Photocatalytically-activated self-cleaning article and method of making same

• US 7,049,002 B2
• Filed: 06/27/2003
• Issued: 05/23/2006
• Est. Priority Date: 03/14/1997
• Status: Expired due to Fees

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Harris, Caroline S., Thiel, James P., Kutilek, Luke A., Greenberg, Charles B., Szanyi, Janos, Singleton, David E., Korthuis, Vincent
• Primary Examiner(s): MCNEIL, JENNIFER C
• Application Number:
  US10/608,486
• Publication Number:
  US 20030235695A1
• Time in Patent Office: 1,061 Days
• Field of Search: 428/432, 428/469, 428/472, 428/472.1, 428/701, 428/702, 428/336, 428/428, 428/448
• US Class Current: 428/432
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: C03C 17/23 Oxides C03C17/02 takes precedence
• CPC Class Codes: C03C 17/245 by deposition from the vapour phase
• CPC Class Codes: C03C 17/2456 Coating containing TiO2
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 17/256 Coating containing TiO2
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: C03C 2217/21 Oxides
• CPC Class Codes: C03C 2217/212 TiO2
• CPC Class Codes: C03C 2217/229 Non-specific enumeration
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C03C 2218/112 by spraying
• CPC Class Codes: C03C 2218/113 by sol-gel processes
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: C03C 2218/154 by sputtering
• CPC Class Codes: C03C 2218/156 by magnetron sputtering
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers

Abstract

A method and article are disclosed wherein a substrate is provided with a photocatalytically-activated self-cleaning surface by forming a photocatalytically-activated self-cleaning coating on the substrate by spray pyrolysis chemical vapor deposition or magnetron sputter vacuum deposition. The coating has a thickness of at least about 500 Angstroms to limit sodium-ion poisoning to a portion of the coating facing the substrate. Alternatively, a sodium ion diffusion barrier layer is deposited over the substrate prior to the deposition of the photocatalytically-activated self-cleaning coating to prevent sodium ion poisoning of the photocatalytically-activated self-cleaning coating. The substrate includes glass substrates, including glass sheet and continuous float glass ribbon.

Claims

1. A photocatalytically-activated self-cleaning article of manufacture comprising:

a substrate having at least one surface; and

a photocatalytically-activated self-cleaning coating deposited over the surface of the substrate at a thickness of less than 1,000 Angstroms by a process selected from the group consisting of chemical vapor deposition, magnetron sputtered vacuum deposition and spray pyrolysis, wherein said photocatalytically-activated self-cleaning coating comprises one layer of a multilayer stack of coatings deposited over the substrate wherein said photocatalytically-activated self-cleaning coating is a layer other than the uppermost layer of said multilayer stack.

2. The photocatalytically-activated self-cleaning article of claim 1 further comprising a sodium ion diffusion barrier layer disposed between the substrate and the photocatalytically-activated self-cleaning coating to inhibit migration of sodium ions from said substrate to said photocatalytically-activated self-cleaning coating.

3. The photocatalytically-activated self-cleaning article of claim 2 wherein the sodium ion diffusion barrier layer is deposited over the substrate by a process selected from the group consisting of chemical vapor deposition, magnetron sputtered vacuum deposition and spray pyrolysis.

4. The photocatalytically-activated self-cleaning article of claim 2 wherein the sodium ion diffusion barrier layer is selected from the group consisting a crystalline metal oxide, an amorphous metal oxide and mixtures thereof.

5. The photocatalytically-activated self-cleaning article of claim 4 wherein the sodium ion diffusion barrier layer is selected from the group consisting of tin oxides, silicon oxides, titanium oxides, zirconium oxides, fluorine-doped tin oxides, aluminum oxides, magnesium oxides, zinc oxides, cobalt oxides, chromium oxides, magnesium oxides, iron oxides and mixtures thereof.

6. The photocatalytically-activated self-cleaning article of claim 5 wherein the sodium ion diffusion barrier layer is at least about 250 Angstroms thick.

7. The photocatalytically-activated self-cleaning article of claim 5 wherein the sodium ion diffusion barrier layer is at least about 400 Angstroms thick.

8. The photocatalytically-activated self-cleaning article of claim 5 wherein the sodium ion diffusion barrier layer is at least about 500 Angstroms thick.

9. The photocatalytically-activated self-cleaning article of claim 1 wherein the substrate is selected from the group consisting of glass, plastic, metal, enamel and mixtures thereof.

