LI2O-AL2O3-SIO2-BASED CRYSTALLIZED GLASS

Abstract

Provided is a Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass that has a high permeability to light in a ultraviolet to infrared range and is less likely to be broken. A Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass contains, in terms of % by mass, 40 to 90% Si.sub.O2, 5 to 30% Al.sub.2O.sub.3, 1 to 10% Li.sub.2O, 0 to 20% SnO.sub.2, 0 to 5% ZrO.sub.2, 0 to 10% MgO, 0 to 10% P.sub.2O.sub.5, and 0 to 4% TiO.sub.2 and a mass ratio of Li.sub.2O/(MgO+CaO+SrO+BaO+Na.sub.2O+K.sub.2O) is 3 or less.

Claims

1. A Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass containing, in terms of % by mass, 40 to 90% SiO.sub.2, 5 to 30% Al.sub.2O.sub.3, 1 to 10% Li.sub.2O, 0 to 20% SnO.sub.2, 0 to 5% ZrO.sub.2, 0 to 10% MgO, 0 to 10% CaO, 0 to 10% SrO, 0 to 10% BaO, 0 to 10% Na.sub.2O, 0 to 10% K.sub.2O, 0 to 10% P.sub.2O.sub.5, and 0 to 4% TiO.sub.2, a mass ratio of Li.sub.2O/(MgO+CaO+SrO+BaO+Na.sub.2O+K.sub.20) being 3 or less.

2. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, further containing, in terms of % by mass, 0 to 10% ZnO and 0 to 10% B.sub.2O.sub.3.

3. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, further containing, in terms of % by mass, 0.10% or less Fe.sub.2O.sub.3.

4. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of MgO/(Li.sub.2O+MgO) is 0.15 or more.

5. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, containing, in terms of % by mass, 2% or more MgO+CaO+SrO+BaO+Na.sub.2O+K.sub.2O.

6. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, containing, in terms of % by mass, 1.5 to 6.7% ZrO.sub.2+TiO.sub.2.

7. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of (SiO.sub.2+Al.sub.2O.sub.3+Li.sub.2O)/SiO.sub.2 is less than 1.553.

8. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of (SiO.sub.2+Al.sub.2O.sub.3+Li.sub.2O)/Al.sub.2O.sub.3 is more than 3.251.

9. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of ZrO.sub.2/Li.sub.2O is 0.4 or more.

10. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of SnO.sub.2/(SnO.sub.2+TiO.sub.2) is 0.092 or more.

11. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of ZnO/(ZnO+MgO) is 0.9 or less.

12. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of Al.sub.2O.sub.3/(SnO.sub.2+ZrO.sub.2) is more than 7.1.

13. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of (Li.sub.2O+Na.sub.2O+K.sub.2O)/ZrO.sub.2 is 3.0 or less.

14. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of TiO.sub.2/ZrO.sub.2 is 0.0001 to 5.0.

15. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a mass ratio of TiO.sub.2/(TiO.sub.2+Fe.sub.2O.sub.3) is 0.001 to 0.999.

16. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, containing, in terms of % by mass, less than 0.05% HfO.sub.2+Ta.sub.2O.sub.5.

17. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, containing, in terms of % by mass, 7 ppm or less Pt.

18. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, containing, in terms of % by mass, 7 ppm or less Rh.

19. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, containing, in terms of % by mass, 9 ppm or less Pt+Rh.

20. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, wherein a β-quartz solid solution is precipitated as a major crystalline phase.

21. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a coefficient of thermal expansion of −20×10.sup.−7/° C. to 30×10.sup.−7/° C. at 20 to 200° C.

22. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a coefficient of thermal expansion of −20×10.sup.−7/° C. to 30×10.sup.−7/° C. at 20 to 380° C.

23. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a coefficient of thermal expansion of −20×10.sup.−7/° C. to 30×10.sup.−7/° C. at 20 to 750° C.

24. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a transparent appearance.

25. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a transmittance of 1% or more at a thickness of 2 mm and a wavelength of 360 nm.

26. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a transmittance of 10% or more at a thickness of 2 mm and a wavelength of 555 nm.

27. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a transmittance of 35% or more at a thickness of 2 mm and a wavelength of 1200 nm.

28. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a liquidus temperature of 1500° C. or below.

29. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a rate of density change of 1.1 to 10% between before and after crystallization.

30. The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to claim 1, having a transmittance of 1% or more at a thickness of 2 mm and a wavelength of 360 nm and a coefficient of thermal expansion of −10×10.sup.−7/° C. to 30×10.sup.−7/° C. at 20 to 200° C.

Description

EXAMPLES

[0103] Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. Tables 1 to 8 show examples (Samples Nos. 1 to 16) of the present invention.

TABLE-US-00001 TABLE 1 No. 1 No. 2 No. 3 No. 4 Composition SiO.sub.2 65.60 65.80 65.80 63.60 [% by mass] Al.sub.2O.sub.3 22.30 22.30 22.30 22.30 Li.sub.2O 2.70 2.50 2.30 3.70 Na.sub.2O 0.32 0.32 0.32 1.30 K.sub.2O 0.26 0.26 0.27 0.26 MgO 1.66 1.82 2.02 1.66 CaO 0.02 0.02 0.00 0.02 SrO 0.00 0.00 0.00 0.00 BaO 1.16 1.17 1.17 1.16 ZnO 0.00 0.00 0.00 0.00 SnO.sub.2 0.28 0.27 0.27 0.28 ZrO.sub.2 2.17 2.15 2.16 2.17 TiO.sub.2 1.96 1.96 1.95 1.96 P.sub.2O.sub.5 1.39 1.42 1.42 1.38 B.sub.2O.sub.3 0.00 0.00 0.00 0.001 Fe.sub.2O.sub.3 0.007 0.007 0.007 0.007 Composition Pt 1.51 1.48 1.63 1.53 [ppm] Rh 0.03 0.02 0.001 0.03 Pt + Rh 1.54 1.5 1.631 1.56 Mg/(Li + Mg) 0.381 0.421 0.468 0.310 Li/(Mg + Ca + Sr + Ba + Na + K) 0.790 0.697 0.608 0.841 Mg + Ca + Sr + Ba + Na + K 3.418 3.586 3.780 4.398 Al/(Sn + Zr) 9.102 9.215 9.177 9.102 (Li + Na + K)/Zr 1.512 1.433 1.338 2.424 Ti/Zr 0.903 0.912 0.903 0.903 Ti/(Ti + Fe) 0.996 0.996 0.996 0.996 Zr + Ti 4.13 4.11 4.11 4.13 Zr/Li 0.804 0.860 0.939 0.586 Sn/(Sn + Ti) 0.125 0.121 0.122 0.125 Zn/(Zn + Mg) 0.000 0.000 0.000 0.000 (Si + Al + Li)/Si 1.381 1.377 1.374 1.409 (Si + Al + Li)/Al 4.063 4.063 4.054 4.018 Before Crystallization Liquidus Temperature [° C.] 1423 1435 unmeasured 1314 Liquidus Viscosity [—] 3.52 3.46 unmeasured 3.90 Primary Phase ZrO2 mullite unmeasured ZrO2 Density [g/cm.sup.3] 2.446 2.450 2.452 2.455 Low-Temperature Strain Point [° C.] 681 648 688 650 Viscosity Annealing Point [° C.] 738 741 745 724 High-Temperature 10{circumflex over ( )}4[° C.] 1344 1345 1347 1298 Viscosity 10{circumflex over ( )}3[° C.] 1521 1519 1521 1476   10{circumflex over ( )}2.5[° C.] 1632 1629 1629 1587 10{circumflex over ( )}2[° C.] 1765 1761 1757 1720 Transmittance [%]  350 nm 77.6 unmeasured unmeasured 76.7 2 mm thick  360 nm 82.7 unmeasured unmeasured 82.1  370 nm 85.7 unmeasured unmeasured 85.2  380 nm 87.6 unmeasured unmeasured 87.3  555 nm 91.3 unmeasured unmeasured 91.4  800 nm 91.5 unmeasured unmeasured 91.5 1070 nm 91.7 unmeasured unmeasured 91.7 1200 nm 91.7 unmeasured unmeasured 91.7 L* 96.5 unmeasured unmeasured 96.5 a* −0.1 unmeasured unmeasured −0.1 b* 0.5 unmeasured unmeasured 0.5

