Corrosion inhibiting compositions and methods of making and using

• US 9,605,162 B2
• Filed: 03/15/2013
• Issued: 03/28/2017
• Est. Priority Date: 03/15/2013
• Status: Active Grant

• Current Assignee: Honda Motor Co., Ltd. (Honda Motor Company)
• Original Assignee: Honda Motor Co., Ltd. (Honda Motor Company)
• Inventors: Fitz, Todd Andrew, Berg, Mariko Elaine
• Primary Examiner(s): Nelson, Michael B
• Application Number:
  US13/839,895
• Publication Number:
  US 20140272392A1
• Time in Patent Office: 1,474 Days
• US Class Current: 1/1
• CPC Class Codes: B32B 2255/06 on metal layer
• CPC Class Codes: B32B 2307/50 having particular mechanical properties
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/714 Inert, i.e. inert to chemical degradation, corrosion
• CPC Class Codes: B32B 2605/00 Vehicles
• CPC Class Codes: B32B 37/14 characterised by the properties of the layers
• CPC Class Codes: C08K 9/10 Encapsulated ingredients
• CPC Class Codes: C09D 5/082 characterised by the anti-corrosive pigment
• CPC Class Codes: C09D 5/086 Organic or non-macromolecular compounds
• CPC Class Codes: C09D 7/63 organic
• CPC Class Codes: C09D 7/69 Particle size larger than 1000 nm
• CPC Class Codes: Y10T 428/263 Coating layer not in excess of 5 mils thick or equivalent
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

A corrosion inhibiting composition includes one or more of a plurality of carriers, each having a carrier body and an organic corrosion inhibitor, such that the carrier body encapsulates the organic corrosion inhibitor, and the carrier body is formed of a degradable material. Coatings and methods for inhibiting corrosion on a metal substrate are also described herein.

Claims

1. A coating for inhibiting corrosion on a metal substrate, the coating comprising a corrosion inhibiting composition comprising:

a first plurality of carriers, each comprising a first carrier body and a first corrosion inhibitor, the first carrier body encapsulating the first corrosion inhibitor, wherein the first corrosion inhibitor is a first organic compound comprising a ring structure and wherein the first carrier body is formed of a first degradable material; and

a second plurality of carriers, each comprising a second carrier body and a second corrosion inhibitor, the second carrier body encapsulating the second corrosion inhibitor, wherein the second carrier body is formed of a second degradable material;

wherein the second corrosion inhibitor is a second organic compound comprising a ring structure, wherein the second corrosion inhibitor is different from the first corrosion inhibitor, wherein the second plurality of carriers does not include the first corrosion inhibitor and the first plurality of carriers does not include the second corrosion inhibitor, and wherein the first degradable material has a mechanical integrity which deteriorates in at least one of an alkaline condition and an acidic condition sufficient to release the first corrosion inhibitor from the first degradable material;

wherein the coating exhibits a creep value of about 0.6 mm or less according to a hot salt water test when the coating is tested at a thickness of 25 microns,

wherein the hot salt water test comprises;

cutting an X-shaped cut into a test piece of a metal substrate comprising a base material using an SK2 cutting knife having a hardness of HV 820+/−

30, wherein the X-shaped cut has a cross angle from 60°

to 90° and

reaches the base material of the metal substrate,

immersing the test piece in a 5 wt % NaCl solution at 55°

C. in a container,

sealing the container,

removing the test piece from the container after 240 hours and rinsing and wiping the test piece,

measuring a width of any rust and/or blister on the test piece in order to determine a blister width, and

attaching a 12 or 24 mm wide piece of cellophane adhesive tape to the rust and/or blister, holding the edge of the adhesive tape to form an angle of 45°

between the adhesive tape and test piece, peeling off the adhesive tape, and measuring a width of any resulting peeled portion in order to determine a peeling width,

wherein the creep value is the larger of the peeling width and the blister width.

