IP Library › Granted Patent US 12,673,888

Granted Patent B2

US 12,673,888 · App. 18/123,637 · Granted Jul 7, 2026

High-index silicoborate and borosilicate glasses

Inventors: Antoine Marie Joseph Lepicard (Melun, FR); Jian Luo (Cupertino, CA); Alexander I Priven (Sejong-si, KR)

Assignee: CORNING INCORPORATED

C03C3/155 C03C3/068

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Quick Facts

Patent No.: US 12,673,888
App. No.: 18/123,637
Granted: Jul 7, 2026
Kind: B2

External Links

USPTO Patent Center↗ Full Patent PDF↗

Abstract

Glass compositions include titania (TiO 2 ), lanthanum oxide (La 2 O 3 ) and boron oxide (B 2 O 3 ) as essential components and may optionally include silica (SiO 2 ), niobia (Nb 2 O 5 ), zirconia (ZrO 2 ), yttria (Y 2 O 3 ), bismuth oxide (Bi 2 O 3 ), tungsten oxide (WO 3 ), zinc oxide (ZnO) and other components. The glasses may be characterized by high refractive index at 587.56 nm at comparably low density at room temperature.

Claims (145)

1 . A glass comprising a plurality of components, the glass having a composition of the components comprising:

greater than or equal to 12.0 mol. % and less than or equal to 35.0 mol. % TiO 2 ,

greater than or equal to 2.5 mol. % and less than or equal to 20.0 mol. % ZrO 2 ,

greater than or equal to 0.5 mol. % and less than or equal to 40.0 mol. % B 2 O 3 ,

greater than or equal to 0.5 mol. % and less than or equal to 30.0 mol. % Nb 2 O 5 ,

greater than or equal to 0.0 mol. % and less than or equal to 20.0 mol. % Bi 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 15.0 mol. % P 2 O 5 ,

greater than or equal to 0.0 mol. % and less than or equal to 10.0 mol. % Al 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 10.0 mol. % Gd 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 8.0 mol. % WO 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 5.0 mol. % PbO,

greater than or equal to 0.0 mol. % and less than or equal to 5.0 mol. % V 2 O 5 ,

greater than or equal to 0.0 mol. % and less than or equal to 1.5 mol. % ZnO,

greater than or equal to 95.0 mol. % R m O n ,

greater than or equal to 0.5 mol. % and less than or equal to 35.0 mol. % RE m O n ,

a sum of SiO 2 +B 2 O 3 +P 2 O 5 greater than or equal to 10.0 mol. % and

a sum of TiO 2 +Nb 2 O 5 less than or equal to 42.0 mol. %,

wherein the composition of the components satisfies the condition:

SiO 2 +B 2 O 3 −P 2 O 5 [mol. %]≥0.000,

wherein none of the ranges of the components is modified by the term “about”,

and wherein the glass satisfies the condition:

P 1 −(1.765+0.057*P d )>0.000,

where

P n is a parameter predicting a refractive index at 587.56 nm, n d , calculated from the glass composition in terms of mol. % of the components according to the Formula (I):

P n =1.844+0.0054162*La 2 O 3 +0.0031113*TiO 2 −0.004212*B 2 O 3 −0.0035692*SiO 2 +0.0027887*ZrO 2 +0.0078026*Nb 2 O 5 −0.00012928*CaO+0.00076566*BaO+0.0043601*Y 2 O 3 +0.00067408*ZnO+0.0068029*Gd 2 O 3 −0.0025106*Na 2 O+0.0039937*WO 3 −0.0043208*Al 2 O 3 −0.0011666*Li 2 O+0.0051727*PbO+0.012958*Bi 2 O 3 −0.0018753*GeO 2 −0.0014084*TeO 2 +0.0086647*Er 2 O 3 +0.0097345*Yb 2 O 3 −0.0038734*K 2 O−0.00041776*SrO−0.0017294*MgO, (I)

and P d is a parameter predicting a density at room temperature, d RT , calculated from the glass composition in terms of mol. % of the components according to the Formula (II):

P d =4.688+0.047868*La 2 O 3 −0.0065829*TiO 2 −0.027601*B 2 O 3 −0.022365*SiO 2 +0.016475*ZrO 2 −0.0052977*Nb 2 O 5 −0.0030466*CaO+0.014971*BaO+0.019511*Y 2 O 3 +0.0076377*ZnO+0.066160*Gd 2 O 3 −0.016932*Na 2 O+0.025764*WO 3 −0.035116*Al 2 O 3 −0.0094315*Li 2 O+0.047388*PbO+0.080813*Bi 2 O 3 −0.0088118*GeO 2 +0.072296*Er 2 O 3 +0.078888*Yb 2 O 3 −0.026242*K 2 O+0.010351*SrO−0.0030424*MgO, (II)

where R m O n is a total sum of all oxides, RE m O n is a total sum of rare earth metal oxides, and an asterisk (*) means multiplication, and neither of the parameters P n and P d is modified by the term “about”.

