Method for depositing a reflective layer on glass, and products obtained

• US 5,939,201 A
• Filed: 02/03/1998
• Issued: 08/17/1999
• Est. Priority Date: 08/07/1996
• Status: Expired due to Fees

• Current Assignee: Saint-Gobain Vitrage
• Original Assignee: Saint-Gobain Vitrage
• Inventors: Boire, Philippe, Joret, Laurent
• Primary Examiner(s): LUSIGNAN, MICHAEL R
• Application Number:
  US08/945,757
• Time in Patent Office: 560 Days
• Field of Search: 65/60.2, 65/60.5, 65/60.8, 65/95, 65/97, 427/166, 427/165, 427/167, 427/255.7, 427/419.2, 427/419.3, 359/839, 359/900, 428/432, 428/702
• US Class Current: 428/432
• CPC Class Codes: C03C 17/002 for flat glass, e.g. float glass
• CPC Class Codes: C03C 17/06 with metals C03C17/34, C03C17/44 take precedence
• CPC Class Codes: C03C 17/10 by deposition from the liquid phase
• CPC Class Codes: C03C 17/36 at least one coating being a metal
• CPC Class Codes: C03C 17/3613 Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
• CPC Class Codes: C03C 17/3626 one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C03C 17/3634 one layer at least containing carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 17/3649 made of metals other than silver
• CPC Class Codes: C03C 17/3652 the coating stack containing at least one sacrificial layer to protect the metal from oxidation
• CPC Class Codes: C03C 17/366 Low-emissivity or solar control coatings
• CPC Class Codes: C03C 17/3663 specially adapted for use as mirrors
• CPC Class Codes: C03C 17/3694 one layer having a composition gradient through its thickness
• CPC Class Codes: C03C 2217/252 Al
• CPC Class Codes: C03C 2217/269 Non-specific enumeration
• CPC Class Codes: C03C 2217/27 Mixtures of metals, alloys
• CPC Class Codes: C03C 2218/13 from melts
• CPC Class Codes: C03C 2218/17 from a solid phase
• CPC Class Codes: Y10S 359/90 Methods

Abstract

The subject of the invention is a process for depositing, especially continuously, on a glass ribbon (10) of a float line, a reflective layer (3) based on a metal whose melting point is less than or equal to the temperature at which the glass ribbon acquires dimensional stability. The deposition is carried out in a controlled atmosphere, this being inert or reducing, when the glass ribbon (10) has already acquired its dimensional stability, by bringing the surface of the said ribbon into contact with the metal (22) in pulverulent form or in molten form, the temperature of the ribbon during contacting being chosen so that the powder melts and coalesces, or so that the molten metal forms a sheet, at the surface of the ribbon, leaving a solid continuous layer when the temperature of the ribbon is at a temperature of less than or equal to the melting point of the metal.

Claims

1. A process, comprising:

depositing a metallic reflective layer on a surface of a ribbon of float glass by contacting the surface of the float glass with a pulverulent metal or molten metal in an inert or reducing atmosphere, wherein

the metal has a melting point that is less than or equal to the temperature at which the ribbon acquires dimensional stability, and wherein

the ribbon temperature during the contacting is such that the pulverulent metal melts and coalesces at the surface of the ribbon or the molten metal forms a sheet at the surface of the ribbon to provide a solid continuous metallic reflecting layer when the ribbon temperature is less than or equal to the melting point of the metal.

2. Process according to claim 1, characterized in that the "metal" is based on a single metal, or based on an intermetallic compound, a metal alloy or a eutectic compound.

3. Process according to claim 1 or claim 2, characterized in that the "metal" is based on at least one of the metals belonging to the group comprising aluminium, zinc, tin, cadmium and, optionally, comprises silicon.

4. Process according to one of the preceding claims, characterized in that the deposition is carried out in the float-bath chamber.

5. Process according to claim 1, characterized in that the deposition is carried out downstream of the float-bath chamber, especially in an essentially sealed box optionally extending the said chamber.

6. Process according to one of the preceding claims, characterized in that the deposition is carried out when the glass is at a temperature greater than or equal to the melting point of the metal.

7. Process according to claim 6, characterized in that the contacting of the metal in pulverulent form with the surface of the glass takes place by spraying a powder in suspension in a carrier gas, this being inert or reducing, especially using a distribution nozzle arranged above the glass ribbon and transversely to its running axis, and capable of distributing the powder over the entire width of the ribbon.

8. Process according to claim 7, characterized in that a powder particle size of between 0.1 and 100 μ

m, especially between 1.0 and 50 μ

m, is chosen.

