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Title:
COMPOSITION FOR REDUCING THE AMOUNT OF SORBED MATERIAL FROM A SUBSTRATE AND METHOD
Document Type and Number:
WIPO Patent Application WO/1991/019776
Kind Code:
A1
Abstract:
An aqueous composition comprising about 0.02 % to about 20 % by weight of the composition of a non-ionic sulfur containing polyether surfactant, and about 0.02 % to about 20 % by weight of the composition of a surfactant agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce an amount of a sorbed material on a substrate. The agent comprises at least one anionic surfactant alone or in combination with at least one non-ionic surfactant. The composition treats the substrate, and a substantial amount of the previously sorbed material and composition is removed from the substrate.

Inventors:
FARHA FLOYD E (US)
FRASIER JERRY G (US)
THOMAS B CLENDON (US)
Application Number:
PCT/US1991/003998
Publication Date:
December 26, 1991
Filing Date:
June 06, 1991
Export Citation:
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Assignee:
CHEMICAL PRODUCTS IND INC (US)
International Classes:
C11D1/72; C11D1/755; C11D1/83; C11D1/00; C11D1/22; C11D1/29; C11D1/66; (IPC1-7): C11D1/72; C11D1/755; C11D1/83; C11D1/831
Foreign References:
US4663082A1987-05-05
US3984480A1976-10-05
Other References:
SCHICK, Nonionic Surfactants, MARCEL DEKKER INC., NEW YORK, 1967, pages 175-185.
SOAPCOSMETICS CHEMICAL SPECIALTIES, "High Performance Cleaning Surfactant", see col. 3.
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Claims:
CIAIMS
1. An aqueous composition, comprising: about 0.02% to about 20% by weight of the composition of a nonionic sulfur containing polyether surfactant; and about 0.02% to about 20% by weight of the composition of a surfactant agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce an amount of a sorbed material on a substrate containing sorbed material.
2. The composition of claim 1 in which the agent comprises an anionic surfactant.
3. The composition of claim 2 in which the anionic surfactant comprises sodium dodecylbenzene sulfonate.
4. The composition of claim 2 in which the anionic surfactant comprises at least one ammonium salt of an alkyl polyether sulfonate and at least one ammonium alkyaryl sulfonate.
5. The composition of claim 1 in which the concentration of the nonionic sulfur containing polyether surfactant is about 0.1% to about 10% by weight of the composition.
6. The composition of claim 1 in which the concentration of the nonionic sulfur containing polyether surfactant is about 0.5% to about 5% by weight of the composition.
7. The composition of claim 1 in which the sulfur containing polyether has a general structure comprising: RB(A)nH wherein: R is a substituted or unsubstituted alkyl of between 4 and 30 carbon atoms; B is selected from a sulfide, sulfoxide, or sulfone group; A is a R'O group, R' being an alkyl group between 2 and 4 carbons, and O being an oxygen atom; n is a positive integer between 2 and 35; and H is a hydrogen atom.
8. The composition of claim 7 in which B is a sulfoxide group.
9. The composition of claim 7 in which B is a sulfide group.
10. The composition of claim 7 in which n is between 3 and 12.
11. The composition of claim 7 in which n is between 5 and 10.
12. The composition of claim 7 in which the R comprises an alkyl group having 12 carbons.
13. The composition of claim 7 in which R comprises an alkyl group having 12 carbon atoms, B is a sulfide atom, R' is an alkyl group having 2 carbon atoms, and n is about 7.
14. The composition of claim 7 in which R comprises an alkyl group having 12 carbon atoms, B is a sulfoxide atom, R' is an alkyl group having 2 carbon atoms, and n is about 7.
15. The composition of claim 7 in which the agent comprises an anionic surfactant.
16. The composition of claim 15 in which the anionic surfactant comprises sodium dodecylbenzene sulfonate.
17. The composition of claim 15 in which the anionic surfactant comprises at least one ammonium salt of an alkyl polyether sulfonate and at least one ammonium alkyaryl sulfonate.
18. The composition of claim 1 in which the composition further comprises an effective amount of a builder.
19. The composition of claim 1 in which the composition further comprises an effective amount of a rust inhibitor.
20. The composition of claim 1 in which the composition further comprises an effective amount of an antifoaming agent.
21. The composition of claim 1 in which the agent comprises a mixture of at least one anionic surfactant and at least one nonionic surfactant.
22. The composition of claim 1 further comprising an effective amount of a lubricant.
