IP Library › Granted Patent US 12692187
Granted Patent B2
US 12692187 · App. 18/123,657 · Granted Jul 28, 2026

High-index high-dispersion phosphate glasses containing bismuth oxide

Inventors: Bruce Gardiner Aitken (Corning, NY); Jian Luo (Cupertino, CA); Lina Ma (Corning, NY); Alexander I Priven (Sejong-si, KR)
Assignee: CORNING INCORPORATED
C03C3/21C03C3/16
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Quick Facts
Patent No.
US 12692187
App. No.
18/123,657
Granted
Jul 28, 2026
Kind
B2
Abstract

Glass compositions include phosphorus oxide (P 2 O 5 ), niobia (Nb 2 O 5 ), titania (TiO 2 ) and bismuth oxide (Bi 2 O 3 ) as essential components and may optionally include barium oxide (BaO), calcium oxide (CaO), potassium oxide (K 2 O), lithium oxide (Li 2 O), sodium oxide (Na 2 O), tungsten oxide (WO 3 ), boron oxide (B 2 O 3 ) and other components. The glasses may be characterized by high refractive index at 587.56 nm at comparably low density at room temperature.

Claims (115)

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

greater than or equal to 15.9 mol. % and less than or equal to 50.0 mol. % P 2 O 5 ,

greater than or equal to 4.5 mol. % and less than or equal to 50.0 mol. % Bi 2 O 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 50.0 mol. % TiO 2 ,

greater than or equal to 0.0 mol. % and less than or equal to 50.0 mol. % Nb 2 O 5 ,

greater than or equal to 0.0 mol. % and less than or equal to 25.0 mol. % Li 2 O,

greater than or equal to 0.0 mol. % and less than or equal to 25.0 mol. % K 2 O,

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

greater than or equal to 0.0 mol. % and less than or equal to 6.0 mol. % WO 3 ,

greater than or equal to 0.0 mol. % and less than or equal to 1.0 mol. % V 2 O 5 ,

a sum of TiO 2 +Nb 2 O 5 greater than or equal to 25.0 mol. % and less than or equal to 70.0 mol. %,

a sum of Alk 2 O greater than or equal to 0.5 mol. % and less than or equal to 30.0 mol. %,

a sum of RO greater than or equal to 0.5 mol. % and less than or equal to 30.0 mol. %,

a sum of GeO 2 +TeO 2 greater than or equal to 0.0 mol. % and less than or equal to 25.0 mol. % and

optionally comprising Al 2 O 3 ,

wherein the composition of the components satisfies the condition:

Alk 2 O+RO+Bi 2 O 3 +3*Al 2 O 3 —P 2 O 5 [mol. %]≥−8.0

where Alk 2 O is a total sum of alkali metal oxides and RO is a total sum of divalent metal oxides, an asterisk (*) means multiplication, and

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

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

P d <4.8 and

P n >2.0,

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 =1.865−0.0052736*P 2 O 5 +0.0071201*Nb 2 O 5 +0.0031659*TiO 2 −0.0008032*BaO−0.0047736*K 2 O−0.00076807*CaO−0.0027991*Na 2 O−0.0016514*Li 2 O−0.00069646*SrO+0.0032628*WO 3 +0.007519*Bi 2 O 3 −0.0040698*B 2 O 3 −0.0035951*SiO 2 −0.00067102*ZnO+0.0022313*ZrO 2 −0.0019531*MgO−0.003506*Al 2 O 3 +0.0019216*TeO 2 +0.0025766*PbO−0.0018844*GeO 2 +0.0065444*Tl 2 O+0.0052048*Ag 2 O,  (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 =4.45−0.020780*Al 2 O 3 −0.020918*B 2 O 3 +0.014152*BaO+0.061008*Bi 2 O 3 −0.0067411*CaO+0.013529*CdO+0.012560*Cs 2 O+0.0028892*Ga 2 O 3 −0.0057012*GeO 2 −0.017838*K 2 O+0.046524*La 2 O 3 −0.013919*Li 2 O−0.010279*MgO−0.0064231*MoO 3 −0.012983*Na 2 O+0.0083294*Nb 2 O 5 −0.028926*P 2 O 5 +0.031742*PbO−0.019022*SiO 2 +0.0045214*SrO+0.050158*Ta 2 O 5 +0.0088486*TeO 2 −0.0063053*TiO 2 −0.018941*V 2 O 5 +0.027483*WO 3 −0.0010277*ZnO+0.0100487*ZrO 2 ,  (II)

wherein neither of the parameters P n and Pa is modified by the term “about”.

