Method of making a glass body with a phosphorous- and porous SiO2-containing coating, glass body made thereby and solution for making same

• US 6,998,177 B2
• Filed: 03/05/2003
• Issued: 02/14/2006
• Est. Priority Date: 03/06/2002
• Status: Expired due to Term

• Current Assignee: Schott AG (Carl-Zeiss-Stiftung)
• Original Assignee: Schott AG (Carl-Zeiss-Stiftung)
• Inventors: Krzyzak, Marta, Helsch, Gundula, Frischat, Guenther Heinz, Heide, Gerhard
• Primary Examiner(s): Jones, Deborah
• Assistant Examiner(s): BLACKWELL, GWENDOLYN
• Application Number:
  US10/379,647
• Publication Number:
  US 20030170465A1
• Time in Patent Office: 1,077 Days
• Field of Search: 428/428, 428/432, 428/697, 428/701, 428/702, 501/54, 106/287.29, 106/287.34
• US Class Current: 428/428
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 2217/213 SiO2
• CPC Class Codes: C03C 2217/23 Mixtures
• CPC Class Codes: C03C 2217/732 made of a single layer
• CPC Class Codes: C03C 2218/113 by sol-gel processes
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick

Abstract

The alkali-free or alkali-poor glass body is provided with an adherent and anti-reflective coating on at least one of its sides. The coating contains P₂O₅ and porous SiO₂, preferably in a weight ratio of SiO₂ to P₂O₅ of 10:1 to 1:1. It has a rubbing resistance criterion according to DIN 58196, intensity of testing H50, of 2 or better. The method of providing the glass body with the coating includes dipping the glass body in a H₃PO₄- and SiO₂-containing volatile solution, withdrawing the glass body at a speed of from 1 mm/s to 20 mm/s from the solution and tempering the glass body at a temperature of under T_g of the glass.

Claims

1. An alkali-free or alkali-poor glass body having a plurality of sides and provided with an adherent and anti-reflective coating on at least one of said sides, wherein said adherent and anti-reflective coating contains phosphorus and porous SiO₂;

and

wherein said alkali-free or alkali-poor glass body contains no alkali metal oxides or less than 12 percent by weight of said alkali metal oxides and said coating is provided with pores with a pore diameter of 2 nm to 50 nm.

2. The glass body as defined in claim 1, wherein said adherent and anti-reflective coating has a rubbing resistance criterion according to DIN 58196-5, intensity of testing H50, of 2 or better.

3. An alkali-free or alkali-poor glass body having a plurality of sides and provided with an adherent and anti-reflective coating on at least one of said sides, wherein said adherent and anti-reflective coating contains phosphorus oxide and porous SiO₂, and said glass body contains no alkali metal oxides or less than 12 percent by weight of said alkali metal oxides, wherein said phosphorus oxide is P₂O₅ and a weight ratio of said SiO₂ to said P₂O₅ in said coating is from 3:

1 to 1.2;

1.

4. The glass body as defined in claim 3, containing at least 1 percent by weight boron oxide.

5. The glass body as defined in claim 4, containing at least 7 percent by weight of said boron oxide.

6. The glass body as defined in claim 4, containing at most 20 percent by weight of said boron oxide.

7. An alkali-free or alkali-poor glass body having a plurality of sides and provided with an adherent and anti-reflective coating on at least one of said sides, wherein said glass body contains, in percent by weight on the basis of oxides:

SiO₂70 to 85,B₂O₃+11 7 to 15,Na₂O +30 +0 K₂O+11 2 to +21 12,Al₂O₃+11 1 to 8,ROO to 11;

wherein RO represents at least one member selected from the group consisting of MgO, CaO, SrO, BaO and ZnO;

wherein said alkali-free or alkali-poor glass body contains no alkali metal oxides or less than 12 percent by weight of said alkali metal oxides; and

wherein said adherent and anti-reflective coating contains phosphorus and porous Si_O2.

