US3909437A - Noncorrosive acid, solvent and nonionic surfactant composition - Google Patents
Noncorrosive acid, solvent and nonionic surfactant composition Download PDFInfo
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- US3909437A US3909437A US324651A US32465173A US3909437A US 3909437 A US3909437 A US 3909437A US 324651 A US324651 A US 324651A US 32465173 A US32465173 A US 32465173A US 3909437 A US3909437 A US 3909437A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
Definitions
- a cleaning solvent useful in the cleaning of metal surfaces contains sulfamic acid, citric acid, a solvent for hydrocarbon residues, and a surfactant.
- the invention relates generally to the cleaning of metal surfaces. More specifically, the invention pertains to a composition useful for the dynamic cleaning of such metals as lnvar alloy, which is a nickel-iron alloy especially suited for cryogenic temperatures because of its low thermal expansivity. A representative sample of this alloy contains the following elements by weight percent:
- the present composition produces minimum corrosive effect while effectively removing hydrocarbon residue and particulate matter from a metal surface.
- the composition is an aqueous solution of sulfamic acid, citric acid, a solvent for hydrocarbon residues, e.g., 2- butoxyethanol. and a surfactant.
- a dynamic cleaning procedure involves flowing this composition over a metal surface to be cleaned at a flow rate and in an amount sufficient to clean the metal surface.
- the composition may be prepared by mixing any or all of the ingredients together and then adding water or by adding the ingredients one at a time to water. All percentages hereafter mentioned are to be taken as weight percentages unless otherwise indicated.
- the sulfamic acid should be present in an amount between 8 and 12 percent of the aqueous solution, preferably 10%.
- the citric acid should be present in an amount between 4 and 6% of the aqueous solution, preferably 5%.
- the solvent for hydrocarbon residues is a substance capable of dissolving hydrocarbon residues, e.g., greases, waxes or oils, present on the metal surface or created during the cleaning. Included within our use of the term solvent are those substances popularly termed degreasers, however, the present solvents will in addition dissolve certain residual organic con-- taminants not properly defined as greases.
- Such solvent must be soluble in and nonreactive with the acid cleaning solution as well as being capable of ethers such as 2-butoxyethanol.
- the solvent should be present in an amount between 4 and 6% of the aqueous cleaning solution, preferably 5%.
- the surfactant serves as a wetting agent, i.e., it lowers the surface tension of the water, and emulsifics and helps to remove hydrocarbon residues.
- Any nonionic surfactant which has a cloud point in excess of about F. and which at a concentration of O. 1% in the present acid cleaning solution has a surface tension of about 32 dynes/cm. or less is usable. Cloudpoint is the temperature at which the surfactant becomes insoluble in the composition.
- Representative substances include linear alcohol ethoxylates, polyoxyethylene esters, and alkyl aryl polyethylene oxides.
- An especially useful surfactant comprises a mixture of primary alcohols with. 10-12 atoms carbon chains, 60% ethoxylated. The surfactant should be present in an amount between 0.095 and 0.15% of the aqueous mixture, preferably 0.1%.
- the present composition is useful in cleaning metal surfaces in general. It is particularly useful in the cleaning of iron-nickel alloys, carbon steel. and titanium.
- the composition will satisfactorily clean metal surfaces at ambient temperatures. At lower temperatures excessive time is required and cleaning is less efficient. Higher temperatures usually ease the cleaning but may cause objectional corrosion rates. Operating temperatures within the range of about 50 to F. are feasible for the use of the present cleaning solution; the preferred operating temperatures are within the range of.
- the present composition is useful in cleaning metal surfaces in static applications, it is particularly useful in dynamic cleaning techniques.
- the length of time over which the flow is continued depends on the amount of contaminant desired to be removed and the amount of corrosion of the metal surface which is tolerable. Corrosion incurred in turn depends, inter alia, on flow rate. Thus, more complete cleaning and higher flow rates cause greater corrosion of the-surfaces.
- An iron-nickel alloy pipe contaminated with triolein and mineral oil in a density of from about .04 to about .08 grams per square inch was preferably cleaned for 2 hours at a cleaning solvent flow rate of 4 ft./sec., for 6 hours at 2 ft./sec., and for 0.5 hour at 30 ft./sec.