23. A method for reducing an amount of sorbed material from a substrate having sorbed material thereon, comprising: treating the substrate for a sufficient amount of time with an effective amount of an aqueous composition, comprising: about 0.02% to about 20% by weight of the composition of a nonionic sulfur containing polyether surfactant; and about 0.02% to about 20% by weight of the composition of an agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce an amount of the sorbed material on the substrate containing sorbed material.
24. The method of claim 23 in which the concentration of the nonionic sulfur containing polyether surfactant is about 0.1% to about 10% by weight of the composition.
25. The method of claim 23 in which the concentration of the nonionic sulfur containing polyether. surfactant is about 0.5% to about 5% by weight of the composition.
26. The method of claim 23 in which treating the substrate comprises soaking the substrate in the composition from about 1 second to about 60 minutes with agitation of the composition.
27. The method of claim 23 in which treating the substrate comprises heating the composition to a temperature above ambient temperature.
28. The method of claim 23 in which treating the substrate is selected from a group consisting of spraying, pouring, rolling or brushing the composition of the substrate, and then removing a substantial amount of the sorbed material and the composition from the substrate.
29. The method of claim 23 in which the agent comprises a mixture of at least one anionic surfactant and at least one nonionic surfactant.
30. The method of claim 23 in which the composition further comprises an effective amount of a builder.
31. The method of claim 23 in which the composition further comprises an effective amount of a rust inhibitor.
32. The method of claim 23 in which the composition further comprises an effective amount of an antifoaming agent.
33. The method of claim 23 in which the sulfur containing polyether surfactant has a general structure comprising: RB(A)nH wherein: R is a substituted or unsubstituted alkyl of between 4 and 30 carbon atoms; B is selected from a sulfide, sulfoxide, or sulfone group; A is a R'O group, R' being an alkyl group between 2 and 4 carbons, 0 being an oxygen atom; n is a positive integer between 2 and 35; and H is a hydrogen atom.
34. The method of claim 33 in which the agent comprises an anionic surfactant.
35. The method of claim 34 in which the anionic surfactant is sodium dodecylalkylbenzene sulfonate.
36. The method of claim 34 in which the anionic surfactant is at least one ammonium salt of an alkylpolyether sulfonate and at least one ammonium alkylaryl sulfonate.
37. The method of claim 23 in which the agent comprises an anionic surfactant.
38. The method of claim 37 in which the anionic surfactant comprises sodium dodecylbenzene sulfonate.
39. The method of claim 37 in which the anionic surfactant is an ammonium salt of an alkylpolyether sulfonate and an ammonium alkylaryl sulfonate.
40. The method of claim 23 in which the composition further comprises an effective amount of a lubricant.
41. An aqueous composition, comprising: about 0.02% to about 20% by weight of the composition of a nonionic sulfur containing polyether surfactant; and 26 about 0.02% to about 20% by weight of the composition of a surfactant agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce the amount of time required to remove an amount of a sorbed material on a substrate containing sorbed material.
Description:
COMPOSITION FOR REDUCING THE AMOUNT OF SORBED MATERIAL FROM A SUBSTRATE AND METHOD FIELD OF THE INVENTION The present invention generally relates to compositions and methods which reduce the amount of sorbed material on a substrate having material sorbed thereon, and more particularly, but not by way of limitation, to cleaning and stripping compositions and methods.

SUMMARY OF THE INVENTION The present invention preferably comprises an aqueous composition comprising about 0.02% to about 20% by weight of the composition of a non-ionic sulfur containing polyether surfactant; and about 0.02% to about 20% by weight of the composition of a surfactant agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce an amount of a sorbed material on a substrate containing sorbed material. The present invention may further comprise a method for reducing an amount of sorbed material from a substrate having sorbed material thereon, comprising treating the substrate for a sufficient amount of time with the composition of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a schematic representation of an aqueous composition bath system in cross-section of the method of the present invention.

