[0001] Water stains do not generally present problems for the structural properties and/or
corrosion performance of an aluminum product Aluminum surface discolorations that
accompany water staining may discomfort some customers who are unfamiliar with the
surface and corrosion properties of aluminum. Customers already aware of the properties
of cold rolled steel may mistakenly believe that water stains on aluminum are the
onset of "rusting", similar to that found on steel. For bright aluminum products,
such as buffed trailer plate, rail cars, tool boxes, running boards, and tread plate
on fire trucks, stain inhibition would preserve the buffed finish and enhance customer
satisfaction. A simple, low-cost solution to inhibit water stain on aluminum could
result in a higher degree of customer confidence in replacing steel with aluminum
for their products. In addition, aesthetics of these products is important to the
end customer. Water stains are aesthetically unattractive and their elimination or
reduction would be valuable to the owner whether it be an aluminum trailer, rail car,
tool box or other aluminum product
[0002] Numerous uses for organophosphonic acids in conjunction with aluminum arc known.
These include U.S. Patent Nos. 4,957,890, 5,032,237, 5,059,258, 5,103,550, 5,124,022,
5,124,289, 5,126,210, 5,132,181, 5,238,715, 5,277,788 and 5,463,804. None of these,
however, mention organophosphonic acids for the inhibition of stains, especially water
stains, on aluminum surfaces. Most of the aforementioned patents describe aluminum
surface pretreatments that enhance the durability of organic coatings or adhesively
bonded joints. They do not describe the use of organophosphonics without a topcoat.
[0003] Other methods for inhibiting corrosion with respect to aluminum and other metals
are disclosed in U.S. Patent Nos. 3,433,577, 3,672,822 and 4,427,448.
[0004] This invention addresses a low cost method for inhibiting water staining on 5000
Series, or 5XXX, aluminum alloys, most notably 5083-H32l and 5454-H32 aluminum (Aluminum
Association designations). Such alloys are used to make rail hopper cars and buffed
trailer tanks. Similar surprising and unexpected results have been observed when this
method was practiced on 6000 Series aluminum alloys, like the 6061-T6 alloys used
to make various products including vehicle wheels. According to this method, it was
determined that spraying a solution consisting of about 0.25 wt% octadecylphosphonic
acid (or "ODPA") in an isopropanol solvent (or other medium) onto these aluminum alloy
products, then allowing the alcohol to evaporate, is effective for inhibiting water
staining. Similar effects were subsequently observed with a carrier composition containing
octylphospbonic acid (or "OPA"). Suitable liquid carriers include alcohols, ketones,
ethers, aldehydes, alkanes, and other organic solvents with sufficient solubility
for the organophosphonic acids. These organophosphonic acid-derived solutions can
be applied to the metal surface by spraying, dipping, painting, or roll coating. It
is also recognized that the stain inhibitor component can be delivered to the aluminum
surfaces from various compositions used in the manufacttwe of aluminum parts, including
but not limited to: aqueous suspensions or solutions; metal forming lubricants, and
metal cleaning and/or rinsing formulations; a buffing compound or wax that incorporates
the stain inhibitor, metal heat treatment quench waters, and/or post-rinsing polishers/sealants
or the like. For certain stain inhibitor compounds, it is possible to buff a paste-like
stain inhibitor directly onto the aluminum product surface.
[0005] Further features, objectives and advantages of the present invention will be made
clearer from the following detailed description made with reference to the drawing
in which:
[0006] The FIGURE shows the schematic formation and orientation of hydrolytically stable
Al-O-P bonds of the stain inhibitor, octylphosphonic acid (OPA), as a reaction product
with an oxidized aluminum surface for effecting the stain inhibition observed according
to this invention.
[0007] Preliminary indications of the effectiveness of this invention, for inhibiting stains,
were observed in an accelerated corrosion test that involved outgassing products of
cthylvinylacetate plastic pellets (obtained from Millennium Petrochemicals), high
humidity and temperature cycling. After 12 temperature cycles, no water stains were
observed on 5000 Series alloy samples initially etched in caustic, then sprayed with
an ODPA-containing solution. Water staining was also inhibited for "mill finish" metal
sprayed with ODPA; though some spots were interspersed with unstained surface in the
latter case. By contrast, mill-finish and etched-only samples were completely covered
with water stains. It is believed that the difference in performance as a result of
pre-etching were most likely due to the removal of residual rolling lubricants via
etching. In that manner, the stain inhibiting molecules of this invention would be
allowed to chemically bond with surface aluminum oxides.