- aqueous solutions of citric acid or sodium nitrite or a combination of the two utilizing, for example, aqueous solutions of citric acid or sodium nitrite or a combination of the two.
- the passivation flush renders the metal surface less susceptible to oxidation thus forming an oxide on the coating alloy exposed metal surface.
- a newly cleaned iron-nickel alloy was passivated by flowing a 1% citric acid solution over the surface at 5.5 ft./sec. for 10 min., followed by a flow ofO. 1% aqueous sodium nitrite solution at 5.5 ft./sec. for 10 min. Thereafter, the surface was rinsed with a 20 min. flow of water at a rate of 3.5
- the iron nickel alloy contained the following in weight percent:
- 'S A surfactant which is a mixture of primary alcohols of about 10m 12 memher carbon chains. about 6054 cthoxylated.
- EXAMPLE 2 In this example dynamic cleaning tests were performed on the interior surface of an iron-nickel alloy pipe. The tests in this example were performed on the same iron-nickel alloy used in Example 1,' which also had been contaminated with the same substances used in Example l. A 12 inch length of 2 inch diameter pipe was subjected to a flow of the present cleaning solution. In each test the cleaning solution was conducted through the pipe at a rate of 5.5 ft./sec. for a period of 2 hours. This flow as flowed by a water flush for 0.17 hours at a rate of 3.5 ft./sec. The cleaning solution was at a temperature of between 66 and 74F. with initial contaminations of varying amounts, the parameters of corrosion metal loss, corrosion penetration depth, and residual hydrocarbon amount were measured and 2 visual evaluation of the cleaning effectiveness was made. The results are tabulated in Table 11.
- composition comprising in percentages by weight the following ingredients:
- soluble nonionic surfactant which surfactant is characterized as having a cloud point of at least about 90F. and having a surface tension of about 32 dynes/cm. or less when present in an amount of 0.1% of said composition
- composition of claim 1 wherein the nonionic solvent for hydrocarbon residues is a glycol ether.
- composition of claim 1 wherein the solvent is chosen from the group consisting of 2-butoxyethanol,
- composition of claim 1 wherein the soluble nonionic surfactant is chosen from the group consisting of linear alcohol ethoxylates, polyoxyethylene esters,.
- composition of claim 1 wherein the soluble to about 12 member carbon chains, about 60% ethoxylated, e. 79.9% water.
Abstract
A cleaning solvent useful in the cleaning of metal surfaces, e.g. nickle-iron alloys, contains sulfamic acid, citric acid, a solvent for hydrocarbon residues, and a surfactant.
Description
AU 165 FX United States Patent [1 1 Alexander et al.
[ NONCORROSWE ACID, SOLVENT AND NoNioNlc SURFACTANT COMPOSITION [75] Inventors: George B. Alexander; Norman F.
Carpenter, both of Tulsa, Okla.
[73] Assignee: The Dow Chemical Company,
Midland. Mich.
221 Filed: Jan. 18,1973
[2i] Appl. No.: 324.651
[52] US. Cl. 252/143; 252/146; 252/DIG. l:
252/87 [51] Int. Cl. Clld 7/50; Cl id 7/08 [58] Field of Search 292/143. 146, X70, DIG. l. 292/87 1 Sept. 30, 1975 Primary E.\'aminerBenjamin R. Padgett Assistant Examiner-E. A. Miller Attorney, Agent, or Firm-Bruce M. Kanuch 5 7 ABSTRACT A cleaning solvent useful in the cleaning of metal surfaces, e.g. nickle-iron alloys, contains sulfamic acid, citric acid, a solvent for hydrocarbon residues, and a surfactant.
6 Claims, No Drawings NONCORROSIVE ACID, SOLVENT AND" NONIONIC SURFACTANT COMPOSITION The invention described herein was made in the performance of work under a NASA contract and is subject to the provisions of section 305 of the National Aeronautics and Space Act of 1958, Public law 85-568 (72 Stat. 435; 42 U. S. C. 2457).