10. The photocatalytically-activated self-cleaning article of claim 1 wherein said substrate is a glass substrate having a first major surface and an opposite major surface defined as a second major surface, the first major surface having a thin layer of a tin oxide diffused therein characteristic of forming a glass ribbon over a molten tin bath, at least one of the major surfaces having said photocatalytically-activated self-cleaning metal oxide coating deposited thereon.

11. The photocatalytically-activated self-cleaning article of claim 10 wherein the photocatalytically-activated self-cleaning coating further comprises a metal oxide selected from the group consisting of titanium oxides, iron oxides, silver oxides, copper oxides, tungsten oxides, aluminum oxides, silicon oxides, zinc stannates, molybdenum oxides, zinc oxides, strontium titanate and mixtures thereof.

12. The photocatalytically-activated self-cleaning article of claim 10 wherein the photocatalytically-activated self-cleaning metal oxide coating is deposited on the first major surface of the glass substrate and the glass substrate is selected from the group consisting of a glass sheet and a continuous float glass ribbon.

13. A photocatalytically active coated article comprising:

a glass substrate having an air side major surface having sodium ions therein and an opposite major surface having tin diffused therein defined as a tin side major surface; and

a coating over the air side major surface, said coating comprising a photocatalytically-active titanium dioxide layer having a first surface and an opposite surface defined as a second surface with the second surface adjacent the air side major surface of the glass substrate and the second surface of the coating having sodium ions diffused therein from the air side major surface of the glass substrate, wherein the photocatalytically-active titanium dioxide layer comprises a combination of anatase phase and amorphous phase of titanium dioxide and said layer has a thickness ranging from about 100 to about 1000 Angstroms.

14. A photocatalytically active coated article comprising:

a glass substrate having an air side major surface and an opposite major surface having tin therein defined as a tin side major surface; and

a coating over the air side major surface, said coating comprising a photocatalytically-active titanium dioxide layer having a first surface and an opposite surface defined as a second surface with the second surface adjacent the air side major surface of the glass substrate, wherein

(a) the photocatalytically-active titanium dioxide layer comprises a combination of anatase phase and an amorphous phase of titanium dioxide,

(b) said layer has a thickness ranging from about 100 to about 1000 Angstrom,

(c) said tin side major surface has tin diffused therein characteristic of glass formed by pulling molten glass in the form of a glass ribbon across a molten tin bath while cooling the glass ribbon,

(d) said photocatalytically-active titanium dioxide layer was deposited by chemical vapor deposition in the tin bath and this coated glass is exposed to ultraviolet radiation, and

(e) said photocatalytically active titanium dioxide layer has a photocatalytically active self-cleaning reaction rate of at least about 2 ×

10<sup>−

3</sup> cm<sup>−

1</sup> min<sup>−

1</sup>.

15. A coated article according to claim 14 wherein the photocatalytically-active self-cleaning reaction rate is at least about 9.95×

10<sup>−

3</sup> cm<sup>−

1</sup> min<sup>−

1</sup>.

16. A coated article according to claim 14, wherein the glass ribbon is at a temperature of at least about 538°

C.

17. A coated article according to claim 14, wherein the glass ribbon is at a temperature of at least about 600°

C.

18. A coated article according to claim 14, wherein the photocatalytically-active titanium dioxide layer is activated by exposure to ultraviolet radiation.

19. A coated article according to claim 14, wherein the majority of the crystalline phase is anatase.

20. A coated article according to claim 14 wherein the second surface of the titanium dioxide layer is directly on and in contact with the air side major surface of the glass substrate.

21. A coated article according to claim 14 wherein the phases of the titanium dioxide layer optionally include rutile, and brookite crystalline forms of titanium dioxide.

22. A coated article according to claim 14, further comprising a sodium ion diffusion barrier layer between the air side major surface of the glass substrate and the photocatalytically-active titanium dioxide layer, wherein the barrier layer has a thickness of at least about 100 Angstroms.

23. A coated article according to claim 22 wherein the photocatalytically-active titanium dioxide layer has a thickness in the range of about 100 to about 2500 Angstroms.

24. A coated article according to claim 22, wherein the photocatalytically-active titanium dioxide layer has a thickness in the range of from about 100 to about 1000 Angstroms.

