Photoactive coating, coated article, and method of making same

• US 20030039843A1
• Filed: 07/11/2002
• Published: 02/27/2003
• Est. Priority Date: 03/14/1997
• Status: Abandoned Application

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Johnson, Christopher, Harris, Caroline S., Greenberg, Charles B.
• Application Number:
  US10/193,447
• Publication Number:
  US 20030039843A1
• Time in Patent Office: Days
• US Class Current: 428/432
• CPC Class Codes: C03C 17/002 for flat glass, e.g. float glass
• 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 17/3435 comprising a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C03C 17/3441 comprising carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 2217/212 TiO2
• CPC Class Codes: C03C 2217/25 Metals
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C03C 2218/112 by spraying
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: C03C 2218/154 by sputtering
• CPC Class Codes: C03C 2218/155 by reactive sputtering
• CPC Class Codes: C03C 2218/156 by magnetron sputtering
• CPC Class Codes: C03C 2218/32 After-treatment
• CPC Class Codes: C03C 2218/36 Underside coating of a glass sheet
• CPC Class Codes: C03C 2218/365 Coating different sides of a glass substrate

Abstract

A method of forming a photocatalytic coating includes depositing a precursor composition over at least a portion of a substrate surface by a coating device. The precursor composition includes a titania precursor material and at least one other precursor material having a metal selected from boron, strontium, zirconium, lead, barium, calcium, hafnium, lanthanum, and mixtures thereof. Sufficient other precursor material is added to the composition such that a molar ratio of the selected metal to titanium in the applied photocatalytic coating is in the range of about 0.001 to about 0.05.

Claims

1. A method of forming a photoactive coating, comprising the step of:

depositing a precursor composition by chemical vapor deposition over at least a portion of a float glass ribbon in a molten metal bath, the precursor composition comprising;

a photoactive coating precursor material; and

at least one other precursor material comprising a dopant that increases photoactivity of the photoactive coating over that of the photoactive coating without the dopant.

2. The method of claim 1, wherein the photoactive coating precursor material comprises a titania precursor material.

3. The method of claim 2, wherein the titania precursor material is selected from titanium alkoxide, titanium tetrachloride, and mixtures thereof.

4. The method of claim 3, wherein the titanium alkoxide is selected from titanium methoxide, titanium ethoxide, titanium tetraethoxide, titanium propoxide, titanium butoxide, isomers thereof, and mixtures thereof.

5. The method of claim 3, wherein the titanium alkoxide is selected from titanium isopropoxide, titanium tetraethoxide, and mixtures thereof.

6. The method of claim 1, wherein the at least one other precursor material comprises an organometallic alkoxide.

7. The method of claim 6, wherein the at least one other precursor material comprises at least one transition metal alkoxide having a boiling point less than 200°

C.

8. The method of claim 6, wherein the organometallic alkoxide is selected from the group consisting of alkoxides of boron, strontium, zirconium, lead, barium, calcium, hafnium, lanthanum, and mixtures thereof.

9. The method of claim 1, wherein the at least one other precursor material is selected from trialkyl borate, strontium alkoxide, alkyllead, zirconium alkylalkoxide, lanthanum alkoxide, strontium ethoxide, strontium-2-ethylhexanoate, strontium hexafluoroacetylacetonate, strontium isopropoxide, strontium methoxide, strontium tantalum ethoxide, strontium titanium isopropoxide, triethyl borate, tetra-n-butyl lead, zirconium-2-methyl-2-butoxide, lanthanum isopropoxide, and mixtures thereof.

10. The method of claim 1, wherein the photoactive coating is photocatalytic.

11. The method of claim 1, wherein the photoactive coating is photoactively hydrophilic.

12. The method of claim 2, including adding sufficient other precursor material such that a molar ratio of the dopant to titanium in the applied photoactive coating is in the range of about 0.001 to 0.05.

13. A method of forming a photoactive coating, comprising the step of:

depositing a precursor composition over at least a portion of a substrate surface, the precursor composition comprising;

a titania precursor material; and

at least one metal alkoxide having a boiling point less than 200°

C.

