tri-, and tetraethylene glycol, di-, and
tripropylene glycol, and the water soluble low molecular weight
ethers of all such foregoing glycols, diacetone alcohol, the water
soluble low molecular weight ethers of diethylene glycol, and
mixtures of the foregoing; and
D. above about 0.0005 volume percent, basis total volume of said
coating composition, of dispersing agent.
2. The coating composition of claim 1 wherein said organic liquid
substance is selected from the group consisting of dipropylene
glycol, tripropylene glycol monomethyl ether, tetraethylene glycol,
diethylene glycol monoethyl ether, dipropylene glycol monomethyl
ether, and mixtures of the foregoing.
3. The coating composition of claim 1 wherein said
chromium-providing-substance supplies not substantially above about
60 grams per liter of chromium, expressed as CrO.sub.3, and said
composition has a weight ratio of chromium, expressed as CrO.sub.3,
to pulverulent metal of between about 1:4 and 1:9.
4. The coating composition of claim 1 wherein said pulverulent
metal is zinc flake and said flake is present in an amount above
about 150 grams per liter of said coating composition.
5. The coating composition of claim 1 wherein said organic liquid
substance is present in an amount above about 20 volume
percent.
6. A pulverulent metal containing precursor constituent adapted for
blending into chromium-containing aqueous blend for preparing a
substantially resin-free, liquid coating composition for metal
substrates, said coating composition having a ratio of chromium,
expressed as CrO.sub.3, to pulverulent metal of between about 1:1
and 1:15, wherein said precursor constituent consists of
pulverulent metal the preponderance of which is zinc flake, water
soluble organic liquid substance that maintains liquidity at
100.degree.C. and is selected from the group consisting of tri, and
tetraethylene glycol, di-, and tripropylene glycol, and the water
soluble low molecular weight ethers of all such foregoing glycols,
diacetone alcohol, the water soluble low molecular weight ethers of
di-ethylene glycol, and mixtures of the foregoing, and 0-3 weight
percent basis the total weight of said precursor constituent, of
dispersing agent, and wherein said precursor constituent has a
weight ratio of said organic liquid substance to said pulverulent
metal of between about 1:2.5 - 1:0.3.
7. The coating composition precursor constituent of claim 6 wherein
said pulverulent metal is 80-100 percent zinc flake by weight.
8. The coating composition precursor constituent of claim 6 wherein
said organic liquid substance is selected from the group consisting
of dipropylene glycol, tripropylene glycol monomethyl ether,
tetraethylene glycol, diethylene glycol monoethyl ether,
dipropylene glycol monomethyl ether, and mixtures of the
foregoing.
9. The coating composition precursor constituent of claim 6 wherein
said dispersing agent contributes between about 0.2-0.9 weight
percent of same and said constituent has a weight ratio of organic
liquid substance to pulverulent metal of between about 1:2 and
1:0.8.
10. A coated metal substrate having on the surface thereof an
adherent alkali and corrosion resistant water-insoluble and
substantially resin free coating, which coating comprises above 10
but not substantially above about 5,000 milligrams per square foot
of coated substrate of pulverulent metal selected from the group
consisting of zinc, aluminum, mixtures thereof, and alloys of same
in intimate mixture with the residue from a substantially
resin-free hexavalent-chromium-containing aqueous coating
composition containing a hexavalent-chromium-providing substance,
below about 50 volume percent but substantially above 15 volume
percent, basis total composition liquid, of water soluble organic
liquid substance that maintains liquidity above 100.degree.C and is
selected from the group consisting of tri-, and tetraethylene
glycol, di-, and tripropylene glycol, and the water soluble low
molecular weight ethers of all such foregoing glycols, diacetone
alcohol, the water soluble low molecular weight ethers of
diethylene glycol, and mixtures of the foregoing, and said coating
composition provides said residue with not above about 500
milligrams per square foot of coated substrate of chromium, wherein
said coating contains a weight ratio of chromium, as chromium, to
pulverulent metal of not substantially above about 0.5:1, and said
residue is obtained by applying to said metal surface said
hexavalent-chromium-containing composition and heating said
substrate at a temperature, and for a period of time, sufficient to
vaporize volatile substituents from said coating composition and
deposit on said surface said residue.
11. The coated metal substrate of claim 10 wherein said residue is
the residue remaining after heating applied coating at a
temperature above about 400.degree.F. and for a time of at least
about 1 second.
12. The method of preparing a coated metal substrate having on the
surface thereof an adherent, alkali and corrosion resistant, water
insoluble and substantially resin-free coating, which method
comprises:
1. applying to said surface a hexavalent-chromium-containing
aqueous coating composition of hexavalent-chromium-providing
substance, supplied by about 80 to 100 weight percent chromic acid,
said composition containing above about 0.0005 volume percent,
basis total composition liquid, of dispersing agent and below about
50 volume percent but substantially above 15 volume percent, same
basis, of water-soluble organic liquid substance that maintains
liquidity above 100.degree.C and is selected from the group
consisting of tri-, and tetraethylene glycol, di-, and tripropylene
glycol, and the water soluble low molecular weight ethers of all
such foregoing glycols, diacetone alcohol, the water soluble low
molecular weight ethers of diethylene glycol, and mixtures of the
foregoing, said composition being applied in an amount sufficient
to provide not above about 500 milligrams per square foot of coated
substrate of chromium, said composition also containing pulverulent
metal selected from the group consisting of zinc, aluminum,
mixtures thereof, and alloys of same in sufficient amount to
provide not substantially above about 5,000 milligrams per square
foot of coated substrate of said pulverulent metal and to provide
said coating with a weight ratio of chromium, as chromium to
pulverulent metal of not substantially above about 0.5:1, and
2. heating said substrate at a temperature, and for a period of
time, sufficient to vaporize volatile substituents from said
aqueous coating composition and deposit on said surface said
coating.
13. The method of claim 12 wherein said substrate is heated at a
substrate temperature above about 400.degree.F and for a time of at
least about one second.
14. The method of claim 13 wherein said aqueous coating composition
is applied to said surface in an amount sufficient to provide from
about 10 to about 200 milligrams per square foot of said
pulverulent metal, said aqueous coating composition further
providing from about 5 to about 15 milligrams per square foot of
chromium, and said coated metal substrate is subsequently
topcoated.
