Corrosion inhibition treatments and method

• US 4,303,568 A
• Filed: 12/10/1979
• Issued: 12/01/1981
• Est. Priority Date: 12/10/1979
• Status: Expired due to Term

• Current Assignee: Betz Laboratories, Inc. (General Electric Company)
• Original Assignee: Betz Laboratories, Inc. (General Electric Company)
• Inventors: Geiger, Gary E., May, Roger C.
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): YARBROUGH, AMELIA
• Application Number:
  US06/101,658
• Time in Patent Office: 722 Days
• Field of Search: 260/29.6 MP, 252/180, 252/181, 252/389 A, 106/14.12, 422/13
• US Class Current: 252/389.2
• CPC Class Codes: C02F 5/105 combined with inorganic substances
• CPC Class Codes: C02F 5/125 combined with inorganic substances
• CPC Class Codes: C02F 5/14 containing phosphorus
• CPC Class Codes: C23F 11/08 in other liquids

Abstract

The invention deals with a method and composition(s) for use in inhibiting corrosion of metallic parts in contact with aqueous systems. It has been discovered that protective oxide films can be formed on the metallic surface if such is allowed to contact an aqueous system containing a sufficient amount for the purpose of a polymer composed primarily of acrylic moieties and hydroxylated lower alkyl acrylate moieties and a water-soluble orthophosphate. Optionally but desirably, polyphosphates, organo-phosphonates, and copper corrosion inhibitors may be included.

Claims

1. A method of inhibiting the corrosion of ferrous metal parts in contact with an aqueous solution with little or no attendant deposition of scale on said ferrous parts, which corrosion inhibition is obtained by providing for the formation of a protective passive oxide film on the metal surface in contact with said aqueous medium, which method comprises

(i) assuring that the pH of said aqueous medium is 5.5 or above;

(ii) assuring that the aqueous medium contains a calcium or other appropriate ion concentration selected from the group consisting of zinc, nickel and chromium and mixtures thereof; and

(iii) adding to said aqueous medium

(a) a water-soluble polymer comprising moieties derived from an acrylic acid or water-soluble salt thereof and moieties of an hydroxylated lower alkyl acrylate, wherein the moieties of the polymer having the following formulas;

##STR14## wherein R is hydrogen or a lower alkyl of from 1 to 3 carbon atoms;

R₁ is OH, OM or NH₂ where M is a water-soluble cation;

R₂ is a lower alkyl of from about 2 to 6 carbon atoms and the mole ratio of x;

y is 34;

1 to 1;

4; and

(b) a water-soluble orthophosphate compound;

said polymer being such that together with the orthophosphate compound is effective to promote the metal oxide film with no attendant deposition, and the amount of (a) and (b) being added being sufficient to provide a substantially scale-free protective passive oxide film on the metallic surface.

2. The method of claim 1, wherein the weight ratio of said polymer to said orthophosphate expressed as PO₄^--- is from about 1:

6 to about 2;

1.

3. A method according to claim 1, wherein the orthophosphate (expressed as PO₄^---) is added to said aqueous medium in an amount of about 6 to 30 parts per million parts of water and said polymer is added in an amount of from 3 to 25 parts per million parts of water.

4. A method according to claim 2, wherein the orthophosphate (expressed as PO₄^---) is added to said aqueous medium in an amount of about 6 to 30 parts per million parts of water and said polymer is added in an amount of from 3 to 25 parts per million parts of water.

5. A method according to claim 4, wherein the pH is maintained or adjusted within the range of 6.5 to 9.5 and said calcium ion concentration is 15 parts per million parts of water or above.

6. A method according to claim 1, wherein additionally is added to said aqueous medium a water-soluble organo phosphonic acid compound or its water-soluble salts.

7. A method according to claim 6, wherein the weight ratio of compounds and polymer added are as follows:

said polymer to said orthophosphate compound expressed as PO₄^--- is from about 1;

6 to about 2;

1; and

said orthophosphate expressed as PO₄^--- to said organo phosphonic acid compound expressed as PO₄^--- is from about 2;

1 to 8;

1.

8. A method according to claim 7, wherein the compounds and polymer are added to said aqueous medium as follows:

orthophosphate compound expressed as PO₄^--- ;

6 to 30 parts per million parts of water;

organo phosphonic acid compound expressed as PO₄^--- ;

1 to 6 parts per million parts of water; and

polymer;

3 to 25 parts per million parts of water.

9. A method according to claim 7, wherein the pH of the aqueous medium is adjusted or maintained at about 6.5 to 9.5 and the calcium ion concentration is 15 parts per million parts of water or above.