According to one aspect of the invention, there is provided an aqueous composition, comprising: about 0.02% to about 20% by weight of the composition of a non-ionic sulfur containing polyether surfactant; and about 0.02% to about 20% by weight of the composition of a surfactant agent capable of acting synergistically with the sulfur containing

polyether surfactant in order to reduce an amount of a sorbed material on a substrate containing sorbed material. According to another aspect of the invention, there is provided a method for reducing an amount of sorbed material from a substrate having sorbed material thereon, comprising: treating the substrate for a sufficient amount of time with an effective amount of an aqueous composition, comprising: about 0.02% to about 20% by weight of the composition of a non-ionic sulfur containing polyether surfactant; and about 0.02% to about 20% by weight of the composition of an agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce an amount of the sorbed material on the substrate containing sorbed material. According to a further aspect of the invention, there is provided an aqueous composition, comprising: about 0.02% to about 20% by weight of composition of a non-ionic sulfur containing polyether surfactant; and about 0.02% to about 20% by weight of the composition of a surfactant agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce the amount of time required to remove an amount of a sorbed material on a substrate containing sorbed material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention comprises a new composition which reduces the amount of sorbed material from a substrate having materials sorbed thereon. The sorbed material may be hydrocarbons, organic compounds, halogenated compounds, oxygenated compounds, nitrogen-containing compounds, sulfur- containing compounds or inorganic compounds. Common examples of the foregoing are oil, ink, carbon black, inorganic and organic toxins, grease, dirt, wax, paints,

varnishes, mineral deposits and rust. "Sorbed material" means material absorbed or adsorbed to the substrate.

The substrate from which the sorbed material is removed may be oil bearing strata, stone, gems, wood, fiberglass, plastic, concrete, glass, all types of fabric, metal surfaces or combinations thereof. The present invention is particularly useful in, but not limited to, cleaning and/or stripping sorbed material from machinery and production equipment including automobile parts for rebuilding, oil recovery, stripping paint from substrates, removal of organic or inorganic toxins from soil, fuel oil boilers, concrete pump pads, electronic equipment, drains and grease traps, carpets, windows, floors, jewelry, heat exchanger coils, circuit boards and the bilges of ships. The present invention comprises an aqueous composition comprising a mixture of surfactants having a synergistic effect which produces a superior cleaning, degreasing, stripping and/or surface preparation agent. "Synergistic effect" as used herein means that an amount of a combination of surfactants performs as described herein more effectively than an equivalent amount of a surfactant alone. The effectiveness of the surfactants may be measured by the amount of sorbed material removed from the substrate, and/or the amount of time required to remove an amount of sorbed material from the substrate.

The aqueous composition is biodegradable, non¬ flammable, non-corrosive to base metals, and cleans substrates to a water break free surface with low toxicity to the user. A "water break free surface" is a test that indicates the degree of lack of contaminants (sorbed material) on a substrate. If a substrate maintains an unbroken film of water after being dipped into distilled

water, the substrate is substantially free from contamination.

The aqueous composition of the present invention comprises about 0.02% to about 20% by weight of the composition of a non-ionic sulfur containing polyether surfactant. More preferably, the concentration of the non¬ ionic sulfur containing polyether surfactant is about 0.1% to about 10% by weight of the composition, and most preferably, about 0.5% to about 5% by weight of the composition.

Preferably, the non-ionic sulfur containing polyether surfactant has a general structure comprising: R-B-(A) n -H wherein: R is a substitute or unsubstituted alkyl of between 4 and 30 carbon atoms, and, more preferably 12 carbons, and most preferably a tertiary alkyl having 12 carbons; B is selected from a sulfide (S) , sulfoxide (SO) , or sulfone (S0 2 ) group, and more preferably either a sulfide or sulfoxide group; A is a R'-O group in which R 1 is an alkyl group bejtween 2 and 4 carbons, and 0 is an oxygen atom; n is a positive integer between 2 and 35, and more preferably between 3 and 12, and most preferably between 5 and 10; and H is a hydrogen atom which is always bonded to the oxygen atom in one of the R'-O groups.