2 . The glass of claim 1 , wherein the glass satisfies the condition:

n d −(1.765+0.057 *d RT )>0.000,

where

n d is a refractive index at 587.56 nm,

d RT [g/cm 3 ] is a density at room temperature.

3 . The glass of claim 1 , wherein the composition of the components comprises:

greater than or equal to 20.0 mol. % and less than or equal to 27.5 mol. % TiO 2 ,

greater than or equal to 15.0 mol. % and less than or equal to 30.0 mol. % La 2 O 3 ,

greater than or equal to 15.0 mol. % and less than or equal to 22.5 mol. % B 2 O 3 ,

greater than or equal to 5.0 mol. % and less than or equal to 20.0 mol. % SiO 2 ,

greater than or equal to 4.0 mol. % and less than or equal to 9.0 mol. % ZrO 2 ,

greater than or equal to 2.5 mol. % and less than or equal to 10.0 mol. % Nb 2 O 5 ,

greater than or equal to 0.0 mol. % and less than or equal to 10.0 mol. % BaO,

greater than or equal to 0.0 mol. % and less than or equal to 10.0 mol. % CaO,

greater than or equal to 0.0 mol. % and less than or equal to 10.0 mol. % Ga 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 10.0 mol. % Y 2 O 3 and

greater than or equal to 0.0 mol. % and less than or equal to 2.0 mol. % WO 3 .

4 . The glass of claim 1 , wherein the composition of the components comprises:

greater than or equal to 22.0 mol. % and less than or equal to 25.0 mol. % TiO 2 ,

greater than or equal to 20.0 mol. % and less than or equal to 30.0 mol. % La 2 O 3 ,

greater than or equal to 16.0 mol. % and less than or equal to 20.0 mol. % B 2 O 3 ,

greater than or equal to 10.0 mol. % and less than or equal to 20.0 mol. % SiO 2 ,

greater than or equal to 6.5 mol. % and less than or equal to 8.0 mol. % ZrO 2 ,

greater than or equal to 5.0 mol. % and less than or equal to 6.7 mol. % Nb 2 O 5 ,

greater than or equal to 0.0 mol. % and less than or equal to 6.0 mol. % Y 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 3.0 mol. % BaO and

greater than or equal to 0.0 mol. % and less than or equal to 2.0 mol. % Gd 2 O 3 and

greater than or equal to 0.0 mol. % and less than or equal to 2.0 mol. % of all other components in total.

5 . The glass of claim 1 , wherein the glass satisfies the conditions:

4.5≤P d ≤5.5 and

1.95≤P n ≤2.07.

6 . The glass of claim 1 , wherein when cooled in air from 1100° C. to 500° C. in 2.5 minutes, the glass does not crystallize.

7 . A glass comprising a plurality of components, the glass having a composition of the components comprising:

greater than or equal to 1.0 mol. % and less than or equal to 13.5 mol. % ZrO 2 ,

greater than or equal to 0.3 mol. % and less than or equal to 35.0 mol. % TiO 2 ,

greater than or equal to 0.3 mol. % and less than or equal to 29.5 mol. % B 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 9.0 mol. % WO 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 5.0 mol. % PbO,

greater than or equal to 0.0 mol. % and less than or equal to 2.0 mol. % Gd 2 O 3 ,

greater than or equal to 0.0 at. % and less than or equal to 2.0 at. % F,

a sum of TiO 2 Nb 2 O 5 La 2 O 3 greater than or equal to 10.0 mol. % and less than or equal to 70.0 mol. %,

a sum of SiO 2 +B 2 O 3 +P 2 O 5 greater than or equal to 10.0 mol. %,

a sum of RE m O n +WO 3 +ZrO 2 greater than or equal to 5.0 mol. %,

a sum of SiO 2 +Y 2 O 3 +Gd 2 O 3 greater than or equal to 0.3 mol. %,

a sum of V 2 O 5 +MoO 3 greater than or equal to 0.0 mol. % and less than or equal to 3.0 mol. % and

optionally comprising one or more components selected from Bi 2 O 3 , CaO, BaO, ZnO, Na 2 O, Al 2 O 3 , Li 2 O, GeO 2 , TeO 2 , K 2 O, SrO and MgO,

wherein the composition of the components satisfies the conditions:

TiO 2 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 ) [mol. %]≥0.050,

SiO 2 +B 2 O 3 −P 2 O 5 [mol. %]≥1.0 and

La 2 O 3 /TiO 2 [mol. %]≤1.5,

wherein none of the ranges of the components is modified by the term “about”, and wherein the glass satisfies the condition:

P n −(1.99+0.083*(TiO 2 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 )))>0.000,

where

P n is a parameter predicting a refractive index at 587.56 nm, n d , calculated from the glass composition in terms of mol. % of the components according to the Formula (I):

where RE m O n is a total sum of rare earth metal oxides, and an asterisk (*) means multiplication, and the parameter P n is not modified by the term “about”.

8 . The glass of claim 7 , wherein the glass satisfies the condition:

n d −(1.99+0.083*(TiO 2 /(TiO 2 +Nb 2 O 5 +WO 3 +Bi 2 O 3 )))>0.000,

where

n d is a refractive index at 587.56 nm.

9 . The glass of claim 7 , wherein the composition of the components satisfies the condition:

0.38≤SiO 2 /(SiO 2 +B 2 O 3 ) [mol. %]≤0.75.

10 . The glass of claim 7 , wherein the composition of the components comprises:

greater than or equal to 22.0 mol. % and less than or equal to 25.0 mol. % TiO 2 ,

greater than or equal to 20.0 mol. % and less than or equal to 30.0 mol. % La 2 O 3 ,

greater than or equal to 16.0 mol. % and less than or equal to 20.0 mol. % B 2 O 3 ,

greater than or equal to 10.0 mol. % and less than or equal to 20.0 mol. % SiO 2 ,

greater than or equal to 6.5 mol. % and less than or equal to 8.0 mol. % ZrO 2 ,

greater than or equal to 5.0 mol. % and less than or equal to 6.7 mol. % Nb 2 O 5 ,

greater than or equal to 0.0 mol. % and less than or equal to 6.0 mol. % Y 2 O 3 and

greater than or equal to 0.0 mol. % and less than or equal to 3.0 mol. % BaO and

greater than or equal to 0.0 mol. % and less than or equal to 2.0 mol. % of all other components in total.

11 . The glass of claim 7 , wherein the glass satisfies the conditions:

4.5≤P d ≤5.5 and

1.95≤P n ≤2.07,

where

P d is a parameter predicting a density at room temperature, d RT , calculated from the glass composition in terms of mol. % of the components according to the Formula (II):

12 . The glass of claim 7 , wherein when cooled in air from 1100° C. to 500° C. in 2.5 minutes, the glass does not crystallize.

13 . A glass comprising a plurality of components, the glass having a composition of the components comprising:

greater than or equal to 0.5 mol. % and less than or equal to 45.0 mol. % B 2 O 3 ,

greater than or equal to 0.1 mol. % and less than or equal to 25.0 mol. % Bi 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 8.0 mol. % WO 3 ,

a sum of SiO 2 +B 2 O 3 +P 2 O 5 greater than or equal to 10.0 mol. %,

a sum of TiO 2 +Nb 2 O 5 greater than or equal to 8.5 mol. %,

a sum of RE m O n +WO 3 +ZrO 2 greater than or equal to 4.5 mol. % and

optionally comprising one or more components selected from CaO, BaO, ZnO, Na 2 O, Al 2 O 3 , Li 2 O, PbO, GeO 2 , TeO 2 , K 2 O, SrO and MgO,

wherein the composition of the components satisfies the condition:

SiO 2 +B 2 O 3 −P 2 O 5 [mol. %]≥0.100,

wherein none of the ranges of the components is modified by the term “about”, and wherein the glass satisfies the condition:

P n >2.045,

where

P n is a parameter predicting a refractive index at 587.56 nm, n d , calculated from the glass composition in terms of mol. % of the components according to the Formula (I):

where RE m O n is a total sum of rare earth metal oxides and an asterisk (*) means multiplication, and the parameter P 1 is not modified by the term “about”.

14 . The glass of claim 13 , wherein the glass has

a refractive index at 587.56 nm, n d that is greater than or equal to 2.045.

15 . The glass of claim 13 , wherein the composition of the components satisfies the condition:

0.38 SiO 2 /(SiO 2 +B 2 O 3 ) [mol. %]≤0.75.

16 . The glass of claim 13 , wherein the composition of the components comprises: