U.S. patent number RE31,198 [Application Number 06/189,743] was granted by the patent office on 1983-04-05 for method for cleaning aluminum at low temperatures.
This patent grant is currently assigned to Amchem Products, Inc.. Invention is credited to Robert E. Binns.
United States Patent |
RE31,198 |
Binns |
* April 5, 1983 |
Method for cleaning aluminum at low temperatures
Abstract
Lubricants and metallic fines are removed from aluminum surfaces
by contacting the surfaces with an aqueous solution containing an
active fluoride compound, sulfuric acid, and a surfactant.
Inventors: |
Binns; Robert E. (Roslyn,
PA) |
Assignee: |
Amchem Products, Inc. (Ambler,
PA)
|
[*] Notice: |
The portion of the term of this patent
subsequent to February 22, 1994 has been disclaimed. |
Family
ID: |
26885460 |
Appl.
No.: |
06/189,743 |
Filed: |
September 23, 1980 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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755928 |
Dec 30, 1976 |
4116853 |
|
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607154 |
Aug 25, 1975 |
4009115 |
|
|
|
442726 |
Feb 14, 1974 |
|
|
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Reissue of: |
755929 |
Dec 30, 1970 |
04124407 |
Nov 7, 1978 |
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Current U.S.
Class: |
134/3; 134/10;
134/40; 134/41; 510/257; 510/487; 510/506 |
Current CPC
Class: |
C23G
1/125 (20130101) |
Current International
Class: |
C23G
1/02 (20060101); C23G 1/12 (20060101); B08B
003/08 (); C23G 001/12 () |
Field of
Search: |
;134/3,10,40,41
;252/142-145,79.3,79.4 ;204/35R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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825546 |
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May 1975 |
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BE |
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536710 |
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Feb 1957 |
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CA |
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850046 |
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Aug 1970 |
|
CA |
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868314 |
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Apr 1971 |
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CA |
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1202615 |
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Oct 1965 |
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DE |
|
881701 |
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May 1943 |
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FR |
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50-115630 |
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Sep 1975 |
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JP |
|
543770 |
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Mar 1942 |
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GB |
|
877240 |
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Sep 1961 |
|
GB |
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Other References
Hess et al., "The Surface Treatment at Room Temperature of Al
Alloys for Spot Welding", J. American Welding Soc., Sep. 1944, pp.
417s-423s. .
Akers et al., "Cleaning Aluminum", Soap and Sanit. Chem., vol. 17,
Apr. 1941, pp. 25-27, 71, 73-74. .
Wernick et al., Surface Treatment and Finishing of Aluminum and its
Alloys, 1956, pp. 74, 89, 129, 147. .
Harris et al., Annotated Bibliography of Aluminum Cleaning, Jan.
1943, (pp. 33-36); Mar. 1943 (pp. 33-38); May 1944 (pp. 35-40).
.
Amchem Products, Inc. Data Sheet, "Ridoline" 121/122/123, Apr.
1975, all pages pertinent. .
Harris, Metal Cleaning Bibliographical Abstracts, Publ. No. 90
(1949-pp. 1-68); Publ. No. 90A (1950, pp. 1-27); Publ. No. 90D
(1957, pp. 1-38). .
Mona Industries Inc., "Monaterge LF-945", Tech. Bulletin No. 230,
Dec. 1975, pp. 1-2..
|
Primary Examiner: Caroff; Marc L.
Attorney, Agent or Firm: Barron; Alexis
Parent Case Text
BACKGROUND OF THE INVENTION
This is a Continaution-In-Part application of application Ser. No.
607,154, filed on Aug. 25, 1975, now U.S. Pat. No. 4,009,115, which
is a continuation-in-part application of application Ser. No.
442,726 filed on Feb. 14, 1974, now abandoned. This application is
a divisional application of copending application Ser. No. 755,928,
filed on Dec. 30, 1976.Iadd., now U.S. Pat. No. 4,116,853.Iaddend..
The entire disclosures of all of said applications are hereby
incorporated by reference.
Claims
What is claimed is:
1. A process for cleaning an aluminum surface having thereon
deposits of aluminum fines and lubricant consisting essentially of
removing said deposits by contacting said surface with an aqueous
cleaning solution comprising hydrofluoric acid in a comcentration
of about .Badd.0.005 to about 0.1 gram per liter of said aqueous
cleaning solution and sulfuric acid in a concentration of about 1.0
to about 10 g/l of said aqueous cleaning solution and having a
surfactant dissolved therein.Iadd., wherein the aluminum of said
surface is 3004 alloy or an aluminum alloy substantially equivalent
thereto.Iaddend..
2. A process according to claim 1 wherein the amount of sulfuric
acid in said cleaning solution is sufficient to reduce the pH of
less than 1.8.
3. A process according to claim 2 wherein the aqueous cleaning
solution is contacted with an aluminum surface by spraying said
solution on to the surface.
4. The process according to claim 3 wherein the temperature of the
spray solution is below 135.degree. F.
5. The process according to claim 4 wherein the aluminum surface is
sprayed with said aqueous cleaning solution for periods of less
than about 2 minutes.
6. A process according to claim 4 wherein the aluminum surface is
an aluminum can.
7. A process for cleaning aluminum surfaces .[.to remove.].
.Iadd.having thereon deposits of aluminum fines and lubricants
consisting essentially of removing said .Iaddend.lubricants and
metallic fines .[.which comprises.]. .Iadd.by .Iaddend.contacting
said surface with an aqueous cleaning solution, comprising active
fluoride expressed as hydrofluoric acid at a concentration in said
solution of about 0.005 to about 0.1 gram per liter and sulfuric
acid in a concentration of about 1.0 to about 10 g/l of said
aqueous cleaning solution and having a surfactant dissolved
therein.Iadd., wherein the aluminum of said surface is 3004 alloy
or aluminum alloy substantially equivalent thereto.Iaddend..