10. A method according to claim 1, wherein the aqueous medium is contained in a cooling water system.

11. A method according to claim 9, wherein the aqueous medium is contained in a cooling water system.

12. A method according to claim 7, wherein R is hydrogen and R₂ is a lower alkyl of 3 carbon atoms.

13. A method of inhibiting the corrosion of ferrous metal parts in contact with an aqueous solution with little or no attendant deposition of scale on said ferrous parts, which corrosion inhibition is obtained by providing for the formation of a protective passive oxide film on the metal surface in contact with said aqueous medium, which method comprises

(i) assuring that the pH of said aqueous medium is 5.5 or above;

(ii) assuring that the aqueous medium contains a calcium or other appropriate ion concentration selected from the group consisting of zinc, nickel and chromium and mixtures thereof; and

(iii) adding to said aqueous medium

(a) a water-soluble polymer comprising moieties derived from an acrylic acid or water-soluble salt thereof and moieties of an hydroxylated lower alkyl acrylate, wherein the moieties of the polymer have the following formulas;

##STR15## wherein R is hydrogen or a lower alkyl of from 1 to 3 carbon atoms;

R₁ is OH, OM or NH₂ where M is a water-soluble cation;

R₂ is a lower alkyl of from about 2 to 6 carbon atoms and the mole ratio of x;

y is 34;

1 to 1;

4; and

(b) a water-soluble orthophosphate compound; and

(c) a water-soluble polyphosphate compound;

said polymer being such that together with the orthophosphate compound is effective to promote the metal oxide film with no attendant deposition, and the amount of (a), (b) and (c) being added being sufficient to provide a substantially scale-free protective passive oxide film on the metallic surface.

14. A method according to claim 13, wherein the weight ratio of said compounds and polymer are:

polymer to orthophosphate expressed as PO₄^--- of about 1;

6 to 2;

1; and

orthophosphate expressed as PO₄^--- to polyphosphate expressed as PO₄^--- of about 2.5;

1 to 1;

1.

15. A method according to claim 14, wherein the compounds and the polymer are added to the aqueous medium in the following amounts:

orthophosphate expressed as PO₄^--- ;

6 to 30 parts per million parts of water;

polymer;

3 to 25 parts per million parts of water; and

polyphosphate expressed as PO₄^--- ;

3 to 10 parts per million parts of water.

16. A method according to claim 15, wherein the pH of the aqueous medium is adjusted or maintained within the range of 6.5 to 9.5 and said calcium ion concentration in the water is 15 parts per million parts of water or above.

17. A method according to claim 16, wherein a copper corrosion inhibitor selected from the group consisting of benzotriazole compounds and benzothiazole compounds is added to said aqueous medium in an amount of from 0.5 to 5 parts per million parts of water.

18. A method according to claim 16, wherein R is hydrogen R₂ is a lower alkyl of 3 carbon atoms.

19. A method according to claim 18, wherein a copper corrosion inhibitor selected from the group consisting of benzotriazole compounds and benzothiazole compounds is added to said aqueous medium in an amount of from 0.5 to 5 parts per million parts of water.

20. A method according to claim 16, wherein the aqueous medium is contained in a cooling water system.

21. A method according to claim 18, wherein the aqueous medium is contained in a cooling water system.

22. A method according to claim 13, wherein additionally a water-soluble organo phosphonic acid compound is added to the aqueous medium and the weight ratio of the compounds and polymer are as follows:

polymer to orthophosphate expressed as PO₄^--- ;

about 1;

6 to about 2;

1;

orthophosphate to polyphosphate both expressed as PO₄^--- ;

about 2.5;

1 to about 1;

1;

orthophosphate to said organo phosphonate both expressed as PO₄^--- ;

about 2;

1 to about 8;

1.

23. A method according to claim 22, wherein the compounds and polymer are added to the aqueous medium in the following amounts:

orthophosphate compound expressed as PO₄^--- ;

about 6 to 30 parts per million parts of water;

polyphosphate compound expressed as PO₄^--- ;

about 3 to 10 parts per million parts of water;

phosphonic acid compound expressed as PO₄^--- ;

about 1 to 6 parts per million parts of water; and

polymer;

about 3 to 25 parts per million parts of water.

24. A method according to claim 23, wherein the pH of the aqueous medium is adjusted or maintained within the range of 6.5 to 9.5 and the calcium ion concentration is 15 parts per million parts of water or above.

25. A method according to claim 24, wherein a copper corrosion inhibitor is added to said aqueous medium in the amount of about 0.5 to 5 parts per million parts of water.

26. A method according to claim 24, wherein said aqueous medium is contained in a cooling water system.

27. A method according to claim 25, wherein said aqueous medium is contained in a cooling water system.

28. A method according to claim 13, wherein the hydroxy alkyl acrylate is hydroxy propyl acrylate and the ratios of the acrylic acid moieties to said hydroxy propyl acrylate moieties is about 3:

1 and the polymer has a molecular weight of about 6,000.