2. The coating of claim 1, wherein the first organic compound comprises a heterocyclic compound.

3. The coating of claim 1, wherein the first corrosion inhibitor is a chelating agent.

4. The coating of claim 2, wherein the heterocyclic compound includes an endocyclic donor atom and an exocyclic donor atom.

5. The coating of claim 4, wherein the exocyclic donor atom is directly bonded to a heterocyclic ring of the heterocyclic compound.

6. The coating of claim 4, wherein the exocyclic donor atom is not directly bonded to a heterocyclic ring of the heterocyclic compound.

7. The coating of claim 2, wherein the heterocyclic compound is selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-(benzothiazol-2-ylsulfanyl)-succinic acid, 8-hydroxyquinoline, 8-hydroxyquinaldine, and any combination thereof.

8. The coating of claim 1, wherein the first corrosion inhibitor and the second corrosion inhibitor comprises from about 10% to about 40%, by weight, of the first plurality of carriers and the second plurality of carriers.

9. The coating of claim 8, wherein the first corrosion inhibitor and the second corrosion inhibitor comprises from about 15% to about 35%, by weight, of the first plurality of carriers and the second plurality of carriers.

10. A coating for inhibiting corrosion on a metal substrate, the coating comprising a corrosion inhibiting composition;

comprising;

a first plurality of carriers, each comprising a first carrier body and a first corrosion inhibitor, the first carrier body encapsulating the first corrosion inhibitor, wherein the first corrosion inhibitor is a first organic compound comprising a ring structure and wherein the first carrier body is formed of a first degradable material; and

a second plurality of carriers, each comprising a second carrier body and a second corrosion inhibitor, the second carrier body encapsulating the second corrosion inhibitor, wherein the second carrier body is formed of a second degradable material;

wherein the second corrosion inhibitor is a second organic compound comprising a ring structure, wherein the second corrosion inhibitor is different from the first corrosion inhibitor, wherein the second plurality of carriers does not include the first corrosion inhibitor and the first plurality of carriers does not include the second corrosion inhibitor, and wherein the first degradable material has a mechanical integrity which deteriorates in at least one of an alkaline condition and an acidic condition sufficient to release the first corrosion inhibitor from the first degradable material;

wherein the coating exhibits a creep value of about 1.6 mm or less according to a salt spray test when the coating is tested at a thickness of 25 microns,

wherein the salt spray test comprises;

cutting an X-shaped cut into a test piece of a metal substrate comprising a base material using an SK2 cutting knife having a hardness of HV 820+/−

30, wherein the X-shaped cut has a cross angle from 60°

to 90° and

reaches the base material of the metal substrate,

affixing the test piece on a salt spray tester conforming to ASTM B117 standard, with a test chamber temperature of 35±

1°

C., an air saturator temperature of 47±

1°

C., a test chamber relative humidity of about 95%, a spraying pressure of from 70 to 180 kPa, an amount of solution collected being from 0.85 to 2.0 mL/hour for 80 cm2, and a pH of solution made by spraying of from 6.5 to 7.2, at 15°

to 30°

to a vertical line,

subjecting the test piece to spraying of 5.0 wt % NaCl solution for 960 hours,

rinsing the test piece to remove any corrosion product,

measuring a width of the largest swollen area of the X-shaped cut in order to determine a blister width,

after two hours at room temperature, attaching a 12 or 24 mm wide piece of cellophane adhesive tape to the test piece, holding the edge of the adhesive tape to form an angle of 45°

between the adhesive tape and test piece, and peeling the tape off the test piece,

measuring a width of an area of the coating which was peeled with the tape to determine a peeling width,

wherein the creep value is the larger of the peeling width and the blister width.

11. The coating of claim 10, wherein the first organic compound comprises a heterocyclic compound.

12. The coating of claim 10, wherein the first corrosion inhibitor is a chelating agent.

13. The coating of claim 11, wherein the heterocyclic compound includes an endocyclic donor atom and an exocyclic donor atom.

14. The coating of claim 13, wherein the exocyclic donor atom is directly bonded to a heterocyclic ring of the heterocyclic compound.