8. An alkali-free or alkali-poor glass body having a plurality of sides and provided with an adherent and anti-reflective coating on at least one of said sides, wherein said adherent and anti-reflective coating contains phosphorus and porous SiO₂;

and

wherein said alkali-free or alkali-poor class body contains no alkali metal oxides or less than 12 percent by weight of said alkali metal oxides and said coating has a porosity of 10 to 60 percent by volume based on a total volume of said coating.

9. The glass body as defined in claim 8, said glass body containing the following ingredients, in percent by weight on the basis of oxides:

SiO₂40 to 60,+11 B₂O₃7 to 15,Al₂O₃8 to 20,RO0 to 30;

wherein RO represents at least one member selected from the group consisting of MgO, CaO, SrO, BaO and ZnO.

10. The glass body as defined in claim 8, said glass body containing at least 95 percent by weight of said SiO₂.

11. The glass body as defined in claim 10, said glass body containing at least 99 percent by weight of said SiO₂.

16. The glass body as defined in claim 8, wherein said coating has a coating thickness of 50 nm to 500 nm.

17. The glass body as defined in claim 16, wherein said coating thickness is 80 nm to 160 nm.

18. The glass body as defined in claim 8, and made by a method comprising the steps of:

a) dipping the glass body in a volatile solution containing H₃PO₄ and SiO₂,

b) withdrawing the glass body in a the volatile solution; and

c) tempering the glass body at a temperature under T_g of the glass.

19. The glass body as defined in claim 18, whereby said adherent and anti-reflective coating has a rubbing resistance criterion according to DIN 58196-5, intensity of testing H50, of 2 or better.

20. The glass body as defined in claim 18, wherein said withdrawing of said glass body from said volatile solution takes place at a withdrawing speed of from 0.1 mm/s to 100 mm/s.

21. The glass body as defined in claim 20, wherein said withdrawing speed is from 1 mm/s to 20 mm/s.

22. The glass body as defined in claim 18, wherein said solution has a pH of from 1 to 2 and contains at least one acid, said SiO₂ and at least one solvent.

23. The glass body as defined in claim 22, wherein said at least one solvent is at least one lower chain alcohol having a formula C_nH_2n+1OH, with n=1, 2, 3, 4 or 5 and said at least one acid is selected from the group consisting of HCl and HNO₃.

24. The glass body as defined in claim 18, wherein said volatile solution has a pH of from 1 to 2 and contains said H₃PO₄, at least one acid, said SiO₂ and at least one solvent.

25. The glass body as defined in claim 24, wherein said at least one solvent is al least one lower chain alcohol having a formula C_nH_2n+1OH, with n=1, 2, 3, 4 or 5 and said at least one acid is selected from the group consisting of HCl and HNO₃.

26. The glass body as defined in claim 18, wherein said volatile solution contains from 0.1 to 2 percent by weight HCl or HNO₃, from 0.5 to 15 percent by weight of an SiO₂ sol and from 0.1 to 6 percent by weight of said H₃PO₄.

27. The glass body as defined in claim 18, wherein said volatile solution contains from 0.1 to 2 percent by weight of HCl or HNO₃, from 0.5 to 7 percent by weight of an SiO₂ sol and from 0.1 to 3.5 percent by weight of said H₃PO₄.

12. An alkali-free or alkali-poor glass body having a plurality of sides and provided with an adherent and anti-reflective coating on at least one of said sides, wherein said adherent and anti-reflective coating contains phosphorus oxide and porous SiO₂ and said glass body contains from 0 to 1 percent by weight of at least one alkali metal oxide, wherein said phosphorus oxide is P₂O₅ and a weight ratio of said SiO₂ to said P₂O₅ in said coating is from 3:

1 to 1.2;

1.

13. The glass body as defined in claim 12, said glass body containing the following ingredients, in percent by weight on the basis of oxides:

SiO₂40 to 60,+11 B₂O₃7 to 15,Al₂O₃8 to 20,RO0 to 30;

wherein RO represents at least one member selected from the group consisting of MgO, CaO, SrO, BaO and ZnO.

14. The glass body as defined in claim 12, said glass body containing at least 95 percent by weight of said SiO₂.

15. The glass body as defined in claim 14, said class body containing at least 99 percent by weight of said SiO₂.