Glasses and glass-ceramics and products made therefrom

Claim 2

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1000 hours and maintains its modulus of rupture of at least about 10,000 psi at such temperatures for said times, said glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 55 - 80 Al.sub.2 O.sub.3 12 - 27 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 + ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 10 and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.65 to 0.97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97.

Claim 3

The thermally crystallizable glass as defined in claim 1, wherein at least 98% by weight of said glass consists of said SiO 2 , Al 2 O 3 , Li 2 O and nucleating agent.

Claim 4

A thermally crystallizable glass as defined in claim 1, wherein said glass contains in weight percent no more than 0.5 K 2 O, or 0.5 Na 2 O, or 0.5 of a mixture of (Na 2 O+K 2 O).

Claim 5

A thermally crystallizable glass as defined in claim 1, wherein said glass contains in weight percent no more than 0.25 K 2 O, or 0.25 Na 2 O, or 0.25 of a mixture of (Na 2 O+K 2 O).

Claim 6

The thermally crystallizable glass as defined in claim 1, wherein said glass consists of said SiO 2 , Al 2 O 3 , Li 2 O and nucleating agent.

Claim 7

The thermally crystallizable glass as defined in claim 1, wherein ZrO 2 is present in an amount of 0.5 to 2.8 weight percent of said composition.

Claim 8

A glass-ceramic article thermally stable at temperatures of about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 55 - 80 Al.sub.2 O.sub.3 12 - 27 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 + ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 10, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.65 to 0.97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97, said glass-ceramic article having a coefficient of linear thermal expansion of -12 to +12 × 10.sup. -7 (0°-700°C).

Claim 9

A glass-ceramic article thermally stable at temperatures of about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 55 - 80 Al.sub.2 O.sub.3 12 - 27 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 + ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 10, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.65 to 0.97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97, said glass-ceramic article having a coefficient of linear thermal expansion of -12 to +12 × 10.sup. -7 (0°-700°C).

Claim 10

The glass-ceramic article as defined in claim 7, wherein at least 98% by weight of said glass-ceramic consists of said SiO 2 , Al 2 O 3 , Li 2 O and nucleating agent.

Claim 11

A glass-ceramic article as defined in claim 7, wherein said glass-ceramic contains in weight percent no more than 0.5 K 2 O, or 0.5 Na 2 O, or 0.5 of a mixture of (Na 2 O+K 2 O).

Claim 12

A glass-ceramic article as defined in claim 7, which is thermally stable at temperatures of about 1,900°F for at least 1000 hours, wherein said glass-ceramic contains in weight percent no more than 0.25 K 2 O, or 0.25 Na 2 O, or 0.25 of a mixture of (Na 2 O+K 2 O).

Claim 13

The glass-ceramic article as defined in claim 7, wherein said glass-ceramic consists of said SiO 2 , Al 2 O 3 , Li 2 O and nucleating agent.

Claim 14

The glass-ceramic article as defined in claim 7, wherein ZrO 2 is present in an amount of 0.5 to 2.8 weight percent of said composition.

Claim 15

The glass-ceramic article as defined in claim 7, wherein said glass-ceramic has a coefficient of linear thermal expansion of -3 to +3×10.sup. -7 (0°-700°C.).

Claim 16

The glass-ceramic article as defined in claim 7, wherein said glass-ceramic has a coefficient of linear thermal expansion of -0.5 to +0.5×10.sup. -7 (0°-700°C.).

Claim 17

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours and maintains its modulus of rupture of at least 10,000 psi at such temperatures for said times, said glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 63 - 78.5 Al.sub.2 O.sub.3 13.8 - 23 Li.sub.2 O 3.5 - 6.5 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 plus ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent but is at least 0.5 weight percent, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 9, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 7.5 to less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97.

Claim 18

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours and maintains its modulus of rupture of at least 10,000 psi at such temperatures for said times, said glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 63 - 78.5 Al.sub.2 O.sub.3 13.8 - 23 Li.sub.2 O 3.5 - 6.5 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 plus ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent but is at least 0.5 weight percent, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 9, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 7.5 to less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97.