15. The method of preparing a weldable substrate for electrical
resistance welding and having desirable corrosion and alkali
resistance, which method comprises:
1. establishing on the surface of said substrate, on at least a
portion thereof where welding will take place, above 10 but not
substantially above about 5,000 milligrams per square foot of
coated substrate of pulverulent metal selected from the group
consisitng of zinc, aluminum, mixtures thereof, and alloys of same
in intimate mixture with the residue from a substantially
resin-free hexavalent-chromium-containing aqueous coating
composition containing a hexavalent-chromium-providing substance,
between below about 50 volume percent, but substantially above 15
volume percent, basis total composition liquid, of water-soluble
organic liquid substance that maintains liquidity above
100.degree.C and is selected from the group consisting of tri-, and
tetraethylene glycol, di-, and tripropylene glycol, and the water
soluble low molecular weight ethers of all such foregoing glycols,
diacetone alcohol, the water soluble low molecular weight ethers of
diethylene glycol, and mixtures of the foregoing, and above about
0.0005 volume percent, same basis, of dispersing agent, and said
coating composition providing said residue with not above about 500
milligrams per square foot of coated substrate of chromium, wherein
said coating contains a weight ratio of chromium, as chromium to
pulverulent metal of between about 1:1 and 1:15,
2. heating said substrate at a temperature, and for a period of
time, sufficient to vaporize volatile substituents from said
coating composition and deposit on said surface a composition
residue and pulverulent metal, thereby preparing said substrate for
welding with a coating providing corrosion resistance and weldable
electroconductivity.
16. The method of claim 15 wherein said substrate is heated at a
temperature in excess of about 400.degree.F. and for a time of at
least about one second.
17. A weldable metal substrate prepared for electrical resistance
welding according to the method of claim 15.
18. The weldable metal substrate of claim 17 wherein said substrate
prepared for electrical resistance welding is the substrate of a
metallic stud.
19. The method of electrical resistance welding metallic articles
which comprises:
1. establishing on the surface of said substrate, on at least a
portion thereof where welding will take place, above 10 but not
substantially above about 5,000 milligrams per square foot of
coated substrate of pulverulent metal selected from the group
consisting of zinc, aluminum, mixtures thereof, and alloys of same
in intimate mixture with the residue from a substantially
resin-free hexavalent-chromium-containing aqueous coating
composition containing a hexavalent-chromium-providing substance,
between below about 50 volume percent, but substantially above 15
volume percent, basis total composition liquid, of water soluble
organic liquid substance in said aqueous liquid medium, and above
about 0.0005 volume percent, same basis, of dispersing agent, with
the organic liquid substance maintaining liquidity above
100.degree.C. and being selected from the group consisting of tri-,
and tetraethylene glycol, di-, and tripropylene glycol, and the
water soluble low molecular weight ethers of all such foregoing
glycols, diacetone alcohol, the water soluble low molecular weight
ethers of diethylene glycol, and mixtures of the foregoing and said
coating composition providing said residue with not above about 500
milligrams per square foot of coated substrate of chromium, wherein
said coating contains a weight ratio of chromium, as chromium, to
pulverulent metal of not substantially above about 0.5:1,;
2. heating said substrate at a temperature and for a period of time
sufficient to vaporize volatile substituents from said coating
composition and deposit on said surface a substantially water
insoluble and resin-free coating of said residue and pulverulent
metal, said coating providing corrosion resistance and weldable
electroconductivity thereon;
3. contacting at least a porition of said one article with another
article of metal to be welded;
4. passing an electrical resistance welding current through said
articles of metal and said coating thereon at the zone selected for
welding; and
5. fusing said articles together in said zone of said welding.
20. The method of claim 19 wherein said coating is deposited on the
substrate of a weldable metal stud and thereafter said stud is
electrically resistance welded to another article of metal.
21. A welded metal article prepared according to the method of
claim 20.
Description
BACKGROUND OF THE INVENTION
Chromic acid and pulverulent metal in a liquid medium have
heretofore been applied to metal substrates followed by baking to
attain a corrosion-resistant coating, such as disclosed in U.S.
Pat. No. 3,687,738. Such compositions are typically dispersions of
pulverulent metal powder or metal flake in water or t-butanol and
resulting coatings offer corrosion resistance and
electroconductivity to coated substrates.
Working with such systems depending primarily upon t-butanol can
present a fire hazard whereas working in such systems that are
essentially aqueous media, and especially where the pulverulent
metal is supplied in flake form, can provide problems in achieving
a resulting coated substrate wherein the coating displays excellent
uniformity and adhesion. It is difficult to upgrade such
characteristics without deleterious effect on other coating
characteristics plus coating bath stability.
Compositions of typically aluminum flake, a polymeric glycol plus a
wetting agent have been taught in U.S. Pat. No. 3,318,716 as useful
anti-foaming compositions in paste or liquid form. They may be used
to supply very minor amounts of pigmentation to coating
compositions but do not ostensibly lend particular advantages to
resulting coatings except as attributed to the metal flake
component.
The compositions containing aluminum flake provide a barrier
coating or film on the underlying substrate. This barrier coating
provides an essentially inert metallic flake that resists attack,
such as from mild alkali, and thus protects the underlying
substrate metal, through the mechanism of its generally inert
nature. On the other hand, compositions containing zinc flake, and
which compositions are of particular interest herein, provide a
coating that under attack sacrifices the coating in place of, and
thereby protects the underlying metal. Such action typically
provides protection through galvanic action.
It has also been found useful to prepare reaction products of
chromium compound, e.g. chromic acid, plus high boiling organic
solvents in coating compositions. For example, in U.S. Pat. No.
2,355,889 the reaction product of chromic acid and ethylene glycol
monoethyl ether is shown to have utility when incorporated into a
paint. More recently, in U.S. Pat. No. 3,679,493 reaction products
of typically glycol-ethers and chromic acid have been shown to be
useful in their own right and when simply used as such reaction
product in water, for obtaining corrosion resistant coatings on
metallic surfaces. For such simple coating compositions, the low
molecular weight ethers of glycols are employed for the reaction
product.
It has also been known in the art of metal treating solutions where
a hexavalent-chromium compound, e.g., chromic acid, is supplied in
such composition as a reaction product, that compatable co-solvents
may be serviceable. For example, in U.S. Pat. No. 3,189,488 where
such a chromium compound and formaldehyde are co-reacted, the
resulting coating composition liquid medium may be water plus up to
20 weight percent of a co-solvent for improving spreadibility and
flow characteristics. Such co-solvents are represented by various
alcohols and ethers of glycol, for example the mono and diethyl
ethers of ethylene glycol.
