Method of preventing corrosion of metals using silanes

• US 5,750,197 A
• Filed: 01/09/1997
• Issued: 05/12/1998
• Est. Priority Date: 01/09/1997
• Status: Expired due to Term

• Current Assignee: University of Cincinnati
• Original Assignee: University of Cincinnati
• Inventors: Zhang, Chunbin, Subramanian, Vijay, van Ooij, Wim J.
• Primary Examiner(s): CAMERON, ERMA C
• Application Number:
  US08/781,126
• Time in Patent Office: 488 Days
• Field of Search: 427/387, 427/379, 427/409, 427/410, 427/388.4, 427/318, 106/14.15, 106/14.42, 106/14.43
• US Class Current: 427/308
• CPC Class Codes: B05D 7/16 using synthetic lacquers or varnishes
• CPC Class Codes: B05D 7/56 Three layers or more
• CPC Class Codes: C08G 77/00 Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
• CPC Class Codes: C08G 77/04 Polysiloxanes
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: C23C 22/50 Treatment of iron or alloys based thereon
• CPC Class Codes: C23C 22/56 Treatment of aluminium or alloys based thereon
• CPC Class Codes: C23C 22/68 using aqueous solutions with pH between 6 and 8
• CPC Class Codes: C23C 2222/20 Use of solutions containing silanes

Abstract

A method of preventing corrosion of metals using silanes. The method comprises applying a first treatment solution directly onto the surface of the metal, wherein the first treatment solution contains at least one multi-functional silane having at least two trisubstituted silyl groups, and wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy. An optional second treatment solution containing an organofunctional silane may also be employed, particularly if the metal is to be painted.

Claims

1. A method of treating a metal substrate to improve corrosion resistance, comprising the steps of:

(a) providing a metal substrate; and

(b) applying a coating of a first treatment solution directly onto the surface of said metal, said first treatment solution consisting essentially of at least one multi-functional silane having at least two trisubstituted silyl groups wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy, wherein said multi-functional silane has been at least partially hydrolyzed, and wherein said first treatment solution has a pH of less than about 7.

2. The method of claim 1, wherein said at least one multi-functional silane comprises:

##STR5## wherein X is an aliphatic or aromatic group, each R is an alkyl or acetyl group, and n is 2 or 3.

3. The method of claim 1, wherein said at least one multi-functional silane comprises:

##STR6## wherein each R is an alkyl or acetyl group.

4. The method of claim 2, wherein each R is individually chosen from the group consisting of:

ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, ter-butyl and acetyl.

5. The method of claim 4, wherein X is chosen from the group consisting of:

C₁ -C₆ alkyl, C₁ -C₆ alkenyl, C₁ -C₆ alkyl substituted with at least one amino group, C₁ -C₆ alkenyl substituted with at least one amino group, benzyl, and benzyl substituted with C₁ -C₆ alkyl.

6. The method of claim 5, wherein said multi-functional silane is 1,2-bis-(triethoxysilyl)ethane.

7. The method of claim 5, wherein said metal is chosen from the group consisting of:

cold-rolled steel, aluminum and aluminum alloy.

8. The method of claim 6, wherein said metal is chosen from the group consisting of:

cold-rolled steel, aluminum and aluminum alloy.

9. The method of claim 2, further comprising the step of curing said coating at a temperature of between about 60°

C. and about 250°

C. for between about one minute and about 2 hours.

10. The method of claim 9, further comprising the step of applying a second coating of said first treatment solution after said curing step.

11. The method of claim 10, further comprising the step of curing said second coating.

12. The method of claim 2, further comprising the step of applying a second coating comprising a second treatment solution after application of said first treatment solution, said second treatment solution containing at least one organofunctional silane which has been at least partially hydrolyzed.

13. The method of claim 12, wherein said at least one organofunctional silane has a trisubstituted silyl group, wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy, and at least one organofunctional group.

14. The method of claim 13, wherein said organofunctional group is chosen from the group consisting of:

amino, vinyl, ureido, epoxy, mercapto, cyanato, methacrylato, and vinylbenzyl.

15. The method of claim 14, wherein said at least one organofunctional silane is chosen from the group consisting of:

.sub.γ

-aminopropyltriethoxysilane, .sub.γ

-mercaptopropyltrimethoxysilane, .sub.γ

-ureidopropyltrialkoxysilane, .sub.γ

-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane.

16. The method of claim 2, wherein said metal is preheated to a temperature of between about 60°

C. and about 250°

C. prior to application of the first treatment solution.

17. A method of treating an aluminum or aluminum alloy surface in order to improve corrosion resistance, comprising the steps of:

(a) providing a treatment solution consisting essentially of at least one multi-functional silane which has been at least partially hydrolyzed, said at least one multi-functional silane having at least two trisubstituted silyl groups wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy; and

(b) applying a coating of said solution directly onto said surface.