8. A process according to claim 7 wherein an aluminum surface is
contacted with said aqueous cleaning solution by spraying said
surface with said solution at a temperature below 135.degree. F.
for a period of less than about 2 minutes.
9. A process according to claim 7 wherein said aluminum surface is
contacted with said aqueous cleaning solution by immersing said
aluminum surface into a bath containing said aqueous solution
maintained at a temperature below about 135.degree. F.
10. A process according to claim 9 wherein the time of immersion is
less than about 2 minutes.
11. A process according to claim 7 wherein the active fluoride
concentration of the cleaning solution is maintained at a level
equivalent to a make-up concentration of about 0.005 to about 0.1
gram per liter of hydrofluoric acid while said solution is
continuously used in cleaning aluminum surfaces by adding
hydrofluoric acid to the solution at a rate sufficient to maintain
electrode potential of the solution as measured by a fluoride
specific ion electrode placed in the solution substantially
constant and adding sulfuric acid at a rate sufficient to maintain
the pH of the solution substantially constant.
12. A process according to claim 11 wherein the aluminum surface is
an aluminum can.
13. A process according to claim 11 wherein the concentration of
active fluoride in the cleaning solution expressed as concentration
of hydrofluoric acid is maintained between about 0.005 and about
0.03 gram per liter. .Iadd. 14. A process for cleaning an aluminum
surface having thereon deposits of aluminum fines and lubricant
consisting essentially of removing said deposits by contacting said
surface with an aqueous cleaning solution consisting essentially of
hydrofluoric acid in a concentration of about 0.005 to about 0.1
g/l of said aqueous cleaning solution and sulfuric acid in a
concentration of about 1.0 to about 10 g/l of said aqueous cleaning
solution and having a surfactant dissolved therein. .Iaddend.
.Iadd. 15. A process for cleaning an aluminum surface having
thereon deposits of aluminum fines and lubricant, the aluminum of
said surface being 3004 alloy or an aluminum alloy substantially
equivalent thereto, consisting essentially of removing said
deposits by contacting said surface with an aqueous cleaning
solution consisting essentially of hydrofluoric acid in a
concentration of about 0.005 to about 0.1 g/l of said aqueous
cleaning solution and sulfuric acid in a concentration of about 1.0
to about 10 g/l of said aqueous cleaning solution and having a
surfactant dissolved therein. .Iaddend..Iadd. 16. A process
according to claim 14 or 15 wherein said surface is that of an
aluminum can. .Iaddend.
Description
Containers comprised of aluminum and alloys thereof are produced in
a drawing and forming operation, referred to as "drawing and
ironing", which results in the deposition of lubricants and forming
oils on the surface. In addition, residual aluminum fines, i.e.
small particles of aluminum, are deposited on the interior and
exterior surfaces of the container during the forming operation.
Ordinarily, the exterior surface of the container will have smaller
quantities of aluminum fines since during the drawing and ironing
step the exterior surface is not subject to as much abrasion from
the die as the interior surface.
Prior to any processing steps, such as conversion coating and
sanitary lacquer deposition, the surfaces of the aluminum
containers must be clean and water-break-free so that there are no
contaminants which prevent further processing and which render the
containers unacceptable for use.
Acid cleaners have been employed to clean the aluminum surfaces and
to remove aluminum fines deposited on the interior walls of
aluminum containers. Acid cleaning is ordinarily accomplished at
temperatures from 185.degree. F. to 200.degree. F. in order to
remove or dissolve the aluminum fines and to remove the lubricants
and forming oils so that the surface is rendered water-break-free.
The cleanliness of the aluminum surface is measured by the ability
of the interior and exterior surfaces of the formed aluminum
container to support a continuous break-free film of water, that is
to be water-break-free.
Due to the high temperatures at which cleaning is accomplished,
that is from 185.degree. F. to 200.degree. F., and the acidity of
the cleaning composition, the processing equipment employed to heat
the cleaning composition, particularly the fire tubes of gas fired
heat exchangers, are susceptible to corrosion. Furthermore, the
high temperatures increase operating costs and fuel
consumption.
Chromic acid or salts thereof have been utilized to minimize the
corrosion of the processing equipment by inhibiting the corrosive
attack of the acid cleaning composition on the processing
equipment. An important shortcoming which cleaners of this kind
possess is the inherent toxicity of the hexavalent and trivalent
chromium compounds contained therein and the resultant waste
disposal problem created by the presence of chromium in the cleaner
effluent.
Attempts have been made to include other additives in the cleaning
compositions to provide efficient cleaning. Such additives have
included fluoride. Maintenance and control of acidic cleaners at
low pH's has proven impractical, especially when fluorides are
present. Furthermore, as such cleaning is effected at high
temperatures, the fluoride when present in high concentrations can
attack the metal surface and etch the surface which is undesirable,
especially when cleaning of containers is to be effected.
The principal object of this invention is to provide a cleaning
composition for aluminum for removing and dissolving aluminum fines
and for cleaning lubricating oils from the aluminum surface.
An object of this invention is to provide a process for cleaning
aluminum surfaces at low temperatures thereby reducing corrosion
and attack of processing equipment and reducing heating costs and
heating fuel consumption.
An added object of this invention is to provide a cleaning
composition possessing good cleaning ability and preventing
corrosive attack of processing equipment while having no chromate
therein.
