Decorative porous inorganic layer compatible with ion exchange processes

Patent metadata

Field	Value
Publication number	US-2016002104-A1
Application number	US-201414768832-A
Country	US
Kind code	A1
Filing date	Feb 24, 2014
Priority date	Feb 26, 2013
Publication date	Jan 7, 2016
Grant date	—

Abstract

Embodiments of methods for forming strengthened glass articles comprise providing an exchangeable glass substrate having a coefficient of thermal expansion (CTE) between about 60×10−7°/C. to about 110×10−7°/C., depositing at least one decorative porous inorganic layer onto at least a portion of the surface of the glass substrate, wherein the decorative porous inorganic layer comprises a glass transition temperature (Tg)≧450° C., a glass softening temperature (Ts)≧650° C., wherein the difference in CTE values between the glass substrate and the decorative porous inorganic layer is within 10×10−7°/C.; and curing the glass substrate and the deposited decorative porous inorganic layer at a temperature greater than the Ts of the decorative porous inorganic layer; and chemically strengthening the cured glass substrate and the decorative porous inorganic layer thereon via ion exchange at a temperature below the Tg of the decorative porous inorganic layer.

First claim

1 . A method for forming a strengthened glass article, the method comprising:
providing an ion exchangeable glass substrate having a coefficient of thermal expansion (CTE) ranging between about 60×10 −7 /° C. to about 110×10 −7 /° C.; depositing at least one decorative porous inorganic layer onto at least a portion of the surface of the glass substrate, wherein the decorative porous inorganic layer comprises a glass transition temperature (Tg)≧450° C., a glass softening temperature (Ts)≦650° C., wherein the difference in CTE values between the glass substrate and the decorative porous inorganic layer is within 10×10 −7 ° C.; curing the glass substrate and the deposited decorative porous inorganic layer at a temperature greater than the glass softening temperature (Ts) of the decorative porous inorganic layer; and chemically strengthening the cured glass substrate and the decorative porous inorganic layer thereon via ion exchange at a temperature above the glass transition temperature (Tg) of the decorative porous inorganic layer.

2 . The method of claim 1 wherein the decorative porous inorganic layer is silica free.

3 . The method of claim 1 further comprising adding a rheology modifier or organic binder to the inorganic glass frit powder to obtain an inorganic paste.

4 . The method of claim 1 wherein the difference in CTE values between the glass substrate and the decorative porous inorganic layer is within 5×10−7/° C.

5 . The method of claim 1 wherein the glass substrate is an aluminosilicate glass or an alurninoborosilicate glass.

6 . The method of claim 1 wherein the decorative porous inorganic layer comprises:
from about 0 to about 10 mot % Al 2 O 3 ;
from about 0 to about 10 mol % CoO;
from about 5 to about 25 mol % Na 2 O;
from about 0 to about 15 mol % K 2 O;
from about 0 to about 10 mol V 2 O 5 ;
from about 0 to about 8 mol % TiO 2 ;
from about 0 to about 15 mol % ZnO;
from about 0 to about 10 mol % CaO;
from about 20 to about 40 mol Fe 2 O 3 ; and
at least about 50 mol % P 7 O 5 .

7 . The method of claim 6 wherein the decorative porous inorganic layer comprises from about 8 to about 25 mol % R 2 O, wherein R 2 O is Na 2 O, K 2 O, or both.

8 . The method of claim 1 wherein the decorative porous inorganic layer comprises from about 50 to about 60 mol % P 2 O 5 .

9 . The method of claim 1 wherein the ratio by mol % of Na 2 O/Fe 2 O 3 is from about 0.2 to about 1.

10 . The method of claim 1 wherein the glass softening temperature Ts is between about 500 to about 650° C.

11 . The method of claim 10 wherein the glass softening temperature Ts is between about 500 to about 600° C.

12 . The method of claim 1 wherein the glass transition temperature Tg is between about 450° C. to about 550° C.

13 . The method of claim 1 wherein the decorative porous inorganic layer comprises from about 10 to about 60 weight % of pigment or from about 20 to about 25 weight % of pigment.