Moreover, in U.S. Pat. No. 3,671,331 it has been disclosed that
compositions containing a hexavalent-chromium-providing substance
along with a pulverulent metal may further contain up to ten volume
percent of a surface active agent. Such agent may be an alkyl ether
of an alkylene glycol or a polyalkylene glycol.
SUMMARY OF THE INVENTION
A coating composition for metals has now been found that offers
excellent coating uniformity on the coated substrate. Resulting
coatings exhibit augmented adhesion and desirable color and
non-staining characteristics. The coating uniformity extends to
non-tearing, a particular problem of prior aqueous medium
compositions that is exhibited by variations in coating uniformity
resulting when parts removed from a coating bath drained unevenly
leaving excessive coating composition build-up where the drainage
was greatest.
Such coating characteristics have been obtained without sacrifice
to coating bath stability, including retention of pulverulent metal
flake inertness in the bath as well as excellent dispersion in the
coating bath. In addition to providing coatings of excellent
protective value, and including augmented resistance to mild
alkali, such coatings exhibit electroconductivity, e.g., for
subsequent weldability or application of electrocoat paint.
These characteristics are obtained through the use of specific high
boiling organic compounds. Since these compounds, to demonstrate
significant performance characteristics for resultant coatings,
must be present in substantial amount, i.e. at least substantially
above 15 volume percent of the liquid medium, they will have some
impact on the flowability of the resultant coating composition.
However, their presence in the coating composition at such
proportions has been found to go beyond a mere modification of the
fluid characteristics of the coating; and furthermore, to provide
the resultant composition with more than merely a supplemental
dispersing agent along with the other compositional ingredients.
Thus, for example, the high boiling hydrocarbons have been found to
provide for a significant increase in corrosion protection of
resulting coatings, as well as for augmented coating adhesion, and
this even when achieving boosted coating weights. Moreover, such
properties of the coating are herein achieved without especial
recourse to the formation of reaction products such as have been
taught in U.S. Pat. No. 3,679,493 which has been discussed
hereinabove.
Broadly, the present invention is directed to an aqueous coating
composition for application to, and curing on, a metal substrate,
thereby preparing an adherent, water insoluble, alkali and
corrosion resistant as well as substantially resinfree coating on
said substrate, which composition before curing comprises an
intimate mixture in aqueous liquid medium of: (a) a
hexavalent-chromium-providing substance, supplied by about 80 to
100 weight percent chromic acid and providing below about 100 grams
per liter of chromium, expressed as CrO.sub.3 ; (b) below about 500
grams per liter of liquid medium of pulverulent metal selected from
the group consisting of zinc, aluminum, mixtures thereof and alloys
of same, said composition having a weight ratio of chromium,
expressed as CrO.sub.3, to pulverulent metal of between about 1:1
and 1:15; (c) below about 50 volume percent but substantially above
15 volume percent, based on the volume of the total liquid of the
aqueous composition, of water soluble organic liquid substance
maintains liquidity above 100.degree.C. and is selected from the
group consisting of tri-, and tetraethylene glycol, di-, and
tripropylene glycol, and the water soluble low molecular weight
ethers of all such foregoing glycols, diacetone alcohol, the water
soluble low molecular weight ethers of diethylene glycol, and
mixtures of the foregoing; and (d) above about 0.0005 volume
percent, basis total volume of such coating composition, of
dispersing agent.
In addition, the present invention relates to a coated metal
substrate, and the preparation of such a substrate, exhibiting the
above described adherent, alkali and corrosion resistant coating.
It is further directed to the preparation of weldable substrates
and to welded articles, and additionally to precursor constituents
for preparing aqueous coating compositions.
The metal substrates contemplated by the present invention are
exemplified by the metal substrates to which a chromic acid plus
pulverulent metal in a liquid coating may or can be applied for
enhancing corrosion resistance of such substrate metals. For
example, such metal substrates may be aluminum and its alloys, zinc
and its alloys, copper and cupriferous, e.g., brass and bronze.
Additionally, exemplary metal substrates include cadmium, titanium,
nickel, and its alloys, tin, lead, chromium, magnesium and alloys
thereof, and for weldability, preferably a ferrous metal substrate
such as iron, stainless steel, or steel such as cold rolled steel
or hot rolled and pickled steel. All of these for convenience are
usually referred to herein simply as the "substrate."
For convenience, the hexavalent-chromium-containing aqueous coating
composition is often referred to herein as "treating compositions"
and the "residue" on a metal surface is such resulting surface
condition obtained after application of such composition to, and
heating resulting applied composition on, a metal substrate. Also
for convenience, the high boiling organic compound is often termed
herein as the "high boiling hydrocarbon" or just the
"hydrocarbon."
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The corrosion-resistant, hexavalent-chromium-containing aqueous
composition contains chromic acid as the
hexavalent-chromium-providing substance or its equivalent in
aqueous medium, for example, chromium trioxide or chromic acid
anhydride. But a minor amount, e.g., 20 percent or less, of such
chromium can be supplied by a salt such as ammonium dichromate, or
by sodium or potassium salts, or by substances such as calcium,
barium, magnesium, zinc, cadmium, and strontium dichromate.
Additionally, a minor amount such as 20 percent or less of the
hexavalent-chromium-providing substance might be a mixed chromium
compound, i.e., include trivalent chromium compounds. Although the
aqueous composition might contain only a small amount, e.g., 5
grams per liter of hexavalent chromium, expressed as CrO.sub.3, and
may contain as much as about 100 grams per liter of composition of
hexavalent chromium, expressed as CrO.sub.3, it will typically
contain between about 20-60 grams.
For supplying the liquid medium, without considering the
contribution by the hydrocarbon, water virtually always supplies
the whole amount. Other liquids may possibly be used, but
preferably only a very minor amount of the aqueous medium, basis
the high boiling organic compound free medium, is such other liquid
material. Such other liquids that might be contemplated include
alcohols, most notably t-butanol, and halogenated hydrocarbon
liquid, some of which have been discussed in U.S. Pat. Nos.
2,762,732 and 3,437,531.
A substantial amount of liquid in the aqueous liquid medium, i.e.,
up to 50 volume percent based on the total volume of liquid in the
aqueous medium, can be supplied by the high boiling hydrocarbon.
Such organic liquid compound also must supply substantially above
15 volume percent, on a similar basis, of such total liquid and
advantageously for enhanced coating characteristics, supplies above
about 20 volume percent. Lesser amounts of such total liquid will
not contribute sufficient hydrocarbon to assure consistently
augmented properties of the coating, although such amounts might
achieve enhanced dispersion and compositional flow characteristics.