Claim 19

A glass-ceramic article thermally stable at temperatures of about 1,900°F for at least 1,000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 63 - 78.5 Al.sub.2 O.sub.3 13.8 - 23 Li.sub.2 O 3.5 - 6.5 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 plus ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent but is at least 0.5 weight percent, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 9, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 7.5 to less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97, said glass-ceramic having a coefficient of linear thermal expansion of -12 to +12 × 10.sup. -7 (0°-700°C).

Claim 20

A glass-ceramic article thermally stable at temperatures of about 1,900°F for at least 1,000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 63 - 78.5 Al.sub.2 O.sub.3 13.8 - 23 Li.sub.2 O 3.5 - 6.5 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 plus ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent but is at least 0.5 weight percent, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 9, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to less than 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 7.5 to less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97, said glass-ceramic having a coefficient of linear thermal expansion of -12 to +12 × 10.sup. -7 (0°-700°C).

Claim 21

A glass-ceramic article thermally stable at temperatures of about 1,900°F for at least 1000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 62.8 - 80 Al.sub.2 O.sub.3 12.7 - 26.7 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 + ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 10, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.65 to 0.97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97, said glass-ceramic article having a coefficient of linear thermal expansion of -12 to +12 × 10.sup. -7 (0°-700°C).

Claim 22

A glass-ceramic article thermally stable at temperatures of about 1,900°F for at least 1000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 62.8 - 80 Al.sub.2 O.sub.3 12.7 - 26.7 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 + ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 10, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.65 to 0.97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97, said glass-ceramic article having a coefficient of linear thermal expansion of -12 to +12 × 10.sup. -7 (0°-700°C).

Claim 23

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1000 hours, said glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and the ZnO + Li 2 O/Al 2 O 3 molar ratio is ≦ 1, and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/A 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O).

Claim 24

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1000 hours, said glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and the ZnO + Li 2 O/Al 2 O 3 molar ratio is ≦ 1, and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/A 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O).

Claim 25

The thermally crystallizable glass as defined in claim 18 wherein at least 98% by weight of said glass consists of said SiO 2 , Al 2 O 3 , Li 2 O, ZnO and nucleating agent.

Claim 26

The thermally crystallizable glass as defined in claim 18 wherein the nucleating agent is a mixture of ZrO 2 plus TiO 2 and said ZrO 2 is present in an amount of 0.5 to 2.8 weight percent of said composition.

Claim 27

A glass-ceramic article dimensionally stable at temperatures up to about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 13,00 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the ZnO + Li 2 O/Al 2 O 3 molar ratio is ≦ 1, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8; up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass and resulting glass-ceramic contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O), said glass-ceramic having a coefficient of linear thermal expansion of -12 to +12 × 10 - 7 (0°-700°C).

Claim 28

A glass-ceramic article dimensionally stable at temperatures up to about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 13,00 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting essentially of the following ingredients Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the ZnO + Li 2 O/Al 2 O 3 molar ratio is ≦ 1, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8; up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass and resulting glass-ceramic contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O), said glass-ceramic having a coefficient of linear thermal expansion of -12 to +12 × 10 - 7 (0°-700°C).

Claim 29

The glass-ceramic article as defined in claim 21 wherein at least 98% by weight of said glass-ceramic consists of said SiO 2 , Al 2 O 3 , Li 2 O, ZnO and nucleating agent.

Claim 30

The glass-ceramic article as defined in claim 21 wherein the nucleating agent is a mixture of ZrO 2 plus TiO 2 and said ZrO 2 is present in an amount of 0.5 to 2.8 weight percent of said composition.

Claim 31

The glass-ceramic article as defined in claim 21 wherein said glass-ceramic has a coefficient of linear thermal expansion of -3 to +3 ×10 - 7 (0°-700° C.).