TABLE-US-00002 TABLE 2 No. 1 No. 2 No. 3 No. 4 After Crystallization Heat Treatment Conditions 780° C.-1.5 h 890° C.-1 h Density [g/cm.sup.3] 2.551 2.557 2.561 2.512 Transmittance [%]  350 nm 33.9 33.4 32.6 8.0 2 mm thick  360 nm 58.6 57.0 55.3 26.3  370 nm 69.1 67.2 65.0 41.4  380 nm 74.6 72.7 70.4 53.5  555 nm 88.6 88.0 87.0 88.5  800 nm 90.5 90.3 90.1 90.8 1070 nm 91.1 91.1 91.0 91.2 1200 nm 91.1 91.1 91.0 91.2 L* 95.3 95.0 94.6 95.1 a* −0.3 −0.3 −0.3 −0.8 b* 2.2 2.7 3.3 3.6 Precipitated Crystals β-quartz β-quartz β-quartz β-quartz solid solution solid solution solid solution solid solution α[×10.sup.−7/° C.] 20-200° C. 9.1 11.7 13.6 9.5 20-380° C. 10.1 12.7 14.7 12.7 20-750° C. 10.1 12.3 14.1 14.2 Young's Modulus [GPa] 93 unmeasured unmeasured unmeasured Modulus of Rigidity [GPa] 38 unmeasured unmeasured unmeasured Poisson’s Ratio 0.22 unmeasured unmeasured unmeasured Breakage good good good good Transparency good good good good Rate of Density Change 4.3 4.4 4.4 2.3 between Before and After Crystallization [%] Rate of Transmittance Change between Before and After Crystallization [%]  350 nm 56.3 unmeasured unmeasured 89.5  360 nm 29.1 unmeasured unmeasured 68.0  370 nm 19.4 unmeasured unmeasured 51.4  380 nm 14.8 unmeasured unmeasured 38.7  555 nm 2.9 unmeasured unmeasured 3.1  800 nm 1.0 unmeasured unmeasured 0.8 1070 nm 0.6 unmeasured unmeasured 0.5 1200 nm 0.6 unmeasured unmeasured 0.5

TABLE-US-00003 TABLE 3 No. 5 No. 6 No. 7 No. 8 Composition SiO.sub.2 66.00 65.80 65.40 65.80 [% by mass] Al.sub.2O.sub.3 21.90 21.90 21.70 21.90 Li.sub.2O 3.24 3.23 3.21 3.23 Na.sub.2O 0.33 1.30 0.32 0.32 K.sub.2O 0.26 0.26 1.70 0.26 MgO 1.26 0.66 0.66 0.65 CaO 0.02 0.02 0.02 0.02 SrO 0.00 0.01 0.00 0.10 BaO 1.17 1.17 1.16 1.17 ZnO 0.01 0.00 0.00 0.00 SnO.sub.2 0.27 0.27 0.27 0.27 ZrO.sub.2 2.16 2.12 2.14 2.14 TiO.sub.2 1.96 1.94 1.93 1.95 P.sub.2O.sub.5 1.41 1.41 1.39 1.40 B.sub.2O.sub.3 0.00 0.00 0.00 0.00 Fe.sub.2O.sub.3 0.007 0.007 0.007 0.007 Composition Pt 1.55 1.51 1.44 1.51 [ppm] Rh 0.03 0.04 0.04 0.04 Pt + Rh 1.58 1.55 1.48 1.55 Mg/(Li + Mg) 0.280 0.170 0.171 0.168 Li/(Mg + Ca + Sr + Ba + Na + K) 1.067 0.946 0.832 1.284 Mg + Ca + Sr + Ba + Na + K 3.036 3.416 3.856 2.516 Al/(Sn + Zr) 9.012 9.163 9.004 9.087 (Li + Na + K)/Zr 1.773 2.259 2.444 1.780 Ti/Zr 0.907 0.915 0.902 0.911 Ti/(Ti + Fe) 0.996 0.996 0.996 0.996 Zr + Ti 4.12 4.06 4.07 4.09 Zr/Li 0.667 0.656 0.667 0.663 Sn/(Sn + Ti) 0.121 0.122 0.123 0.122 Zn/(Zn + Mg) 0.008 0.000 0.000 0.000 (Si + Al + Li)/Si 1.381 1.382 1.381 1.382 (Si + Al + Li)/Al 4.162 4.152 4.162 4.152 Before Crystallization Liquidus Temperature [° C.] unmeasured unmeasured unmeasured unmeasured Liquidus Viscosity [—] unmeasured unmeasured unmeasured unmeasured Primary Phase unmeasured unmeasured unmeasured unmeasured Density [g/cm.sup.3] 2.440 2.435 2.443 2.432 Low-Temperature Strain Point [° C.] 672 670 674 671 Viscosity Annealing Point [° C.] 730 728 732 730 High- 10{circumflex over ( )}4[° C.] 1340 1353 1346 1359 Temperature  10{circumflex over ( )}3[° C.] 1519 1535 1526 1542 Viscosity   10{circumflex over ( )}2.5[° C.] 1631 1648 1640 1655 10{circumflex over ( )}2[° C.] 1763 1780 1775 1787 Transmittance  350 nm unmeasured unmeasured unmeasured unmeasured [° C.]  360 nm unmeasured unmeasured unmeasured unmeasured 2 mm thick  370 nm unmeasured unmeasured unmeasured unmeasured  380 nm unmeasured unmeasured unmeasured unmeasured  555 nm unmeasured unmeasured unmeasured unmeasured  800 nm unmeasured unmeasured unmeasured unmeasured 1070 nm unmeasured unmeasured unmeasured unmeasured 1200 nm unmeasured unmeasured unmeasured unmeasured L* unmeasured unmeasured unmeasured unmeasured a* unmeasured unmeasured unmeasured unmeasured b* unmeasured unmeasured unmeasured unmeasured