25. A coated article according to claim 22, wherein the photocatalytically-active titanium dioxide layer has a thickness in the range of from about 100 to about 500 Angstroms.

26. A coated article according to claim 22, wherein the photocatalytically-active titanium dioxide layer has a thickness in the range of from about 100 to about 400 Angstroms.

27. A coated article according to claim 22, wherein the photocatalytically-active titanium dioxide layer has a thickness in the range of from about 100 to about 200 Angstroms.

28. A coated article according to claim 22, wherein the sodium ion diffusion barrier layer comprises at least one of amorphous and crystalline phase metal oxides selected from cobalt oxides, chromium oxides, iron oxides, tin oxides, titanium oxides, zirconium oxides, fluorine-doped tin oxides, aluminum oxides, magnesium oxides, zinc oxides, and super-oxides and sub-oxides of any of the foregoing.

29. A coated article according to claim 22, wherein the sodium ion diffusion barrier layer comprises at least one metal oxide selected from magnesium oxides, aluminum oxides, zinc oxides, tin oxides, and super-oxides and sub-oxides of any of the foregoing.

30. A coated article according to claim 22, wherein the sodium ion diffusion barrier layer comprising silicon oxide and has a thickness of at least about 100 Angstroms.

31. A coated article according to claim 22 wherein the glass substrate is an annealed glass substrate.

32. A coated article according to claim 14 wherein the titanium dioxide layer is formed on a float ribbon at a temperature ranging from about 538°

to less than about 800°

C.

33. A coated article according to claim 14, wherein the titanium dioxide layer is physically durable.

34. A coated article according to claim 14, wherein the titanium dioxide layer is resistant to chemical attack.

35. A coated article according to claim 14, wherein the photocatalytically-active titanium dioxide layer is capable of having a photocatalytically-activated self-cleaning reaction rate of at least about 5×

10<sup>−

3</sup> cm<sup>−

1</sup> min¹.

36. A coated article according to claim 14, wherein the photocatalytically-active titanium dioxide layer is capable of having a photocatalytically-activated self-cleaning reaction rate of at least about 7.79×

10<sup>−

3</sup> cm<sup>−

1</sup> min^'"'"'1.

37. A coated article according to claim 14, wherein the photocatalytically-active titanium dioxide layer is capable of having a photocatalytically-activated self-cleaning reaction rate of at least about 12.29×

10<sup>−

3</sup> cm<sup>−

1</sup> min<sup>−

1</sup>.

38. A photocatalytically-activatable self-cleaning article of manufacture comprising:

a glass substrate having a first major surface and an opposite major surface defined as a second major surface, the first major surface having tin diffused therein characteristic of being formed by pulling molten glass in the form of a glass ribbon across a molten tin bath while cooling the glass ribbon, and

a photocatalytically-activatable self-cleaning metal oxide coating having a thickness of less than 1,000 Angstroms over the second major surface capable of having a photocatalytically-activated self-cleaning reaction rate of at least about 2×

10<sup>−

3</sup> cm¹ min<sup>−

1</sup>, where the metal oxide coating was deposited by chemical vapor deposition at a temperature in the range of at least 400–

800°

C.

39. The photocatalytically-activatable self-cleaning article of claim 38 wherein the photocatalytically-activatable coating has a crystalline phase characteristic of chemical vapor deposition of the metal oxide over the second major surface in a molten tin bath where the first major surface is in contact with said tin bath.

40. The photocatalytically-activatable self-cleaning article of claim 38 further comprising at least one layer interposed between the photocatalytically-activatable self-cleaning coating and the substrate.

41. The photocatalytically-activatable self-cleaning article of claim 40, wherein the at least one layer has at least one oxide chosen from crystalline metal oxides, amorphous metal oxides, crystalline silicon oxides and amorphous silicon oxides.

42. The photocatalytically-activatable self-cleaning article of claim 40, wherein at least one layer is chosen from iron oxides, silver oxides, copper oxides, tungsten oxides, zinc oxides, zinc/tin oxides, strontium titanate, and titanium oxides chosen from anatase, rutile, and brookite crystalline forms of titanium dioxide.

43. The photocatalytically-activatable self-cleaning article of claim 38 wherein the photocatalytically-activatable coating has an anatase titanium oxide phase characteristic of chemical vapor deposition over the second major surface in a molten tin bath where the first major surface is in contact with said tin bath and wherein the article has at least one layer interposed between the photocatalytically-activatable self-cleaning coating and the substrate where the at least one layer comprises at least one oxide chosen from amorphous and crystalline metal oxides, and silicone oxides.

