Method for coating a moving glass substrate

• US 5,464,657 A
• Filed: 06/23/1994
• Issued: 11/07/1995
• 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: Stewart-Davis, Royann L., Athey, Patricia R., Dauson, Douglas S., Lecocq, David E., Neuman, George A., Sopko, John F.
• Primary Examiner(s): King, Roy V.
• Application Number:
  US08/264,816
• Time in Patent Office: 502 Days
• Field of Search: 427/255.5, 427/255.7, 427/166, 427/167, 427/108, 427/109, 427/255.3, 427/255.2, 427/255.1, 427/126.3, 427/419.2
• US Class Current: 427/255.5
• 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

A method for coating a moving substrate provides a coating having a chemical composition which varies continuously from the interface with the substrate to the opposite surface of the coating. The method involves directing a vapor coating composition toward a substrate surface and moving portions of the vapor in opposite directions. A vapor coating mixture may include a tin-containing precursor and a silicon-containing precursor. 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 substrate has regions of continuously varying weight percent of silicon oxide and tin oxide as the distance from the substrate-coating interface increases, with the surface of the coating farthest from the substrate-coating interface being predominantly tin oxide. The regions of varying composition provide the coating with varying indices of refraction to eliminate iridescence to provide a coated article, particularly a tin oxide coated glass article, with a neutral color.

Claims

1. A method of coating a moving substrate to provide a coating having a continuously varying chemical composition as the distance from the substrate increases, comprising the steps of:

directing a vapor coating composition onto the surface of the substrate at a first position;

thereafter moving a first portion of the vapor coating composition along a first region of the substrate surface in a first direction and a second portion of the vapor coating composition along a second region of the substrate surface in a second direction opposite to the first direction, and

maintaining the first portion of the coating composition on the first region of the substrate surface for a longer period of time than the second portion of the vapor coating composition on the second region of the substrate surface in order to coat the substrate with the coating having the continuously varying chemical composition as the distance from the substrate increases.

2. The method of claim 1 wherein the vapor coating composition has at least two metal containing precursors.

3. The method of claim 2 wherein the substrate is a glass substrate, and said first direction is substantially parallel with the direction in which the substrate is moving.

4. The method of claim 3 wherein one of the metal containing precursors contains a metal selected from the group consisting of tin, titanium, tungsten, and antimony.

5. The method of claim 2 further including practicing said directing step at a second position spaced from and on one side of the first position and a third position spaced from the first and second positions such that the second position is between the first and third positions.

6. The method of claim 5 wherein the substrate is coated in a chamber having a non-oxidizing atmosphere and further including providing a curtain of inert gas to prevent the non-oxidizing atmosphere from moving to the positions wherein the curtain of inert gas and the positions therebetween define a coating zone.

7. The method of claim 6 wherein said chamber contains a bath of oxidizable molten metal and the substrate is a glass ribbon supported the molten metal and advanced through the chamber through the coating position.

8. The method of claim 2 wherein said maintaining step is accomplished by providing exhaust means on each side of said first position wherein one exhaust means is spaced a distance "x" from the first position and the other exhaust means is spaced a distance "y" from said first position, and further wherein the ratio of x/y is greater than 1.

9. The method as set forth in claim 1 wherein the substrate is a glass substrate and the coating composition has at least one silicon containing precursor containing at least one silicon-oxygen bond.

10. The method as set forth in claim 9 wherein said directing step includes mixing the silicon containing precursor with an accelerant to increase the coating deposition rate of the silicon oxide in the glass substrate.

11. The method as set forth in claim 1 wherein the vapor coating composition has at least one metal containing precursor and one silicon containing precursor.

12. The method of claim 4, wherein one of the metal containing precursors contains tin.

13. The method of claim 1 further comprising practicing said step of directing at a second position spaced from the first position.

14. The method of claim 5 further comprising the step of exhausting vapor from both sides of the first and third positions.

15. The method of claim 8, wherein the ratio of x/y is greater than about 1.2.

16. The method of claim 15, wherein the ratio of x/y is from about 1.2 to about 50.

17. The method of claim 16, wherein the ratio of x/y is from about 1.5 to 30.

18. The method of claim 5, wherein the substrate is a glass ribbon which is coated in a chamber having a reducing atmosphere and is supported on a pool of molten oxidizable metal.

19. The method of claim 5, wherein the substrate is a glass ribbon and further comprising the step of depositing a single metal oxide layer over the coating having the continuously varying chemical composition.

20. The method of claim 19, wherein the single metal oxide layer is tin oxide and the coating having the continuously varying chemical composition comprises tin oxide and silicon oxide.