14 . The method of claim 1 wherein the decorative porous inorganic layer is a non-crystallizing glass frit or a crystallizing glass frit defining a particle size of about 50 μm and below, defining a median particle size (d50)≦15 μm, defining a particle size diameter wherein at least 90% of the particles have a diameter (d90)≦40 μm, or defining a particle size of about 125 μm and below.

15 . The method of claim 1 wherein the chemical strengthening achieves flexural strength value defined by ring on ring testing (ROR) 300 MPa and a depth of layer DOL greater than or equal to about 30 μm.

16 . The method of claim 15 wherein the DOL is greater than or equal to about 50 μm.

17 . A strengthened glass article comprising:
a glass substrate having a coefficient of thermal expansion (CTE) ranging between about 60×10 −7 /° C. to about 110×10 −7 /° C.; and at least one decorative porous inorganic layer bonded onto at least a portion of the surface of the glass substrate, wherein the decorative porous inorganic layer comprises a glass transition temperature (Tg,≧450° C., a glass softening temperature (Ts)≦650° C., wherein the difference in CTE values between the glass substrate and the decorative porous inorganic layer is within 10×10 −7 /° C.; wherein the strengthened glass article comprises a compressive stress layer extending through the decorative glass frit layer and into the glass substrate, the compressive stress layer having a depth of layer DOL≧30 μm, and wherein the strengthened glass article comprises a flexural strength value defined by ring on ring testing (ROR)≧300 MPa or ≧400 MPa.

18 . The strengthened glass article of claim 17 wherein the decorative porous inorganic layer defines a median particle size (d50)≦15 μm, defines a particle size of about 50 μm and below, defines a particle size diameter wherein at least 90% of the particles have a diameter (d90)≦40 μm, or defines a particle size of about 125 μm and below.

19 . The strengthened glass article of claim 17 wherein the decorative porous inorganic layer is silica free.

20 . The strengthened glass article of claim 17 wherein the glass substrate is an aluminosilicate glass or an aluminoborosilicate glass.

21 . The strengthened glass article of claim 17 wherein the decorative porous inorganic layer comprises:
from about 0 to about 10 mol % Al 2 O 3 ;
from about 0 to about 10 mol % CoO;
from about 5 to about 25 mol % Na 2 O;
from about 0 to about 15 mol % K 2 O;
from about 0 to about 10 mol % V 2 O 5 ;
from about 0 to about 8 mol % TiO 2 ;
from about 0 to about 15 mol % ZnO;
from about 0 to about 10 mol % CaO;
from about 20 to about 40 mol % Fe 2 O 3 ; and
at least about 50 mol % P 2 O 5 .

22 . The strengthened glass article of claim 21 wherein the decorative porous inorganic layer comprises from about 8 to about 25 mol % R 2 O, wherein R 2 O is Na 2 O, K 2 O, or both.

23 . The strengthened glass article of claim 21 wherein the decorative porous inorganic layer comprises from about 50 to about 60 mol % P 2 O 5 .

24 . The strengthened glass article of claim 21 wherein the ratio by mol % of Na 2 O/Fe 2 O 3 is from about 0.2 to about 1.

25 . The strengthened glass article of claim 17 wherein the glass softening temperature Ts is between about 500 to about 650° C.

26 . The strengthened glass article of claim 25 wherein the glass softening temperature Ts is between from about 525 to about 600° C.

27 . The strengthened glass article of claim 17 wherein the glass transition temperature Tg is between about 450° C. to about 500° C.

28 . The strengthened glass article of claim 17 wherein the decorative porous inorganic layer comprises from about 10 to about 60 weight % of pigment or from about 20 to about 25 weight % of pigment comprises from about 10 to about 60 weight % of pigment.

29 . The strengthened glass article of claim 17 wherein the depth of layer DOL is greater than or equal to about 50 μm.

30 . The strengthened glass article according to any one of claims 17 to 29 wherein the strengthened glass is used in automotive glazing.

Assignees

• Corning Inc

Inventors

• Lehuede Philippe
• Monique Marie Jacqueline

Classifications

• C03C2217/425

  consisting of a porous layer · CPC title

• C03C8/14

  Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions · CPC title

• C03C17/007

  containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase · CPC title

• C03C8/08

  containing phosphorus · CPC title

• C03C2217/72

  Decorative coatings · CPC title