BACKGROUND OF THE INVENTION I The invention relates generally to the cleaning of metal surfaces. More specifically, the invention pertains to a composition useful for the dynamic cleaning of such metals as lnvar alloy, which is a nickel-iron alloy especially suited for cryogenic temperatures because of its low thermal expansivity. A representative sample of this alloy contains the following elements by weight percent:
Iron 61 .4 64.4 Nickel 34.5 36.5 Cobalt 0.50 Titanium 0.30 0.60 Manganese 0.30 0.60 Silicon $0.30 Carbon $0.05 Phosphorus 50.015 Sulfur $0.015
Lead 5 0.0l5
Tin $0.015 Selenium $0.010
Cleaning. alloys for use in cryogenic applications, such as piping for extremely low temperature fuel and oxidizer systems in rockets and spacecraft presents difficult problems: for example, the systems must be devoid of all hydrocarbon and particulate contamination. Conventional cleaning solvents are not satisfactory for the present purpose.
Although acids such as phosphoric, sulfuric, and hydrochloric display low corrosion rates, they produce objectionable smut on the metal surface. Smut is de- SUMMARY OF THE INVENTION The present composition produces minimum corrosive effect while effectively removing hydrocarbon residue and particulate matter from a metal surface. The composition is an aqueous solution of sulfamic acid, citric acid, a solvent for hydrocarbon residues, e.g., 2- butoxyethanol. and a surfactant. A dynamic cleaning procedure involves flowing this composition over a metal surface to be cleaned at a flow rate and in an amount sufficient to clean the metal surface.
DETAILED DESCRIPTION OF THE INVENTION The composition may be prepared by mixing any or all of the ingredients together and then adding water or by adding the ingredients one at a time to water. All percentages hereafter mentioned are to be taken as weight percentages unless otherwise indicated. The sulfamic acid should be present in an amount between 8 and 12 percent of the aqueous solution, preferably 10%. The citric acid should be present in an amount between 4 and 6% of the aqueous solution, preferably 5%.
The solvent for hydrocarbon residues is a substance capable of dissolving hydrocarbon residues, e.g., greases, waxes or oils, present on the metal surface or created during the cleaning. Included within our use of the term solvent are those substances popularly termed degreasers, however, the present solvents will in addition dissolve certain residual organic con-- taminants not properly defined as greases.
Such solvent must be soluble in and nonreactive with the acid cleaning solution as well as being capable of ethers such as 2-butoxyethanol.-'
2-methoxyethanol, and Z-ethoxyethanol. The solvent should be present in an amount between 4 and 6% of the aqueous cleaning solution, preferably 5%. l
The surfactant serves as a wetting agent, i.e., it lowers the surface tension of the water, and emulsifics and helps to remove hydrocarbon residues. Any nonionic surfactant which has a cloud point in excess of about F. and which at a concentration of O. 1% in the present acid cleaning solution has a surface tension of about 32 dynes/cm. or less is usable. Cloudpoint is the temperature at which the surfactant becomes insoluble in the composition. Representative substances include linear alcohol ethoxylates, polyoxyethylene esters, and alkyl aryl polyethylene oxides. An especially useful surfactant comprises a mixture of primary alcohols with. 10-12 atoms carbon chains, 60% ethoxylated. The surfactant should be present in an amount between 0.095 and 0.15% of the aqueous mixture, preferably 0.1%.
The present composition is useful in cleaning metal surfaces in general. It is particularly useful in the cleaning of iron-nickel alloys, carbon steel. and titanium.
The composition will satisfactorily clean metal surfaces at ambient temperatures. At lower temperatures excessive time is required and cleaning is less efficient. Higher temperatures usually ease the cleaning but may cause objectional corrosion rates. Operating temperatures within the range of about 50 to F. are feasible for the use of the present cleaning solution; the preferred operating temperatures are within the range of.
about 70-80F.
It is found that although the present composition is useful in cleaning metal surfaces in static applications, it is particularly useful in dynamic cleaning techniques.
such as cleansing the interior of a pipe by passing the cleaning solvent through the pipe. In such applications,
it is important to choose an appropriate flow rate. This rate depends on the pipe size and the degree of cleaning required. Higher flow rates are found to induce greater turbulence at the metal surface which allows the solvent to pick up occluded particles. Thus, removal of particulate contamination to leave only a very small residue will require higher flow rates. For exam- -tioners of this invention to effect the desired degree of cleaning based on the parameters present. A representative range of rates is from 2 to about 30 feet per secend; on iron-nickel alloys the preferred rate is 4 feet per second.