3 . The glass of claim 1 , wherein the glass has

an Abbe number, v d , that is less than or equal to 20.

4 . The glass of claim 1 , wherein when cooled in air from 1100° C. to 500° C. in 15 minutes, the glass does not crystallize.

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

greater than or equal to 23.5 mol. % and less than or equal to 25.5 mol. % P 2 O 5 ,

greater than or equal to 10.0 mol. % and less than or equal to 40.0 mol. % Nb 2 O 5 ,

greater than or equal to 4.5 mol. % and less than or equal to 30.0 mol. % Bi 2 O 3 ,

greater than or equal to 0.3 mol. % and less than or equal to 40.0 mol. % TiO 2 ,

greater than or equal to 0.0 mol. % and less than or equal to 15.0 mol. % B 2 O 3 ,

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. % K 2 O,

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

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

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

greater than or equal to 24.2 mol. % and less than or equal to 25.0 mol. % P 2 O 5 ,

greater than or equal to 16.5 mol. % and less than or equal to 30.5 mol. % Nb 2 O 5 ,

greater than or equal to 13.0 mol. % and less than or equal to 33.0 mol. % TiO 2 ,

greater than or equal to 5.0 mol. % and less than or equal to 23.0 mol. % Bi 2 O 3 ,

greater than or equal to 1.75 mol. % and less than or equal to 8.00 mol. % BaO,

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

greater than or equal to 0.0 mol. % and less than or equal to 7.5 mol. % K 2 O,

greater than or equal to 0 mol. % and less than or equal to 5.75 mol. % Li 2 O and

greater than or equal to 0 mol. % and less than or equal to 5.75 mol. % Na 2 O.

7 . The glass of claim 1 , wherein the composition of the components satisfies the condition:

Alk 2 O+RO+Bi 2 O 3 +3*Al 2 O 3 —P 2 O 5 [mol. %]≥0.000.

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

greater than or equal to 0.1 mol. % Li 2 O and

a sum of Na 2 O+K 2 O is greater than or equal to 0.3 mol. %.

9 . A method for manufacturing an optical element, the method comprising processing a glass, wherein the glass is the glass of claim 1 .

10 . An optical element comprising glass, wherein the glass is the glass of claim 1 .

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

greater than or equal to 23.0 mol. % and less than or equal to 35.0 mol. % P 2 O 5 ,

greater than or equal to 4.5 mol. % and less than or equal to 35.0 mol. % Bi 2 O 3 ,

greater than or equal to 0.5 mol. % and less than or equal to 55.0 mol. % Nb 2 O 5 ,

greater than or equal to 0.5 mol. % and less than or equal to 55.0 mol. % TiO 2 ,

greater than or equal to 0.3 mol. % and less than or equal to 20.0 mol. % Li 2 O and

optionally comprising one or more components selected from BaO, K 2 O, CaO, Na 2 O, SrO, WO 3 , B 2 O 3 , SiO 2 , ZnO, ZrO 2 , MgO, Al 2 O 3 , TeO 2 , PbO, GeO 2 , Tl 2 O, Ag 2 O, CdO, Cs 2 O, Ga 2 O 3 , La 2 O 3 , MoO 3 , Ta 2 O 5 and V 2 O 5 ,

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

wherein the glass satisfies the condition:

P n −(1.14+0.192* Pa )>0.000,

where

P n is 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 =1.865−0.0052736*P 2 O 5 +0.0071201*Nb 2 O 5 +0.0031659*TiO 2 −0.0008032*BaO−0.0047736*K 2 O−0.00076807*CaO−0.0027991*Na 2 O−0.0016514*Li 2 O−0.00069646*SrO+0.0032628*WO 3 +0.007519*Bi 2 O 3 −0.0040698*B 2 O 3 −0.0035951*SiO 2 −0.00067102*ZnO+0.0022313*ZrO 2 −0.0019531*MgO−0.003506*Al 2 O 3 +0.0019216*TeO 2 +0.0025766*PbO−0.0018844*GeO 2 +0.0065444*Tl 2 O+0.0052048*Ag 2 O,  (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 =4.45−0.020780*Al 2 O 3 −0.020918*B 2 O 3 +0.014152*BaO+0.061008*Bi 2 O 3 −0.0067411*CaO+0.013529*CdO+0.012560*Cs 2 O+0.0028892*Ga 2 O 3 −0.0057012*GeO 2 −0.017838*K 2 O+0.046524*La 2 O 3 −0.013919*Li 2 O−0.010279*MgO−0.0064231*MoO 3 −0.012983*Na 2 O+0.0083294*Nb 2 O 5 −0.028926*P 2 O 5 +0.031742*PbO−0.019022*SiO 2 +0.0045214*SrO+0.050158*Ta 2 O 5 +0.0088486*TeO 2 −0.0063053*TiO 2 −0.018941*V 2 O 5 +0.027483*WO 3 −0.0010277*ZnO+0.0100487*ZrO 2 ,  (II)

where an asterisk (*) means multiplication and neither of the parameters P n and Pais modified by the term “about”.

12 . The glass of claim 11 , wherein the glass satisfies the condition:

n d −(1.14+0.192* 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.

13 . The glass of claim 11 , wherein the glass has

an Abbe number, v d , that is less than or equal to 20.

14 . The glass of claim 11 , wherein when cooled in air from 1100° C. to 500° C. in 15 minutes, the glass does not crystallize.

15 . The glass of claim 11 , wherein the composition of the components comprises:

greater than or equal to 23.5 mol. % and less than or equal to 25.5 mol. % P 2 O 5 ,

greater than or equal to 10.0 mol. % and less than or equal to 40.0 mol. % Nb 2 O 5 ,

greater than or equal to 4.5 mol. % and less than or equal to 30.0 mol. % Bi 2 O 3 ,

greater than or equal to 0.5 mol. % and less than or equal to 40.0 mol. % TiO 2 ,

greater than or equal to 0.3 mol. % and less than or equal to 10.0 mol. % Li 2 O,

greater than or equal to 0.0 mol. % and less than or equal to 15.0 mol. % B 2 O 3 ,

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. % K 2 O,

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

greater than or equal to 0.0 mol. % and less than or equal to 10.0 mol. % WO 3 .

16 . The glass of claim 11 , wherein the composition of the components comprises:

greater than or equal to 24.2 mol. % and less than or equal to 25.0 mol. % P 2 O 5 ,

greater than or equal to 16.5 mol. % and less than or equal to 30.5 mol. % Nb 2 O 5 ,

greater than or equal to 13.0 mol. % and less than or equal to 33.0 mol. % TiO 2 ,

greater than or equal to 5.0 mol. % and less than or equal to 23.0 mol. % Bi 2 O 3 ,

greater than or equal to 1.75 mol. % and less than or equal to 8.00 mol. % BaO,

greater than or equal to 0.3 mol. % and less than or equal to 5.8 mol. % Li 2 O,

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

greater than or equal to 0.0 mol. % and less than or equal to 7.5 mol. % K 2 O,

greater than or equal to 0.0 mol. % and less than or equal to 6.0 mol. % WO 3 and

greater than or equal to 0 mol. % and less than or equal to 5.75 mol. % Na 2 O.

17 . The glass of claim 11 , wherein the composition of the components satisfies the condition:

Alk 2 O+RO+Bi 2 O 3 +3*Al 2 O 3 —P 2 O 5 [mol. %]≥0.000,

where chemical formulas mean the content of corresponding components in the glass, Alk 2 O is a total sum of alkali metal oxides and RO is a total sum of divalent metal oxides.

18 . The glass of claim 11 , wherein the composition comprises:

a sum of Na 2 O+K 2 O is greater than or equal to 0.3 mol. %.

19 . The glass of claim 11 , wherein the composition of the components comprises:

greater than or equal to 0.3 mol. % and less than or equal to 20.0 mol. % R 2 O and

greater than or equal to 0.3 mol. % and less than or equal to 20.0 mol. % RO, where R 2 O is a total sum of monovalent metal oxides and RO is a total sum of divalent metal oxides.

20 . An optical element comprising glass, wherein the glass is the glass of claim 11 .