Another object is to provide a cleaning solution which produces no
sludge during operation.
A concomitant object of this invention is to provide a cleaning
solution having relatively low concentrations of hydrofluoric acid,
which can be easily controlled and which enables the cleaning of
aluminum surfaces with little or no etching of the surface.
DETAILED DESCRIPTION OF THE INVENTION
I have discovered a composition and process for removing and
dissolving aluminum fines and lubricating oils from an aluminum
surface, said composition comprising a concentration of
hydrofluoric acid of from about 0.005 to about 0.7 grams per liter
and a sufficient concentration of sulfuric acid to maintain the pH
between about 0.6 and about 2.5 ordinarily below 2.0. When the
foregoing aqueous cleaning composition is utilized removing and
dissolving aluminum fines and lubricating oils may be accomplished
at temperatures as low as from about 70.degree. F. to about
140.degree. F.
It should be understood that the term aluminum surface used herein
includes aluminum and aluminum alloys in which aluminum is the
principal constituent. It should be understood that by "cleaning
composition", or "cleaning solution" I mean the aqueous acidic
cleaning bath of the present invention comprising hydrofluoric acid
and sulfuric acid.
The surprising results obtained with the use of the cleaning
solution include the removal and dissolution of aluminum fines from
a formed aluminum container, both on the interior walls and dome of
said container, at temperatures within the range of from about
70.degree. F. to about 140.degree. F. In addition, it has been
found that with the use of the cleaning solution of the present
invention corrosive attack of the processing equipment,
particularly the fire tubes of gas fired heat exchangers, is
reduced considerably. This is accomplished without the use of any
inhibitors in the cleaning solution, such as hexavalent
chromium.
I have found that active fluoride is a necessary constituent which
is responsible for assisting in dissolution of the aluminum fines
and oil film removal. In the present cleaning process it is
essential that the active fluoride be maintained within specified
limits, since the active fluoride affects the aluminum fine
dissolution and oil film removal.
The term "active fluoride" means the fluoride present in the
operating cleaning solution and measurable at a given pH by a
fluoride sensitive electrode of the potentiometric type. For
example, electrodes of this type and their use are described in
U.S. Pat. No. 3,431,182 which is hereby incorporated by reference.
The electrodes described therein are known to the art as fluoride
specific ion electrodes.
Due to the low concentration of hydrofluoric acid in the cleaning
solution of this invention, a potentiometric type electrode is
found to be preferable for measuring active fluoride. Other
measuring devices that are not of the potentiometric type are
insensitive to the concentration of hydrofluoric acid in the
cleaning solutions of the present invention, as they are useful
only in concentrated solutions or solutions having higher
concentrations of hydrofluoric acid.
With the use of the potentiometric type electrode, the active
fluoride measurement is measured as a potential which is
proportional to or related to the actual fluoride ion concentration
in the solution.
It is known that in acid solutions containing fluoride, hydrogen
ion complexes a portion of the fluoride forming undissociated HF
and HF.sub.2.sup.-. In addition, when aluminum is dissolved in such
solutions, Al.sup.+3 also complexes fluoride. Due to the presence
of these complexing agents, it is difficult to measure actual free
fluoride ion concentration without extensive sample manipulation.
However, by the use of the potentiometric type electrode, once a
reference point has been arrived at by measuring a make-up cleaning
solution potential and taking this potential as the zero point, it
is inconsequential how much fluoride is actually complexed. The
potential increases negatively in more concentrated solutions, that
is when the active fluoride concentration increases, and the
potential increases positively in more dilute solutions, that is
when the active fluoride concentration decreases. When aluminum
ions enter the solution as aluminum fines are removed from the
surface, the electrode potential becomes more positive as the
amount of active fluoride decreases. When additions of hydrofluoric
acid are effected, the potential becomes less positive and
approaches the zero point again. Since the potentiometric type
electrode will measure the active fluoride in the solution, taking
no account of any complexed fluoride, additions of active fluoride,
preferably as hydrofluoric acid, can be made to the operating
cleaning solution to return the potential measurement to the
original zero reference point.
Such potentiometric type electrodes may also be utilized to measure
the actual concentration of hydrofluoric acid present in a cleaning
composition. Exemplary of a procedure which may be utilized to
determine the concentration of hydrofluoric acid in a cleaning
solution is as follows:
EXEMPLARY PROCEDURE FOR DETERMINING HYDROFLUORIC ACID
CONCENTRATION
Utilizing standard solutions and a potentiometric type electrode,
standard curves of "Millivolt Response" vs "pH of Cleaning
Solution", at various concentrations of hydrofluoric acid are
determined. FIG. 1 is exemplary of such standard curves.
The potentiometric type electrode used to prepare FIG. 1 and which
may be utilized for determining the concentration of hydrofluoric
acid is generally, any pH meter with an expanded millivolt scale,
equipped with an Orion fluoride ion electrode and a standard
calomel reference electrode. Exemplary of such meters are the
Ionalyzer.RTM. Fluoride Ion Activity Electrode Model 94-09 (Orien
Research, Incorporated).
In order to measure the concentration of hydrofluoric acid in a
sample cleaning solution three standard solutions are prepared:
Cleaning Solution Standard I-0.010 grams/liter HF
Cleaning Solution Standard II-0.020 grams/liter HF
Cleaning Solution Standard III-0.040 grams/liter HF
The above standard solutions are prepared from hydrofluoric acid
and a sufficient concentration of sulfuric acid to maintain the pH
between 1.29 and 1.45 at 25.degree. C. and, optionally surfactants,
that is, from ingredients substantially similar to the sample
cleaning composition for which the concentration of hydrofluoric
acid is to be determined.
The following procedures should be followed:
Step 1. Rinse electrodes with DI water and wipe dry with soft
tissue paper.
Step 2. Immerse the electrodes into Cleaning Solution Standard II.
The .[.soluton.]. .Iadd.solution .Iaddend.should be stirred or
swirled during measurements. Switch the function selector to the
expanded millivolt scale. At 100% slope and 25.degree. C., adjust
the meter response to read 0.0 millivolts using the calibration
knob. This corresponds to 0.020 grams/liter HF;
Step 3. Repeat Step 1;
Step 4. Immerse the electrodes into one of the other solution
standards. While stirring and having the meter set at 100% slope
and 25.degree. C., make the measurement. Cleaning Solution Standard
I should read +18 millivolts .+-.2.0 m.v. Cleaning Solution
Standard III should read -22 millivolts .+-.2.0 m.p.
This procedure should be carried out once every 24 hours under
normal plant conditions. In case of deviations greater than
indicated above the fluoride ion electrode should be checked by
changing to a new fluoride ion electrode using the above procedure.
After the correct fluoride ion electrode response has been
established, Cleaning Solution Standard II should be used for
standardization between sample measurements.
SAMPLE MEASUREMENT
After standardization and proper rinsing and drying of the
electrodes, the sample to be checked should be cooled to 25.degree.
C. and the electrodes immersed into it. The bath sample should be
stirred. After noting the millivolt response on the expanded scale,
the pH of the bath sample is determined in a known manner. After
establishing the correct pH and millivolt reading, the
concentration of HF is determined by reading the value from, for
example, FIG. 1.
Eg. At a pH of 1.1. and a m.v. reading of +20, the concentration is
equivalent to 0.0185 grams/liter HF At pH 1.2 and +5 m.v.=0.025
grams/liter HF.
It has been discovered that as a cleaning solution is used,
aluminum is dissolved off the surface being treated at a specific
rate. In general, cleaning solutions of the present invention will
have operating characteristics such that at make-up the aluminum
dissolution rate is from about 8 to about 25 milligrams per square
foot (0.009 to 0.027 mg/cm.sup.2) of aluminum surface treated. It
has been observed that best results, with minimal etch of the
surface, are obtained when the aluminum dissolution rate is from 9
to 20 milligrams per square foot (0.01 to 0.022 mg/cm.sup.2) of
aluminum surface treated. This dissolution rate occurs at make-up
of a cleaning solution having a preferred concentration of
hydrofluoric acid of from about 0.005 to about 0.1 grams/liter of
hydrofluoric acid. By establishing a zero potential point with a
potentiometric type electrode at make-up of the cleaning solution,
and by recording the potential measurements as metal surfaces are
processed and cleaned, the aluminum dissolution rate is maintained
within the preferred range by additions of active fluoride,
preferably as hydrofluoric acid.
The potentiometric electrode is therefore used as a guideline for
determining when to adjust the amounts of active fluoride in
solution, also to maintain sufficient active fluoride therein to
effect a desirable aluminum dissolution rate, and also in
determining the hydrofluoric acid concentration of unknown cleaning
solutions.
The active fluoride suitable for use herein is preferably added to
the cleaning composition as hydrofluoric acid. A simple fluoride
salt can also be utilized, for example, an alkali metal fluoride or
bifluoride such as sodium fluoride, ammonium fluoride or
bifluoride. Complex fluoride can be employed. However, greater
concentrations of complex fluoride will be necessary to yield
desirable amounts of active fluoride, as the hydrolysis of complex
fluorides is not as substantial as with the simple fluoride, to
liberate the required active fluoride.
The amount of active fluoride in the cleaning solution is expressed
herein as a concentration of hydrofluoric acid. This means that the
active fluoride is in the form of dissociated fluoride whose
concentration is expressed as the concentration of hydrofluoric
acid.
The active fluoride in the cleaning solution aids in the removal of
aluminum fines on the metal substrate which have formed during the
forming operation. A surprising aspect of this invention is that
the cleaning process can be effected when the amount of
hydrofluoric acid present in the solution, is as low as 0.005
grams/liter. I have found that by employing the preferred amount of
hydrofluoric acid, resulting in the presence of sufficient active
fluoride, removal of the aluminum fines is accomplished without
vigorous attack of the underlying aluminum surface. Of course,
should the active fluoride be depleted in the cleaning solution,
preferably it can be replenished by addition of hydrofluoric
acid.
Sulfuric acid in the cleaning solution should be present in
sufficient concentration to maintain the pH between 0.6 and 2.5.
This concentration of sulfuric acid is an amount from about 0.1 to
about 60 grams/liter, preferably from about 1.0 to about 10
grams/liter. It is particularly preferred that the concentration of
sulfuric acid be present in an amount from about 3 to about 5
grams/liter.
The hydrofluoric acid should be present in the cleaning solution in
an amount from about 0.005 to about 0.7 grams/liter, preferably
about 0.005 to about 0.1 grams/liter. For optimum results, it is
preferred that the hydrofluoric acid be present in an amount from
about 0.01 to about 0.03 grams/liter.
In the preferred embodiment of this invention an operating cleaning
solution is employed comprising hydrofluoric acid and sulfuric acid
wherein the concentration of constituents, at the beginning of
operation as well as upon replenishment, is maintained such that
the sulfuric acid is present in amount from about 3 to about 5
grams/liter, and the active fluoride is maintained at the level
measured at make-up, that is when the hydrofluoric acid
concentration at make-up is about 0.01 to about 0.03 grams/liter.