It is most important that this high boiling organic compound be
liquid at 100.degree.C., and by such herein it is meant to be
liquid at 100.degree.C. at atmospheric pressure.
Since for economy and efficiency water supplies such a large amount
of the aqueous composition liquid medium, and since the high
boiling hydrocarbon is a critical ingredient in the formation of
the resulting coating, it is necessary for such hydrocarbon to be
liquid at the water boiling point. The hydrocarbon should also be
easily soluble in water to at least contribute to twenty volume
percent of the liquid medium at ambient temperature. It is meant
herein to include such hydrocarbons as may be termed "miscible" in
water at such proportion under such temperature condition. Hence,
those hydrocarbons as are more specifically detailed hereinbelow
are serviceable as being soluble in water so long as they mix or
blend uniformly with water and preferably at the 20-50 volume
percent range. Yet, such hydrocarbons must not be highly toxic to
avoid uneconomical expense in handling and use.
Such hydrocarbons as are serviceable in the present invention are
also those that are retained during baking on the metal substrate
in sufficient amount and duration to permit participation of the
hydrocarbon in the formation of a coating. This participation is
best exemplified by such characteristics as reduction of chromium
in the coating from hexavalent to the trivalent state, most
desirable leafing into a layered, substantially uniform coating of
the metallic flake as well as characteristics of the resultant
coating, for example as exhibited from mild alkali resistance
testing. The organic compounds contain carbon, oxygen and hydrogen
and have at least one oxygen-containing constitutent that may be
hydroxyl, or oxo, or a low molecular weight ether group, i.e., a
C.sub.1 -C.sub.4 ether group. Since water solubility is sought,
polymeric hydrocarbons are not particularly suitable and
advantageously serviceable hydrocarbons contain less than about 15
carbon atoms. Particular hydrocarbons which can or have been used
include tri-, and tetraethylene glycol, di-and tripropylene glycol,
the monomethyl, dimethy, and ethyl ethers of these glycols, as well
as diacetone alcohol, the low molecular weight ethers of diethylene
glycol, and mixtures of the foregoing. It will be appreciated that
because of their limited water solubility, it is not meant to
include herein either the hexyl or dibutyl ethers of diethylene
glycol.
The pulverulent metal flake, e.g., zinc flake or aluminum flake, or
mixtures of such flakes, but preferably zinc flake for galvanic
protection and coatability, is most typically such a pulverulent
metal flake having a thickness on the order of 0.1-0.3 micron and
most typically a size in the longest dimension of not substantially
above about 50 microns. Aluminum flake, also sometimes termed
leafing aluminum pigment has been discussed, for example, in U.S.
Pat. No. 2,312,088. Flake may be blended with pulverulent metal
powder, but typically in only minor amounts of the powder, and such
powder should have particle size so that all particles pass 100
mesh and a major amount pass 325 mesh ("mesh" is used herein as
U.S. Standard Sieve Series). The powders are generally spherical as
opposed to the leafing characteristic of the flake.
The coating composition, should be made up with an amount of
pulverulent metal sufficient to supply not substantially above
about 500 grams of metal per liter of coating composition liquid
medium. The presence of greater than about 500 grams per liter of
pulverulent metal flake is undesirable, for example, can add
expense without a significant increase in protection for the coated
substrate. Advantageously, for economy and desirable coating
characteristic, the composition contains at a minimum about 50
grams of metal per liter and preferably contains between about
150-400 grams of metal per liter.
With the preferred zinc flake it has been found to be particularly
serviceable to preblend this flake with the hydrocarbon.
Optionally, a very minor amount of dispersing agent is also added
in this pre-blend. Such a pre-blend, or admix, is desirably stable
and may therefore have advantages in mixing prior to storage or
shipment. It can thereafter be readily admixed with other
ingredients, e.g., water and chromic acid, for the formation of the
coating composition.
In the admix, when the dispersing agent is present it will form
less than about 3 weight percent, and typically from about 0.2 to
about 0.9 weight percent, of such blend basis of the total weight
of the blend. Further, because the pre-blend has been found to be
suitable with the preferred zinc flake, such flake preferably
contributes from about 80 to 100 weight percent of the pulverulent
metal present therein. The admix, which may also be termed a
coating composition precursor constituent, is prepared to contain a
weight ratio of the hydrocarbon to the pulverulent metal flake of
between about 1:2.5 - 1:0.3. Within this ratio, and preferably
within a weight ratio of hydrocarbon to pulverulent metal flake of
between about 1:2 to 1:0.8, the admix will exhibit desirable
stability while providing ready mixing with further compositional
constituents to yield the aqueous coating composition.
Also, for such coating compositions, the chromium, expressed as
CrO.sub.3, should not exceed more than about 100 grams per liter of
composition medium. Greater than about 100 grams per liter of
chromium is uneconomical and can deleteriously detract from the
characteristics of the coated metal surface, for example, the most
desirable corrosion resistance for the coated metal substrate.
Further such composition should have a weight ratio of chromium,
expressed as CrO.sub.3, to metal flake of between about 1:1 to
1:15.
A ratio of beyond about 1:15 may not provide sufficient chromium in
the coating to achieve augmented bonding of the pulverulent metal
to the metal substrate. A ratio of about 1:1 may be achieved, but
should preferably be at metal concentrations of less than about 100
grams per liter. As the metal content approaches about 500 grams
per liter and thus the chromium content can approach about 100
grams per liter the upper weight ratio of chromium, expressed as
CrO.sub.3, to pulverulent metal approaches 1:5. These coating
compositons are virtually always made as very concentrated coating
compositions at a ratio of between about 1:4 and 1:9 and have
particular utility in the coating of small parts as opposed to
application to large substrate areas such as metal coils.
As touched upon hereinbefore, the coating ingredients may be
combined into separate packages, e.g., a two package system with
one containing the hexavalent-chromium-providing substance in an
aqueous medium, and the other package being a water-free dispersion
in high boiling hydrocarbon of pulverulent metal; each package may
additionally contain some surface active agent, or it may all be in
the package with the metal. Such separate packages are then mixed
before application to the metal substrate.