44. The photocatalytically-activatable self-cleaning article of claim 43 wherein the metal oxides are chosen from cobalt oxides, chromium oxides, iron oxides, tin oxides, titanium oxides, zirconium oxides, fluorine-doped tin oxides, aluminum oxides, magnesium oxides, and zinc oxides.

45. A photocatalytically-activatable coated glass comprising:

a glass substrate having an air side major surface and a tin side major surface having been formed in a tin bath of a float glass process;

a coating over the air side major surface, said coating comprising a photocatalytically-activatable titanium dioxide layer having a first surface and a second surface with the second surface adjacent the air side major surface,

wherein the photocatalytically-activatable titanium dioxide layer comprises anatase titanium dioxide and said layer has a thickness ranging from about 100 to about 1000 Angstroms;

and wherein the coated glass comprises an interlayer between the photocatalytically-activatable layer second surface and the air side major surface of the substrate, said interlayer comprising amorphous silicon oxide.

46. A photocatalytically-active coated glass comprising:

a glass substrate having an air side major surface and a tin side major surface having been formed in a tin bath of a float glass process;

a coating over the air side major surface of the substrate, said coating comprising a photocatalytically-active titanium dioxide layer having a first surface and a second surface with the second surface adjacent the air side major surface wherein the photocatalytically-active titanium dioxide layer comprises anatase titanium dioxide having a thickness of less than 1000 Angstroms, and

an interlayer between the second surface of the photocatalytically-active layer and the air side major surface of the substrate, said interlayer comprising amorphous silicon oxide,

wherein said tin side major surface has tin diffused therein characteristic of being formed from a glass ribbon floated in a molten tin bath;

wherein said photocatalytically-active titanium dioxide layer was deposited by chemical vapor deposition in said tin bath and exposed to ultraviolet radiation, and

further wherein said photocatalytically-active titanium dioxide layer has a photocatalytically-active self-cleaning reaction rate of at least about 2×

10<sup>−

3</sup> cm<sup>−

1</sup> min<sup>−

1</sup>.

47. A coated glass according to claim 46, wherein the photocatalytically-active titanium dioxide layer is deposited at a temperature ranging from 544°

to less than about 800°

C. (1029°

to 1472°

F.).

48. The article of claim 46 wherein the photocatalytically-active self-cleaning reaction rate is at least about 9.95×

10<sup>−

3</sup> cm<sup>−

1</sup> min¹.

49. A photocatalytically-active coated glass comprising:

a glass substrate having an air side major surface and a tin side major surface, the tin side major surface having tin oxide characteristic of glass formed by pulling molten glass in the form of a glass ribbon across a molten tin bath while cooling the glass ribbon; and

a coating over the air side major surface, said coating comprising a photocatalytically-active titanium dioxide layer having a first surface and a second surface with the second surface adjacent the air side major surface, wherein said layer

(a) has a thickness ranging from about 100 to about 1000 Angstroms,

(b) was deposited by chemical vapor deposition in said tin bath and exposed to ultraviolet radiation, and

(c) has a photocatalytically-active self-cleaning reaction rate of at least 2×

10<sup>−

3</sup> cm<sup>−

1</sup> min<sup>−

1</sup>.

50. A photocatalytically active coated glass comprising:

a glass substrate having an air side major surface and a tin side major surface, the tin side major surface having tin oxide therein characteristic of glass formed by pulling molten glass in the form of a glass ribbon across a molten tin while cooling the glass ribbon;

a sodium ion diffusion barrier layer over said air side major surface, and

a coating over the sodium ion diffusion barrier layer, said coating comprising a photocatalytically-active titanium dioxide layer having a first surface and a second surface with the second surface adjacent the sodium ion diffusion barrier layer, wherein the photocatalytically active titanium dioxide layer has a thickness ranging from about 100 to about 1000 Angstroms, was deposited by chemical vapor deposition in said tin bath, and has a photocatalytically active self-cleaning reaction rate of at least about 9.95×

10<sup>−

1</sup> cm^{1 −}

min<sup>−

1</sup>.

51. The coated glass of claim 50 wherein the photocatalytically-active titanium dioxide layer comprises a combination of an anatase phase and an amorphous phase of titanium dioxide.