Precursor and related method of forming for use in forming electrochromic coatings

• US 5,457,218 A
• Filed: 09/02/1993
• Issued: 10/10/1995
• Est. Priority Date: 05/20/1992
• Status: Expired due to Fees

• Current Assignee: Donnelly Corporation (Magna International Incorporated)
• Original Assignee: Donnelly Corporation (Magna International Incorporated)
• Inventors: Zhang, Raymond L., Agrawal, Anoop, Cronin, John P., Tarico, Daniel J.
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US08/115,855
• Time in Patent Office: 768 Days
• Field of Search: 556/44, 556/49, 556/57, 556/61, 556/136, 556/146
• US Class Current: 556/44
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: G02B 1/10 Optical coatings produced by application to, or surface treatment of, optical elements G02B1/08 takes precedence

Abstract

Electrochromic coating solutions are prepared by reacting a transition metal with a mixture of hydrogen peroxide and an organic acid. The resulting transition metal-peroxy acid product is esterified by reacting with lower carbon alcohols to produce a peroxyester-transition metal derivative. This derivative in solution in lower carbon alcohols provides a working solution into which a substrate having a conductive surface is preferable dipped and removed at a rate sufficient to give a coating of a desired thickness over the conductive surface. Spray or spin coating can be used to apply the coating to the conductive surface of the substrate. The coating is then dried and is externally fired in an oven to complete the necessary reactions to yield an electrochromic oxide coating having exceptional electrochromic properties.

Claims

1. A method for preparing a precursor for use in forming electrochromic coatings comprising:

reacting a transition metal with hydrogen peroxide and an organic acid to form a transition metal-peroxy acid product.

2. A method in accordance with claim 1 wherein said transition metal-peroxy acid product is isolated.

3. A method in accordance with claim 2 wherein said transition metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium and nickel.

4. A method in accordance with claim 3 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

5. A method in accordance with claim 4 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

6. A method in accordance with claim 1 wherein said transition metal is allowed to react with said hydrogen peroxide and organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours, to form said transition metal-peroxy acid product.

7. A method for preparing a precursor for use in forming electrochromic coatings comprising:

reacting a transition metal with hydrogen peroxide and an organic acid to form a transition metal-peroxy acid product and reacting said transition metal-peroxy acid product with a lower carbon alcohol to form a peroxyester transition metal derivative.

8. A method in accordance with claim 7 wherein said transition metal-peroxy acid product is isolated prior to reacting with said lower carbon alcohol.

9. A method in accordance with claim 8 wherein said transition metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium and nickel.

10. A method in accordance with claim 9 wherein said lower carbon alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, sec-butanol and mixtures thereof.

11. A method in accordance with claim 10 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

12. A method in accordance with claim 11 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

13. A method in accordance with claim 7 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

14. A method in accordance with claim 7 further comprising the step of reacting a second metal with hydrogen peroxide and an organic acid to form a second metal-peroxy acid product and mixing said second metal-peroxy acid product with said peroxyester-transition metal derivative to form a peroxyester-transition metal/second metal-peroxy acid mixture.

15. A method in accordance with claim 14 further comprising the step of reacting said second metal-peroxy acid product with a lower carbon alcohol to form a peroxyester-second metal derivative prior to mixing with said peroxyester-transition metal derivative.

16. A method in accordance with claim 15 wherein said second metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium, nickel, silicon and titanium.

17. A method in accordance with claim 16 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

18. A method in accordance with claim 17 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

19. A precursor for forming a coating for a substrate comprising a transition metal-peroxy acid product formed by:

reacting a transition metal with hydrogen peroxide and an organic acid to form a transition metal-peroxy acid product.

20. The precursor of claim 19 wherein said transition metal-peroxy acid product is isolated.

21. The precursor of claim 20 wherein said transition metal is selected from the group consisting of tungsten, molybdenum, manganese, chromium, rhenium, iridium and nickel.

22. The precursor of claim 21 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

23. The precursor of claim 22 wherein said transition metal is allowed to react with said hydrogen peroxide and an organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours to form said transition metal-peroxy acid product.

24. The precursor of claim 19 wherein said transition metal is allowed to react with said hydrogen peroxide and organic acid at a temperature of from about -10°

C. to about 12°

C. for a period of from about 18 to about 30 hours, and is then refluxed at from about 45°

C. to about 60°

C. for a period of from about 18 to about 10 hours, to form said transition metal-peroxy acid product.

25. A precursor for forming a coating for a substrate by a coating technique selected from the group consisting of dip coating, spray coating and spin coating, said precursor comprising a transition metal-peroxy acid product formed by reacting a transition metal with hydrogen peroxide and an organic acid to form a transition metal-peroxy acid product.

26. A precursor for forming a coating having electrochromic, electrically conducting, optical, wear-resistant or anti-reflective properties, or combinations of these properties, for a substrate, said precursor comprising a transition metal-peroxy acid product formed by reacting a transition metal with hydrogen peroxide and an organic acid to form a transition metal-peroxy acid product.

27. A precursor for forming a coating for a substrate comprising a transition metal-peroxy acid product formed by:

reacting an oxidizable transition metal species with a solution of a mixture of hydrogen peroxide and an organic acid.

28. The precursor of claim 27, wherein said oxidizable transition metal species is selected from the group consisting of a metal halide and a metal carbide.

29. The precursor of claim 28 wherein said oxidizable transition metal species is tungsten carbide.

30. The precursor of claim 27 wherein said organic acid is selected from the group consisting of acetic acid and propionic acid.

31. A precursor for forming a coating for a substrate by a coating technique selected from the group consisting of dip coating, spray coating and spin coating, said precursor comprising a transition metal-peroxy acid product formed by reacting an oxidizable transition metal species with a solution of a mixture of hydrogen peroxide and an organic acid.

32. A precursor for forming a coating having electrochromic, electrically conducting, optical, wear-resistant or anti-reflective properties, or combinations of these properties, for a substrate, said precursor comprising a transition metal-peroxy acid product formed by reacting an oxidizable transition metal species with a solution of a mixture of hydrogen peroxide and an organic acid.