18. The method of claim 17, further comprising the step of curing said coating.

19. The method of claim 18, wherein said at least one multi-functional silane comprises:

##STR7## wherein X is an aliphatic or aromatic group, each R is an alkyl or acetyl group, and n is 2 or 3.

20. The method of claim 19, wherein each R is individually chosen from the group consisting of:

ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, ter-butyl and acetyl.

21. The method of claim 20, wherein X is chosen from the group consisting of:

C₁ -C₆ alkyl, C₁ -C₆ alkenyl, C₁ -C₆ alkyl substituted with at least one amino group, C₁ -C₆ alkenyl substituted with at least one amino group, benzyl, and benzyl substituted with C₁ -C₆ alkyl.

22. The method of claim 21, wherein said multi-functional silane is 1,2-bis-(triethoxysilyl)ethane.

23. The method of claim 17, wherein the total concentration of multi-functional silanes in said treatment solution is greater than about 0.1% by volume, based upon the total volume of treatment solution components.

24. The method of claim 23, wherein the total concentration of multi-functional silanes in said treatment solution is between about 2% and about 5%.

25. The method of claim 18, wherein curing is performed at a temperature of between about 60°

C. and about 250°

C. for between about one minute and about 2 hours.

26. The method of claim 18, further comprising the steps of applying a second coating of said treatment solution, and curing said second coating.

27. The method of claim 17, further comprising the step of applying a final coating of a solution containing at least one organofunctional silane which has been at least partially hydrolyzed.

28. The method of claim 27, wherein said at least one organofunctional silane has a trisubstituted silyl group, wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy, and at least one organofunctional group.

29. The method of claim 28, wherein said organofunctional group is chosen from the group consisting of:

amino, vinyl, ureido, epoxy, mercapto, cyanato, methacrylato, and vinylbenzyl.

30. The method of claim 29, wherein said organofunctional silane is a vinyl silane.

31. The method of claim 17, wherein said surface is preheated to a temperature of between about 60°

C. and about 250°

C. prior to application of said treatment solution.

36. The method of claim 30, wherein said multi-functional silane is 1,2-bis-(triethoxysilyl)ethane.

32. A method of pretreating cold-rolled steel prior to painting in order to improve corrosion resistance, comprising the steps of:

(a) providing a first treatment solution consisting essentially of at least one multi-functional silane which has been at least partially hydrolyzed, wherein said multi-functional silane has at least two trialkoxysilyl groups;

(b) providing a second treatment solution comprising at least one organofunctional silane which has been at least partially hydrolyzed;

(c) applying a coating of said first treatment solution directly onto the surface of the steel; and

(d) thereafter applying a coating of said second treatment solution onto said steel.

33. The method of claim 32, wherein said multi-functional silane comprises ##STR8## wherein X is an aliphatic or aromatic group, each R is an alkyl or acetyl group, and n is 2 or 3.

34. The method of claim 33, wherein each R is individually chosen from the group consisting of:

ethyl, methyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, ter-butyl and acetyl.

35. The method of claim 34, wherein X is chosen from the group consisting of:

C₁ -C₆ alkyl, C₁ -C₆ alkenyl, C₁ -C₆ alkyl substituted with at least one amino group, C₁ -C₆ alkenyl substituted with at least one amino group, benzyl, and benzyl substituted with C₁ -C₆ alkyl.

37. The method of claim 32, wherein said at least one organofunctional silane has one trisubstituted silyl group, wherein the substituents are individually chosen from the group consisting of alkoxy and acetoxy, and at least one organofunctional group.

38. The method of claim 37, wherein said organofunctional group is chosen from the group consisting of:

amino, vinyl, ureido, epoxy, mercapto, cyanato, methacrylato, and vinylbenzyl.

39. The method of claim 38, wherein said at least one organofunctional silane is chosen from the group consisting of:

.sub.γ

-aminopropyltriethoxysilane, .sub.γ

-mercaptopropyltrimethoxysilane, .sub.γ

-ureidopropyltrialkoxysilane, .sub.γ

-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriacetoxysilane.

40. The method of claim 39, wherein said organofunctional silane is .sub.γ

-aminopropyltriethoxysilane.

41. The method of claim 32, wherein the total concentration of multi-functional silanes in said first treatment solution is between about 0.1% and about 10% by volume, based upon the total volume of first treatment solution components, and wherein the total concentration of organofunctional silanes in said second treatment solution is between about 0.1% and about 10% by volume, based upon the total volume of second treatment solution components.

42. The method of claim 41, wherein the pH of said first treatment solution is less than about 7.

43. The method of claim 42, wherein said at least one organofunctional silane is .sub.γ

-aminopropyltriethoxysilane, and the total concentration of multi-functional silanes in said first treatment solution is between about 1 and about 5%.