Nanostructured glasses and vitroceramics that are transparent in visible and infra-red ranges

1. A nanostructured vitroceramic, either transparent or translucent, with essentially zero Li 2 O content and zero Al 2 O 3 content, containing 97% to 100% by weight in relation to the overall weight of the material, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected from among ZnO, MgO, NbO 2.5 , WO 3 , NiO, SnO, TiO 2 , BiO 1.5 , AgO, CaO, MnO, or a mixture thereof, and

Oxy 2 is an oxide selected from Na 2 O, K 2 O, or a mixture thereof, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦20,

x, y, z are such that 40≦x+y+z≦98,

0.1≦x≦50,

0≦b≦35, and

0≦k≦7, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100.

2. Nanostructured glass, either transparent or translucent, with essentially zero Li 2 O content and zero Al 2 O 3 content, containing 97% to 100% by weight in relation to the overall weight of the material, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected from among ZnO, MgO, NbO 2.5 , WO 3 , NiO, SnO, TiO 2 , BiO 1.5 , AgO, CaO, MnO, or a mixture thereof, and

Oxy 2 is an oxide selected from among Na 2 O, K 2 O or a mixture thereof, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦20,

x, y, z are such that 40≦x+y+z≦98,

0.1≦x≦50,

0≦b≦35, and

0≦k≦7, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100.

3. Vitroceramic according to claim 1 , wherein x and y are such that x+y≧40, in particular x+y≧50.

4. Vitroceramic according to claim 1 , wherein x is equal to 0 and 40≦y≦60 or 43≦y≦55.

5. Vitroceramic according to claim 1 , wherein y is equal to 0 and 50≦x≦98 and z is equal to 0.

6. Vitroceramic or glass according to claim 1 , wherein x and y are each independently

−10≦x≦80; and

−10≦y≦60, and

x and y are such 50≦x+y≦95, 60≦x+y≦98 or 80≦x+y≦95.

7. Vitroceramic according to claim 1 , containing dopants in addition to the composition formula (I) in order to attain 100% per unit mass.

8. Manufacturing process of a nanostructured glass according to claim 2 , comprising the successive steps of:

1—melting of initial oxides, or if applicable precursors thereof, present in powder form, at a temperature within the range between 900° C. and 1700° C.;

2—cooling,

producing a transparent or translucent nanostructured glass with essentially zero Li 2 O content and zero Al 2 O 3 content, containing 97% to 100% by weight, in relation to the overall weight of the glass, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected from among ZnO, MgO, NbO 2.5 , WO 3 , NiO, SnO, TiO 2 , BiO 1.5 , AgO, CaO, MnO, or a mixture thereof, and

Oxy 2 is an oxide selected from among Na 2 O, K 2 O or a mixture thereof, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦20,

40≦x+y+z≦98,

0.1≦x≦50,

0≦b≦35, and

0≦k≦7, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100.

9. Manufacturing process of a nanostructured vitroceramic according to claim 1 , comprising the successive steps of:

1—manufacture of a transparent or translucent nanostructured glass with essentially zero Li 2 O content and zero Al 2 O 3 content, and containing 97% to 100% by weight in relation to the overall weight of the material, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected from among ZnO, MgO, NbO 2.5 , WO 3 , NiO, SnO, TiO 2 , BiO 1.5 , AgO, CaO, MnO, or a mixture thereof, and

Oxy 2 is an oxide selected from Na 2 O, K 2 O or a mixture thereof, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦20,

40≦x+y+z≦98,

0.1≦x≦50,

0≦b≦35, and

0≦k≦7, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100, according to a process comprising the successive steps of:

melting of the initial oxides, or if applicable their precursors, present in powder form, at a temperature within the range between 900° C. and 1700° C., and then cooling;

2—thermal crystallisation treatment of the glass at a temperature within the range between 400° C. and 900° C., for a period within the range between 15 minutes and 48 hours.

10. Use of a glass according to claim 2 ,

for the manufacture of optical material, including masses, powders, fibres or layers;

for the manufacture of material for medical imaging, for lighting or for displays; or

for laser marking.

11. The nanostructured vitroceramic of claim 1 , containing 99% to 100% by weight in relation to the overall weight of the material, of a composition of the formula I.

12. The nanostructured vitroceramic of claim 1 , wherein Oxy 1 is an oxide selected from ZnO, MgO, AgO, BiO 1.5 , NbO 2.5 , or a mixture thereof.

