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

• US 6,413,581 B1
• Filed: 04/01/1999
• Issued: 07/02/2002
• Est. Priority Date: 03/14/1997
• Status: Expired due to Term

• Current Assignee: Vitro, S.A.B. De C.V. (Compagnie De Saint-Gobain)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Harris, Caroline S., Thiel, James P., Kutilek, Luke A., Szanyi, Janos, Greenberg, Charles B., Singleton, David E., Korthuis, Vincent
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): MCNEIL, JENNIFER C
• Application Number:
  US09/282,943
• Time in Patent Office: 1,188 Days
• Field of Search: 428/325, 428/412, 428/432, 428/469, 428/472, 428/701, 428/702, 427/226, 427/255.5, 427/255.7, 427/374.1, 427/424, 427/427, 65/605, 65/605.1, 65/605.2, 204/192.12, 204/192.15, 204/192.26, 204/192.27
• US Class Current: 427/226
• 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 method comprising the steps of:

manufacturing a continuous glass float ribbon 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 forming the glass float ribbon on a molten tin bath,

positioning a chemical vapor deposition coating apparatus over the surface of the float ribbon at a point in the manufacture of the float ribbon where the float ribbon has a temperature of at least about 400°

C. (752°

F.);

directing a metal oxide precursor selected from the group consisting of titanium tetrachloride, titanium tetraisopropoxide and titanium tetraethoxide in a carrier gas stream through said chemical vapor deposition apparatus over a surface of the float ribbon and annealing the float ribbon to produce titanium dioxide in the crystalline phase as a photocatalytically-activatable self-cleaning coating over the glass float ribbon,

whereby said coating is capable of having a photocatalytically-activated self-cleaning reaction rate of least about 2×

10<sup>−

3</sup> cm<sup>−

1</sup> min<sup>−

1</sup>.

2. A method comprising the steps of:

manufacturing a continuous glass float ribbon 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 forming the glass float ribbon on a molten tin bath;

depositing a photocatalytically-activatable self-cleaning coating over at least one of the major surfaces by positioning a spray pyrolysis coating apparatus over the surface of the float ribbon at a point in the manufacture of the float ribbon where the float ribbon has a temperature of at least about 400°

C. (752°

F.), directing an aqueous suspension of titanyl acetylacetonate and wetting agent in an aqueous medium, wherein the concentration of the titanyl acetylacetonate is in the range from about 5 to about 40 weight percent of the aqueous suspension, through said spray pyrolysis coating apparatus over a surface of the float ribbon and annealing the float ribbon in air to produce titanium dioxide in the crystalline phase as a photocatalytically-activatable self-cleaning coating over the glass float ribbon, whereby said coating is capable of having a photocatalytically-activated self-cleaning reaction rate of at least about 2×

10<sup>−

3</sup> cm<sup>−

1</sup>min<sup>−

1</sup>.

3. In a method for forming a glass float ribbon wherein the method includes the steps of melting glass batch materials in a furnace;

delivering the molten glass onto a bath of molten tin;

pulling the molten glass across the tin bath whereupon the glass is sized and controllably cooled to form a dimensionally stable glass float ribbon;

removing the float ribbon from the tin bath;

moving the float ribbon by conveying roller through a lehr to anneal the float ribbon;

moving the float ribbon to a cutting station on conveying rollers where the ribbon is out into glass sheets, the improvement comprising;

depositing by a process selected from the group consisting of spray pyrolysis and chemical vapor deposition a crystalline phase of a photocatalytically-activatable self-cleaning coating over a surface of said float ribbon as the float ribbon is formed, whereby said coating is capable of having a photocatalytically-activated self-cleaning reaction rate of at least about 2×

10³ cm<sup>−

1</sup> min<sup>−

1</sup>.

4. A method comprising the steps of:

providing a glass article having at least one surface by a float manufacturing process;

depositing a photocatalytically-activatable self-cleaning coating over the surface of the article by a process selected from the group consisting of chemical vapor deposition and spray pyrolysis during the glass manufacturing process so that the coating has titanium dioxide in the crystalline phase and has a thickness in the range of at least 200 Å and

less than 1 micron whereby said coating is capable of having a photocatalytically-activated self-leaning reaction rate of at least about 2×

10<sup>−

3</sup> cm<sup>−

1</sup> min<sup>−

1</sup>.

5. A method comprising the steps of:

providing an article of manufacture having at least one surface;

depositing a sodium ion diffusion barrier layer by a process selected from the group consisting of chemical vapor deposition, magnetron sputtered vacuum deposition (MSVD), and spray pyrolysis having a thickness of at least 100 Å

over said surface; and

depositing a photocatalytically-activatable self-cleaning coating by a process selected from the group consisting of chemical vapor deposition, MSVD, and spray pyrolysis over said sodium ion diffusion barrier layer whereupon said sodium ion diffusion barrier layer inhibits migration of sodium ions from the surface of said article to said photocatalytically-activatable self cleaning coating.

6. In a method for forming a glass float ribbon wherein the method includes the steps of melting glass batch materials in a furnace;

delivering the molten glass onto a bath of molten tin;

pulling the molten glass across the tin bath whereupon the glass is sized and controllably cooled to form a dimensionally stable glass float ribbon;

removing the float ribbon from the tin bath;

moving the float ribbon by conveying roller through a lehr to anneal the float ribbon;

moving the float ribbon to a cutting station on conveying rollers where the ribbon is cut into glass sheets, the improvement comprising;

depositing as the float ribbon is formed a photocatalytically-activatable self cleaning coating over said float ribbon which has a major surface and an opposing other major surface, wherein the major surface which contacted the tin bath has tin diffused therein so that the deposition is on the major surface having the diffused tin which forms a sodium ion barrier layer for the photocatalytically-activatable self cleaning coating.