In a preferred embodiment, R comprises an alkyl group having 12 carbon atoms, B is a sulfoxide group, R 1 is an alkyl group having 2 carbon atoms, and n is about 7. In another preferred embodiment, R comprises an alkyl group having 12 carbon atoms, B is a sulfide group, R' is an alkyl group having 2 carbon atoms, and n is about 7.

Non-ionic sulfur containing polyether surfactants useful in the practice of the present invention are the non-

ionic surfactant sold by Phillips 66 Company of Bartlesville, Oklahoma, under the trademark Aqua-Clean Degreaser Additive, the non-ionic surfactant sold by Alcolac of Baltimore, Maryland, under the trademark Alcodet MC- 2000.

The aqueous composition of the present invention further comprises about 0.02% to about 20% by weight of the composition of a surfactant agent capable of acting synergistically with the sulfur containing polyether surfactant in order to reduce an amount of a sorbed material on a substrate containing sorbed material. More preferably the concentration of the agent comprises about 0.1% to about 5%, and most preferably, about 0.5% to about 5% by weight of the composition. The agent preferably comprises an effective amount of at least one anionic surfactant alone or in combination with other surfactants.

Examples of anionic surfactants of the agent used in accordance with the present invention are the alkylpolyether sulfonate and ammonium alkylaryl sulfonates, preferably combined; and, more preferably, sodium dodecylbenzene sulfonate. The anionic surfactants are in the present invention in concentrations of about 0.02% to about 20%, more preferably about 0.5% to about 10%, and most preferably about 1% to about 5% by weight f the composition. A preferred agent of the present invention is the anionic surfactant sodium dodecylbenzene sulfonate obtained from Witco of Houston, Texas under the trademark Witconate 90 Flakes. Another preferred agent is the combination of the ammonium salt of an aklylpolyether sulfonate and ammonium alkylaryl sulfonates in methanol and water provided by Petrolite Corporation of St. Louis, Missouri, product TF0009 marketed under the trademark Tolfoam.

Another preferred agent of the present invention is a mixture of anionic surfactants and non-ionic surfactants: oxyalkylated alkanolamines (non-ionic) , oxyalkylated alkylphenols (non-ionic) ; and ammonium salts of an alkylpolyether sulfate (anionic) sold by Petrolite

Corporation of St. Louis, Missouri, under the trademark X- Tol (XT-39) .

The non-ionic surfactants combined with anionic surfactants to produce the agent are present in the composition of the present invention from about 0.02% to about 20%, and more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5% by weight of the composition.

The concentrations of various components of the agent may change with the number and types of components selected as long as the desired synergism with the sulfur containing polyether surfactant is achieved. Also, a more concentrated form of the composition may be manufactured which can be diluted by the user or distributor. The composition of the present invention is generally in a liquid form, but may be in any other usable forms as well, e.g., gels or foams. Some examples of thickening agents used to produce, gel forms of the present invention are any of the cellulose base thickening agents such as methylcellulose or beta-hydroxyethylcellulose or the xanthan gums. A preferred thickening agent is Methoσel™ sold by Dow Chemical of Midland, Michigan used in an amount of about 5 g to about 200 gm per gallon of composition of the present invention. The composition of the present invention may further comprise additives which commercially enhance the composition such as builders, rust inhibitors, freeze point

depressants, performance enhancers, lubricants and anti- foaming agents.

A builder is an additive which aids in removing the previously sorbed material from the substrate. Some examples of builders effective in the practice of the present invention which are commercially available are sodium sulfite, disodium sulfate, sodium hydroxide, tetrapotassium pyrophosphate, tetrasodium pyrophosphate (from Monsanto) , sodium silicate or sodium carbonate. Any effective amount of the builder may be used. About 2% by weight of the composition has been found to be effective in the examples given.

An example of rust (or corrosion) inhibitors effective in the practice of the present invention is phosphate esters of alkyl polyols in water at an amount of about 400ppm. Another effective rust inhibitor used in the practice of the present invention is Rodine 213™ sold by Parker-Amchem of Madison Heights, Michigan. Yet another effective rust inhibitor is AMP-95 Corrosion Control or Alkaterge T-IV sold by Angus of Northbrook, Illinois.