TABLE-US-00004 TABLE 4 No. 5 No. 6 No. 7 No. 8 After Crystallization Heat Treatment Conditions 780° C.-1.5 h 890° C.-1 h Density [g/cm.sup.3] 2.535 2.502 2.533 2.489 Transmittance [%]  350 nm 26.5 24.9 31.8 20.0 2 mm thick  360 nm 54.6 47.2 60.4 37.7  370 nm 67.7 58.5 72.0 48.1  380 nm 74.6 65.4 77.5 55.3  555 nm 89.5 87.1 89.4 84.2  800 nm 90.8 90.4 90.8 89.9 1070 nm 91.3 91.2 91.2 91.3 1200 nm 91.3 91.2 91.2 91.3 L* 95.7 94.6 95.7 93.3 a* −0.3 −0.5 −0.2 −0.6 b* 1.7 4.1 1.6 6.5 Precipitated Crystals β-quartz β-quartz β-quartz β-quartz solid solution solid solution solid solution solid solution α[×10.sup.−7/° C.] 20-200° C. 3.6 4.9 2.4 6.2 20-380° C. 4.9 6.2 2.9 7.8 20-750° C. 4.8 7.7 3.8 9.4 Young's Modulus [GPa] unmeasured unmeasured unmeasured unmeasured Modulus of Rigidity [GPa] unmeasured unmeasured unmeasured unmeasured Poisson's Ratio unmeasured unmeasured unmeasured unmeasured Breakage good good good good Transparency good good good good Rate of Density Change between 3.9 −99.8 −99.8 −99.8 Before and After Crvstallization [%] Rate of Transmittance Change between Before and After Crystallization [%]  350 nm unmeasured unmeasured unmeasured unmeasured  360 nm unmeasured unmeasured unmeasured unmeasured  370 nm unmeasured unmeasured unmeasured unmeasured  380 nm unmeasured unmeasured unmeasured unmeasured  555 nm unmeasured unmeasured unmeasured unmeasured  800 nm unmeasured unmeasured unmeasured unmeasured 1070 nm unmeasured unmeasured unmeasured unmeasured 1200 nm unmeasured unmeasured unmeasured unmeasured