When a cleaning solution is operated and maintained within these
preferred limits it has been found that excellent cleaning of the
aluminum surface will result. A most surprising result is that the
surface will be free of oils and aluminum fines without the
corrosive attack of processing equipment occurring.
The cleaning solution preferably is prepared by employing aqueous
concentrates consisting of sulfuric acid and water, and
hydrofluoric acid and water. The aqueous concentrates can be added
to an appropriate amount of water to prepare a working cleaning
solution having constituent concentrations and pH within the
operative ranges set forth herein. Alternatively, the hydrofluoric
acid and sulfuric acid can be prepared as a concentrate and can be
added simultaneously as one component to water to form the aqueous
cleaning composition at concentrations for use.
Surfactants are desirably included in the cleaning composition.
Such materials enhance the cleaning performance considerably. It
has been observed that the use of surfactants in the cleaning
solution assist in more rapid wetting of the surface and the
removal of lubricant and oils. The surface active agents to be
employed herein can be anionic, cationic, or nonionic. Preferably
nonionic or anionic surface active agents are used.
Examples of surface active agents that can be utilized are:
Tergitol Anionic--08 (Union Carbide Corporation) an anionic
surfactant believed to be sodium 2-ethyl hexyl sulfate;
Triton DF-16 (Rohm & Haas Co.) a nonionic surfactant believed
to be a modified polyethoxylated straight chain alcohol;
Polytergent S-505 LF (Oline Corp.) a nonionic surfactant believed
to be a modified polyethoxylated straight chain alcohol;
Surfonic LF-17 (Jefferson Chemical Co.) a nonionic surfactant
believed to be an alkyl polyethoxylated ether;
Plurafac RA-30 (BASF Wyandotte Corp.) a nonionic surfactant,
believed to be a modified oxyethylated straight chain alcohol;
Plurafac D-25 (BASF Wyandotte Corp.) a nonionic surfactant believed
to be a modified oxyethylated straight chain alcohol;
Triton X-102 (Rohm & Haas Co.) a nonionic surfactant believed
to be an octyl phenoxy poly ethoxy ethanol;
Antarox BL 330 (GAF Corp.) a nonionic surfactant believed to be an
alkyl poly (ethyl-eneoxy) ethanol;
Triton CF-10 (Rohm & Haas Co.) a nonionic surfactant, and
believed to be an alkylaryl polyether having a carbon chain of
about 14 carbon atoms and approximately 16 moles of
ethoxylation;
Surfactant AR 150 (Hercules, Inc.) a nonionic surfactant, and
believed to be an ethoxylated abietic acid derivative with
approximately 15 moles of ethoxylation;
Pluronic L061 (BASF Wyandotte, Inc.) a nonionic surfactant, and
believed to be a condensate containing only ethylene oxide and
propylene oxide chains;
Antarox LF-330 (GAF Corp.) a nonionic surfactant, believed to be an
alkyl poly(ethyleneoxy) ethanol;
Pegosperse 700-TO (Glyco Chemicals, Inc.) a nonionic surfactant,
and believed to be an abietic acid ester containing approximately
14 to 16 moles of ethoxylation;
Igepal CA-630 (GAF Corp.) a nonionic surfactant, believed to be an
alkyl phenoxy poly (ethyleneoxy) ethanol;
Trycol LF-1 (Emery Industries, Inc.) a nonionic surfactant believed
to be an alkyl poly ether; and
Renex 20 (I.C.I. United States, Inc.) a nonionic, polyoxyethylene
ester of mixed fatty acids and resin acids.
The surface active agent present in the cleaning composition can be
a combination of one or more particular surface active agents. The
surface active agent can be present in the cleaning composition in
an amount from about 0.1 to about 10 grams/liter.
Concentrates which may be used in the formulation of aqueous
cleaning compositions are exemplified below.
______________________________________ CONCENTRATES CONTAINING
HYDROFLUORIC ACID Weight % ______________________________________
FORMULA l 70% Hydrofluoric Acid 20.55 Water 79.45 100% Specific
Gravity: 1.043 .+-. .005 at 60.degree. F. Freezing Point:
-2.degree. F. Flash Point: None FORMULA 2 Hydrofluoric Acid (70%)
20.5 non-ionic surfactant Plurafac D-25 3.0 Water 76.5 100%
Specific Gravity: 1.051 .+-. .005 Freezing Point: -5.degree. F.
Flash Point: None Cloud Point: 78.degree. F.
______________________________________
______________________________________ CONCENTRATES CONTAINING
SULFURIC ACID ______________________________________ FORMULA 3
Weight % ______________________________________ 66.degree. Sulfuric
Acid 34.52 water 65.48 100% Specific Gravity: 1.239 .+-. .005 at
60.degree. F. ______________________________________ FORMULAS 4-8
Weight % 4 5 6 7 8 ______________________________________
66.degree. Be Sulfuric Acid 45 45 34.3 34.2 34.2 Non-ionic
Surfactant 10 14 5.3 7.5 10.6 Surfonic LF-17 Water 45 41 60.4 58.3
55.2 100% 100% 100% 100% 100% Specific Gravity 1.337 1.335 1.246
1.248 1.249 [at 60.degree. F. (.+-..005)] Freezing Point Below
Below Below Below Below 0.degree. F. 0.degree. F. 0.degree. F.
