Trivalent chromium-containing composition for use in corrosion resistant coatings on metal surfaces

• US 9,487,866 B2
• Filed: 05/10/2007
• Issued: 11/08/2016
• Est. Priority Date: 05/10/2006
• Status: Active Grant

• Current Assignee: Henkel AG & Co KGaA
• Original Assignee: Henkel AG & Co KGaA
• Inventors: Kramer, Kirk, Salet, Lisa K.
• Primary Examiner(s): ZHENG, LOIS L
• Application Number:
  US11/746,802
• Publication Number:
  US 20100132843A1
• Time in Patent Office: 3,470 Days
• Field of Search: 148/247, 148/267
• US Class Current: 1/1
• CPC Class Codes: B32B 15/017 one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
• CPC Class Codes: B32B 15/043 of metal B32B15/01 takes precedence
• CPC Class Codes: B32B 15/20 comprising aluminium or copper B32B15/016 and B32B15/017 take precedence
• CPC Class Codes: B32B 2307/752 Corrosion inhibitor
• 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 8/04 Treatment of selected surface areas, e.g. using masks
• CPC Class Codes: C23C 8/42 only one element being applied

Abstract

A low sludge trivalent chromium based conversion coating bath is provided which forms corrosion resistant coatings on aluminum and aluminum alloys by immersion in aqueous solutions containing trivalent chromium ions and fluorometallate ions followed by optional rinsing. Trivalent chromium coated aluminum also serves as an effective base for paint primers.

Claims

1. A storage stable composition made by mixing together a first mass of water and at least the following components:

(A) a second mass of a water-soluble source of fluorometallate anions to provide in the composition from about 1 to about 100 g/kg of the fluorometallate anion, each of said anions consisting of;

(i) at least four fluorine atoms; and

(ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and, optionally, one or both of

(iii) at least one ionizable hydrogen atom; and

(iv) at least one oxygen atom;

(B) a third mass in an amount of about 23 g/l to about 100 g/l of a water soluble source of chromium fluoride;

(C) an optional fourth mass of water-soluble source of fluorine anions;

(D) an optional fifth mass of a component of surfactant and/or water soluble thickener;

said composition being free of water-soluble organic corrosion inhibitor and water-soluble organic stabilizing agents, having a pH of at least 2.1 and no more than 4.4, being storage stable at ambient temperature for at least 2 weeks and capable of producing no more than 3 pits per panel after being exposed to 336 hour salt spray testing according to ASTM B-117.

2. The composition according to claim 1, wherein said liquid composition comprises not more than 0.06% of dispersed silica and silicates.

3. The composition according to claim 1, wherein:

the second mass comprises fluorozirconate anions in an amount that corresponds to a concentration, in said composition, that is within a range from about 1 to about 8 g/kg; and

there is mixed into said composition a fifth mass of fluorinated alkyl ester surfactant molecules that corresponds to a concentration, in said composition, that is within a range from about 0.070 to about 0.13 ppt.

4. The composition according to claim 1, wherein the third mass is present in an amount of 33 g/l to about 100 g/l of a water soluble solution of trivalent chromium cations.

5. The composition according to claim 1, wherein the third mass is present in an amount of 50 g/l to about 100 g/l of a water soluble solution of trivalent chromium cations.

6. The composition according to claim 1, wherein each fluorometallate anion consists of:

(i) at least four fluorine atoms;

(ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and, one or both of

(iii) at least one ionizable hydrogen atom; and

(iv) at least one oxygen atom.

7. The composition according to claim 1, wherein the fourth mass is mixed together with the first, second and third masses to form the composition.

8. The composition according to claim 7, wherein the weight ratio of trivalent chromium to metal in the fluorometallate anions is 0.725:

1 to 39;

1.

9. The composition according to claim 1, wherein the weight ratio of trivalent chromium to metal in the fluorometallate anions is 0.725:

1 to 39;

1.

10. The composition according to claim 1, wherein the fluorometallate anions are selected from the group consisting of fluorosilicate, fluorotitanate, and fluorozirconate anions.

11. The composition according to claim 1, wherein the fluorometallate anions include fluorozirconate anions in a concentration within a range from about 0.4 to 100 g/kg;

and said liquid composition comprising not more than 0.06% of dispersed silica and silicates.

12. The composition according to claim 1, wherein an acid or base pH adjuster is present to maintain the pH within the range of at least 2.1 and no more than 4.4.

13. The composition according to claim 1, wherein the pH is at least 3.0 and no more than 4.2.

14. A composition for coating a metal surface, said composition consisting of water and:

(A) a component of fluorometallate anions, each of said anions consisting of;

(i) at least four fluorine atoms; and

(ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and, optionally, one or both of

(iii) at least one ionizable hydrogen atom; and

(iv) at least one oxygen atom;

(B) a component of water soluble chromium fluoride;

(C) an optional component of water-soluble source of fluorine anions;

(D) an optional component of surfactant;

(E) and optional component of water soluble thickener;

wherein the concentration of trivalent chromium is at least 6.0 g/l and said composition is substantially free of hexavalent chromium and has a pH of no more than 4.4 and is storage stable at ambient temperature for at least 2 weeks.

15. The composition according to claim 14, wherein the fluorometallate anions are selected from the group consisting of fluorosilicate, fluorotitanate, and fluorozirconate anions.

16. The composition according to claim 15, wherein the fluorometallate anions include fluorozirconate anions in a concentration within a range from about 0.4 to 100 g/kg;

water soluble chromium fluoride in a concentration within a range from about 4 to 100 g/l and said liquid composition comprising not more than 0.06% of dispersed silica and silicates.

17. The composition according to claim 16, wherein trivalent chromium and zirconium are present in a ratio of trivalent chromium to zirconium in a range of 0.725:

1 to 39;

1.

18. The composition according to claim 14, wherein:

the fluorometallate anions include fluorozirconate anions;

the concentration of fluorozirconate anions is within a range from about 1 to about 10 g/kg;

the concentration of chromium fluoride is within a range from about 4 g/l to about 100 g/l; and

the ratio of trivalent chromium to zirconium is in the range of 7 to 17.

19. The composition according to claim 14, wherein each fluorometallate anion consist of:

(i) at least four fluorine atoms;

(ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron, and, one or both of

(iii) at least one ionizable hydrogen atom; and

(iv) at least one oxygen atom.

20. The composition according to claim 14, wherein the pH is at least 3.6 and no more than 4.0, and wherein total add-on mass of the coating is not greater than 120 mg/ft².

21. A composition for coating a metal surface, said composition comprising water and:

(A) a component of hexafluorozirconate anions present within a range from about 1 g/kg to about 4.5 g/kg;

(B) a component of water soluble chromium fluoride present in an amount of about 5.0 g/l to about 50.0 g/l; and

(C) fluorinated alkyl ester surfactant;

wherein a ratio of trivalent chromium to zirconium is in a range of 12;

22, the composition being substantially free of hexavalent chromium and having a pH of at least 2.1 and no more than 4.4.

22. The composition according to claim 21, wherein said composition dried in place on an aluminum substrate provides corrosion resistance such that less than about 3 pits per 24 square inches develop when said substrate is subjected to 5% neutral salt spray at 95°

F. ASTM B-117 for at least 336 hours.

23. The composition according to claim 21, further comprising ammonium hydroxide.

24. The composition according to claim 21, wherein the pH is at least 3.6 and no more than 4.0, and wherein total add-on mass of the coating is not greater than 120 mg/ft².