Substrate with a photocatalytic coating

• US 6,103,363 A
• Filed: 05/28/1998
• Issued: 08/15/2000
• Est. Priority Date: 09/15/1995
• Status: Expired due to Term

• Current Assignee: Saint-Gobain Glass France (Compagnie De Saint-Gobain)
• Original Assignee: Saint-Gobain Recherche
• Inventors: Boire, Philippe, Talpaert, Xavier
• Primary Examiner(s): Speer, Timothy M.
• Assistant Examiner(s): YOUNG, BRYANT L
• Application Number:
  US09/029,855
• Time in Patent Office: 810 Days
• Field of Search: 428/325, 428/428, 428/432, 428/701, 428/702, 428/697, 428/698, 428/938, 427/255, 427/255.2, 427/255.7, 427/164-166, 427/294, 359/580, 359/582, 359/585, 359/586
• US Class Current: 428/325
• 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 subject of the invention is a glass-, ceramic- or vitroceramic-based substrate (1) provided on at least part of at least one of its faces with a coating (3) with a photocatalytic property containing at least partially crystalline titanium oxide. It also relates to the applications of such a substrate and to its method of preparation.

Claims

1. A coated substrate which is a glass, ceramic or vitro-ceramic substrate provided on at least a portion of one of its faces with a coating having photocatalytic properties, and comprising titanium oxide at least partly crystallized in the anatase form, and obtained by thermal decomposition of titanium precursors selected from the group consisting of organo-metallic precursors and metallic halide precursors, wherein said coating has a thickness between 5 and 50 nm, wherein the crystallized titanium oxide is in the form of crystallites with an average size of between 0.5 and 60 nm.

15. A multi-layer glazing wherein at least one layer thereof is the coated substrate of claim 1.

2. A coated substrate which is a glass, ceramic or vitro-ceramic substrate provided on at least a portion of one of its faces with a coating having photocatalytic properties, and comprising a mixture of (1) titanium oxide at least partly crystallized in the anatase form, and (2) an inorganic material in the form of an amorphous or partially crystalline oxide or mixture of oxides selected from the group consisting of SiO₂, TiO₂, SnO₂, ZrO₂ and Al₂ O₃, wherein said component (1) is obtained by thermal decomposition of titanium precursors selected from the group consisting of organo-metallic precursors and metallic halide precursors.

6. The coated substrate according to claim 2, wherein the crystallized titanium oxide is in the form of crystallites with an average size of between 0.5 and 60 nm.

7. The coated substrate according to claim 2, wherein the inorganic material is a mixture of silicon oxide and titanium oxide.

8. The coated substrate according to claim 2, wherein the inorganic material is zirconium oxide.

9. The coated substrate according to claim 2, wherein the inorganic material is a mixture of zirconium oxide and silicon oxide.

10. The coated substrate according to claim 2, wherein the coating has a thickness of between 5 and 100 nm.

16. A multi-layer glazing wherein at least one layer thereof is the coated substrate of claim 2.

3. A coated substrate which is a glass, ceramic or vitro-ceramic substrate provided on at least a portion of one of its faces with a coating having a photocatalytic properties, and comprising titanium oxide at least partly crystallized in the anatase form, and a thin layer forming a barrier to alkali metals originating from the substrate, and located between said substrate and said coating, wherein the crystallized titanium oxide is in the form of crystallites with an average size of between 0.5 and 60 nm.

11. The coated substrate according to claim 3, wherein the coating has a thickness of between 5 and 100 nm.

14. The coated substrate according to claim 3, wherein the thin layer comprises silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, Al₂ O₃ :

F or aluminum nitride.

17. A multi-layer glazing wherein at least one layer thereof is the coated substrate of claim 3.

4. A coated substrate which is a glass, ceramic or vitro-ceramic substrate provided on at least a portion of one of its faces with a coating having photocatalytic properties, and comprising titanium oxide at least partly crystallized in the anatase form, and wherein said coating is hydrophilic, and has a contact angle with water below 5°

after exposure to luminous rays, wherein the crystallized titanium oxide is in the form of crystallites with an average size of between 0.5 and 60 nm.

12. The coated substrate according to claim 4, wherein the coating has a thickness of between 5 and 100 nm.

18. A multi-layer glazing wherein at least one layer thereof is the coated substrate of claim 4.

5. A coated substrate which is a glass, ceramic or vitro-ceramic substrate provided on at least a portion of one of its faces with a coating having photocatalytic properties, and comprising titanium oxide at least partly crystallized in the anatase form, and wherein said coating has a root mean square (RMS) rugosity between 2 and 20 nm, wherein the crystallized titanium oxide is in the form of crystallites with an average size of between 0.5 and 60 nm.

13. The coated substrate according to claim 5, wherein the coating has a thickness of between 5 and 100 nm.

19. A multi-layer glazing wherein at least one layer thereof is the coated substrate of claim 5.

20. A process for obtaining a coated substrate which is a glass, ceramic or vitro-ceramic substrate provided on at least a portion of one of its faces with a coating having photocatalytic properties, and comprising titanium oxide at least partly crystallized in the anatase form, comprising depositing a coating of titanium oxide at least partly crystallized in the anatase form on said substrate, to form said coating, followed by subjecting said coating to at least one annealing heat treatment, wherein the depositing of the coating of titanium oxide at least partly crystallized in the anatase form is by vacuum deposition.

21. The process according to claim 20, wherein the depositing of the coating of titanium oxide at least partly crystallized in the anatase form is by thermal decomposition of titanium precursors selected from the group consisting of organo-metallic precursors and metallic halide precursors.

22. A process for obtaining a coated substrate which is a glass, ceramic or vitro-ceramic substrate provided on at least a portion of one of its faces with a coating having photocatalytic properties and comprising titanium oxide at least partly crystallized in the anatase form, comprising depositing a coating of titanium oxide at least partly crystallized in the anatase form on said substrate, to form said coating, followed by subjecting said coating to at least one annealing heat treatment, wherein the depositing of the coating of titanium oxide at least partly crystallized in the anatase form is by reactive or non-reactive cathodic sputtering.