14. The method of claim 13, wherein the metal alkoxide includes a metal selected from boron, strontium, zirconium, lead, barium, calcium, hafnium, lanthanum, and mixtures thereof.

15. The method of claim 13, wherein the titania precursor material is selected from titanium alkoxide, titanium tetrachloride, and mixtures thereof.

16. A method of forming a photoactive coating, comprising the steps of:

depositing a precursor composition over at least a portion of a substrate surface, the precursor composition comprising;

a titania precursor material; and

at least one other precursor material having a metal selected from boron, strontium, zirconium, lead, barium, calcium, hafnium, lanthanum, and mixtures thereof; and

adding sufficient other precursor material to the composition such that a molar ratio of the selected metal to titanium in the applied photoactive coating is in the range of about 0.001 to about 0.05.

17. The method of claim 16, wherein the titania precursor material is selected from titanium tetrachloride, titanium alkoxides, and mixtures thereof.

18. The method of claim 17, wherein the titania precursor material is selected from titanium isopropoxide and titanium tetraethoxide.

19. The method of claim 16, wherein the at least one other precursor material is selected from trialkyl borate, strontium alkoxide, alkyllead, zirconium alkylalkoxide, lanthanum alkoxide, strontium ethoxide, strontium-2-ethylhexanoate, strontium hexafluoroacetylacetonate, strontium isopropoxide, strontium methoxide, strontium tantalum ethoxide, strontium titanium isopropoxide, triethyl borate, tetra-n-butyl lead, zirconium-2-methyl-2-butoxide, lanthanum isopropoxide, and mixtures thereof.

20. The method of claim 16, wherein the titania precursor material is titanium isopropoxide and the other precursor material is soluble in titanium isopropoxide.

21. The method of claim 16, wherein the other precursor material has a boiling point less than 200°

C.

22. The method of claim 16, including:

heating the titania precursor material and the other precursor material to a temperature sufficient to vaporize the precursor materials; and

introducing the vaporized precursor composition into a carrier gas such that a ratio of the vaporized precursor materials to the carrier gas is in the range of 0.01 volume percent to 0.06 volume percent.

23. The method of claim 16, including depositing the photocatalytic coating by a process selected from chemical vapor deposition, magnetron sputtered vacuum deposition, and spray pyrolysis.

24. The method of claim 16, wherein the substrate is a float glass ribbon in a float chamber and the method includes depositing the precursor composition onto the float glass ribbon in the float chamber by chemical vapor deposition.

25. The method of claim 16, including depositing sufficient precursor composition such that the photocatalytic coating has a thickness in the range of about 50 Å

to about 2000 Å

.

26. The method of claim 16, including depositing an intermediate layer between the substrate and the photocatalytic coating.

27. The method of claim 26, wherein the intermediate layer is an antireflective layer.

28. The method of claim 27, wherein the antireflective layer comprises at least one of aluminum oxide, tin oxide, indium oxide, silicon oxide, silicon oxycarbide, and silicon oxynitride.

29. The method of claim 26, wherein the intermediate layer is a sodium ion diffusion barrier layer.

30. The method of claim 29, wherein the barrier layer includes at least one of silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, aluminum oxide, fluorine doped aluminum oxide, and aluminum nitride.

31. A method of forming a photocatalytic coating, comprising the steps of:

depositing a precursor composition over at least a portion of a substrate surface, the precursor composition comprising titanium isopropoxide and at least one other organometallic precursor material selected from triethyl borate, strontium isopropoxide, tetra-n-butyl lead, zirconium-2-methyl-2-butoxide, and lanthanum isopropoxide.

32. The method of claim 31, including adding sufficient other organometallic precursor material to the composition such that a molar ratio of the metal of the organometallic precursor material to titanium in the applied photocatalytic coating is in the range of about 0.001 to about 0.05.