Such coating compositions may be applied to the metal substrate by
any conventional method for coating a substrate with a liquid, for
example, dip coating, roller coating or reverse roller coating, or
combinations of techniques as, for example, spray and brush
techniques. Typically the composition is applied by simply dipping
the article into the composition. The metal surface can be a
preheated metal surface to assist in the curing of the composition,
or the coating composition may be applied from a heated bath, for
example, one heated up to 200.degree.F.
The coating composition should contain some, and generally contains
up to, for example, about 0.05 volume percent, basis total
composition liquid, and typically not above about 1-2 volume
percent, of a dispersing agent. Such agent may be present in as
little as 0.0005 volume percent, also on a total liquid basis. It
is generally contemplated to employ a dispersing agent that is a
nonionic surfactant which may be an ethoxylated alkylphenol such as
a nonyl or octyl phenol. It is also contemplated to employ the
nonionic ethoxylated aliphatic alcohols, representatives of which
include the oleyl, lauryl, and stearyl alcohols. Other suitable
nonionic surfactants that are also readily commercially available
and are contemplated for use in the present invention include, for
example, carboxylic esters that encompass the glycerol esters and
the anhydrosorbitol esters, as well as the polyoxyethylene esters
of fatty, rosin, and tall oil acids. It is also further
contemplated to use carboxylic amide nonionic surfactants for
dispersing the pulverulent metal and these are meant herein to
include the polyoxyethylene fatty acid amides. The preferred agents
for effecting pulverulent metal dispersibility are polyethoxy
adducts, exemplified by the alkylphenoxypolyethoxyalkanols, and
derivatives thereof, some of which are described in U.S. Pat. No.
3,281,475. Such agents are nonionic and have between about 7 and 50
oxyethylene units in the molecule. Advantageously, for best
dispersibility the agent is present in the coating composition in
an amount between about 0.001-0.02 volume percent, on a total
liquid basis.
The resulting coating weights on the metal substrate may vary to a
considerable degree but, exclusive of the metal flake the residue
will most typically always be present in an amount supplying above
about 5 milligrams per square foot of chromium, expressed as
chromium and not CrO.sub.3. Furthermore, residues containing below
about 15 milligrams per square foot of chromium, expressed as
chromium and not CrO.sub.3, should be topcoated to impart
significant enhancement in corrosion resistance of the coated
substrate. Also if the coated metal substrate is to be subsequently
formed, the residue should contain not substantially above about
150 milligrams per square foot of chromium as the coating may be
subjected to cracking or crazing during forming operation, although
for typically finished products when subsequent forming is not
contemplated, and extended corrosion resistance without topcoating
may be desirable, such residue may contain up to about 500
milligrams per square foot of chromium.
A subsequent paint topcoating is also a consideration for the
amount of pulverulent metal that should be present on the surface
of the substrate in the coating residue. Such residues containing
about 10-200 milligrams per square foot of pulverulent metal are
virtually always topcoated. However, subsequently topcoated
residues can contain substantially more pulverulent metal, e.g.,
600-700 milligrams per square foot of such metal, and the substrate
may contain up to about 5,000 milligrams per square foot of
pulverulent metal, whereas an excess of that amount is usually
uneconomical.
It can be appreciated that the present invention is directed to
coatings wherein there is an excess of pulverulent metal to
chromium, even at the lesser concentrations of the metal.
Generally, the coating should have a weight ratio of chromium,
expressed as chromium and not CrO.sub.3, to pulverulent metal of
less than about 0.5:1, and such ratio is most usually for the less
heavy coating weights, since as the coating weights approach, for
example, 5,000 milligrams per square foot of pulverulent metal, the
weight ratio of chromium to pulverulent metal will be less than
about 0.2:1. It has also been found that for coating small parts,
e.g., parts adapted for individual dipping in a coating bath, which
can be final products that will not be normally subjected to
subsequent forming, and where coating weights may approach 5,000
milligrams per square foot of pulverulent metal, the weight ratio
of chromium to pulverulent metal in the coating may be as low as
about 0.02:1.
Other compounds may be present in the
hexavalent-chromium-containing liquid compositions but, even in
combination, are present in very minor amounts so as not to
deleteriously affect the coating integrity, e.g., with respect to
electroconductivity and galvanic protection. Thus, such
compositions should be substantially resin-free and can be
substantially pigment free, i.e., contain little, if any, pigment
or resin such as 10 grams per liter total of both or less and
should preferably be resin free. It may however be desirable to
include, within such total of 10 grams per liter, substances that
can thicken the coating composition. And although these substances,
e.g., water soluble cellulose ethers such as hydroxyethylcellulose,
may be considered as resinous substances, they will be used for
their thickening ability. Thus, and especially when present in
typical amounts of 2-5 gram per liter, such agents do not impart a
resin film to the coating composition residue. Other such agents
include xanthan gum hydrophilic colloids, as well as additional
gums, e.g., guar gum and karaya gum. Also, since the adherence for
the particulate metal to the metal substrate is achieved by the
chromium-providing-substance ostensibly through the interaction of
such substance with the high boiling hydrocarbon during baking,
such coating compositions need not contain resin, and such coatings
that will be subsequently topcoated are virtually always
pigment-free, exclusive of the pulverulent metal.
These other compounds further include inorganic salts and acids as
well as organic substances, often typically employed in the metal
coating art for imparting some corrosion resistance or enhancement
in corrosion resistance for metal surfaces. Such materials include
zinc chloride, magnesium chloride, various chromates, e.g.
strontium chromate, molybdates, glutamic acid, succinic acid, zinc
nitrate, and succinimide and these are all preferably avoided, but
if present, are most usually employed in the liquid composition in
a total maximum amount of less than 5 grams per liter.
For the metal substrates containing applied liquid composition and
pulverulent metal, the preferred temperature for the subsequent
heating, which is also often referred to as curing and which may be
preceded by drying such as air drying, is within the range from
about 400.degree.F. but more typically from about 450.degree.F. at
a pressure of 760 mm. Hg up to not essentially above about
1,000.degree.F. Such an elevated substrate temperature may be
attained by preheating the metal prior to application of the liquid
composition. However, such curing temperatures do not often exceed
a temperature within the range of about 450.degree.-700.degree.F.
At the elevated curing temperatures the heating can be carried out
in as rapidly as about one second or less but is often conducted
for several minutes at a reduced temperature.