15. The coating of claim 13, wherein the exocyclic donor atom is not directly bonded to a heterocyclic ring of the heterocyclic compound.

16. The coating of claim 11, wherein the heterocyclic compound is selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-(benzothiazol-2-ylsulfanyl)-succinic acid, 8-hydroxyquinoline, 8-hydroxyquinaldine, and any combination thereof.

17. The coating of claim 10, wherein the first corrosion inhibitor and the second corrosion inhibitor comprises from about 10% to about 40%, by weight, of the first plurality of carriers and the second plurality of carriers.

18. The coating of claim 17, wherein the first corrosion inhibitor and the second corrosion inhibitor comprises from about 15% to about 35%, by weight, of the first plurality of carriers and the second plurality of carriers.

19. A coating for inhibiting corrosion on a metal substrate, the coating comprising a corrosion inhibiting composition comprising:

a first plurality carriers, each comprising a first carrier body and a first corrosion inhibitor, the first carrier body encapsulating the first corrosion inhibitor, the first corrosion inhibitor is a first organic compound including a ring structure, wherein the first carrier body is formed of a first degradable material; and

a second plurality of carriers, each comprising a second carrier body and a second corrosion inhibitor, the second carrier body encapsulating the second corrosion inhibitor, the second corrosion inhibitor is a second organic compound including a ring structure, wherein the second corrosion inhibitor is different from the first corrosion inhibitor, wherein the first plurality of carriers does not include the second corrosion inhibitor and the second plurality of carriers does not include the first corrosion inhibitor, and wherein the second carrier body is formed of a second degradable material,

wherein the coating exhibits a creep value of about 0.6 mm or less according to a hot salt water test when the coating is tested at a thickness of 25 microns,

wherein the hot salt water test comprises;

cutting an X-shaped cut into a test piece of a metal substrate comprising a base material using an SK2 cutting knife having a hardness of HV 820+/−

30, wherein the X-shaped cut has a cross angle from 60°

to 90° and

reaches the base material of the metal substrate,

immersing the test piece in a 5 wt % NaCl solution at 55°

C. in a container,

sealing the container,

removing the test piece from the container after 240 hours and rinsing and wiping the test piece,

measuring a width of any rust and/or blister on the test piece in order to determine a blister width, and

attaching a 12 or 24 mm wide piece of cellophane adhesive tape to the rust and/or blister, holding the edge of the adhesive tape to form an angle of 45°

between the adhesive tape and test piece, peeling off the adhesive tape, and measuring a width of any resulting peeled portion in order to determine a peeling width,

wherein the creep value is the larger of the peeling width and the blister width.

20. The coating of claim 19, wherein the coating exhibits a creep value of about 0.4 mm or less according to the hot salt water test.

21. The coating of claim 20, wherein the coating exhibits a creep value of about 0.2 mm or less according to the hot salt water test.

22. The coating of claim 19, wherein said first carriers and said second carriers each form microparticles.

23. The coating of claim 19, wherein the first corrosion inhibitor is a chelating agent.

24. The coating of claim 19, wherein the second corrosion inhibitor is a chelating agent.

25. The coating of claim 19, wherein the first corrosion inhibitor includes at least one donor atom that is different than donor atoms included in the second corrosion inhibitor.

26. The coating of claim 19, wherein the first organic compound is a first heterocyclic compound.

27. The coating of claim 26, wherein the first heterocyclic compound includes an endocyclic donor atom and an exocyclic donor atom.

28. The coating of claim 27, wherein the exocyclic donor atom is directly bonded to a heterocyclic ring of the first heterocyclic compound.

29. The coating of claim 19, wherein the first organic compound includes a thiazole compound, an imidazole compound, or any combination thereof.

30. The coating of claim 19, wherein the first organic compound includes 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, or any combination thereof.

31. The coating of claim 19, wherein the second organic compound is a second heterocyclic compound.

32. The coating of claim 31, wherein the second heterocyclic compound includes an endocyclic donor atom and an exocyclic donor atom.