0.degree. F. 0.degree. F. Flash Point None None None None None
______________________________________ FORMULAS 9-10 Weight % 9 10
______________________________________ 66.degree. Be Sulfuric Acid
45.0 45.58 Non-ionic Surfactants 10.0 10.90 Triton DF-16 9.3 10.12
Plurafac D-25 .7 .78 Water 45.0 43.52 100% 100% Specific Gravity
1.318 1.320 [at 60.degree. F. (.+-..005)]
______________________________________ FORMULA 11 Weight %
______________________________________ 66.degree. Be Sulfuric Acid
34.50 Non-ionic Surfactants 5.00 Triton DF-16 4.62 Plurafac D-25
.38 Water 60.50 100% Specific Gravity: 1.235 .+-. .005 at
60.degree. F. Freezing Point: Below 0.degree. F.
______________________________________ FORMULA 12 Weight %
______________________________________ 66.degree. Be Sulfuric Acid
34.50 Non-ionic Surfactants 7.00 Triton DF-16 5.43 Plurafac D-25
1.57 Water 58.50 100% Specific Gravity: 1.237 .+-. .005 at
60.degree. F. Freezing Point: Below 0.degree. F. Flash Point: None
______________________________________ FORMULA 13 Weight %
______________________________________ 66.degree. Be Sulfuric Acid
34.50 Non-ionic Surfactants 7.0 Plurafac RA-30 4.0 Plurafac D-25
3.0 Water 58.50 100% Specific Gravity: 1.236 .+-. .005 at
60.degree. F. Freezing Point: Below 0.degree. F. Flash Point: None
______________________________________
______________________________________ CONCENTRATES CONTAINING
SURFACTANTS ______________________________________ FORMULA 14
Weight % ______________________________________ Non-ionic
surfactant 100% Plurafac D-25 Specific Gravity: 1.010 .+-. .005 at
60.degree. F. Freezing Point: 0.degree. F. (-18.degree. C.) Flash
Point: 465.degree. F. Refractive Index: 1.4560 at 25.degree. C.
(77.degree. F.) ______________________________________ FORMULA 15
Weight % ______________________________________ Anionic Surfactant
100% Tergitol Anionic-08 Specific Gravity: 1.144 .+-. .005 at
20.degree. C. Freezing Point: +22.degree. F. Flash Point: None
______________________________________ FORMULA 16 Weight %
______________________________________ Non-ionic Surfactant 100%
Triton DF-16 Specific Gravity: .984 .+-. .005 Flash Point: None
______________________________________ FORMULA 17 Weight %
______________________________________ Non-ionic Surfactant 30.0
Surfonic LF-17 Sodium Nitrite .01 Water 69.9 100% Specific Gravity:
1.018 .+-. .005 at 60.degree. F. The sodium nitrite is added to
inhibit rusting of the steel shipping containers
______________________________________ FORMULA 18 Weight %
______________________________________ Non-ionic surfactants 30.0
Plurafac RA-30 27.9 Plurafac D-25 2.1 Isopropanol (91%) 3.3 Water
66.7 100% Specific Gravity: 1.00 .+-. .005 Freezing Point:
32.degree. F. Flash Point: 140.degree. F. T.C.C. Aqueous cleaning
compositions which may be employed are exemplified below.
______________________________________ FORMULA 19 Grams
______________________________________ Hydrofluoric Acid 0.02
Sulfuric Acid 4.0 Anionic Surfactant 1.0 Tergitol 08 Water to make
1 liter ______________________________________ FORMULA 20 Grams
______________________________________ Hydrofluoric Acid .005
Sulfuric Acid 6.0 Nonionic Surfactant 1.0 Triton DF 16 Water to
make 1 liter ______________________________________ FORMULA 21
Grams ______________________________________ Hydrofluoric Acid 0.1
Sulfuric Acid 4.0 Nonionic Surfactant 2.0 Plurafac RA-30 Water to
make 1 liter ______________________________________
The metal surface should be cleaned employing techniques that
result in a completely water-break-free surface. The cleaning
solution can be applied to the aluminum surface utilizing any of
the contacting techniques to the art. Preferably, application will
be effected by conventional spray or immersion methods. The time of
treatment of the surface with the cleaning solution need only be
long enough to insure complete wetting of the surface and can be as
long as 10 minutes. Preferably, the surface should be treated for a
time from about 15 seconds to about 2 minutes.
The aluminum fines and forming oils are removed from the aluminum
surface by the cleaning solution at temperatures lower than
ordinarily expected. The cleaning process can be operated at
temperatures from about 70.degree. F. to about 140.degree. F.,
preferably from about 90.degree. F. to about 135.degree. F. It is
highly preferred that the cleaning process be operated at
temperatures from about 110.degree. F. to about 125.degree. F.
Optimum results are obtained when the cleaning process is operated
at temperatures from about 120.degree. F. to about 125.degree. F.
This is a distinct advantage of the present invention over prior
art processes, as the low operating temperatures with good cleaning
results prevents accelerated corrosion and attack of processing
equipment.
In accordance with the invention the cleaning solution is highly
acidic, having pH below 2.5. The amount of sulfuric acid and
hydrofluoric acid can be varied within limits in accordance with
the ranges set forth hereinabove so that the pH of the cleaning
solution can be adjusted. Preferably the pH of the cleaning
solution is adjusted to from about 1.0 to about 1.8, and optimum
results, that is excellent cleaning with minimal etching, are
obtained when the pH of the cleaning solution is adjusted to from
about 1.2 to about 1.5. The pH of the cleaning solution should not
go below 0.6 or excessive etching will occur.