Antifoaming agents are useful in the mixing of the components of the present invention since the components may be mixed at a faster rate without an excessive amount of foam. An excessive amount of foam hinders the mixing process. Examples of anti-foaming agents effective in the practice of the present invention are H-10™ sold by Dow Corning of Midland, Michigan or the product sold by Petrolite Corporation of St. Louis, Missouri under the trademark TET 1940, used in amounts of about 400ppm. Another additive to the composition of the present invention is a lubricant. A "lubricant" as used herein means an oily substance normally used to reduce friction between surfaces. A lubricant may be added to the

σomposition of the present invention to produce an emulsion which functions as a self cleaning friction reducer. Another way to use the lubricant and composition of the present invention is as a cleaning agent which removes sorbed material and then leaves a thin film of the lubricant on the substrate to inhibit corrosion of the substrate. Often a water-break free substrate is desired in order to plate, paint or charge the substrate with freon which requires the removal of the lubricant retained on the substrate. This removal of the retained lubricant may be easily accomplished by treating the substrate with a sufficient amount of the composition without the lubricant as described herein or rinsing the substrate with a sufficient amount of deionized water. Preferably, the deionized water and the composition also contains a corrosion inhibitor as described herein.

The application of the composition of the present invention containing a lubricant as a self cleaning friction reducer is particularly useful in the air conditioning coil industry where copper tubings are flared or bent to 180° angles. The self cleaning friction reducer comprising the composition of the present invention and the lubricant may be applied to the areas of the copper tubing to be manipulated, a rod is inserted into those areas to produce the flare or the desired degree of bend in the tubing, and the tubing may then be rinsed with water to remove the composition containing lubricant from the tubing.

A preferred lubricant used in accordance with the present invention is sold by Nalco under the trademark of Nalco XL174 D&I Lubricant which is a blend of fatty acids, glycerides and a naphthenic hydrocarbon (CAS #64742-68-3) . The lubricant is used in an amount of about 5% to about 50%,

and preferably about 15%, by volume of the composition of the present invention.

Another additive useful in the practice of the present invention is a performance enhancer such as propylene glycol monomethyl ether (glycol ether) sold by Union Carbide Chemicals and Plastics Company, Inc. of Danbury, Connecticut under the trademark Methyl Propasol Solvent (PM) (CAS # 1070-98-2) . This performance enhancer permits a reduction in the sorbed material from the substrate at a faster rate under cold conditions. "Cold conditions" means temperatures generally below about 32*F. Cold conditions can be encountered when the substrate is located out of doors in cold weather. This particular performance enhancer also acts as a freezing point depressant which permits the activity of the composition at temperatures below that of the composition without the freezing point depressant. Preferably, the performance enhancer is present in the composition in any amount which permits the enhancement of performance e.g., cleaning activity. The glycol ether is preferably used in the amount of 0.95% by weight of the composition.

Other additives or solvents may be added to the composition to increase solubility and/or stability of the components so long as the components of the composition are permitted to function as described herein.

The preferred order of mixing of the composition of the present invention is that a builder (if one is to be used) is dissolved in warm water. Then an antifoam agent (if one is to be used) is added to the builder. The non- ionic sulfur containing polyether compound and the agent are mixed together and then added to the above described mixture containing the builder and antifoam agent (if used) . The

other additives described herein may then be added and thoroughly mixed.

In operation, the substrate is treated for a sufficient amount of time with an effective amount of the aqueous composition in order to reduce the amount of the sorbed material from the substrate. The amount of time and the amount of composition which is respectively "sufficient" or "effective" may vary with the type of substrate to be treated, the type of sorbed material to be removed and the degree of removal of the material desired, as further described in the following examples. Also, the degree of agitation of the aqueous composition, the amount of aqueous composition in relation to the amount of substrate to be treated, and the temperature of the aqueous composition will have a bearing on the amount of time required to reduce the amount of sorbed material from the substrate. Preferably, the temperature of the aqueous composition is elevated above the ambient temperature to about 140 β F to about 190 C F which has been shown to decrease the amount of time required ten fold over that obtainable at ambient temperature to reduce the amount of sorbed material from a substrate.

