Substrate with a photocatalytic coating

• US 7,597,930 B2
• Filed: 06/01/2004
• Issued: 10/06/2009
• Est. Priority Date: 09/15/1995
• Status: Expired due to Fees

• Current Assignee: Saint-Gobain Glass France (Compagnie De Saint-Gobain)
• Original Assignee: Saint-Gobain Glass France (Compagnie De Saint-Gobain)
• Inventors: Boire, Philippe, Talpaert, Xavier
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US10/856,876
• Publication Number:
  US 20040216487A1
• Time in Patent Office: 1,953 Days
• Field of Search: 427/255.36, 427/166, 427/255.394, 65/605, 65/605.2
• US Class Current: 427/166
• CPC Class Codes: C03C 17/002 for flat glass, e.g. float glass
• CPC Class Codes: C03C 17/007 containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous 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 17/3441 comprising carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 2217/211 SnO2
• CPC Class Codes: C03C 2217/212 TiO2
• CPC Class Codes: C03C 2217/213 SiO2
• CPC Class Codes: C03C 2217/214 Al2O3
• CPC Class Codes: C03C 2217/22 ZrO2
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2217/24 Doped oxides
• CPC Class Codes: C03C 2217/45 Inorganic continuous phases
• CPC Class Codes: C03C 2217/477 Titanium oxide
• CPC Class Codes: C03C 2217/479 Metals
• CPC Class Codes: C03C 2217/71 Photocatalytic coatings
• CPC Class Codes: C03C 2217/94 Transparent conductive oxide layers [TCO] being part of a multilayer coating
• CPC Class Codes: C03C 2218/113 by sol-gel processes
• CPC Class Codes: C04B 2111/00818 Enzyme carriers
• CPC Class Codes: C04B 2111/80 Optical properties, e.g. transparency or reflexibility
• CPC Class Codes: C04B 35/00 : Shaped ceramic products characterised by their composition porous ceramic products C04B38/00; ceramic articles characterised by particular shape, see the relevant classes, e.g. linings for casting ladles, tundishes, cups or the like B22D41/02; ceramic substrates for microelectronic semi-conductors H01L23/15; Ceramics compositions containing free metal bonded to carbides, diamond, oxides, borides, nitrides, silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides or sulfides other than as macroscopic reinforcing agents C22C; shaping of ceramics B28B; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products chemical preparation of powders of inorganic compounds C01; infiltration of sintered ceramic preforms with molten metal C04B41/51
• CPC Class Codes: C04B 41/0072 : Heat treatment
• CPC Class Codes: C04B 41/009 : characterised by the material treated
• CPC Class Codes: C04B 41/4562 : Photographic methods, e.g. making use of photo-sensitive materials
• CPC Class Codes: C04B 41/5027 : Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
• CPC Class Codes: C04B 41/5041 : Titanium oxide or titanates
• CPC Class Codes: C04B 41/51 : Metallising , e.g. infiltration of sintered ceramic preforms with molten metal covering materials with metals in general C23C; ceramic compositions containing free metal bonded to carbides, diamond, oxides, borides, nitrides, silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides or sulfides, other than as macroscopic reinforcing agents C22C; infiltration of preforms containing free metal, e.g. cermets C22C
• CPC Class Codes: C04B 41/5105 : with a composition mainly composed of one or more of the noble metals or copper
• CPC Class Codes: C04B 41/52 : Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
• CPC Class Codes: C04B 41/81 : Coating or impregnation
• CPC Class Codes: C04B 41/89 : for obtaining at least two superposed coatings having different compositions
• CPC Class Codes: G02F 1/1333 : Constructional arrangements; Manufacturing methodsG02F1/135, G02F1/136 take precedence
• CPC Class Codes: G02F 1/133502 : Antiglare, refractive index matching layers
• CPC Class Codes: G02F 1/1533 : structural features not otherwise provided for
• CPC Class Codes: G02F 1/157 : Structural association of cells with optical devices, e.g. reflectors or illuminating devices
• CPC Class Codes: Y10T 428/12611 : Oxide-containing component
• CPC Class Codes: Y10T 428/12993 : Surface feature [e.g., rough, mirror]
• CPC Class Codes: Y10T 428/24802 : Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/24975 : No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/25 : Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/252 : Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
• CPC Class Codes: Y10T 428/256 : Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/265 : 1 mil or less
• CPC Class Codes: Y10T 428/31841 : Next to cellulosic
• CPC Class Codes: Y10T 428/31938 : Polymer of monoethylenically unsaturated hydrocarbon

Abstract

The present invention provides a process for a producing a coating float-glass substrate, comprising chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide.

Claims

1. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the crystalline titanium oxide is in the form of crystallites with an average size of between 0.5 and 60 nm.

2. The process of claim 1, wherein the crystalline titanium oxide is in the form of crystallites with an average size of between 1 and 50 nm.