33. The coating of claim 32, wherein the exocyclic donor atom is not directly bonded to a heterocyclic ring of the second heterocyclic compound.

34. The coating of claim 19, wherein the second organic compound includes a quinolone, a quinolone derivative, or any combination thereof.

35. The coating of claim 33, wherein the second corrosion inhibitor is 8-hydroxyquinoline, 8-hydroxyquinaldine, or any combination thereof.

36. A coating for inhibiting corrosion on a metal substrate, the coating comprising a corrosion inhibiting composition comprising:

a first plurality carriers, each comprising a first carrier body and a first corrosion inhibitor, the first carrier body encapsulating the first corrosion inhibitor, the first corrosion inhibitor is a first organic compound including a ring structure, wherein the first carrier body is formed of a first degradable material; and

a second plurality of carriers, each comprising a second carrier body and a second corrosion inhibitor, the second carrier body encapsulating the second corrosion inhibitor, the second corrosion inhibitor is a second organic compound including a ring structure, wherein the second corrosion inhibitor is different from the first corrosion inhibitor, wherein the first plurality of carriers does not include the second corrosion inhibitor and the second plurality of carriers does not include the first corrosion inhibitor, and wherein the second carrier body is formed of a second degradable material,

wherein the coating exhibits a creep value of about 1.6 mm or less according to a salt spray test when the coating is tested at a thickness of 25 microns,

wherein the salt spray test comprises;

cutting an X-shaped cut into a test piece of a metal substrate comprising a base material using an SK2 cutting knife having a hardness of HV 820+/−

30, wherein the X-shaped cut has a cross angle from 60°

to 90° and

reaches the base material of the metal substrate,

affixing the test piece on a salt spray tester conforming to ASTM B117 standard, with a test chamber temperature of 35±

1°

C., an air saturator temperature of 47±

1°

C., a test chamber relative humidity of about 95%, a spraying pressure of from 70 to 180 kPa, an amount of solution collected being from 0.85 to 2.0 mL/hour for 80 cm2, and a pH of solution made by spraying of from 6.5 to 7.2, at 15°

to 30°

to a vertical line,

subjecting the test piece to spraying of 5.0 wt % NaCl solution for 960 hours,

rinsing the test piece to remove any corrosion product,

measuring a width of the largest swollen area of the X-shaped cut in order to determine a blister width,

after two hours at room temperature, attaching a 12 or 24 mm wide piece of cellophane adhesive tape to the test piece, holding the edge of the adhesive tape to form an angle of 45°

between the adhesive tape and test piece, and peeling the tape off the test piece,

measuring a width of an area of the coating which was peeled with the tape to determine a peeling width,

wherein the creep value is the larger of the peeling width and the blister width.

37. The coating of claim 36, wherein the coating exhibits a creep value of about 1.3 mm or less according to the salt spray test.

38. The coating of claim 37, wherein the coating exhibits a creep value of about 1.0 mm or less according to the salt spray test.

39. The coating of claim 36, wherein said first carriers and said second carriers each form microparticles.

40. The coating of claim 36, wherein the first corrosion inhibitor is a chelating agent.

41. The coating of claim 36, wherein the second corrosion inhibitor is a chelating agent.

42. The coating of claim 36, wherein the first corrosion inhibitor includes at least one donor atom that is different than donor atoms included in the second corrosion inhibitor.

43. The coating of claim 36, wherein the first organic compound is a first heterocyclic compound.

44. The coating of claim 43, wherein the first heterocyclic compound includes an endocyclic donor atom and an exocyclic donor atom.

45. The coating of claim 44, wherein the exocyclic donor atom is directly bonded to a heterocyclic ring of the first heterocyclic compound.

46. The coating of claim 36, wherein the first organic compound includes a thiazole compound, an imidazole compound, or any combination thereof.

47. The coating of claim 36, wherein the first organic compound includes 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, or any combination thereof.

48. The coating of claim 36, wherein the second organic compound is a second heterocyclic compound.

49. The coating of claim 48, wherein the second heterocyclic compound includes an endocyclic donor atom and an exocyclic donor atom.