[0008] Chemical reaction of the inhibitor to the surface can also be achieved by changing
the means of application or using a different solvent. The surface ODPA inhibits access
of water to the aluminum oxide and forms hydrolytically stable bonds with the oxide,
thus inhibiting water staining. ODPA is a commercial compound manufactured and sold
by Albright & Wilson Ltd. Working solution concentrations and surface coverages of
this invention are relatively low, which results in low treatment costs of cents per
square foot of Al plate or sheet product. The same would be true for other aluminum
product forms, including castings, forgings and extrusions.
[0009] Another potential stain inhibitor, octylphosphonic acid (OPA), was evaluated. It
showed even better performance results than the ODPA samplings above. OPA has the
following chemical structure: CH
3(CH
2)
7P(O)(OH)
2. It can be applied with a water and surfactant carrier as effectively as with an
isopropanol carrier. OPA is more soluble than ODPA in isopropanol thus allowing for
increased solution concentrations. And while OPA is not water soluble, it forms a
suspension of solids with water. In either case, no volatile organic carbons (or VOC's)
result therefrom.
[0010] Preliminary humidity test results show that OPA is highly effective for inhibiting
stains on mill finish or buffed aluminum products without cleaning, pickling or pre-etching.
After three hours at 50°C (125°F) and 100% relative humidity, the OPA treated surface
was unstained, whereas "as-buffed", untreated surfaces were considerably stained.
[0011] It may also be possible to apply certain formulations by the methods of this invention
with no carrier solution. For example, one may directly buff a more solid form of
OPA onto an aluminum product surface. It is also possible, actually even more practical
depending on the aluminum surface to be treated, to incorporate the stain inhibiting
compounds of this invention into mill lubricants for providing an
in situ type of stain inhibition and eliminating subsequent processing steps. It may also
be possible to similarly add such stain inhibitors to buffing, sealing and/or polishing
compound formulations.
[0012] When the aluminum to be treated is mill finish or "as-buffed", a preferred carrier/solvent
is an alcohol, more preferably 2-propanol or isopropanol. Isopropanol is also beneficial
in that its solvent action is believed to displace residual mill lubricants or buffing
compounds and wet the surface aluminum resulting in the formation of Al-O-P bonds
with the oxidized aluminum surface. Isopropanol is also non-toxic. When the aluminum
surface has been pre-cleaned or etched, the choice of solvent is not as critical.
In many instances, water may be used to transport (or apply) such stain inhibitors.
[0013] In addition to forming hydrolytically stable Al-O-P bonds, organophosphonic acids
may provide yet another mechanism for stain inhibition. For example, when OPA or ODPA
reacts on the Al surface, the reaction end product is believed to orient or align
so that its hydrocarbon chains extend away from said surface. A schematic representation
of the bonding that is believed to take place is shown in the accompanying FIGURE.
The latter surface takes on a "hydrophobic" or non-wetting quality thereby further
inhibiting the conversion of oxides to hydroxides (or effecting a water stain thereon).
Under the latter scenario, longer chained organophosphonic acids become the preferred
stain inhibitors for this invention.
[0014] In some embodiments of this invention, a full (and not partial or non-uniform) haze
on the aluminuin product surface may form. It is preferred that such haze be wiped
away with a dry cloth to further enhance stain inhibition. On a less preferred basis,
this haze may removed by rinsing the aluminum product's outer surface.
[0015] Certain classes of phosphorus oxo acids, acid esters, and acid salts are effective
to various degrees in preventing water stains according to this invention. Phosphate
salts, phosphate esters, and phosphonic acids each impart some stain inhibition. In
comparative tests, however, octadecylphosphonic (C-18) acid (ODPA) and several fluoro-phosphonic
acids were not as effective as OPA (C-8) in inhibiting stains. Poly(vinylphosphonic
acid), and copolymers thereof, may work even better than OPA, but it is currently
cost prohibitive to use in commercial quantities. Some of the representative stain
inhibitors can be grouped by the following "families":
a) acidic aluminum phosphate salts

b) inorganic phosphorus oxo acids

c) organophosphonic and organophosphinic acids


d) phosphate acid esters

e) organo phosphonic acid polymers and copolymers; and
for example, poly(vinyl phosphonic-co-acrylic acid)
f) phosphate ester polymers
for example, poly(vinyl phosphoric acid)
[0016] This invention can be used to improve the stain inhibition of numerous aluminum alloy
surfaces, including various sheet or plate products, extrusions and forgings, regardless
of whether such products have welded joints or other connections. It is best suited
for any aluminum product that its purchaser, the end user/consumer, would prefer that
said product "look good" (i.e. brighter, less stained, etc.) longer! This includes
a whole family of building/architectural products, appliances, lighting supplies,
and other household cosmetics like vertical blind stock. On a preferred basis, the
method of this invention works well with 5000 and 6000 Series alloys (Aluminum Association
designation). It should also enhance the stain inhibiting performance of products
made from other aluminum alloys, including but not limited to 1000 and 3000 Series
alloys.