TABLE-US-00005 TABLE 5 No. 9 No. 10 No. 11 No. 12 Composition SiO.sub.2 64.13 64.61 66.90 64.00 [% by mass] Al.sub.2O.sub.3 21.77 21.93 23.30 24.20 Li.sub.2O 3.59 3.62 2.67 3.51 Na.sub.2O 0.40 0.40 0.40 0.45 K.sub.2O 0.29 0.29 0.00 0.30 MgO 1.63 1.18 1.68 0.68 CaO 1.01 0.73 0.02 0.01 SrO 0.00 0.00 0.00 1.14 BaO 1.18 1.19 1.18 0.00 ZnO 0.00 0.00 0.02 0.61 SnO.sub.2 0.28 0.28 0.63 1.15 ZrO.sub.2 2.16 2.17 2.62 2.23 TiO.sub.2 1.96 1.98 0.02 0.25 P.sub.2O.sub.5 1.37 1.38 1.40 1.38 B.sub.2O.sub.3 0.00 0.00 0.00 0.00 Fe.sub.2O.sub.3 0.014 0.014 0.007 0.007 Composition Pt 1.44 1.51 1.55 0.01 [ppm] Rh 0.04 0.04 0.03 0.01 Pt + Rh 1.48 1.55 1.58 0.02 Mg/(Li + Mg) 0.312 0.246 0.386 0.162 Li/(Mg + Ca + Sr + Ba + Na + K) 0.796 0.955 0.816 1.360 Mg + Ca + Sr + Ba + Na + K 4.510 3.790 3.274 2.580 Al/(Sn + Zr) 8.922 8.951 7.169 7.160 (Li + Na + K)/Zr 1.981 1.986 1.170 1.910 Ti/Zr 0.907 0.912 0.008 0.112 Ti/(Ti + Fe) 0.993 0.993 0.741 0.973 Zr + Ti 4.12 4.15 2.64 2.48 Zr/Li 0.602 0.599 0.981 0.635 Sn/(Sn + Ti) 0.125 0.124 0.969 0.821 Zn/(Zn + Mg) 0.000 0.000 0.012 0.473 (Si + Al + Li)/Si 1.395 1.395 1.388 1.433 (Si + Al + Li)/Al 4.111 4.111 3.986 3.790 Before Crystallization Liquidus Temperature [° C.] unmeasured unmeasured 1416 unmeasured Liquidus Viscosity [—] unmeasured unmeasured 3.71 unmeasured Primary Phase unmeasured unmeasured ZrO2 unmeasured Density [g/cm.sup.3] 2.450 2.450 2.447 unmeasured Low-Temperature Strain Point [° C.] unmeasured unmeasured 691 unmeasured Viscosity Annealing Point [° C.] unmeasured unmeasured 750 unmeasured High- 10{circumflex over ( )}4[° C.] unmeasured unmeasured 1369 1340 Temperature 10{circumflex over ( )}3[° C.] unmeasured unmeasured 1548 1518 Viscosity   10{circumflex over ( )}2.5[° C.] unmeasured unmeasured 1661 1631 10{circumflex over ( )}2[° C.] unmeasured unmeasured 1795 1768 Transmittance  350 nm unmeasured unmeasured 0.0 unmeasured [%]  360 nm unmeasured unmeasured 0.0 unmeasured 2 mm thick  370 nm unmeasured unmeasured 0.0 unmeasured  380 nm unmeasured unmeasured 0.0 unmeasured  555 nm unmeasured unmeasured 0.0 unmeasured  800 nm unmeasured unmeasured 0.0 unmeasured 1070 nm unmeasured unmeasured 0.0 unmeasured 1200 nm unmeasured unmeasured 0.0 unmeasured L* unmeasured unmeasured 96.6 unmeasured a* unmeasured unmeasured 0.0 unmeasured b* unmeasured unmeasured 0.2 unmeasured