50. The coating of claim 49, wherein the exocyclic donor atom is not directly bonded to a heterocyclic ring of the second heterocyclic compound.

51. The coating of claim 36, wherein the second organic compound includes a quinolone, a quinolone derivative, or any combination thereof.

52. The coating of claim 50, wherein the second corrosion inhibitor is 8-hydroxyquinoline, 8-hydroxyquinaldine, or any combination thereof.

53. A coating for inhibiting corrosion on a metal substrate, the coating comprising:

a coating base comprising an organic layer; and

a corrosion inhibiting composition dispersed in the coating base, the corrosion inhibiting composition comprising;

a first plurality carriers, each comprising a first carrier body and a first corrosion inhibitor, the first carrier body encapsulating the first corrosion inhibitor, the first corrosion inhibitor is a first organic compound including a ring structure, wherein the first carrier body is formed of a first degradable material; and

a second plurality of carriers, each comprising a second carrier body and a second corrosion inhibitor, the second carrier body encapsulating the second corrosion inhibitor, the second corrosion inhibitor is a second organic compound including a ring structure, wherein the second corrosion inhibitor is different from the first corrosion inhibitor, wherein the first plurality of carriers does not include the second corrosion inhibitor and the second plurality of carriers does not include the first corrosion inhibitor, and wherein the second carrier body is formed of a second degradable material;

wherein the coating exhibits a salt spray creep value of 1.6 mm or less according to a salt spray test when the coating is tested at a thickness of 25 microns and wherein the coating exhibits a hot salt water creep value of 0.6 mm or less according to a hot salt water test when the coating is tested at a thickness of 25 microns,

wherein the salt spray test comprises;

cutting an X-shaped cut into a first test piece of a metal substrate comprising a base material using an SK2 cutting knife having a hardness of HV 820+/−

30, wherein the X-shaped cut has a cross angle from 60°

to 90° and

reaches the base material of the metal substrate,

affixing the first test piece on a salt spray tester conforming to ASTM B117 standard, with a test chamber temperature of 35±

1°

C. an air saturator temperature of 47±

1°

C., a test chamber relative humidity of 95%, a spraying pressure of from 70 to 180 kPa, an amount of solution collected being from 0.85 to 2.0 mL/hour for 80 cm2, and a pH of solution made by spraying of from 6.5 to 7.2, at 15°

to 30°

to a vertical line,

subjecting the first test piece to spraying of 5.0 wt % NaCl solution for 960 hours,

rinsing the first test piece to remove any corrosion product,

measuring a width of the largest swollen area of the X-shaped cut in order to determine a salt spray blister width,

after two hours at room temperature, attaching a 12 or 24 mm wide piece of cellophane adhesive tape to the first test piece, holding the edge of the adhesive tape to form an angle of 45°

between the adhesive tape and first test piece, and peeling the tape off the first test piece,

measuring a width of an area of the coating which was peeled with the tape to determine a salt spray peeling width,

wherein the salt spray creep value is the larger of the salt spray peeling width and the salt spray blister width;

wherein the hot salt water test comprises;

cutting an X-shaped cut into a second test piece of a metal substrate comprising a base material using an SK2 cutting knife having a hardness of HV 820+/−

30, wherein the X-shaped cut has a cross angle from 60°

to 90° and

reaches the base material of the metal substrate,

immersing the second test piece in a 5 wt % NaCl solution at 55°

C. in a container,

sealing the container,

removing the second test piece from the container after 240 hours and rinsing and wiping the second test piece,

measuring a width of any rust and/or blister on the second test piece in order to determine a hot salt water blister width, and

attaching a 12 or 24 mm wide piece of cellophane adhesive tape to the rust and/or blister, holding the edge of the adhesive tape to form an angle of 45°

between the adhesive tape and the second test piece, peeling off the adhesive tape, and measuring a width of any resulting peeled portion in order to determine a hot salt water peeling width,

wherein the hot salt water creep value is the larger of the hot salt water peeling width and the hot salt water blister width.