Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces

• US 8,092,617 B2
• Filed: 02/13/2007
• Issued: 01/10/2012
• Est. Priority Date: 02/14/2006
• Status: Active Grant

• Current Assignee: Henkel AG & Co KGaA
• Original Assignee: Henkel AG & Co KGaA
• Inventors: Kramer, Kirk, Salet, Lisa
• Primary Examiner(s): Mayes, Melvin
• Assistant Examiner(s): COHEN, STEFANIE J
• Application Number:
  US11/674,339
• Publication Number:
  US 20070187001A1
• Time in Patent Office: 1,792 Days
• Field of Search: 148/247
• US Class Current: 148/247
• 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: C25D 11/24 Chemical after-treatment

Abstract

Corrosion resistant coatings are formed on aluminum by contacting with aqueous solutions containing trivalent chromium ions and fluorometallate ions, the solutions being substantially free of hexavalent chromium. Trivalent chromium films formed on the aluminum surface when tested in 5% NaCl salt spray chamber showed corrosion resistance in excess of 168 hours. Trivalent chromium coated aluminum also serves as an effective base for paint primers.

Claims

1. A composition for coating or touching-up or both coating and touching-up a metal surface, said composition comprising water and:

(A) from about 4.5 millimoles per kilogram to about 27 millimoles per kilogram of a component of fluorometallate anions and mixtures of fluorometallate anions, each of said anions comprising;

(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) at least 6.5 g/l to about 46 g/l of trivalent chromium cations;

said composition being substantially free of hexavalent chromium.

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

3. The composition according to claim 1, wherein the fluorometallate anions include fluorozirconate anions in a concentration within a range from about 5.1 to about 24 mM/kg;

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

4. The composition according to claim 3 which contains substantially no zinc.

5. The composition according to claim 1, wherein:

the fluorometallate anions include fluorozirconate anions at a concentration within a range from about 5.1 to about 24 mM/kg;

the concentration of chromium(III) cations is within a range from about 7.5 g/l to about 46 g/l; and

the ratio of trivalent chromium to zirconium is in the range of 12 to 22.

6. The composition according to claim 5 which further includes from about 0.070 to about 0.13 parts per thousand fluorinated alkyl ester surfactant molecules.

7. The composition according to claim 1, wherein the trivalent chromium cations are sourced from the group consisting of fluorides and chlorides of chromium (III).

8. The composition according to claim 7, wherein component (A) is present as hexafluorozirconic acid and component (B) is sourced as 31.0 to 46.0 g/l CrF₃×

4H₂O.

9. A process for coating or touching-up or both coating and touching-up a surface, said surface comprising at least one area of bare metal, at least one area of coating over an underlying metal substrate, or both of at least one area of bare metal and at least one area of coating over an underlying metal substrate, said process comprising operations of:

(I) covering the surface to be coated, touched-up, or both coated and touched-up with a layer of a liquid composition of claim 1; and

(II) drying into place the liquid layer formed in operation (I) to form a coated surface without rinsing between operation (I) and said drying.

10. The process according to claim 9, wherein the surface comprises at least one area of bare metal and at least one area of coating over an underlying metal substrate;

and

in operation (I), the liquid layer is formed over the at least one area of bare metal.

11. The process according to claim 9, wherein, in said liquid composition used in operation (I):

the fluorometallate anions are selected from the group consisting of fluorosilicate, fluorotitanate, and fluorozirconate anions, and mixtures thereof.

12. The process according to claim 11, wherein, in the liquid composition used in operation (I):

the fluorometallate anions include fluorozirconate anions in a concentration within a range from about 5.1 to about 24 mM/kg;

the concentration of chromium(III) ions is at least 7.0 g/l and not more than 46 g/l;

a concentration of hydrofluoric acid is present within a range from about 0.70 to about 1.3 parts per thousand; and

the composition includes fluorinated alkyl ester surfactant molecules in a concentration that is within a range from about 0.070 to about 0.13 parts per thousand.

13. The process according to claim 9, wherein, in said liquid composition used in operation (I):

the fluorometallate anions include fluorozirconate anions in a concentration range from about 4.5 to about 27 mM/kg;

the concentration of chromium(III) ions is at least 7.0 g/l and not more than 46 g/l; and

the composition further includes a surfactant comprising fluorinated alkyl ester molecules in a concentration that is within a range from about 0.070 to about 0.13 parts per thousand.

14. The process according to claim 13, wherein:

the surface comprises at least one area of bare metal adjacent to at least one area of coating over an underlying metal substrate,

said at least one area of coating over an underlying metal substrate comprising a first portion and a second portion,

in operation (I), the liquid layer is formed over both the area of bare metal and at least the first portion of said adjacent area of coating over an underlying metal substrate; and

the coating over an underlying metal substrate is selected from the group consisting of a phosphate conversion coating, a chromate conversion coating, and a conversion coating produced by contacting a surface consisting predominantly of iron, titanium, aluminum, magnesium and/or zinc and alloys thereof with an acidic treating solution comprising at least one of fluorosilicate, fluorotitanate, and fluorozirconate.

15. An article of manufacture having at least one portion that comprises the coated surface of claim 9.

16. The article of manufacture of claim 15 wherein the at least one portion comprises aluminum, aluminum alloy or anodized aluminum and passes ASTM B117 salt spray testing of 336 hours with no pits.

17. A composition for coating or touching-up or both coating and touching-up a metal surface, said composition being made by mixing together a first mass of water and at least the following components:

(A) a second mass of at least one water-soluble source of fluorometallate anions to provide in the composition from about 4.5 to about 27 mM/kg of the fluorometallate anions and mixtures thereof, each of said anions comprising;

(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 of a component to provide the composition with from about 3.8 g/l to about 46 g/l of trivalent chromium cations;

wherein the composition comprises less than 0.04 wt % hexavalent chromium cations and said at least one water-soluble source of fluorometallate anions comprises fluorozirconic acid;

said composition further comprising fourth mass of a pH adjusting component that is ammonium hydroxide, the ratio of trivalent chromium to zirconium being in the range of 12 to 22.

18. The composition according to claim 17, wherein the third mass of a component is selected from the group consisting of fluorides and chlorides of chromium (III).