13. The nanostructured vitroceramic of claim 1 , wherein Oxy 2 is Na 2 O.

14. The nanostructured vitroceramic of claim 1 , wherein 0≦z≦10.

15. The nanostructured vitroceramic of claim 1 , wherein 0.5≦a≦25.

16. The nanostructured vitroceramic of claim 1 , wherein 1≦b≦25.

17. The nanostructured vitroceramic of claim 1 , wherein 0≦k≦5.

18. A nanostructured vitroceramic, either transparent or translucent, with essentially zero Li 2 O content and zero Al 2 O 3 content, containing 99% to 100% by weight in relation to the overall weight of the material, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected from ZnO, MgO, AgO, BiO 1.5 , NbO 2.5 , or a mixture thereof, and

Oxy 2 is Na 2 O, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦10,

40≦x+y+z≦98,

0.5≦x≦25,

1≦b≦25, and

0≦k≦5, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100.

19. The nanostructured glass of claim 2 , containing 99% to 100% by weight in relation to the overall weight of the material, of a composition of the formula I.

20. The nanostructured glass of claim 2 , wherein Oxy 1 is an oxide selected from ZnO, MgO, AgO, BiO 1.5 , NbO 2.5 , or a mixture thereof.

21. The nanostructured glass of claim 2 , wherein Oxy 2 is Na 2 O.

22. The nanostructured glass of claim 2 , wherein 0≦z≦10.

23. The nanostructured glass of claim 2 , wherein 0.5≦a≦25.

24. The nanostructured glass of claim 2 , wherein 1≦b≦25.

25. The nanostructured glass of claim 2 , wherein 0≦k≦5.

26. Nanostructured glass, either transparent or translucent, with essentially zero Li 2 O content and zero Al 2 O content, containing 99% to 100% by weight in relation to the overall weight of the material, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected preferably from ZnO, MgO, AgO, BiO 1.5 , NbO 2.5 , or a mixture thereof, and

Oxy 2 is Na 2 O, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦10,

x, y, z are such that 40≦x+y+z≦98,

0.5≦x≦25,

1≦b≦25, and

0≦k≦5, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100.

27. Manufacturing process of a nanostructured glass according to claim 26 , comprising the successive steps of:

1—melting of initial oxides, or if applicable precursors thereof, present in powder form, at a temperature within the range between 900° C. and 1700° C.;

2—cooling,

producing a transparent or translucent nanostructured glass with essentially zero Li 2 O content and zero Al 2 O 3 content, containing 99% to 100% by weight, in relation to the overall weight of the glass, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected from among ZnO, MgO, AgO, BiO 1.5 , NbO 2.5 , or a mixture thereof, and

Oxy 2 is Na 2 O, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦10,

x, y, z are such that 40≦x+y+z≦98,

0.5≦x≦25,

1≦b≦25, and

0≦k≦5, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100.

28. The process according to claim 9 , wherein the thermal crystallisation treatment is performed at a temperature within the range 600° C. and 800° C., for a period within the range between 15 minutes and 6 hours.

29. Manufacturing process of a nanostructured vitroceramic according to claim 1 , comprising the successive steps of:

1—manufacture of a transparent or translucent nanostructured glass with essentially zero Li 2 O content and zero Al 2 O 3 content, and containing 99% to 100% by weight in relation to the overall weight of the material, of a composition of the following formula I:

(GeO 2 ) x (SiO 2 ) y (B 2 O 3 ) z (Ga 2 O 3 ) a (Oxy 1 ) b (Oxy 2 ) k   (I)

where

Oxy 1 is an oxide selected from among ZnO, MgO, AgO, BiO 1.5 , NbO 2.5 , or a mixture thereof, and

Oxy 2 is Na 2 O, and

0≦x≦98, and

0≦y≦60, and

x and y are not simultaneously zero, and

0≦z≦10,

x, y, z are such that 40≦x+y+z≦98,

0.5≦x≦25,

1≦b≦25, and

0≦k≦5, and

x, y, z, a, b and k are such that x+y+z+a+b+k=100, according to a process comprising the successive steps of:

melting of the initial oxides, or if applicable their precursors, present in powder form, at a temperature within the range between 900° C. and 1700° C., and then cooling;

2—thermal crystallisation treatment of the glass at a temperature within the range between 600° C. and 800° C., for a period within the range between 15 minutes and 6 hours, and preferably between 30 minutes and 2 hours.

30. Glass according to claim 2 , wherein x and y are such that x+y≧40, in particular x+y≧50.

31. Glass according to claim 2 , wherein x is equal to 0 and 40≦y≦60 or 43≦y≦55.

32. Glass according to claim 2 , wherein y is equal to 0 and 50≦x≦98 and z is equal to 0.

33. Vitroceramic or glass according to claim 2 , wherein x and y are each independently

−10≦x≦80; and

−10≦y≦60; and

x and y are such that 50≦x+y≦95, 60≦x+y≦98 or 80≦x+y≦95.

34. Glass according to claim 2 , containing dopants in addition to the composition formula (I) in order to attain 100% per unit mass.

35. Use of a vitroceramic according to claim 1 ,

for the manufacture of optical material, including masses, powders, fibres or layers;

for the manufacture of material for medical imaging, for lighting or for displays; or

for laser marking.