The length of time over which the flow is continued depends on the amount of contaminant desired to be removed and the amount of corrosion of the metal surface which is tolerable. Corrosion incurred in turn depends, inter alia, on flow rate. Thus, more complete cleaning and higher flow rates cause greater corrosion of the-surfaces. An iron-nickel alloy pipe contaminated with triolein and mineral oil in a density of from about .04 to about .08 grams per square inch was preferably cleaned for 2 hours at a cleaning solvent flow rate of 4 ft./sec., for 6 hours at 2 ft./sec., and for 0.5 hour at 30 ft./sec.
It is desirable to follow the cleaning flow with a water flush to remove residual cleaning solution. With some surfaces it is also desirable to use a passivation flush,
utilizing, for example, aqueous solutions of citric acid or sodium nitrite or a combination of the two. The passivation flush renders the metal surface less susceptible to oxidation thus forming an oxide on the coating alloy exposed metal surface. For example, a newly cleaned iron-nickel alloy was passivated by flowing a 1% citric acid solution over the surface at 5.5 ft./sec. for 10 min., followed by a flow ofO. 1% aqueous sodium nitrite solution at 5.5 ft./sec. for 10 min. Thereafter, the surface was rinsed with a 20 min. flow of water at a rate of 3.5
ft./sec.
1n the following examples cleaning mixtures comprising various proportions of ingredients were tested in static and dynamic cleaning applications.
EXAMPLE l .thus to introduce air into the liquid. The amount of metal lost by corrosion and the depth of corrosion penetration were measured, and the cleaning effectiveness was evaluated visually. The results of these tests are tabulated in Table l.
all
The iron nickel alloy contained the following in weight percent:
lron 61.4 64.4 Nickel 34.5 36.5 Cobalt 0.50 Titanium 0.30 0.60 Manganese 0.30 0.60 Silicon S 0.30 Carbon 0.05 Phosphorus 5 0.015 Sulfur 5 0.015
Lead 5 0.015
Tin 5 0.015 Selenium 5 0.010
TABLE I STATIC CLEANING OF IRON-NICKEL ALLOY COUPONS Metal Loss Wt. 'Corrosion Penetration Test No. Cleanliness (mg/dmlhr) (mils/yr) 1 Clean 6 2.9 2 17 8.2 3 21 10.0 4 47 23.0 5 Trace 6 2.9 6 4.8 7 12 5.8 8 Minor 9 4.3 9 Some 5.1
COMPOSITION Z-butoxy Sulfamic Citric ethanol S" Test No. Weight percent of aqueous solution 1 20 2 20 5 0.1 3 0.1 4 l5 5 0.1 5 l5 0.1 6 10 5 5 0.1 7 5 0.1 8 5 5 5 0.1 9 l8 2 0.1
'S=A surfactant which is a mixture of primary alcohols of about 10m 12 memher carbon chains. about 6054 cthoxylated.
EXAMPLE 2 In this example dynamic cleaning tests were performed on the interior surface of an iron-nickel alloy pipe. The tests in this example were performed on the same iron-nickel alloy used in Example 1,' which also had been contaminated with the same substances used in Example l. A 12 inch length of 2 inch diameter pipe was subjected to a flow of the present cleaning solution. In each test the cleaning solution was conducted through the pipe at a rate of 5.5 ft./sec. for a period of 2 hours. This flow as flowed by a water flush for 0.17 hours at a rate of 3.5 ft./sec. The cleaning solution was at a temperature of between 66 and 74F. with initial contaminations of varying amounts, the parameters of corrosion metal loss, corrosion penetration depth, and residual hydrocarbon amount were measured and 2 visual evaluation of the cleaning effectiveness was made. The results are tabulated in Table 11.
TABLE ll DYNAMIC CLEANING OF lRON-NlCKEl. ALLOY PIPE lnitial Concentration mg. (triolein Cleanliness +mineral oil) visual +1.0 m1. Residual observation Metal Loss Corrosion particulate Hydrocarbon smut Weight Penetration Test No. solids (mg) present (mg/dmlhr) (mils/yr.)
l 5300 1.6 Clean 102 49 2 5800 1.7 22 3 4400 1.7 72 5.8
5 TABLE II-Continued DYNAMIC CLEANING OF IRON-NICKEL ALLOY PIPE Initial Concentration mg. (triolein Cleanliness +mineral oil) visual +l .0 ml. Residual observation Metal Loss Corrosion particulate Hydrocarbon smut Weight Penetration Test N0. solids (mg.) present (mg/dmlhr) (mils/yr.)