33. A method of depositing a photocatalytic coating over a substrate, comprising the steps of:

positioning a chemical vapor deposition coating device over a float glass ribbon in a float chamber;

directing a precursor composition from the coating device onto the ribbon, the precursor composition comprising a titania precursor material and at least one other precursor material having a metal selected from boron, strontium, lead, barium, calcium, hafnium, lanthanum, and mixtures thereof;

adding sufficient other precursor material to the composition such that a molar ratio of the selected metal to titanium in the applied photocatalytic coating is in the range of about 0.001 to about 0.05; and

heating the substrate to a temperature sufficient to decompose the precursor materials to form the photocatalytic coating.

34. A method of increasing the photocatalytic activity of a titania coating, comprising the steps of:

adding to the titania coating at least one metal selected from boron, strontium, zirconium, lead, barium, calcium, hafnium, and lanthanum, such that a molar ratio of the selected metal to titanium in the photocatalytic coating is in the range of about 0.001 to about 0.05.

35. A method of forming a photocatalytic coating, comprising the steps of:

depositing a precursor composition over at least a portion of a substrate, the precursor composition comprising titanium tetrachloride, a source of organic oxygen, and a boron containing precursor material.

36. The method of claim 35, wherein the source of organic oxygen is an alkyl ester having a C₂ to C₁₀ alkyl group.

37. The method of claim 35, wherein the precursor material comprises triethyl borate.

38. The method of claim 35, including depositing the photocatalytic coating directly onto the substrate surface.

39. The method of claim 35, including depositing an intermediate coating between the substrate surface and the photocatalytic coating.

40. The method of claim 39, wherein the intermediate coating comprises at least one of tin oxide, aluminum oxide, and zirconium oxide.

41. An article, comprising,

a substrate having at least one surface;

and

a photocatalytic coating deposited over at least a portion of the substrate surface,

wherein the photocatalytic coating comprises titania and at least one additional material comprising at least one metal selected from boron, strontium, zirconium, lead, barium, calcium, hafnium, and lanthanum, and

wherein the additional material is present in the coating in an amount such that a molar ratio of the selected metal to titanium in the photocatalytic coating is in the range of about 0.001 to about 0.05.

42. The article of claim 41, wherein the substrate is selected from glass, plastic, and ceramic.

43. The article of claim 41, wherein the article is monolithic.

44. The article of claim 41, wherein the article is laminated.

45. The article of claim 41, wherein the article is an insulating glass unit and the substrate is at least one of the panes of the insulating glass unit.

46. The article of claim 41, wherein the substrate is selected from annealed glass, tempered glass, and heat strengthened glass.

47. The article of claim 41, wherein the article is an architectural transparency.

48. The article of claim 41, wherein the photocatalytic coating is deposited directly on the substrate surface.

49. The article of claim 41, wherein the photocatalytic coating comprises titania at least partly in the anatase phase.

50. The article of claim 41, wherein the photocatalytic coating comprises titania at least partly in the rutile phase.

51. The article of claim 41, wherein the photocatalytic coating is deposited by a process selected from chemical vapor deposition, magnetron sputtered vacuum deposition, and spray pyrolysis.

52. The article of claim 41, wherein the substrate includes at least one surface having tin diffused therein.

53. The article of claim 41, wherein the photocatalytic coating has a thickness of about 50 Å

to about 2000 Å

.

54. The article of claim 41, wherein the substrate is a float glass ribbon and the process is selected from chemical vapor deposition and spray pyrolysis.

55. The article of claim 41, including at least one intermediate layer located between the substrate surface and the photocatalytic coating.

56. The article of claim 55, wherein the intermediate layer is an antireflective layer.

57. The article of claim 55, wherein the intermediate layer is a sodium ion diffusion barrier layer.

58. The article of claim 56, wherein the antireflective layer comprises at least one of aluminum oxide, tin oxide, indium oxide, silicon oxide, silicon oxycarbide, and silicon oxynitride.

59. The article of claim 57, wherein the barrier layer comprises at least one of tin oxide, silicon oxide, titanium oxide, zirconium oxide, fluorine-doped tin oxide, aluminum oxide, magnesium oxide, zinc oxide, cobalt oxide, chromium oxide, iron oxide, and mixtures thereof.