In accordance with broader aspects of the invention, there is
considerable flexibility available with respect to portions of the
overall processing of the aluminum substrate. In particular,
chemical processing steps can be effected prior to cleaning such
as, for example, a hot water prerinse of the surface. Following
application of the cleaning solution, the surface can be rinsed
with water and then dried. Ordinarily a water rinse is necessary to
remove any remaining residues which may have remained after the
cleaning step. After the rinse step, the aluminum surface may be
contacted with conversion coating solutions or siccative finish
coating compositions well known to the art. Generally, the coating
solution will be applied directly after the cleaning operation or a
short period of time thereafter. However, as specified hereinabove,
the cleaned surface can be dried and the coating steps may be
accomplished at a later time.
The following Examples are illustrative of this invention and are
not considered as limiting for other materials and operating
conditions falling within the scope of this invention which might
be substituted.
EXAMPLE I
Aluminum container test specimens of 3004 alloy, drawn into single
piece containers, were employed in this procedure. The containers
had been subjected to a drawing operation and were covered with
aluminum fines and drawing oils.
The test specimens were treated as follows:
1. Treated for 60 seconds by spraying the interior and exterior of
the specimens with the solutions listed in Table 1.
2. Rinsed with water by immersion in cold water for 30 seconds at
ambient temperature.
Control specimens were treated with aqueous compositions comprising
acids, as indicated in Table 1, such as sulfuric, hydrochloric,
phosphoric, and nitric acid, as well as specified combinations or
mixtures of these acids. The concentrations of the aqueous
solutions and the constituents therein are listed in Table 1. The
temperature of each of the respective solutions when employed to
treat the test and control specimens is listed in Table 1.
Except when an anionic surfactant (Tergitol 08) was employed in the
solutions as indicated in Table 1, all other compositions contained
0.1 grams/liter of a nonionic surfactant (.1 gram/liter of Triton
X-102).
In all cases the pH of the cleaning solutions were between 0.6 and
2.5.
The aluminum surfaces were tested for water-break following
cleaning. The container surfaces were treated by measuring the
percent of water-break on the surface, that is the percent of the
total surface area which did not support a continuous film of
water. The results are listed in Table 1.
The results reported in Table 1 include a determination of the
presence of aluminum fines remaining on the surface after
processing was completed. The brightness and appearance of the test
specimens at the end of the processing procedure was also observed.
The brightness quality was determined by visually rating the degree
of brightness of the surface from 1 to 5 wherein the brightness
rating of 1 represents best performance and appearance and rating
of 5 represents poor appearance. The presence of aluminum fines on
the interior surface was determined by rubbing the surface with a
clean white cloth and observing the fines deposited on the cloth.
The presence of fines is evidenced by a dark black residue on the
white cloth. The amount of fines present is expressed in Table 1 in
gradations from excellent (E) for no residue, good (G) for very
light residue, fair (F) for moderate residue, to poor (P) for very
heavy residue.
TABLE 1
__________________________________________________________________________
Percent Waterbreak Interior Interior Temperature Exterior Interior
Wipe Appearance
__________________________________________________________________________
Aqueous Composition 2 g/l H.sub.2 SO.sub.4 150.degree. F. 80 80 G 4
4 g/l H.sub.2 SO.sub.4 150.degree. F. 60 30 F 4 6 g/l H.sub.2
SO.sub.4 150.degree. F. 50 10 P 4 2 g/l HCl 150.degree. F. 100 90 G
4 4 g/l HCl 150.degree. F. 100 80 G 4 6 g/l HCl 150.degree. F. 100
80 G 4 2 g/l H.sub.3 PO.sub.4 150.degree. F. 90 80 G 4 4 g/l
H.sub.3 PO.sub.4 150.degree. F. 50 80 E 4 6 g/l H.sub.3 PO.sub.4
150.degree. F. 70 50 E 3 2 g/l HNO.sub.3 150.degree. F. 100 100 E 5
4 g/l HNO.sub.3 150.degree. F. 100 90 E 5 6 g/l HNO.sub.3
150.degree. F. 100 90 G 5 2 g/l H.sub.2 SO.sub.4 + 2 g/l HCl
150.degree. F. 90 30 P 3 3 g/l H.sub.2 SO.sub.4 + 3 g/l HCl
150.degree. F. 80 30 P 3 Bath Composition 2 g/l H.sub.2 SO.sub.4 +
2 g/l H.sub.3 PO.sub.4 150.degree. F. 70 5 F 2 3 g/l H.sub.2
SO.sub.4 + 3 g/l H.sub.3 PO.sub.4 150.degree. F. 70 5 G 2 2 g/l
H.sub.2 SO.sub.4 + 2 g/l HNO.sub.3 150.degree. F. 90 30 P 3 3 g/l
H.sub.2 SO.sub.4 + 2 g/l HNO.sub.3 150.degree. F. 90 5 P 3 2 g/l
H.sub.2 SO.sub.4 + H.sub.3 PO.sub.4 120.degree. F. 100 10 P 4 3 g/l
H.sub.2 SO.sub.4 + 3 g/l H.sub.3 PO.sub.4 120.degree. F. 100 10 P 4
4 g/l H.sub.2 SO.sub.4 + 0.01 g/l NH.sub.4 HF.sub.2 120.degree. F.
80 50 P 4 4 g/l H.sub.2 SO.sub.4 + 0.02 g/l NH.sub.4 HF.sub.2
120.degree. F. 50 10 P 4 4 g/l H.sub.2 SO.sub.4 + 0.04 g/l NH.sub.