Claim 32

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours, said glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 58.2 - 78.4 Al.sub.2 O.sub.3 13.7 - 26.5 Li.sub.2 O 3.2 - 6.9 ZnO 0.3 - 6.5 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and the ZnO + Li 2 O/Al 2 O 3 molar ratio is ≦ 1, and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio from 0.04 to 0.5; and c. when the SiO 2 O/Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O).

Claim 33

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours, said glass consisting essentially of the following ingredients: Ingredients Weight Percent ______________________________________ SiO.sub.2 58.2 - 78.4 Al.sub.2 O.sub.3 13.7 - 26.5 Li.sub.2 O 3.2 - 6.9 ZnO 0.3 - 6.5 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and the ZnO + Li 2 O/Al 2 O 3 molar ratio is ≦ 1, and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio from 0.04 to 0.5; and c. when the SiO 2 O/Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O).

Claim 34

The thermally crystallizable glass as defined in claim 25 wherein at least 98% by weight of said glass consists of said SiO 2 , Al 2 O 3 , ZnO and nucleating agent.

Claim 35

A thermally crystallizable glass according to claim 18 capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,900°F for at least 1,000 hours, said glass being selected from the group consisting of A. glass having a. a SiO 2 /Al 2 O 3 molar ratio of 5-8 b. a Li 2 O/Al 2 O 3 molar ratio of 0.55 to 0.75, and c. a ZnO/Li 2 O molar ratio of 0.04 - 0.5 B. a glass having a. a SiO 2 /Al 2 O 3 molar ratio of 4 to less than 5 b. a Li 2 O/Al 2 O 3 molar ratio of 0.55 - 0.75, and c. a ZnO/Li 2 O molar ratio of 0.06 - 0.5.

Claim 36

The glass-ceramic article of claim 16 wherein said ceramic has a dimensional stability of less than 250 parts per million after being subjected to a temperature of 1,900°F for at least 1,000 hours.

Claim 37

The glass-ceramic article of claim 21 wherein said ceramic has a dimensional stability of less than 250 parts per million after being subjected to a temperature of 1,500°F for at least 1,000 hours.

Claim 38

The glass-ceramic article of claim 29 wherein said dimensional stability is retained after said article is subjected to said 1,500°F temperature for 2,000 hours.

Claim 39

A glass-ceramic according to claim 21 dimensionally stable at temperatures of about 1,900°F for at least 1,000 hours and maintaining its modulus of rupture of at least 13,000 psi when subjected to such temperatures for said times, said article being formed by thermally in situ crystallizing a glass selected from the group consisting of A. a glass having a. SiO 2 /Al 2 O 3 molar ratio of 5-8 b. a Li 2 O/Al 2 O 3 molar ratio of 0.55 to 0.75 c. a ZnO/Li 2 O molar ratio of 0.04 - 0.5, and d. a ZnO+Li 2 O/Al 2 O 3 molar ratio ≦ 1; and B. a glass having a. a SiO 2 /Al 2 O 3 molar ratio of 4 to less than 5 b. a Li 2 O/Al 2 O 3 molar ratio of 0.55 - 0.75 c. a ZnO/Li 2 O molar ratio of 0.06 - 0.5, and d. a ZnO+Li 2 O/Al 2 O 3 molar ratio ≦ 1 said glass-ceramic having a coefficient of linear thermal expansion of -12 to +12 ×10 - 7 (0°-700°C.).

Claim 40

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours and maintains its modulus of repture of at least about 10,000 psi at such temperatures for said times, said glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 55 - 80 Al.sub.2 O.sub.3 12 - 27 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO.sub.2 + ZrO.sub.2, wherein the ZrO.sub.2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio is from 4 to 10 and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.65 to 0.97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, to Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97.

Claim 41

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours and maintains its modulus of repture of at least about 10,000 psi at such temperatures for said times, said glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 55 - 80 Al.sub.2 O.sub.3 12 - 27 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO.sub.2 + ZrO.sub.2, wherein the ZrO.sub.2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio is from 4 to 10 and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5, the Li 2 O/Al 2 O 3 molar ratio is from 0.65 to 0.97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, to Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97.