TABLE-US-00006 TABLE 6 No. 9 No. 10 No. 11 No. 12 After Crystallization Heat Treatment Conditions 780° C.-1.5 h 840° C.-3 h 810° C.-10 h 890° C.-1 h 920° C.-1 h 920° C.-3 h  Density [g/cm.sup.3] unmeasured unmeasured 2.543 unmeasured Transmittance  350 nm unmeasured unmeasured 65.2 0.0 [%]  360 nm unmeasured unmeasured 67.7 unmeasured 2 mm thick  370 nm unmeasured unmeasured 69.6 unmeasured  880 nm unmeasured unmeasured 71.3 unmeasured  555 nm unmeasured unmeasured 71.3 unmeasured  800 nm unmeasured unmeasured 84.9 unmeasured 1070 nm unmeasured unmeasured 89.9 unmeasured 1200 nm unmeasured unmeasured 90.4 0.0 L* unmeasured unmeasured 93.7 unmeasured a* unmeasured unmeasured −0.3 unmeasured b* unmeasured unmeasured 4.1 unmeasured Precipitated Crystals β-quartz β-quartz β-quartz β-quartz solid solution solid solution solid solution solid solution α[×10.sup.−7/° C.] 20-200° C. 2.7 6.7 8.1 unmeasured 20-380° C. 3.4 8.4 8.2 unmeasured 20-750° C. 4.7 9.4 7.2 unmeasured Young’s Modulus [GPa] unmeasured unmeasured unmeasured unmeasured Modulus of Rigidity [GPa] unmeasured unmeasured unmeasured unmeasured Poisson's Ratio unmeasured unmeasured unmeasured unmeasured Breakage good good good good Transparency good good good good Rate of Density Change between unmeasured unmeasured 3.9 unmeasured Before and After Crystallization [%] Rate of Transmittance Change between Before and After Crystallization [%]  350 nm unmeasured unmeasured 25.7 unmeasured  360 nm unmeasured unmeasured 24.1 unmeasured  370 nm unmeasured unmeasured 22.6 unmeasured  380 nm unmeasured unmeasured 21.2 unmeasured  555 nm unmeasured unmeasured 22.0 unmeasured  800 nm unmeasured unmeasured 7.1 unmeasured 1070 nm unmeasured unmeasured 1.4 unmeasured 1200 nm unmeasured unmeasured 1.1 unmeasured

TABLE-US-00007 TABLE 7 No. 13 No. 14 No. 15 No. 16 Composition SiO.sub.2 65.90 65.90 65.90 65.90 [% by mass] Al.sub.2O.sub.3 22.40 22.40 22.40 22.40 Li.sub.2O 2.70 2.70 2.70 2.70 Na.sub.2O 0.31 0.31 0.31 0.31 K.sub.2O 0.26 0.26 0.26 0.26 MgO 1.63 1.63 1.63 1.63 CaO 0.00 0.00 0.00 0.00 SrO 0.00 0.00 0.00 0.00 BaO 1.14 1.14 1.14 1.14 ZnO 0.00 0.00 0.00 0.00 SnO.sub.2 0.23 0.23 0.23 0.23 ZrO.sub.2 2.10 2.10 2.10 2.10 TiO.sub.2 1.93 1.93 1.93 1.93 P.sub.2O.sub.5 1.39 1.39 1.39 1.39 B.sub.2O.sub.3 0.00 0.00 0.00 0.00 Fe.sub.2O.sub.3 0.006 0.006 0.006 0.006 Composition Pt 0.32 0.57 0.74 1.2 [ppm] Rh 0.01 0.01 0.43 0.44 Pt + Rh 0.33 0.58 1.17 1.64 Mg/(Li + Mg) 0.376 0.376 0.376 0.376 Li/(Mg + Ca + Sr + Ba + Na + K) 0.808 0.808 0.808 0.808 Mg + Ca + Sr + Ba + Na + K 3.340 3.340 3.340 3.340 Al/(Sn + Zr) 9.614 9.614 9.614 9.614 (Li + Na + K)/Zr 1.557 1.557 1.557 1.557 Ti/Zr 0.919 0.919 0.919 0.919 Ti/(Ti + Fe) 0.997 0.997 0.997 0.997 Zr + Ti 4.03 4.03 4.03 4.03 Zr/Li 0.778 0.778 0.778 0.778 Sn/(Sn + Ti) 0.106 0.106 0.106 0.106 Zn/(Zn + Mg) 0.000 0.000 0.000 0.000 (Si + Al + Li)/Si 1.381 1.381 1.381 1.381 (Si + Al + Li)/A 4.063 4.063 4.063 4.063 Before Crystallization Liquidus Temperature [° C.] 1423 1423 1423 1423 Liquidus Viscosity [—] unmeasured unmeasured unmeasured unmeasured Primary Phase ZrO2 ZrO2 ZrO2 ZrO2 Density [g/cm.sup.3] 2.445 2.445 2.445 2.445 Low-Temperature Strain Point [° C.] 681 681 681 681 Viscosity Annealing Point [° C.] 738 738 738 738 High- 10{circumflex over ( )}4[° C.] 1344 1344 1344 1344 Temperature 10{circumflex over ( )}3[° C.] 1521 1521 1521 1521 Viscosity   10{circumflex over ( )}2.5[° C.] 1632 1632 1632 1632 10{circumflex over ( )}2[° C.] unmeasured unmeasured unmeasured unmeasured  350 nm unmeasured unmeasured unmeasured unmeasured  360 nm unmeasured unmeasured unmeasured unmeasured  370 nm unmeasured unmeasured unmeasured unmeasured Transmittance  380 nm unmeasured unmeasured unmeasured unmeasured [%]  555 nm unmeasured unmeasured unmeasured unmeasured 2 mm thick  800 nm unmeasured unmeasured unmeasured unmeasured 1070 nm unmeasured unmeasured unmeasured unmeasured 1200 nm unmeasured unmeasured unmeasured unmeasured L* unmeasured unmeasured unmeasured unmeasured a* unmeasured unmeasured unmeasured unmeasured b* unmeasured unmeasured unmeasured unmeasured

