Process and composition for treating metal surfaces using trivalent chromium compounds

• US 9,422,431 B2
• Filed: 10/21/2013
• Issued: 08/23/2016
• Est. Priority Date: 05/07/2008
• Status: Active Grant

• Current Assignee: Bulk Chemicals, Inc.
• Original Assignee: Bulk Chemicals, Inc.
• Inventors: Church, Richard J.
• Primary Examiner(s): ZHENG, LOIS L
• Application Number:
  US14/058,902
• Publication Number:
  US 20140050855A1
• Time in Patent Office: 1,037 Days
• US Class Current: 1/1
• CPC Class Codes: C09D 5/002 Priming paints C09D5/08 takes precedence
• CPC Class Codes: C09D 5/08 Anti-corrosive paints
• CPC Class Codes: C09D 5/084 Inorganic compounds
• CPC Class Codes: C23C 22/34 containing fluorides or complex fluorides
• CPC Class Codes: C23C 22/83 Chemical after-treatment
• CPC Class Codes: C23C 2222/10 Use of solutions containing trivalent chromium but free of hexavalent chromium
• CPC Class Codes: C23C 2222/20 Use of solutions containing silanes

Abstract

An acidic, aqueous composition contains a trivalent chromium compound, an organo-functional silane, and a compound of a group IV-B element. The composition protects metal surfaces, preferably aluminum and aluminum alloys, against corrosion and improves their paint adhesion. The trivalent chromium compound may comprise chromium fluoride and optionally others, such as chromium nitrate. The organo-functional silane is preferably an aminopropyltriethoxy silane, and the compound of a group IV-B element is preferably fluorozirconic acid. The composition can either be dried-in-place or rinsed before a further coating layer is applied. The composition may also include at least one polymer having a plurality of both carboxylic functional groups, alone or with hydroxyl groups. A process uses the aqueous composition either with or without the organo-functional silane along with a sealing step following the application of the aqueous composition; the sealing step involves applying a sealing composition, including an organo-functional silane, to the metal surface.

Claims

1. A composition for treating a metal surface, said composition comprising water, a trivalent chromium compound, an organo-functional silane, a compound of a group IV-B element, and at least one polymer comprising a plurality of carboxylic functional groups and poly (vinyl alcohol).

2. The composition of claim 1, wherein the compound of a group IV-B element is an acid selected from the group consisting of fluorozirconic acid, fluorotitanic acid, and fluorohafnic acid.

3. The composition of claim 2, wherein the acid is fluorozirconic acid.

4. The composition of claim 1, wherein the organo-functional silane is selected from the group consisting of an aminopropyltriethoxy silane, a mercapto silane, and an epoxy silane.

5. The composition of claim 4, wherein the organo-functional silane is an aminopropyltriethoxy silane.

6. The composition of claim 1, wherein the trivalent chromium compound comprises chromium fluoride.

7. The composition of claim 6, wherein the trivalent chromium compound further comprises chromium nitrate.

8. The composition of claim 1, wherein the composition further comprises ammonium bifluoride.

9. The composition of claim 1, wherein the composition has a pH of from 3.5 to 4.5.

10. The composition of claim 1, wherein the trivalent chromium compound is chromium fluoride, the organo-functional silane is an aminopropyltriethoxy silane, and the compound of a group IV-B element is fluorozirconic acid, and the chromium fluoride is present in an amount from 0.01 to 0.15 wt % (as CrF₃.4H₂O);

the aminopropyltriethoxy silane is present in an amount 0.04 to 0.5 wt %; and

the fluorozirconic acid is present in an amount from 0.01 to 0.2 wt %, and the composition has a pH of from 3.5 to 4.5.

11. The composition of claim 10, wherein the chromium fluoride is present in an amount from 0.02 to 0.04 wt % (as CrF₃.4H₂O);

the aminopropyltriethoxy silane is present in an amount from 0.09 to 0.2 wt %; and

the fluorozirconic acid is present in an amount from 0.03 to 0.08 wt %, and the composition has a pH of from 3.8 to 4.2.

12. The composition of claim 1, wherein the at least one polymer comprising a plurality of carboxylic functional groups is poly (methyl vinyl ether/maleic acid).

14. A process for treating a metal surface, said process comprising the step of contacting the metal surface with the composition of claim 1.

15. The process of claim 14, wherein the compound of a group IV-B element is an acid selected from the group consisting of fluorozirconic acid, fluorotitanic acid, and fluorohafnic acid.

16. The process of claim 15, wherein the acid is fluorozirconic acid.

17. The process of claim 14, wherein the organo-functional silane is selected from the group consisting of an aminopropyltriethoxy silane, a mercapto silane, and an epoxy silane.

18. The process of claim 17, wherein the organo-functional silane is the aminopropyltriethoxy silane.

19. The process of claim 14, wherein the trivalent chromium compound comprises chromium fluoride.

20. The process of claim 19, wherein the trivalent chromium compound further comprises chromium nitrate.

21. The process of claim 14, wherein the trivalent chromium compound is chromium fluoride, the organo-functional silane is an aminopropyltriethoxy silane, and the compound of a group IV-B element is fluorozirconic acid, and the chromium fluoride is present in an amount from 0.01 to 0.15 wt % (as CrF₃.4H₂O);

the aminopropyltriethoxy silane is present in an amount 0.04 to 0.5 wt %; and

the fluorozirconic acid is present in an amount from 0.01 to 0.2 wt %, and the composition has a pH of from 3.5 to 4.5.

22. The process of claim 21, wherein the chromium fluoride is present in an amount from 0.02 to 0.04 wt % (as CrF₃.4H₂O);

the aminopropyltriethoxy silane is present in an amount from 0.09 to 0.2 wt %; and

the fluorozirconic acid is present in an amount from 0.03 to 0.08 wt %, and the composition has a pH of from 3.8 to 4.2.

23. The process of claim 14, wherein the metal surface is aluminum or an aluminum alloy.

24. The process of claim 14, wherein the composition further comprises ammonium bifluoride.

25. The process of claim 14, wherein the at least one polymer comprising a plurality of carboxylic functional groups is poly (methyl vinyl ether/maleic acid).

26. A process for treating a metal surface, said process comprising the steps of:

cleaning the metal surface to form a cleaned metal surface;

rinsing the cleaned metal surface with water to form a rinsed metal surface; and

contacting the rinsed metal surface with the composition of claim 1.

27. The process of claim 26 further comprising, after the contacting step:

rinsing the metal surface with water; and

then sealing the metal surface.

13. A composition for treating a metal surface, said composition consisting essentially of water, at least one trivalent chromium compound, an organo-functional silane, fluorozirconic acid, and at least one polymer comprising a plurality of carboxylic functional groups and poly (vinyl alcohol).

28. A process for treating a metal surface, said process comprising the steps of:

contacting a metal surface with a composition comprising water, a trivalent chromium compound, an organo-functional silane a compound of a group IV-B element, and at least one polymer comprising a plurality of carboxylic functional groups and poly(vinyl alcohol);

sealing the metal surface by contacting the metal surface with a sealing composition comprising water and an organofunctional silane.

29. The process of claim 28 further comprising, after the contacting step and before the sealing step, rinsing the metal surface with water.

30. The process of claim 28, wherein the sealing composition further comprises a compound of a group IV-B element.

31. The process of claim 28 further comprising, after the sealing step, applying a decorative coating to the metal surface.

32. The process of claim 28, wherein the at least one polymer comprising a plurality of carboxylic functional groups is poly (methyl vinyl ether/maleic acid).