Coating apparatus, method of coating glass, compounds and compositions for coating glasss and coated glass substrates

• US 5,356,718 A
• Filed: 02/16/1993
• Issued: 10/18/1994
• Est. Priority Date: 02/16/1993
• Status: Expired due to Term

• Current Assignee: Vitro Flat Glass LLC (Compagnie De Saint-Gobain)
• Original Assignee: PPG Industries Incorporated (Nouryon BV)
• Inventors: Athey, Patricia R., Dauson, Douglas S., Neuman, George A., Stewart-Davis, Royann L., Sopko, John F., Lecocq, David E.
• Primary Examiner(s): TURNER, ARCHENE A
• Application Number:
  US08/017,930
• Time in Patent Office: 609 Days
• Field of Search: 428/426, 428/428, 428/432, 428/697, 428/701, 428/702
• US Class Current: 428/428
• 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 17/2453 Coating containing SnO2
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• 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 2217/215 In2O3
• CPC Class Codes: C03C 2217/216 ZnO
• CPC Class Codes: C03C 2217/218 V2O5, Nb2O5, Ta2O5
• CPC Class Codes: C03C 2217/219 CrOx, MoOx, WOx
• CPC Class Codes: C03C 2217/228 Other specific oxides
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2217/241 with halides
• CPC Class Codes: C03C 2217/244 with Sb
• CPC Class Codes: C03C 2218/152 by cvd
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/4412 Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
• CPC Class Codes: C23C 16/453 passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD C23C16/513 takes precedence; for flame or plasma spraying of coating material in the molten state C23C4/00
• CPC Class Codes: C23C 16/545 for coating elongated substrates

Abstract

An apparatus for coating a glass ribbon has an exhaust on each side of a coating unit at different distances therefrom. With this arrangement, portions of the ribbon upstream and downstream of the coating unit are exposed to coating vapors from the coating unit for different periods of time. A coating mixture includes tin containing precursors and a silicon containing precursor. The silicon containing precursor has the structural formula ##STR1## where R₁ is a group which does not have an oxygen available to form a peroxide, R₂ is a functional group giving the silicon containing precursor the ability to be easily converted to silicon oxide coating, R₃ is a bridging group to provide for multiple silicon atoms and R₄ completes the bonding on the foundation silicon atom. An accelerant e.g. a phosphorus containing precursor may be used with the metal containing precursors to increase the deposition rate of the coating. The coating deposited on the glass has regions of continuously varying weight percent of silicon oxide and tin oxide as the distance from the glass-coating interface increases, with the surface of the coating farthest from the glass-coating interface being predominantly tin oxide. The regions within the coating provide the coating with different indices of refraction to eliminate iridescence resulting from increased thickness of the tin oxide at the outer coating surface and to provide the coated glass article with a neutral color. When phosphorus is used as the accelerant, the percent of crystallinity is reduced and approaches O, thereby reducing or eliminating the coating haze.

Claims

1. A transparent substrate having an amorphous coating thereon composed of one or more mixed metal oxides and having up to 15 atomic percent of an element dispersed therethrough selected from the group consisting of phosphorus, aluminum and boron wherein the mixed metal oxide itself excludes phosphorus, aluminum and boron.

5. A transparent substrate according to claim 1, wherein said metal oxide is selected from the group consisting of the oxides of silicon, tin, titanium, tungsten, antimony and mixtures thereof.

6. A transparent substrate according to claim 5, wherein the element dispersed through the coating is phosphorus.

7. A transparent substrate according to claim 5, wherein the element is aluminum.

8. A transparent substrate according to claim 5, wherein the element is boron.

9. A transparent substrate according to claim 5, wherein the metal oxide is selected from the group consisting of the oxides of silicon, tin and mixtures thereof.

10. A transparent substrate according to claim 9, wherein the element dispersed through the coating is phosphorus.

11. A transparent substrate according to claim 9, wherein the element is aluminum.

12. A transparent substrate according to claim 9, wherein the element is boron.

2. A transparent substrate having an amorphous coating thereon composed of mixed metal oxides with regions in the coating of continuously varying ratio of the metal oxides with the substantial absence of strata of a fixed ratio of the metal oxides and up to 15 atomic percent of an element dispersed therethrough selected from the group consisting of phosphorus, aluminum, and boron.

3. The substrate of claim 2 wherein the substrate is glass, mixed metal oxides are silicon oxide and tin oxide with a weight percent of 70-100% of silicon oxide at the glass-coating interface, and a weight percent of 70-100% of tin oxide at the opposite coating surface and the element therethrough is phosphorus.

4. An article according to claim 3, wherein one to twelve atomic percent of phosphorus is dispersed in the coating.

13. A transparent substrate according to claim 2, wherein the mixed metal oxides are selected from the group consisting of the oxides of silicon, tin, titanium, tungsten and antimony.

14. A transparent substrate according to claim 13, wherein the mixed metal oxides are the oxides of silicon and tin.

15. A transparent substrate according to claim 14, wherein the element dispersed through the coating is phosphorus.

16. A transparent substrate according to claim 14, wherein the element is aluminum.

17. A transparent substrate according to claim 14, wherein the element is boron.