TABLE-US-00008 TABLE 8 No. 13 No. 14 No. 15 No. 16 After Crystallization Heat Treatment Conditions 765° C.-1.5 h 935° C.-1 h Density [g/cm.sup.3] 2.575 2.574 2.573 2.573 Transmittance [%]  350 nm 49.7 46.3 47.8 46.0 2 mm thick  360 nm unmeasured unmeasured unmeasured unmeasured  370 nm unmeasured unmeasured unmeasured unmeasured  380 nm unmeasured unmeasured unmeasured unmeasured  555 nm unmeasured unmeasured unmeasured unmeasured  800 nm unmeasured unmeasured unmeasured unmeasured 1070 nm unmeasured unmeasured unmeasured unmeasured 1200 nm 91.1 90.9 90.9 90.9 L* unmeasured unmeasured unmeasuredunmeasured a* unmeasured unmeasured unmeasured unmeasured b* unmeasured unmeasured unmeasured unmeasured Precipitated Crystals β-quartz β-quartz β-quartz β-quartz solid solution solid solution solid solution solid solution α[×10.sup.−7/° C.] 20-200° C. 12.8 12.8 12.8 12.8 20-380° C. unmeasured unmeasured unmeasured unmeasured 20-750° C. unmeasured unmeasured unmeasured unmeasured Young’s Modulus [GPa] unmeasured unmeasured unmeasured unmeasured Modulus of Rigidity [GPa] unmeasured unmeasured unmeasured unmeasured Poisson's Ratio unmeasured unmeasured unmeasured unmeasured Breakage good good good good Transparency good good good good Rate of Density Change between 5.3 5.3 5.2 5.2 Before and After Crystallization [%] Rate of Transmittance Change between Before and After Crystallization [%]  350 nm unmeasured unmeasured unmeasured unmeasured  360 nm unmeasured unmeasured unmeasured unmeasured  370 nm unmeasured unmeasured unmeasured unmeasured  380 nm unmeasured unmeasured unmeasured unmeasured  555 nm unmeasured unmeasured unmeasured unmeasured  800 nm unmeasured unmeasured unmeasured unmeasured 1070 nm unmeasured unmeasured unmeasured unmeasured 1200 nm unmeasured unmeasured unmeasured unmeasured

[0104] First, raw materials were formulated in the form of an oxide, a hydroxide, a carbonate or a nitrate or other forms so that each of glasses having respective compositions shown in Tables 1, 3, 5, and 7 was obtained, thus obtaining a glass batch. The obtained glass batch was put into a crucible containing platinum and rhodium, a rhodium-free strengthened-platinum crucible, a refractory crucible or a quartz crucible, melted therein at 1600° C. for 4 to 100 hours, then melted at an increased temperature of 1650 to 1680° C. for 0.5 to 20 hours, formed with a thickness of 5 mm by roll forming, and subjected to heat treatment at 700° C. for 30 minutes using a slow-cooling furnace, and then the slow-cooling furnace was cooled at a rate of 100° C./h to room temperature, thus obtaining a crystallizable glass. The melting was performed by the electric melting method widely used for the development of glass materials.