EXAMPLES:
First Study -
[0017] Several sections of buffed trailer tank plate product (made from 5454 aluminum alloy)
were sprayed with two comparative stain inhibiting compositions:
Set 1: 0.2 wt% octylphosphonic acid (OPA) in isopropanol; and
Set 2: 0.2 wt% octadecylphosphonic acid (ODPA) in isopropanol.
Haze on both sets of sprayed plates was rinsed away with water, then gently buffed
with dry cheesecloth. These treated plates, along with an "as-buffed" control, were
then placed in a humidity cabinet at 50°C (125°F) with 100% relative humidity for
3 hours. After exposure, the plates were removed from the cabinet, dried with a towel,
and visually examined for staining.
[0018] No noticeable loss of specularity was observed with either of the above stain inhibition
treatments. All surfaces had the same visual appearance as the "as-buffed" sample.
After humidity exposure, however, brownish colored, water stains were evident over
a majority of the "as-buffed" and ODPA-treated surfaces. The OPA treated surface did
not exhibit any water stains and appeared the same as unexposed specimens. While ODPA
specimens did not fare as well as OPA in this particular study, as compared with its
earlier positive results, different application techniques are believed to have caused
its reduced stain inhibiting performance here.
Second Study - Tanker Trial results
[0019] A covered hopper trailer, made from 5454 aluminum Bulk Transportation Sheet ("BTS")
was treated with various applications according to the invention before being exposed
to harsh, in-service conditions: from an aggressive environment of salt air due to
seacoast proximity; and harsh winter conditions with numerous road salt applications.
Subsections of this hopper/tanker were treated as follows: (a) 1 wt.% solution of
OPA, in isopropanol, was sprayed on the first section of tanker, dried to a film,
water rinsed and air dried thereafter; (b) the same solution as above was sprayed
onto another adjoining section of the same hopper/tanker, then dried to a film and
wiped to an initial shine using cheesecloth; (c) for this section of hopper/tanker,
the treatment material was 1 wt% OPA, suspended in water. After spraying, this water-based
solution was allowed to sit on the product surface for about 10 minutes before being
dried and wiped to a shine with cheesecloth. The last comparative section of hopper/tanker
was sprayed with a 5 wt.% solution of OPA, in water, before being allowed to sit for
10 minutes, then water rinsed and air dried.
[0020] After three months of service along the U.S. East Coast, this hopper/trailer was
brought back for inspection. While OPA treatments were observed to provide a substantial
degree of water stain inhibition over that 3 month trial period, one of the first
conclusions drawn from that inspection was that monthly reapplications could ensure
a pristine, polished surface on such trailer stock.
[0021] Following a wash with non-etching alkaline cleaner, various sides and subsections
of this hopper/tanker were photographed and closely compared by visual inspection.
From that inspection, it was noted that the water-based sections of treated hopper
fared better than their alcohol-based counterparts (in terms of water staining inhibition).
In addition, wiping to a shine after application of the OPA, as per example (a) above,
was most effective, even more than merely applying, rinsing and air drying, the latter
treatment resulting in a noticeable, residual haze at first
Third Study - Coil Line Trial
[0022] A coil of 5182-H19 aluminum sheet was roll coated with a 5% aqueous suspension of
OPA. Phosphorus surface concentrations were measured on the treated surface using
X-ray fluorescence spectroscopy (XRF). From previous bench scale tests, it was observed
that phosphorus surface levels of about 2 Kcps were sufficient for inhibiting water
staining. Phosphorus surface levels on the aforementioned sheet product were measured
at about 10 Kcps, however.
Fourth Study - Forged Truck Wheels
[0023] Forged and polished truck wheels made from aluminum alloy 6061-T6 were treated with
comparative solutions of 0.5 and 1 wt.% OPA in isopropanol. For testing, the treated
wheels were placed into a cabinet with condensing humidity set at 100°F. The wheels
were examined every hour for water stains. The tests were stopped after 120 hours
of humidity exposure. Untreated wheels (as-polished) were substantially stained within
11 hours of humidity exposure. The wheels that were treated with OPA, then buffed
to shine lasted the longest without substantial water staining. On certain OPA-treated
wheels, only a few small, widely dispersed spots were observed after 120 hours of
exposure testing, but that level of staining was insignificant compared to the gross
quantities of water staining observed on the untreated wheels after only 11 hours
of humidity exposure.