4 HF.sub.2 120.degree. F. 20 0 G 2 4 g/l H.sub.2 SO.sub.4 + 0.05
g/l NH.sub.4 HF.sub.2 120.degree. F. 10 0 E 1 4 g/l H.sub.2
SO.sub.4 + 1 g/l anionic surfactant + .02 g/l HF 120.degree. F. 0 0
E 1 10.0 g/l H.sub.2 SO.sub.4 + 1.0 g/l anionic surfactant + 0.005
g/l HF 135.degree. F. 0 0 G 2 1.0 g/l H.sub.2 SO.sub.4 + 1.0 g/l
anionic surfactant + 0.10 g/l HF 110.degree. F. 0 0 E 1
__________________________________________________________________________
EXAMPLE II
An aqueous acidic cleaning bath was prepared by adding 4.0 grams of
sulfuric acid, 0.02 grams of hydrofluoric acid, and 1.0 gram of an
anionic surfactant (Tergitol 08) to each one liter of water. The
temperature of the bath was elevated to and maintained at
120.degree. F. A fluoride specific ion electrode and a saturated
calomel reference electrode were coupled to a potentiometric meter
capable of discerning changes in electrode potential of .+-.1.0
millivolt. The electrodes were immersed into the bath and the meter
adjusted, by the zero offset control, to read on the center of the
scale.
Aluminum containers of 3004 alloy drawn into single piece
containers were sprayed with the prepared bath and the meter
readings became more positive. When the electrode potential reached
+3 millivolts from center scale, hydrofluoric acid additions were
made to restore the electrode potential to center scale. Electro
metric pH measurements, and sulfuric acid additions were made to
maintain the pH at 1.3 to 1.5.
The containers were observed to be water-break-free and bright in
appearance.
EXAMPLE III
An aqueous acidic cleaning bath was prepared by adding 4.0 grams of
sulfuric acid, 0.02 grams of hydrofluoric acid, and 1.0 gram of a
nonionic surfactant (Triton DF-16) to each one liter of water. The
temperature of the bath was elevated to and maintained at
120.degree. F. A fluoride specific ion electrode and a saturated
calomel reference electrode were coupled to a potentiometric meter
capable of discerning changes in electrode potential of .+-.1.0
millivolt. The electrodes were immersed into the bath and the meter
adjusted, the zero offset control, to read on the center of the
scale.
Aluminum containers of 3004 alloy drawn into single piece
containers were sprayed with the prepared bath and the meter
readings became more positive. When the electrode potential reached
+5 millivolts from center scale, hydrofluoric acid additions were
made to restore the electrode potential to center scale. Electro
metric pH measurements, and sulfuric acid additions were made to
maintain the pH at about 1.2.
The containers were observed to be water-break-free and bright in
appearance.
EXAMPLE IV
Aluminum container test specimens, drawn into single piece
containers, were employed in this procedure. The containers had
been subjected to a drawing operation and were covered with
aluminum fines and drawing oils.
The test specimens were treated as follows:
1. Treated for various times of from 20 to 60 seconds and various
temperatures by spraying the interior and exterior of the specimens
with the solutions listed in table 2.
2. Rinsed with water by immersion in cold water for about 30
seconds at ambient temperature.
All of the cleaning solutions contained 1.2 grams/liter of
surfactant comprising 92.86% Triton DF-16 and 7.14% Plurafac
D-25.
The aluminum surfaces were tested for water-break following
cleaning. The container surfaces were treated by measuring the
percent of water-break on the surface, that is the percent of the
total surface area which did not support a continuous film of
water. Separate evaluations were made for the interior and exterior
of the cans.
The results reported in Table 2 include a determination of the
presence of aluminum fines remaining on the surface after
processing by observing the brightness of the cans.
The degree of etching of the test specimens at the end of the
processing procedure was also observed.
The interior and exterior appearance (brightness quality--removal
of fines) was determined by visually rating the degree of
brightness of the surface excellent, good, fair, or poor (E,G,F,P),
"Excellent" meaning that all fines are removed, "Good" meaning most
fines are removed, "Fair" meaning few fines are removed, and "Poor"
meaning no fines are removed.
TABLE 2 ______________________________________ Tem- Aqueous Percent
Appearance Test per- Composition Waterbreak (Fines) Num- ature
H.sub.2 SO.sub.4 HF Ex- In- In- Ex- ber (.degree.F.) (g/l) (g/l)
terior terior terior terior ______________________________________
1 70 35.21 0.252 2.5 1.0 E E 2 70 35.21 0.336 1.5 .5 E E 3 70 23.47
0.336 3.5 1.0 E G 4 70 46.94 0.504 0 0 E E 5 90 11.74 0.252 .5 0 E
E 6 90 0.117 0.252 2.5 1.0 E E 7 90 0.117 0.336 .5 0 E E 8 90 0.117
0.504 0 .5 E E 9 84 35.21 0.336 3.0 3.0 G E 10 90 46.94 0.672 1.5
.5 E G 11 90 58.68 0.672 5.0 1.5 E E 12 125 5.87 0.042 5.0 3.5 G G
13 125 5.87 0.336 2.5 0 E E 14 125 1.17 0.336 2.5 2.5 E E 15 125
5.87 0.336 3.5 0 E E 16 125 5.87 0.672 1.0 1.0 E E 17 140 5.87
0.336 1.0 0 E E 18 140 3.51 0.336 1.0 .5 E E 19 140 3.51 0.336 2.5
.5 E E 20 140 2.34 0.336 5.0 2.5 E E 21 140 58.68 0.672 5.0 3.0 E E
22 140 5.87 0.252 1.0 3.5 E E 23 140 5.87 0.168 3.5 3.5 E E 24 125
3.51 0.672 .5 1.0 E E ______________________________________
* * * * *