Before starting the treatment of the present invention it is, in
most cases, advisable to remove foreign matter from the metal
surface by thoroughly cleaning and de-greasing. Degreasing may be
accomplished with known agents, for instance, with agents
containing sodium metasilicate, caustic soda, carbon tetrachloride,
trichloroethylene, and the like. Commercial alkaline cleaning
compositions which combine washing and mild abrasive treatments can
be employed for cleaning, e.g., an aqueous trisodium
phosphate-sodium hydroxide cleaning solution. In addition to
cleaning, the substrate may undergo cleaning plus etching.
After heating, the resulting coated substrate of the present
invention can be further topcoated with any suitable paint, i.e., a
paint, primer, including electrocoating primers, and weldable
primers such as the zinc-rich primers that can be applied before,
typically, electrical resistance welding, and paints such as
enamel, varnish, or lacquer. Since the coated metal surfaces of the
present invention can exhibit a desirable upgrading in topcoat
adhesion when compared, for example, to the uncoated substrate
metal, paints are often applied over such coated substrates. Such
paints may contain pigment in a binder or can be unpigmented, e.g.,
generally cellulose lacquers, rosin varnishes, and oleoresinous
varnishes, as for example tung oil varnish. The paints can be
solvent reduced or they may be water reduced, e.g., latex or
watersoluble resins, including modified or soluble alkyds, or the
paints can have reactive solvents such as in the polyesters or
polyurethanes. Additional suitable paints which can be used include
oil paints, including phenolic resin paints, solvent-reduced
alkyds, epoxys, acrylics, vinyl, including polyvinyl butyral and
oil-wax-type coatings such as linseed oil-paraffin wax paints. The
paints may be applied as mill finishes.
The weldability of coated substrates is of particular interest in
regard to electrical resistance welding that can be exemplified by
electrical resistance spot welding wherein opposing electrodes are
closed against weldable substrates maintained for welding within
the gap between the electrodes. For this spot welding the opposing
electrodes are closed onto the substrate to be welded under
pressure, for example of a 500-600 pound load, and for a weld heat
that is measured in ampseconds. Also of particular interest is the
application of the coating composition to weldable metal studs that
are typically solid, cylindrical metallic articles having a length
of a few inches or less and are used in a welding gun for
electrically resistance welding to a metal substrate. The coatings
of the present invention on the surface of these steels, in
addition to providing the other coating characteristics, offer
reduced sputtering during welding that can be a problem at the weld
when studs are used that have a galvanized protective surface
coating.
The following examples show ways in which the invention has been
practiced but should not be construed as limiting the invention. In
the examples the following procedures have been employed:
PREPARATION OF TEST PARTS
Test parts are typically prepared for subsequent treatment by
immersing in water which has incorporated therein 2-5 ounces of
cleaning solution per gallon of water. The cleaning solution is
typically 75% by weight of potassium hydroxide and 25 weight
percent tripotassium phosphate. The bath is maintained at a
temperature of about 150.degree.-180.degree.F. After the cleaning
treatment the panels are rinsed with warm water and may be
dried.
APPLICATION OF COATING TO TEST PARTS AND COATING WEIGHT
Clean parts are typically coated by placing in a wire basket and
dipping the basket into coating composition, removing the basket
and draining excess composition therefrom with a mild shaking
action and then immediately baking or air drying at room
temperature until the coating is dry to the touch and then baking,
the parts being usually placed on a sheet for baking. Baking
proceeds under infrared lamps or in a hot air convection oven at a
substrate temperature of about 450.degree.F. unless otherwise
specified, for a time up to 1 minute, also unless otherwise
specified.
Coating weights for parts, generally expressed as a weight per unit
of surface area, are determined by selecting a random sampling of
parts of a known surface area and weighing the sample before
coating. After the sample has been coated, it is reweighed and the
coating weight per selected unit of surface area, most always
presented as milligrams per square foot (mgms./sq.ft.), is arrived
at by straightforward calculation.
CORROSION RESISTANCE TEST (ASTM B-117-64) AND RATING
Corrosion resistance of coated parts is measured by means of the
standard salt spray (fog) test for paints and varnishes ASTM
B-117-64. In this test, the parts are placed in a chamber kept at
constant temperature where they are exposed to a fine spray (fog)
of a 5% salt solution for specified periods of time, rinsed in
water and dried. The extent of corrosion on the test parts are then
compared one with the other by visual inspection.
In the following examples the efficacy of the corrosion resistance
obtained on coated parts is, in part, quantatively evaluated on a
numerical scale from 0 to 10. The parts are visually inspected and
compared with one another and the system is used for convenience in
the reviewing of results. In the rating system the following
numbers are used to cover the following results:
10. retention of film integrity, no red rust;
8. initial coating degradation, pinpoints of red rust;
6. less than 3% red rust basis total surface area of the part;
4. 3 to 10% red rust, i.e., a significant amount of rust;
2. 10 to 25 percent surface area red rust;
0. greater than 25 percent red rust.
EXAMPLE 1
Sufficient zinc flake having particle thickness of about 0.1-0.2
micron and a longest dimension of discrete particles of about 15
microns is dispersed in diethylene glycol monoethyl ether (DGME)
together with 3 milliliters (mls.) of wetter which is a nonionic,
modified polyethoxy adduct having a viscosity in centiposes at
25.degree.C. of 180 and a density at 25.degree.C. of 8.7 pounds per
gallon, to provide in a final mixed dispersion 300 grams per liter
(g./l.) of the D.G.M.E. Separately there is added to deionized
water sufficient chromic acid to provide 60 g./l. of CrO.sub.3 in
the final mixture.
The chromic acid solution is slowly added to the metal flake
dispersion to form the final mixture. During the addition, a slight
evolution of heat is observed and some surface foam is formed which
is removed by skimming. An additional blend is prepared in the same
manner but the blend contains 250 mis./l. of tripropylene glycol
monomethyl ether (TGME) in place of the DGME and only 2 mls. of
wetter.
Each bath is used to coat five grade 8 bolts which are 11/16 inches
long by about 1/4 inch in diameter at the threaded end and have
.beta. inch of threading on the shaft topped by a 5/8 inch smooth
shaft section that terminates in the bolt head. Also, each bath is
used to coat five No. 10-A clips, sometimes referred to as "speed
clips," that are formed by doubling over an about 0.5 inch by 1.75
inch strip of thin sheet metal to provide a clip type configuration
when viewed on edge, followed by punching a hole through the
doubled configuration and leaving opposing, outwardly extending
flanges around one outer clip section of the hole. These parts are
coated as described above and the coating cured for 6-12 minutes at
475.degree.F. On analysis, as described above, the bolts are
calculated to average 1,135 mgms./sq.ft. of coating from the DGME
bath and 1,370 mgms./sq.ft. from the TGME bath.