9. Process according to claim 4, characterized in that the metal is generated in pulverulent form (22) above the glass ribbon, from metal derivatives, especially gaseous ones, the decomposition of which into metal is brought about by thermal activation and/or bringing them into contact with each other.

10. Process according to claim 9, characterized in that the derivatives are chosen from metal alkyls, metal hydrides, mixed metal hydride/metal alkyl compounds complexed by ammonia or by a primary, secondary or tertiary amine.

11. Process according to claim 9 or 10, characterized in that the derivatives decompose into metal at a temperature of between 50°

C. and 600°

C., especially between 100°

C. and 450°

C.

12. Process according to one of claims 9 to 11, characterized in that at least one additive which promotes nucleation or growth of the metal particles is associated with the metal derivative(s).

13. Process according to one of claims 9 to 12, characterized in that the metal derivative(s) are introduced above the glass ribbon (10) in gaseous form using a device (12) comprising a cavity (15) whose walls (14, 14'"'"') define a channel for guiding the powder (22) generated by the said derivatives towards the glass ribbon (10).

14. Process according to claim 13, characterized in that the walls (14) of the cavity (15) are substantially vertical, possibly convergent or divergent towards the glass ribbon (10), and in that a thermal gradient is created over at least part of the height (h) of the said cavity.

15. Process according to either of claims 13 and 14, characterized in that the metal derivative(s) are injected in the upper part (16) of the cavity (15) and in that the effluents arising from the decomposition of the derivatives are extracted by side evacuation means (23) made in the walls (14) of the said cavity (15), preferably at the level, or near the level, where the metal powder is formed and where it reaches a sufficient particle size.

16. Process according to one of claims 13 to 15, characterized in that an inert or reducing gas is injected at at least one point (19) in the cavity (15).

17. Process according to one of claims 7 to 16, characterized in that the metal powder liquefies on the glass ribbon (10) or in the vicinity of it.

18. Process according to claim 1, characterized in that the molten metal is sprayed towards the glass ribbon, especially using a static distributing nozzle delivering a curtain of molten metal above the ribbon and transversely to its running axis, or using a moving nozzle, given a to-and-fro movement transverse to the running axis of the ribbon.

19. Process according to one of the preceding claims, characterized in that the surface of the glass ribbon is treated before depositing the metal-based reflective layer (3), especially by a contacting/adsorption of vapour of the TiCl₄ type, or by depositing at least one interlayer, especially made of silicon Si, made of an oxide such as aluminium oxide Al₂ O₃, silicon oxide, oxynitride or oxycarbide, SiO₂, SiON or SiOC, zirconium oxide ZrO₂, cerium oxide, titanium oxide TiO₂, zinc oxide ZnO, or boron oxide, yttrium oxide, magnesium oxide, or a mixed oxide of Al and of Si, made of fluorinated aluminium oxide, of magnesium fluoride or of a nitride such as aluminium nitride AlN, silicon nitride Si₃ N₄, titanium nitride, zirconium nitride, or a carbide, which layer is deposited, for example, by chemical vapour deposition.

20. Process according to one of the preceding claims, characterized in that the metal-based reflective layer (3) is covered with at least one additional layer (5) intended to protect it from oxidation, especially when the glass ribbon is still in the inert and/or reducing controlled atmosphere in which the deposition of the said reflective layer was carried out.

21. Process according to claim 19, characterized in that the additional layer(s) chosen is (are) based on a nitride, such as aluminium nitride, silicon nitride or titanium nitride.

22. Process according to claim 19 or 20, characterized in that the additional layer(s) chosen, optionally deposited on a thin silicon "sacrificial" layer (4), is (are) based on an oxide(s) comprising at least one oxide of the following group:

titanium oxide TiO₂, tin oxide SnO₂, zirconium oxide ZrO₂, silicon oxide, oxycarbide and/or oxynitride SiO₂, SiOC or SiON, aluminium oxide Al₂ O₃, vanadium oxide, zinc oxide, niobium oxide, tungsten oxide, antimony oxide, bismuth oxide, tantalum oxide or yttrium oxide, made of aluminium nitride or silicon nitride, or of fluorinated tin oxide or made of carbon-like diamond.

23. Process according to claim 19 or 20, characterized in that the reflective layer (3) is covered with an additional layer (5) having a composition gradient or a refractive index gradient through its thickness, especially by depositing a material such as silicon oxide, which becomes gradually richer in a material such as titanium oxide.

24. Process according to claims 19, characterized in that the reflective layer (3) is covered with at least one sequence of low-index and high-index layers, for example a SiO₂ /TiO₂ sequence.