Claim 42

A glass-ceramic article thermally stable at temperatures of about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 55 - 80 Al.sub.2 O.sub.3 15 - 27 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 + ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 10, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5 the Li 2 O/Al 2 O 3 molar ratio is from 0.67 to 97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97. said glass-ceramic article having a coefficient of linear thermal expansion of -12 to +12 × 10 - 7 (0°-700°C).

Claim 43

A glass-ceramic article thermally stable at temperatures of about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 10,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 55 - 80 Al.sub.2 O.sub.3 15 - 27 Li.sub.2 O 3.2 - 7.6 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is a mixture of TiO 2 + ZrO 2 , wherein the ZrO 2 does not exceed 3 weight percent, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 10, and wherein a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.75 to 0.97; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 7.5 the Li 2 O/Al 2 O 3 molar ratio is from 0.67 to 97; and c. when the SiO 2 /Al 2 O 3 molar ratio is more than 7.5 and less than 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.97; and d. when the SiO 2 /Al 2 O 3 molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3 molar ratio is from 0.87 to 0.97. said glass-ceramic article having a coefficient of linear thermal expansion of -12 to +12 × 10 - 7 (0°-700°C).

Claim 44

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours, said glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and the ZnO + Li 2 O/Al 2 O 3 molar ratio is 1, and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O).

Claim 45

A thermally crystallizable glass capable of being thermally in situ crystallized to a glass-ceramic which is thermally stable at temperatures of about 1,500°F for at least 1,000 hours, said glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and the ZnO + Li 2 O/Al 2 O 3 molar ratio is 1, and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93, and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O, or 0.2 (Na 2 O + K 2 O).

Claim 46

A glass-ceramic article dimensionally stable at temperatures up to about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 13,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the ZnO + Li 2 O/Al 2 O 3 molar ratio is 1, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass resulting glass-ceramic contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O or 0.2 (Na 2 O + K 2 O). said glass-ceramic having a coefficient of linear thermal expansion of -12 to +12 × 10 - 7 (0°-700°C).

Claim 47

A glass-ceramic article dimensionally stable at temperatures up to about 1,500°F for at least 1,000 hours and retaining its modulus of rupture of at least about 13,000 psi when subjected to said temperatures for said times, said article being formed by thermally in situ crystallizing a glass consisting of the following ingredients, exclusive of fining agents: Ingredients Weight Percent ______________________________________ SiO.sub.2 52 - 78.4 Al.sub.2 O.sub.3 12.8 - 27.5 Li.sub.2 O 2.4 - 7 ZnO 0.25 - 6.7 Nucleating Agent 3 - 9 ______________________________________ wherein said nucleating agent is selected from the group consisting of ZrO 2 and a mixture of TiO 2 and ZrO 2 and wherein the ZrO 2 is present in an amount not in excess of 3% by weight, but is at least 0.5 weight percent, wherein the ZnO + Li 2 O/Al 2 O 3 molar ratio is 1, and wherein the SiO 2 /Al 2 O 3 molar ratio is from 4 to 9 and a. when the SiO 2 /Al 2 O 3 molar ratio is from 4 to less than 5, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.91, and the ZnO/Li 2 O molar ratio is from 0.06 to 0.5; and b. when the SiO 2 /Al 2 O 3 molar ratio is from 5 to 8, the Li 2 O/Al 2 O 3 molar ratio is from 0.55 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and c. when the SiO 2 /Al 2 O 3 molar ratio is from more than 8 up to 9, the Li 2 O/Al 2 O 3 molar ratio is from 0.8 to 0.93 and the ZnO/Li 2 O molar ratio is from 0.04 to 0.5; and d. the glass resulting glass-ceramic contains in weight percent no more than 0.2 K 2 O, or 0.2 Na 2 O or 0.2 (Na 2 O + K 2 O). said glass-ceramic having a coefficient of linear thermal expansion of -12 to +12 × 10 - 7 (0°-700°C).