4 5700 2.0 69 33 5 3300 0.6 rust 20 9.7 6 4 I I .9 22 l l 7 4700 2.6 dirty 44 22 COM POSITION Z-hutoxy Sulfamic Citric ethanol Test No. Weight percent of aqueous solution I I0 5 5 ().l
2 l0 5 5 ()fl '5' herein is the same mixture as that defined by S in Table I.
What is claimed is:
l. A composition comprising in percentages by weight the following ingredients:
a. about 8 to 12% sulfamic acid,
b. about 4 to 6% citric acid;
0. about 4 to 6% of a nonionic solvent for hydrocarbon residues which solvent is characterized as not producing turbidity at 75F. when present in said composition,
d. about 0.095 to 0.15% ofa soluble nonionic surfactant which surfactant is characterized as having a cloud point of at least about 90F. and having a surface tension of about 32 dynes/cm. or less when present in an amount of 0.1% of said composition, and
e. the balance, water.
2. The composition of claim 1 wherein the nonionic solvent for hydrocarbon residues is a glycol ether.
3. The composition of claim 1 wherein the solvent is chosen from the group consisting of 2-butoxyethanol,
2-( 2-butoxyethoxy)ethanol, thanol, Z-methoxyethanol, and 2-ethoxyethanol.
4. The composition of claim 1 wherein the soluble nonionic surfactant is chosen from the group consisting of linear alcohol ethoxylates, polyoxyethylene esters,.
and allyl aryl polyethylene oxides.
s. The composition of claim 1 wherein the soluble to about 12 member carbon chains, about 60% ethoxylated, e. 79.9% water.
2-(2-ethoxyethoxy)e-
Claims (6)
1. A COMPOSITION COMPRISING IN PERCENTAGE BY WEIGHT THE FOLLOWING INGREDIENTS: A. ABOUT 8 TO 12% SULFAMIC ACID, B. ABOUT 4 TO 6% CITRIC ACID C. ABOUT 4 TO 6% OF A NONIONIC SOLVENT FOR HYDROCARBON RESIDUES WHICH SOLVENT IS CHARACTERIZED AS NOT PRODUCING TURBIDITY AT 75*F. WHEN PRESENT IN SAID COMPOSITION, D. ABOUT 0.095 TO 15% OF A SOLUBLE NONIONIC SURFACTANT WHICH SURFACTANT IS CHARACTERIZED AS HAVING A CLOUD POINT OF AT LEAST ABOUT 90*F. AND HAVING A SURFACE TENTION OF ABOUT 32 DYNES/CM. OR LESS WHEN PRESENT IN AN AMOUNT OF 0.1% OF SAID COMPOSITION, AND E. THE BALANCE, WATER.
2. The composition of claim 1 wherein the nonionic solvent for hydrocarbon residues is a glycol ether.
3. The composition of claim 1 wherein the solvent is chosen from the group consisting of 2-butoxyethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-methoxyethanol, and 2-ethoxyethanol.
4. The composition of claim 1 wherein the soluble nonionic surfactant is chosen from the group consisting of linear alcohol ethoxylates, polyoxyethylene esters, and allyl aryl polyethylene oxides.
5. The composition of claim 1 wherein the soluble nonionic surfactant is a mixture of primary alcohols of about 10 to about 12 member carbon chains, about 60% ethoxylated.