25. Process according to one of the preceding claims, characterized in that the glass ribbon of a float line is substituted either by a glass ribbon not coming from a float line or a non-continuous glass substrate, such as a glass plate.

26. Glazing panel (1) obtained by cutting up the float-glass ribbon (10) covered according to the process in accordance with one of the preceding claims, characterized in that it is provided with an aluminium reflective layer (3) having a thickness less than or equal to 30 nm, depending on the solar protection.

27. Mirror (1) obtained by cutting up the float ribbon (10) covered according to the process in accordance with one of the preceding claims, characterized in that it is provided with an aluminium reflective layer (3) having a thickness greater than or equal to 30 nm.

28. Glazing panel (1) according to claim 26 or mirror according to claim 26, characterized in that it is provided with the aluminium/SiOC or aluminium/AlN or aluminium/TiN or aluminium/Si/oxide sequence.

32. Glass substrate (1) according to claim 28, characterized in that the "internal" complementary layer (2) and/or the "external" complementary layer (4) are based on material(s) which is(are) transparent within the wavelengths lying within the visible and of the carbon-like-diamond type.

29. Glass substrate provided with at least one reflective layer (3) based on a metal of the intermetallic-compound, alloy or eutectic compound type, especially based on at least one of the metals belonging to the group comprising aluminium, zinc, tin and cadmium and, optionally, also comprising silicon, characterized in that the substrate (1) is also provided with an "external" complementary layer (4) and/or with an internal complementary layer (2), with respect to the said reflective layer (3), the complementary layer(s) being intended to ensure its chemical and/or mechanical durability.

30. Glass substrate (1) according to claim 29, characterized in that the "internal" complementary layer (2) and/or the "external" complementary layer (4) are based on material(s) which is(are) transparent in the wavelengths lying within the visible and of the oxide(s) type chosen from at least one of the compounds comprising the oxides, oxycarbides or oxynitrides of the elements in Group IIA, IIIB, IVB, IIIA and IVA and of the lanthanides in the Periodic Table, such as the oxides of Mg, Ca, Y, Ti, Zr, Hf, Ce, Al, Si, Sn, or else based on transparent doped metal oxides such as F:

SnO₂.

31. Glass substrate (1) according to either of claims 29 and 30, characterized in that the "internal" complementary layer (2) and/or the "external" complementary layer (4) are based on material(s) which is(are) transparent in the wavelengths lying within the visible and of the nitride(s) type, especially based on a nitride of at least one of the elements in Group IIIA in the Periodic Table, such as the nitride of Al, of Ga or of boron, or else based on silicon nitride.

33. Glass substrate (1) according to claim 29, characterized in that the "internal" complementary layer (2) and/or the "external" complementary layer (4) are based on material(s) which is(are) absorbent in wavelengths lying within the visible and are different from those of which the reflective layer (3) is composed, of the transition-metal nitride type, such as the nitride of W, of Zr, of Hf, of Nb or of Ti, or carbon nitride, or else made of silicon Si, these preferably being confined to geometric thicknesses of less than or equal to 10 nm, especially of about 1 to 8 nm.

34. Glass substrate (1) according to claim 29, characterized in that the "internal" complementary layer (2) and/or the "external" complementary layer (4) has a chemical composition gradient through its thickness, especially an "internal" complementary layer (2) based on SiO₂ or SIO_x C_y becoming gradually richer in silicon, or based on SiO₂ or SiO_x C_y becoming gradually richer in Al₂ O₃, and/or an "external" complementary layer (4) based on Al₂ O₃ or SiO_x C_y or SiO₂ becoming gradually richer in TiO₂, or based on Si becoming gradually richer in SiO_x C_y or in SiO₂.

35. Glass substrate (1) according to claim 29, characterized in that the geometric thickness of the "internal" complementary layer (2) and the "external" complementary layer (4) is between 1 and 200 nm, especially between 30 and 160 nm.

36. Glass substrate (1) according to one of claims 29 to 35, characterized in that the reflective layer (3) lies between an "internal" complementary layer (2) and an "external" complementary layer (4), the nature and thickness of which are chosen so as to preserve the properties of the reflective layer (3) during its hot deposition and, optionally subsequently in the case where the glass substrate (1) is intended to undergo, after deposition of the layers, a heat post-treatment of the annealing, bending or tempering type.

37. Glass substrate according to one of claims 29 to 36, characterized in that the reflective layer (3) has a density at least than 80 and especially of at least 90 or 95% of its theoretical density.

38. Glass substrate according to one of claims 29 to 37, characterized in that the reflective layer (3) has a level of impurities, especially C, N, O, of at most 3 at. %, especially of at most 1 at. %.