The substrate may be treated in any manner which applies the aqueous composition to the substrate such as spraying, brushing, pouring or rolling the aqueous composition onto the substrate. In one preferred embodiment shown in Figure 1, an aqueous composition bath system 10 is available for the immersion of the substrate in the aqueous composition. Preferably, a soaking procedure as described herein will take about 1 second to about 1 hour. Referring to Figure 1, a container 12 is utilized which is sized to hold a substrate 14 having sorbed material 15 thereon and a sufficient quantity of the aqueous composition 16 of the present invention to completely

immerse the substrate 14 therein. The container 12 comprises at least one side wall 18 and a bottom 20 having a drain 22 therein in order to selectively drain the aqueous composition 16 from the container 12 with valve 23. A support grate 24 is disposed in the container 12 and secured to the side wall 18 in a position which permits the substrate 14 to be disposed thereon, and remain immersed in the aqueous composition 16.

As an alternative to draining the aqueous composition from the container 12, the aqueous composition 16 may be pumped from the container 12 by pump 26 through conduit 28, and passed through a filter 30 to filter the material previously sorbed on the substrate 14 from the aqueous composition 16. The filtered aqueous composition 32 in conduit 28 may be passed through a heating system 34 before returning to the container 12 for use with the next substrate (not shown) . A heater system (not shown) may optionally be positioned within the container 12. It has been shown that heating the composition significantly increases the effectiveness of the cleaning and/or stripping operation, and decreases the amount of time required for the operation.

This system may. also be used as a method of spraying the substrate 14 instead of completely immersing same. The aqueous composition may be continually recirculated and/or drained from the container 12 as more composition is introduced through a spray nozzle (not shown) positioned over the conduit opening 37 which opens into the container 12. Generally, some activity is required to remove the sorbed material from the substrate 14 such as agitation of the aqueous composition 16 in the bath 10, or brushing or wiping the loosened sorbed material from the substrate after

the aqueous composition has been applied thereto. In the bath 10, a blade 38 activated by motor 40 is disposed in the container 12 such that the aqueous composition 16 will circulate and more easily remove the sorbed material 15 from the substrate 14. Other methods to circulate or agitate the aqueous composition 16 may be utilized such as spinning or shaking the container 12 or providing ultrasonic waves in the composition.

The composition of the present invention may also be used in tertiary oil recovery. One method of oil recovery is for the composition of the present invention to be injected into injection wells, preferably in about 6-7% of the expected sweep pore volume. Then a mobility control buffer is injected into the injection wells in about 30% of the expected sweep pore volume. A sufficient amount of water is then injected into the injection wells to flood the formation and drive the oil into producing wells. The injection and producing wells can be in any pattern such as the so called "5-spot pattern". In this arrangement, the injection well is in the center of a square, and the producing wells are positioned at the corners of the square.

The methods of treating the substrate as described herein are only a few of the methods available for treatment of the substrate to reduce the amount of sorbed material thereon. Some other methods include volume spraying of the composition at low pressure where large quantities of the composition contact the substrate, and high velocity spraying of the substrate. Any other means of treatment may be used which reduces the amount of the sorbed material from the substrate.

The present invention is illustrated in preferred embodiments shown in the examples that follow. The present invention is not, however, limited to these examples.

EXAMPLE NO. 1 Preparation of a preferred embodiment of the composition:

A builder, 2% by weight of the composition of tetrapotassium pyrophosphate from Monsanto, is added to 20 gallons of warm water and permitted to dissolve in a container. Antifoam agent Dow H-10 400ppm is added to the dissolved builder solution. A previously mixed solution of 1.5 gallons of Aqua-Cleen from Phillips Petroleum Co., and 1.5 gallons of XT-39 from Petrolite Corporation (no preferred order of mixing these two) is added to the builder and antifoam solution. Corrosion inhibitor AMP-95 400ppm is added to the above-described mixture, and the mixture is mixed with a sigma mixer of about 15 minutes. This produces about 55 gallons of an embodiment of the composition. EXAMPLE NO. 2

Carbon steel coupons are cut to 1/2" x 3" x 0.06". Under conditions of ambient temperature with no agitation, the coupons were immersed in Pennzoil A-8 lubricant simultaneously for 15 seconds. The following samples were prepared and disposed into three separate petri dishes containing water and the following components:

Sample #1, Petri dish #1 containing 4% Aqua-Cleen Surfactant from Phillips Petroleum Co.; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

Sample #2, Petri dish #2 containing 4% xτ-39 Surfactant from Petrolite Corporation; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent. Sample #3, Petri dish #3 containing 2% Aqua-Cleen

Surfactant from Phillips Petroleum Co.; 2% XT-39 Surfactant from Petrolite Corporation; 2% Tetrasodium pyrophosphate;

400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

All three coupons were immersed into the three samples simultaneously. After 2 minutes the coupons were removed from the samples. At that point, the coupons from samples 1 and 2 were not water break-free. However, the coupon tested in sample 3 was water break-free.

Upon visual observation, the coupon in sample 3 was completely free of surface oil. The coupons from samples 1 and 2 had surface oil visible thereon.

This test demonstrates the synergism of the present invention. Double the amount of Sample 1 surfactant or double the amount of Sample 2 surfactant could not produce the effect of the combination of the two surfactants. EXAMPLE NO. 3

Carbon steel coupons are cut to 1/2" x 3" x 0.6" were immersed in Nalco lubricant #6460 simultaneously for 15 seconds. Under conditions of ambient temperature with no agitation, the three samples were disposed into three separate petri dishes by the same method as in Example 2 with the following results:

All three coupons were immersed into the three samples simultaneously.. Observation of the absence of this lubricant on the coupons is visible in solution since the lubricant emits a white color in the solution. After two minutes, all three coupons were removed from the samples. At this time, Sample #3 was found to be water break-free. Samples #1 and #2 were reimmersed into the samples for another two minutes. Only sample #1 was found to be water break-free. Sample #3 required about 3 minutes to obtain a water break-free surface.

EXAMPLE NO. 4

Carbon steel coupons are cut to 1/2" x 3" x 0.06" were immersed in Pennzoil gear lubricant #4096 simultaneously for 15 seconds. Under conditions of ambient temperature with no agitation, the following samples were prepared and disposed into two separate petri dishes containing water and the following components:

Sample #1, Petri dish #1 containing 2% Aqua-Cleen Surfactant; 2% XT-39 Surfactant; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

Sample #2, Petri dish #2 containing 2% Aqua-Cleen Surfactant; 2% hexadecyl pyridinium chloride; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent. The two coupons are immersed into the two samples simultaneously. After one minute the coupons were removed. It was visually evident that the coupon in Sample #1 was water break-free. However, it was necessary that Sample #2 remain in solution for another three minutes to obtain a water break-free surface. Sample #2 containing a cationic hexadecyl pyridinium chloride surfactant was not an effective cleaner.

. EXAMPLE NO. 5 Carbon steel coupons are cut to 1/2" x 3" x 0.06" were immersed in Pennzoil gear lubricant #4096 simultaneously for 15 seconds. Under conditions of ambient temperature with no agitation, the following samples were prepared and disposed into two separate petri dishes containing water: Sample #1, Petri dish #1 containing 2% Aqua-Cleen

Surfactant; 2% XT-39 Surfactant; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

Sample #2, Petri dish #2 containing 2% Aqua-Cleen Surfactant; 2% sodium dodecyl benzene sulfonate; 2% Terasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent. The two coupons are immersed into the two samples simultaneously. After forty-five seconds the samples were removed. Sample #2 was found to be water break-free at this point. It was necessary to continue immersion of Sample #1 for fifteen seconds to obtain a water break-free surface. Sample #2 appeared to outperform Sample #1. The solution in Sample #2 containing the anionic sodium dodecyl benzene sulfonate surfactant was clearly more active as a cleaning agent.

EXAMPLE NO. 6 Carbon steel coupons are cut to 1/2" x 3" x 0.06" were immersed in Pennzoil gear lubricant #4096 simultaneously for 15 seconds. Under conditions of ambient temperature with no agitation, the following samples were prepared and disposed into two separate petri dishes containing water and the following components:

Sample #1, Petri dish #1 containing 2% Aqua-Cleen Surfactant; 2% XT-39 Surfactant; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent. Sample #2, Petri dish #2 containing 2% Aqua-Cleen

Surfactant; 2% ethoxylated nonyl phenol; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

The two coupons were immersed into the two samples simultaneously. After one minute it was obvious that the Sample #1 coupon was water break-free. It required an additional four minutes for Sample #2 to become water break-free. Sample #2 containing the non-ionic ethoxylated

nonyl phenol surfactant as an agent was not an active cleaner.