Fifth Study - Lighting Sheet
[0024] Aluminum alloy 5657-H18, used for making bright lighting sheet, was treated with
a 5 wt.% solution of OPA stain inhibitor in isopropanol. Specular reflectance measurements
showed that after buffing the resultant haze from said sheet surfaces, the OPA treatment
did not reduce reflectivity. Furthermore, such OPA-treated panels lasted up to 13
days in condensing humidity at 100°F without staining, as compared to their untreated
sheet equivalents that were significantly stained within 24 hours of such humidity
exposure.
Sixth Study - Quench Water Additions
[0025] Phosphorus compounds, like those described above, were added to the quench waters
used for making extruded tubes and rolled sheet from 6061-T6 alloy. In this comparison,
the aluminum product forms were heated to about 1000°F before being cold water quenched,
said quenching solution containing various phosphorus compounds. Thereafter, these
products were allowed to remain in the quench water for 24 hours. By visually examining
these aluminum product forms, and by further measuring the amount of hydroxides formed
thereon using Fourier-transform infrared spectroscopy (FT-IR), it was determined separately
that 10 g/L solutions of dibasic ammonium phosphate - (NH
4)
2HPO
4 - and 10 g/L phytic acid best prevented the formation of water stains on these products.
They also prevented the formation of bayerite powders on the interior aluminum surfaces
of these extruded tubes.
1. A method for inhibiting formation of stains on an exposed exterior of an aluminum
alloy product, said method comprising:
contacting the exposed exterior with a material that is capable of forming a hydrolytically
stable Al-O-P bondtherewith, said material selected from an organophosphonic acid
or organophosphonic acid polymer, or copolymer; an acidic aluminum phosphate salt;
and inorganic phosphorus oxo acid; an organophosphinic acid; a phosphate acid ester;
and an organophosphate acid ester polymer or copolymer, or mixtures thereof.
2. The method of claim 1, wherein the material consists essentially of an organophosphonic
or organophosphinic acid.
3. The method of claim 2, wherein the material is a solid or semi-solid at room temperature
and manually applied to the exposed exterior of the aluminum alloy product.
4. The method of claim 2, wherein the material is a liquid at room temperature and combined
with a carrier selected from the group consisting of: an alcohol, a ketone, an ether,
an aldehyde, an alkane, water and mixtures thereof.
5. The method of claim 4, wherein the, material consists essentially of octadecylphosphonic
acid and the carrier includes isopropanol.
6. The method of claim 4, wherein the material consists essentially of octylphosphonic
acid and the carrier is isopropanol, water or mixtures thereof.
7. The method of claim 4, wherein said exposed exterior is contacted with an aqueous
solution containing up to 10 wt.% octadecylphosphonic acid or octylphosphonic acid,
5-90 wt.% isopropanol, a balance of water and impurities.
8. The method of claim 4, wherein said exposed exterior is contacted with an aqueous
solution containing 0.5-10 wt.% octylphosphonic acid, a balance of water and impurities.
9. The method of claim 4, wherein said contacting includes: spraying, dipping, painting
or rolling material on said exposed exterior of said alloy product.
10. The method of claim 9, wherein said material is incorporated into a composition for
surface treating said alloy product.
11. The method of claim 10, wherein said composition is a mill lubricant, a quenching
solution, an intermediate rinse, an etching solution, a solvent, a surfactant, a cleaner,
a polish, a post-rinse, a sealant or mixtures thereof.
12. The method of claim 2, wherein said alloy product is sheet product, plate product,
an extrusion or a forging.
13. The method of claim 12, wherein said alloy product is:
(a) a sheet or plate product having at least one bright exterior surface and is suitable
for making transportation goods therefrom, said goods consisting of trailer plate,
rail car skin, tool boxes, vehicle running boards or tread plate;
(b) a sheet product used to make reflective lighting sheet;
(c) an extrusion used to make transportation or household goods therefrom, said goods
consisting of: truckbed rails, hydraulic tubing, window frames, tub and shower frames,
and greenhouse structural supports; or
(d) a vehicle wheel.
14. The method of claim 1, which further includes rinsing said material from the exposed
exterior, and/or wiping said exposed exterior.
15. The method of claim 1, wherein said alloy product is made from a 1000, 3000, 5000
or 6000 Series aluminum alloy (Aluminum Association designations).
16. The method of claim 15, wherein said 5000 Series aluminum alloy is: 5083, 5086, 5454,
5657, 5182, or 5454 aluminum (Aluminum Association designations).
17. The method of claim 15, wherein said 6000 Series aluminum alloy is 6061, 6111 or 6022
aluminum (Aluminum Association designations).