6. The composition of claim 1 comprising the following proportions: a. 10% sulfamic acid, b. 5% citric acid, c. 5% 2-butoxyethanol, d. 0.1% of a mixture of primary alcohols of about 10 to about 12 member carbon chains, about 60% ethoxyLated, e. 79.9% water.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US324651A US3909437A (en) | 1973-01-18 | 1973-01-18 | Noncorrosive acid, solvent and nonionic surfactant composition |
| US05/475,704 US3957529A (en) | 1973-01-18 | 1974-06-03 | Method for cleaning and passivating a metal surface |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US324651A US3909437A (en) | 1973-01-18 | 1973-01-18 | Noncorrosive acid, solvent and nonionic surfactant composition |
| US05/475,704 US3957529A (en) | 1973-01-18 | 1974-06-03 | Method for cleaning and passivating a metal surface |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/475,704 Division US3957529A (en) | 1973-01-18 | 1974-06-03 | Method for cleaning and passivating a metal surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3909437A true US3909437A (en) | 1975-09-30 |
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|---|---|---|---|
| US324651A Expired - Lifetime US3909437A (en) | 1973-01-18 | 1973-01-18 | Noncorrosive acid, solvent and nonionic surfactant composition |
| US05/475,704 Expired - Lifetime US3957529A (en) | 1973-01-18 | 1974-06-03 | Method for cleaning and passivating a metal surface |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
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| US05/475,704 Expired - Lifetime US3957529A (en) | 1973-01-18 | 1974-06-03 | Method for cleaning and passivating a metal surface |
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| US4392977A (en) * | 1980-01-26 | 1983-07-12 | Henkel Kommanditgesellschaft Auf Aktien | Liquid cleaning and maintenance composition especially for dishwashers |
| US4469525A (en) * | 1983-01-19 | 1984-09-04 | Tennant Company | Membrane remover/etchant |
| US4470920A (en) * | 1981-05-11 | 1984-09-11 | Custom Research And Development | Metal oxide remover for stainless steels |
| US4496470A (en) * | 1981-01-12 | 1985-01-29 | The B. F. Goodrich Company | Cleaning composition |
| US4501680A (en) * | 1983-11-09 | 1985-02-26 | Colgate-Palmolive Company | Acidic liquid detergent composition for cleaning ceramic tiles without eroding grout |
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| US4935158A (en) * | 1986-10-30 | 1990-06-19 | Aszman Harry W | Solid detergent cleaning composition, reusable cleaning pad containing same and method of manufacture |
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| EP0778338A1 (en) * | 1995-12-07 | 1997-06-11 | The Procter & Gamble Company | Use of sulphamic acid in an acidic composition for improved skin mildness |
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| US4190463A (en) * | 1979-02-05 | 1980-02-26 | Nalco Chemical Company | Method of removing iron oxide deposits from heat transfer surfaces |
| US4365359A (en) * | 1979-02-15 | 1982-12-28 | Raab S | PMMA Coated bone connective prostheses and method of forming same |
| US4363741A (en) * | 1980-12-19 | 1982-12-14 | Borden, Inc. | Automotive cooling system cleaner |
| US4587030A (en) * | 1983-07-05 | 1986-05-06 | Economics Laboratory, Inc. | Foamable, acidic cleaning compositions |
| US4604144A (en) * | 1985-09-11 | 1986-08-05 | At&T Technologies, Inc. | Process for cleaning a circuit board |
| FR2697032B1 (en) * | 1992-10-19 | 1995-01-06 | Lorraine Laminage | Pickling process for steel materials. |
| US5421906A (en) * | 1993-04-05 | 1995-06-06 | Enclean Environmental Services Group, Inc. | Methods for removal of contaminants from surfaces |
| US5728660A (en) * | 1993-04-05 | 1998-03-17 | Eet, Inc. | Extraction fluids for removal of contaminants from surfaces |
| US5961736A (en) * | 1993-04-05 | 1999-10-05 | Active Environmental Technologies, Inc. | Method for removal of contaminants from surfaces |
| FR2722511B1 (en) * | 1994-07-15 | 1999-04-02 | Ontrak Systems Inc | PROCESS FOR REMOVING METALS FROM A SCOURING DEVICE |
| JP3693441B2 (en) * | 1996-12-27 | 2005-09-07 | 富士通株式会社 | Manufacturing method of recording medium |
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| US6984236B2 (en) * | 2001-10-24 | 2006-01-10 | Faro Technologies, Inc. | Bone connective prosthesis and method of forming same |