The parts are subjected to the above described corrosion resistance
salt spray test and results of such testing are shown in the table
below. In the table below the test results are reported on the
scale hereinabove described.
TABLE 1 ______________________________________ Bath Salt Spray
Results Bolts Clips Flake CrO.sub.3 66 168 66 168 Type g./l. g./l.
hrs. hrs. hrs. hrs. ______________________________________ DGME 300
60 10 9 9 2 TGME 300 60 10 10 10 10
______________________________________
The above results demonstrate the excellent corrosion resistance
that can be obtained on small parts where the coating composition
employs either the diethylene glycol monoethyl ether or the
tripropylene glycol monomethyl ether. As is evident from these
results, the clips present a challenging problem in coating, but
baths of the present invention can nevertheless achieve excellent
results, as shown by the TGME bath, and for a greatly extended
duration of testing.
EXAMPLE 2
Various coating compositions are prepared in the manner of Example
1 and using 300 grams per liter in each composition of the zinc
flake described in Example 1. Each composition also contains 5
milliliters of the Example 1 wetter and contains a concentration of
chromic acid as shown in Table 2 below. Also as shown in the table
below, the compositions contain various amounts of organic
compound. The first four compositions containing diethylene glycol
monethyl ether (MEE) and compositions 5-8 contain dipropylene
glycol monomethyl ether (MME).
The baths identified in the table below as Nos. 3, 4, 7 and 8 are
aged one day prior to use. Bath No. 8 is very viscous prior to use
but is readily mixed to a smooth consistency. Bath No. 7 is smooth
and viscous without noticeable viscosity change during the one day
ageing. Bath No. 3 has a lower viscosity than 4 and both stir up
very readily.
Each bath is used to coat both Grade 8 bolts and No. 10-A clips, as
have been described in Example 1 and the coated parts are cured as
described in Example 1 for curing times up to 14 minutes at a
temperature of 475.degree.F. With reference again to baths 3, 4, 7
and 8, the adhesion for the cured coating on the parts is rated as
good except for the adhesion on the parts coated in Bath No. 8
where it does not exhibit the good coating adhesion of the other
baths. Such adhesion is determined simply by holding the part
firmly in the hand and scratching with a thumbrail and comparing
many parts under such scratch test. The coating appearance for all
such parts from the baths is metallic.
Coating weights per bolt for coatings obtained from each bath are
determined, in the manner described hereinbefore, based upon a five
bolt sample from each bath and the results are reported in Table 2
below. Also shown in the table below are the results of salt spray
testing for both the bolts and the clips.
TABLE 2 ______________________________________ Salt Spray Bath
coating Results Compound CrO.sub.3 Weight 168 Hours Compound Conc.
conc. on Bolts No. Type Mls./l. g/l. mgms./ft..sup.2 Bolts Clips
______________________________________ 1 MEE 250 60 850 9 10 2 MEE
250 90 935 10 10 3 MEE 125 60 785 10 6 4 MEE 375 60 2,180 10 6 5
MME 250 60 1,030 10 10 6 MME 250 90 1,100 10 10 7 MME 125 60 970 10
10 8 MME 375 60 1,975 10 10 ______________________________________
MEE = Monoethyl ether of diethylene glycol MME = Monomethyl ether
of dipropylene glycol
The above results show excellent, consistent corrosion resistance,
at a very extended test duration of 168 hours, for small parts
having a considerable range in the weight of coating on the parts.
The corrosion resistance under the salt spray testing has been
rated in accordance with the manner hereinbefore discussed, and 13
out of the 16 parts rated scored the highest possible rating.
In further testing, i.e., beyond just the salt spray testing
represented in Examples 1 and 2, it became apparent that for the
10-12 volume percent level of addition for the organic liquid
substance, that although such results might, as above, be
occasionally obtained under idealized laboratory conditions, they
could neither be desirably reproduced nor consistently achieved. As
already inferred, such results could not be obtained for a breadth
of coating characteristics beyond the salt spray test, for example,
such results as noted above in Table 2 for the lowest concentration
of the glycols could neither with consistency nor assurance be
translated over to desirable coating adhesion, or corrosion
resistance in water soak, or corrosion resistance under an
electrocoat paint. Such findings are most dramatically represented
by the results as detailed hereinbelow.
EXAMPLE 3
Various coating compositions are prepared in the manner of Example
1 and using 300 grams per liter (g/l) in each composition of zinc
flake. Each composition is also prepared to contain 40 g/l of
chromic acid. Further, with one exception, each composition is
prepared with 3 milliliters per liter (m/./l) of the wetter
described in Example 1. The one compositional exception, as shown
in Table 3 below, is the last formulation reported in the table. In
this last formulation, test results are obtained from a composition
wherein the dispersing agent is used in an amount supplying 21
volume percent of the coating bath. This coating blend is prepared
to determine the suitability of the dispersing agent as a complete
replacement for the high boiling organic liquid substance that
would otherwise be present. As above noted, all of the other
compositions that are represented in the table, include the 3 ml./l
of dispersing agent, including the composition first reported in
the table. This formulation first reported then contains no further
organic liquid substance and is used for comparative purposes.
The other coating blends listed in the table contain, as shown in
the table, either 10 volume percent of tetraethylene glycol (TEG)
or 10, 11 or 21 volume percent, of dipropylene glycol (DPG). Each
coating composition is then employed for the coating of 1/4 inch
.times. 3/4 inch hex head screws or for the coating of 1/4 .times.
5/8 SAE grade 2 hex bolts. The coating is conducted in a manner and
the coated parts are cured as described in Example 1. Coating
weights for the parts, as are shown in the table below, are
determined in the manner as described hereinabove.
In the table below corrosion resistance test results are shown for
the parts in the water soak test. In this test, 3-5 coated parts,
selected at random, are submersed in 50 milliliters of deionized
water contained in a glass beaker. The beaker is then covered. The
test quickly provides corrosion resistance data in a testing
procedure that is readily conducted.
Test results are reported, as determined for various submersion
times, all as shown in the table below; such a showing underscores
the achievement of significant results in a short elapsed time. In
the test, parts are rated in accordance with the system as
described hereinabove for salt spray testing and the results as
reported in the table are an average for the parts subjected to the
test.