3. The process of claim 1, wherein the crystalline titanium oxide is in the form of crystallites with an average size of between 10 and 40 nm.

4. The process of claim 1, wherein the crystalline titanium oxide is in the form of crystallites with an average size of between 20 and 30 nm.

5. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the thickness of the coating containing the at least partially crystalline titanium oxide is between 5 nm and 100 nm.

6. The process of claim 5, wherein the thickness of the coating containing the at least partially crystalline titanium oxide is 10 nm to 25 nm.

7. The process of claim 5, wherein the thickness of the coating containing the at least partially crystalline titanium oxide is between 5 nm and 20 nm.

8. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the surface of the coating containing the at least partially crystalline titanium oxide has a contact angle with water of less than 5°

after exposure to light radiation.

9. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the coating containing the at least partially crystalline titanium oxide of the coating has a contact angle with water of less than 1°

after exposure to light radiation.

10. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the RMS roughness of the coating containing the at least partially crystalline titanium oxide is between 2 and 20 nm.

11. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the RMS roughness of the coating containing the at least partially crystalline titanium oxide is between 5 and 20 nm.

12. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the coating containing the at least partially crystalline titanium oxide also contains at least one additive capable of accentuating the photocatalytic activity of the titanium oxide.

13. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide, and

incorporating metal particles or particles based on such a metal into the coating containing the at least partially crystalline titanium oxide, wherein the metal is selected from the group consisting of cadmium, tin, tungsten, zinc, cerium, and zirconium.

14. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide, and

inserting into the crystal lattice of the titanium oxide at least one the metal is selected from the group consisting of niobium, tantalum, iron, bismuth, cobalt, nickel, copper, ruthenium, cerium, and molybdenum.

15. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide, and

covering at least part of the coating containing the at least partially crystalline titanium oxide with a layer of metal oxides or salts, wherein the metal is selected from the group consisting of iron, copper, ruthenium, cerium, molybdenum, vanadium, and bismuth.

16. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the coating containing the at least partially crystalline titanium oxide also contains an amorphous or partially crystalline oxide or mixture of oxides selected from the group consisting of silicon oxide, tin oxide, zirconium oxide, and aluminum oxide.

17. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide, and

coating at least a portion of the coating containing the at least partially crystalline titanium oxide with a noble metal.

18. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide, and

coating at least a portion of the coating containing the at least partially crystalline titanium oxide with a noble metal,

wherein the noble metal is selected from the group consisting of platinum, rhodium, silver, and palladium.

19. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the substrate is coated with at least one thin layer, wherein the thin layer has an anti-static function, a thermal function or an optical function, or forms a barrier to the migration of alkali metals, and

the coating containing the at least partially crystalline titanium oxide is coated on the thin layer.

20. The process of claim 19, wherein the thin layer has an anti-static function.

21. The process of claim 20, wherein the thin layer is based on a conductive metal or metal oxide.

22. The process of claim 19, wherein the thin layer is based on ITO, SnO₂:

F, ZnO;

F, ZnO;

Al, ZnO;

Sn or a metal oxide which is stoichiometrically deficient in oxygen.

23. The process of claim 22, wherein the metal oxide which is stoichiometrically deficient in oxygen is SnO₂₋

x or ZnO<sub>2−

x</sub>, wherein x<

2.

24. The process of claim 19, wherein the thin layer is based on a conductive metal or of the doped metal oxide.

25. The process of claim 24, wherein the thin layer is based on ITO, SnO₂:

F, ZnO;

F, ZnO;

AI, ZnO;

Sn or a metal oxide which is stoichiometrically deficient in oxygen.

26. The process of claim 25, wherein the metal oxide which is stoichiometrically deficient in oxygen is SnO₂₋

x or ZnO<sub>2−

x</sub>, wherein x<

2.

27. The process of claim 19, wherein the thin layer is based on an oxide or on a mixture of oxides with a refractive index which is intermediate between that of the coating containing the at least partially crystalline titanium oxide and that of the substrate.

28. The process of claim 19, wherein the thin layer is composed of Al₂O₃, SnO₂, In₂O₃, silicon oxycarbide, or silicon oxynitride.

29. The process of claim 19, wherein the thin layer forms a barrier to the migration of alkali metals.

30. The process of claim 29, wherein the thin layer is based on silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, Al₂O₃:

F, or aluminum nitride.

31. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the coating containing the at least partially crystalline titanium oxide is the final layer of a stack of anti-glare layers.

32. A process for a producing a coated float-glass substrate, comprising:

chemical vapor depositing at least one titanium precursor on at least part of at least one face of a float-glass substrate produced in a float-bath chamber, to produce a photocatalytic coating containing at least partially crystalline titanium oxide,

wherein the coating containing the at least partially crystalline titanium oxide is deposited in at least two successive stages.