29. A method according to claim 28, wherein the aqueous medium is the cooling water of a cooling water system.

30. A method according to claim 29, wherein a copper corrosion inhibitor is added and said inhibitor is selected from the group consisting of tolyltriazole, benzotriazole, and benzothiazole compounds.

31. A method according to claim 28, wherein the hydroxy alkyl acrylate is hydroxy propyl acrylate and the ratios of the acrylic acid moieties to said hydroxy propyl acrylate moieties is about 3:

1 and the polymer has a molecular weight of about 6,000, and said organo phosphonic acid compound is hydroxyethylidene diphosphonic acid or its water-soluble salt.

32. A composition for providing a protective passive oxide film on the surface of a ferrous metallic part in contact with an aqueous solution with little or no attendant deposition of scale on said part, which comprises

(i) a water-soluble polymer consisting essentially of moieties derived from an acrylic acid or water-soluble salt thereof and moieties of an hydroxylated lower alkyl acrylate, wherein the moieties of the polymer have the following formulas:

##STR16## wherein R is hydrogen or a lower alkyl of from 1 to 3 carbon atoms;

R₁ is OH, OM or NH₂ where M is a water-soluble cation;

R₂ is a lower alkyl of from about 2 to 6 carbon atoms and the mole ratio of x;

y is 34;

1 to 1;

4; and

(ii) a water-soluble orthophosphate compound, the ratio on a weight basis of the polymer to the orthophosphate expressed as PO₄^--- being from about 1;

8 to about 4;

1.

33. A composition according to claim 32, wherein the hydroxy alkyl acrylate is hydroxy propyl acrylate and the ratios of the acrylic acid moieties to said hydroxy propyl moieties is about 3:

1 and the polymer has a molecular weight of about 6,000.

34. A composition according to claim 32, which additionally contains a compound selected from the group consisting of an organo phosphonic acid compound or derivatives thereof and a copper corrosion inhibitor selected from the group of benzothiazole compounds and benzotriazole compounds, or mixtures thereof.

35. A composition according to claim 34, wherein the organo phosphonic acid derivative and said compound is present in said composition on a weight ratio of orthophosphate to organo phosphonic derivative both expressed as PO₄^--- of about 1:

2 to about 13;

1.

36. A composition according to claim 35, which contains a mixture of copper corrosion inhibitors and said organo phosphonic acid derivative.

37. A composition according to claim 36, wherein the copper corrosion inhibitor is tolyltriazole.

38. A composition according to claim 35, wherein the hydroxy alkyl acrylate is an hydroxy propyl acrylate, and the phosphonic acid derivative is hydroxyethylidene diphosphonic acid or its water-soluble salt.

39. A composition for providing a protective passive oxide film on the surface of a metallic part in contact with an aqueous solution with little or no attendant deposition of scale on said part, which comprises

(i) a water-soluble polymer consisting essentially of moieties derived from an acrylic acid or water-soluble salt thereof and moieties of an hydroxylated lower alkyl acrylate, wherein the moieties of the polymer have the following formulas:

##STR17## wherein R is hydrogen or a lower alkyl of from 1 to 3 carbon atoms;

R₁ is OH, OM or NH₂ where M is a water-soluble cation;

R₂ is a lower alkyl of from about 2 to 6 carbon atoms and the mole ratio of x;

y is 34;

1 to 1;

4;

(ii) a water-soluble orthophosphate compound, the ratio on a weight basis of the polymer to the orthophosphate expressed as PO₄^--- being from about 1;

8 to about 4;

1, and

(iii) a water-soluble polyphosphate compound, the ratio of orthophosphate to polyphosphate both expressed as PO₄^--- being about 15;

1 to about 1;

3.

40. A composition according to claim 39, wherein the hydroxy alkyl acrylate is hydroxy propyl acrylate.

41. A composition according to claim 40, wherein the ratios of the acrylic acid moieties to said hydroxy propyl acrylate moieties is about 3:

1 and the polymer has a molecular weight of about 6,000.

42. A composition according to claim 39, which additionally contains a compound selected from the group consisting of an organo phosphonic acid compound or derivatives thereof and a copper corrosion inhibitor selected from the group consisting of benzothiazole compounds and benzotriazole compounds, or mixtures thereof.

43. A composition according to claim 42, wherein the compound is an organo phosphonic acid derivative and said compound is present in said composition on a weight ratio of orthophosphate to organo phosphonic derivative both expressed as PO₄^--- of about 1:

2 to about 13;

1.

44. A composition according to claim 43, which contains a mixture of said copper inhibitor and said organo phosphonic acid.

45. A composition according to claim 44, which contains a copper corrosion inhibitor selected from the group consisting of tolyltriazole, benzotriazole compounds, and benzothiazole compounds.

46. A composition according to claim 43, wherein the hydroxy alkyl acrylate is an hydroxy propyl acrylate, and the phosphonic acid derivative is hydroxyethylidene diphosphonic acid or its water-soluble salt.