| JP4159334B2 (en) * | 2002-09-30 | 2008-10-01 | 新日本製鐵株式会社 | Discoloration removal cleaning agent and discoloration removal cleaning method for titanium and titanium alloy building materials |
| CN100386832C (en) * | 2004-06-22 | 2008-05-07 | 陆福荣 | Surface treatment of electric contact |
| MD3008G2 (en) * | 2005-06-27 | 2006-10-31 | Государственный Университет Молд0 | Process for repatination of old restored bronze and brass articles |
| US7923425B2 (en) * | 2006-08-21 | 2011-04-12 | Henkel Ag & Co. Kgaa | Low-foaming, acidic low-temperature cleaner and process for cleaning surfaces |
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| US2994664A (en) * | 1958-02-19 | 1961-08-01 | Nalco Chemical Co | Dry acid cleaning compositions |
| US3239467A (en) * | 1962-02-15 | 1966-03-08 | Lord Corp | Metal cleaning and treating compositions |
| US3330769A (en) * | 1964-01-23 | 1967-07-11 | Minnesota Mining & Mfg | Metal cleaning |
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| US3114657A (en) * | 1960-08-29 | 1963-12-17 | John W Stilwell | Composition and method for cleaning and stripping metals |
| US3162547A (en) * | 1961-07-31 | 1964-12-22 | Rohr Corp | Secondary deoxidizer for aluminum and its alloys |
| US3522093A (en) * | 1967-02-27 | 1970-07-28 | Chem Cleaning & Equipment Serv | Processes of cleaning and passivating reactor equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2994664A (en) * | 1958-02-19 | 1961-08-01 | Nalco Chemical Co | Dry acid cleaning compositions |
| US3239467A (en) * | 1962-02-15 | 1966-03-08 | Lord Corp | Metal cleaning and treating compositions |
| US3330769A (en) * | 1964-01-23 | 1967-07-11 | Minnesota Mining & Mfg | Metal cleaning |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4392977A (en) * | 1980-01-26 | 1983-07-12 | Henkel Kommanditgesellschaft Auf Aktien | Liquid cleaning and maintenance composition especially for dishwashers |
| US4496470A (en) * | 1981-01-12 | 1985-01-29 | The B. F. Goodrich Company | Cleaning composition |
| US4470920A (en) * | 1981-05-11 | 1984-09-11 | Custom Research And Development | Metal oxide remover for stainless steels |
| US4469525A (en) * | 1983-01-19 | 1984-09-04 | Tennant Company | Membrane remover/etchant |
| US4608086A (en) * | 1983-01-19 | 1986-08-26 | Tennant Company | Membrane remover/etchant |
| US4501680A (en) * | 1983-11-09 | 1985-02-26 | Colgate-Palmolive Company | Acidic liquid detergent composition for cleaning ceramic tiles without eroding grout |
| FR2591791A1 (en) * | 1985-12-18 | 1987-06-19 | Gallo Lucien | Composition permitting the decontamination of clothing for protection against nuclear radiations |
| EP0256148A1 (en) * | 1986-08-12 | 1988-02-24 | Joh. A. Benckiser GmbH | Liquid, granulated or powdery detergent, in particular for dish-washing machines |
| US4935158A (en) * | 1986-10-30 | 1990-06-19 | Aszman Harry W | Solid detergent cleaning composition, reusable cleaning pad containing same and method of manufacture |
| US5061393A (en) * | 1990-09-13 | 1991-10-29 | The Procter & Gamble Company | Acidic liquid detergent compositions for bathrooms |
| EP0778338A1 (en) * | 1995-12-07 | 1997-06-11 | The Procter & Gamble Company | Use of sulphamic acid in an acidic composition for improved skin mildness |
| EP0875554A1 (en) * | 1997-04-30 | 1998-11-04 | The Procter & Gamble Company | Acidic limescale removal compositions |
| US20020102359A1 (en) * | 2001-01-30 | 2002-08-01 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| US6846512B2 (en) * | 2001-01-30 | 2005-01-25 | The Procter & Gamble Company | System and method for cleaning and/or treating vehicles and the surfaces of other objects |
| CN113073314A (en) * | 2021-03-31 | 2021-07-06 | 深圳市腾基建设工程有限公司 | Surface renovation liquid and renovation method for titanium-zinc plate |
Also Published As
| Publication number | Publication date |
|---|---|
| US3957529A (en) | 1976-05-18 |
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| AS | Assignment |
Owner name: DOWELL SCHLUMBERGER INCORPORATED, 400 WEST BELT SO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:DOW CHEMICAL COMPANY, THE, 2030 DOW CENTER, ABBOTT ROAD, MIDLAND, MI. 48640;DOWELL SCHLUMBERGER INCORPORATED, 500 GULF FREEWAY, HOUSTON, TEXAS 77001;REEL/FRAME:004398/0131;SIGNING DATES FROM 19850410 TO 19850417 |