EXAMPLE NO. 7 Carbon steel coupons are cut to 1/2" x 3" x 0.06" were immersed in Pennzoil gear lubricant #4096 simultaneously for 15 seconds. Under conditions of ambient temperature with no agitation, the following samples were prepared and disposed into two separate petri dishes containing water and the following components: Sample #1, Petri dish #1 containing 2% Aqua-Cleen

Surfactant; 2% XT-39 Surfactant; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

Sample #2, Petri dish #2 containing 2% Aqua-Cleen Surfactant; 2% ammonium salt of a mixture of an alkylpolyether sulfonate and ammonium alkylaryl sulfonates in methanol and water; 2% Tetrasodium pyrophosphate, marketed under the trademark TF-9 obtained from Petrolite Corporation; 400ppm AMP-95 Corrosion Control; and 400ppm H- 10 Antifoam Agent.

The two coupons were immersed into the two samples simultaneously. After one minute both coupons from both samples were water break-free. Samples #1 and #2 were similar in performance. EXAMPLE NO. 8

Carbon steel coupons are cut to 1/2" x 3" x 0.6" were immersed in Pennzoil gear lubricant #4096 simultaneously for 15 seconds. Under conditions of ambient temperature of with no agitation, the following samples were prepared and disposed into two separate petri dishes containing water and the following components:

Sample #1, Petri dish #1 containing #2 Aqua-Cleen Surfactant; 2% XT-39 Surfactant; 2% Tetrasodium

pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

Sample #2, Petri dish #2 containing 2% MC-2000; 2% XT-39 Surfactant; 2% Terasodium pyrophosphate; 400ppm AMP- 95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

The two coupons were immersed into the two samples simultaneously. After one minute both coupons were found to be water break-free. Sample #1 containing Aqua-Cleen appeared to slightly outperform Sample #2 containing MC- 2000. However, the difference in cleaning ability was not significant.

EXAMPLE NO. 9 Carbon steel coupons are cut to 1/2" x 3" x 0.06" were immersed in Pennzoil gear lubricant #4096 simultaneously for 15 seconds. Under conditions of ambient temperature with no agitation, the following samples were prepared and disposed into two separate petri dishes containing water and the following components:

Sample #1, Petri dish #1 containing 2% Aqua-Cleen Surfactant, 2% XT-39 Surfactant; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

Sample #2, Petri dish #2 containing 2% MC-2000; 2% ethoxylated nonyl phenol; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

The two coupons were immersed respectively into the two samples simultaneously. After one minute Sample #1 was water break-free. After four additional minutes Sample #2 was water break-free. Sample #2 containing MC-2000 and the non-ionic ethoxylated nonyl phenol surfactant was not an effective cleaning agent.

EXAMPLE NO. 10 Carbon steel coupons are cut to 1/2" x 3" x 0.06" were immersed in Pennzoil gear lubricant #4096 simultaneously for 15 seconds. Under conditions of ambient temperature with no agitation, the following samples were prepared and disposed into two separate petri dishes containing water and the following components:

Sample #1, Petri dish #1 containing 2% Aqua-Cleen Surfactant; 2% XT-39 Surfactant; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

Sample #2, Petri dish #2 containing 2% MC-2000; 2% sodium dodecyl benzene sulfonate; 2% Tetrasodium pyrophosphate; 400ppm AMP-95 Corrosion Control; and 400ppm H-10 Antifoam Agent.

The two coupons were immersed respectively into the two samples simultaneously. After one minute both coupons were water break-free. Sample #2 containing MC-2000 and the anionic surfactant sodium dodecyl benzene sulfonate slightly outperformed Sample #1.

Changes may be made in the components of the various elements, steps and procedures described herein without departing from the spirit and scope of the invention as defined in the following claims.