TABLE 3 ______________________________________ Compound Coating
Compound Conc. Weight Water Soak, Hours Type Vol.% mgms./ft..sup.2
16 65 72 144 ______________________________________ None 0- 1824 --
10 -- 4 TEG 10 1734 8+ -- 5 -- DPG 10 1472 7 -- 5 -- DPG 11 1185 8
-- -- -- DPG 21 1920 10 10 -- 9 WETTER 21 2608 -- 8 -- 5
______________________________________ TEG= Tetraethylene glycol
DPG= Dipropylene glycol
As highlighted in the above reported results, the absence of a high
boiling organic liquid substance, although providing a significant
coating weight, does not result in a composition that will yield a
coating having desirable extended corrosion resistance. Moreover,
as shown by the results last reported in the table, the simple
addition of high boiling organic liquid substance, i.e. dispersing
agent, which also can lead to significant coating weights, will
also yield a very undesirable corrosion resistant coating. As is
also further evidenced in the table, the 10-11 volume percent of
high boiling organic liquid substance is insufficient to achieve
coatings that will assure excellent corrosion resistance.
EXAMPLE 4
The coating compositions of Example 3, with the exception of the
formulation containing 11 volume percent DPG, are used in the
manner of Example 3 to coat screws or bolts all in the manner of
Example 3. Coated parts, selected at random, are then subjected to
a coating adhesion test. This test, which may be conveniently
termed a "wipe adhesion" test, is manually conducted with the bolt
or screw and a paper towel.
While the threaded portion of the screw or bolt is firmly held in
one hand, a paper towel is held on a flat surface with the other
hand. A flat portion of the head of the coated part is then
manually pressed on to the towel and the part drawn across the
towel in a short firm stroke as the towel is held in place.
Following this procedure, the paper towel is then removed and
visually inspected for the size and area of the grayish-silver
streak that will be left on the towel.
From this visual observation, and by comparing many such streaks
one with the other, the wipe adhesion for parts is rated in
accordance with a system using the following guidelines:
10 no coating removal;
8 initial coating removal, incipient deposit on paper towel;
6 light removal;
4 medium coating removal, i.e. darker, large deposit on paper towel
than for (6);
2 heavy removal;
0 heavy removal approaching complete removal of coating.
In accordance with the above guidelines, the results for the parts
are shown below in Table 4.
TABLE 4 ______________________________________ Compound Coating
Compound Conc. Weight Type Vol.% mgms./ft..sup.2 Wipe Adhesion
______________________________________ None 0- 1824 5 TEG 10 1734 4
DPG 10 1472 4 DPG 21 1920 9+ WETTER 21 2608 2
______________________________________ TEG= Tetraethylene glycol
DPG= Dipropylene glycol
As detailed in the above reported results, wipe adhesion is more
than a function of coating weight. It is further interesting to
note that the replacement of the high boiling organic liquid
substance simply with the dispersing agent provides for a coating
of very poor adhesion. Moreover, simply eliminating the high
boiling organic liquid substance, provides for better coating
adhesion than for adding such substance in insufficient amount,
e.g. 10 volume percent. However, better than doubling this amount
of high boiling organic liquid substance provides for excellent
coating adhesion.
EXAMPLE 5
Many of the coating compositions of Example 3, with the exception
of the formulation containing 11 volume percent DPG, are again
employed in the manner of Example 3 to coat hex head screws. An
additional formulation, prepared and used in the manner as
described for the compositions of Example 3, is used; in this fresh
formulation, 21 volume percent TEG is employed. As in the above
Table 3, in Table 5 below the high boiling organic compound, as
well as its concentration, is shown for each formulation in further
combination with the coating weight obtained from the
formulation.
Some of the coated screws, selected at random, are subjected to the
above described salt spray test. In the test, parts are rated in
accordance with the system described hereinabove for salt spray
testing. The results are reported in Part B in Table 5 below. In
Part A of Table 5, results are listed for the salt spray test, and
in accordance with the rating systems described hereinabove for
such test, but it is conducted with coated panels.
These panels tested in Part A are 4 .times. 8 inches cold rolled,
low carbon steel panels. These panels are typically prepared for
coating in the manner described hereinabove for preparing parts for
coating. They are then simply coated by immersing the panels in the
coated formulation, removing the panel from the formulation and
permitting it to drain, followed by baking as described hereinabove
for curing coated test parts.
In Part C of Table 5, results are shown for salt spray testing
rated in the manner described hereinabove for such test, but prior
to the test the screws have had applied thereto a coating of
electrocoat paint. Thus, this testing provides an indication of the
adaptability of the coating for receiving subsequent topcoatings.
The electrocoat paint is a commercial water-based, black-pigmented
polyester-based paint. It is anodically deposited with an impressed
voltage of 100-150 volts for a duration of 30-60 seconds. Upon
removal from the electrocoat paint bath, the coating is rinsed and
then baked and the resulting coated articles are dry to the touch
and have the visual appearance of articles ready for commercial
use, prior to their being subjected to the salt spray test.
TABLE 5 ______________________________________ Part A: Panels
Compound Coating Compound Conc. Weight Salt Spray Type Vol.%
mgms./ft..sup.2 72 Hours ______________________________________ DPG
10% 728 1 DPG 21% 720 8 Part B: Hex-Head Screws Compound Coating
Compound Conc. Weight Salt Spray Type Vol.% mgms./ft..sup.2 72
Hours ______________________________________ DPG 10% 1472 1 TEG 10%
1734 1 DPG 21% 1920 9 Part C Under Electrocoat; Hex-Head Screws
Compound Coating Compound Conc. Weight Salt Spray Type Vol.%
mgms./ft..sup.2 One Week ______________________________________
None 0- 1824 4 DPG 10% 1472 2 TEG 10% 1734 3 TEG 21% 2336 6 DPG 21%
1920 7 WETTER 21% 2608 3 ______________________________________
The above tabulated results most particularly underscore the
significant enhancement of corrosion resistance that can be
obtained when the high boiling organic liquid is used above the 20
volume percent level as opposed to around the 10 volume percent
level. Further, it is especially noteworthy that a mere use of the
dispersing agent, and at a substantial concentration in a coating
composition, will not yield a coating that is a desirable topcoat
base. Also, for receiving a topcoating and forming a corrosion
resistant composite, the above results in Part C underscore that it
would be more desirable to omit the high boiling organic liquid
substance rather than employ it at a mere 10 volume percent
concentration. For achieving excellent corrosion resistance in the
coating composite, one must employ the high boiling organic liquid
substance at a substantial level, e.g., the 21 volume percent
level.
* * * * *