[0105] It has been confirmed that, with the use of a glass composition of Sample No. 11, the glass can be melted by heating with a burner, ohmic heating, laser irradiation, or so on, and has also been confirmed that the glass sample can be subsequently formed into a semispherical, spherical, fibrous, powdered, thin-plate-like, tubular or valve-like shape by pressing, redrawing, spraying, a roll process, a film process, an overflow (fusion) process, a hand-brown process or other processes. It has also been confirmed that, with the use of a glass composition of Sample No. 13, the glass melt can be solidified into a plate by flowing it onto a liquid having a larger specific gravity than Sample No. 13 and subsequently cooling it. The glasses produced by every method described above could be crystallized under the conditions shown in the tables.

[0106] The respective contents of Pt and Rh in the produced samples were analyzed with an ICP-MS instrument (Agilent 8800 manufactured by Agilent Technologies, Inc.). First, the produced glass sample was ground and wetted with pure water and, then, perchloric acid, nitric acid, sulfuric acid, hydrofluoric acid or the like was added to the glass sample to fuse the glass sample with the acid. Thereafter, the respective contents of Pt and Rh in the sample were measured with ICP-MS. Based on calibration curves made using prepared Pt and Rh solutions the concentrations of which had been known, the respective contents of Pt and Rh in each measurement sample were determined. The measurement modes were a He gas/HMI (low mode) for Pt and a HEHe gas/HMI (middle mode) for Rh. The mass numbers were 198 for Pt and 103 for Rh. The content of Li.sub.2O in the produced samples was analyzed with an atomic absorption spectrometer (contrAA 600 manufactured by Analytik Jena). The manner of the analysis for this component was fundamentally the same as the analysis for Pt and Rh, such as the flow of fusion of the glass sample and the use of the calibration curve. With respect to the other components, the content of each component was measured with ICP-MS or atomic absorption spectrometry, like Pt, Rh, and Li.sub.2O, or otherwise a calibration curve was made with an XRF analyzer (ZSX Primus IV manufactured by Rigaku Corporation) using as a sample for determining the calibration curve a glass sample the concentration of which had been known by previously examining it with an ICP-MS or atomic absorption spectrometer and the actual content of the component was determined from an XRF analysis value of the measurement sample based on the calibration curve. In doing XRF analysis, the tube voltage, the tube current, the exposure time, and so on were adjusted according to the analytical component as needed.

[0107] Each of the produced glasses was subjected to nucleation under the heat treatment conditions described in the tables, then subjected to crystal growth, and thus crystallized. The obtained crystallized glasses were evaluated in terms of transmittance, lightness, chromaticity, type of precipitated crystals, coefficient of thermal expansion, liquidus temperature, density, Young's modulus, modulus of rigidity, Poisson's ratio, breakage, and transparency. Furthermore, as to the crystallizable glasses before crystallization, the transmittance, the lightness, the chromaticity, and so on were measured in the same manners as for the crystallized glasses. In addition, the crystallizable glasses were measured in terms of viscosity and liquidus temperature.

[0108] The transmittance was evaluated by measuring a crystallized glass plate optically polished on both sides to have a thickness of 2 mm with a spectro-photometer. A spectro-photometer V-670 manufactured by JASCO Corporation was used for the measurement. The spectro-photometer V-670 was fitted with an integrating sphere unit “ISN-723” and, therefore, the measured transmittance corresponds to the total transmittance. Furthermore, the measurement wavelength range was 200 to 1500 nm, the scan speed was 200 nm/min, the sampling pitch was 1 nm, and the band widths were 5 nm in a wavelength range of 200 to 800 nm and 20 nm in the other wavelength range. Prior to the measurement, a baseline correction (adjustment to 100%) and a dark measurement (adjustment to 0%) were performed. The dark measurement was conducted in a state where a barium sulfate plate attached to ISN-723 was removed. Using the measured transmittance, tristimulus values X, Y, and Z were calculated based on JIS Z 8781-4:2013 and its corresponding International Standard. The lightness and chromaticity were calculated from each stimulus value (light source)C/10°.

[0109] The precipitated crystals were evaluated with an X-ray diffractometer (an automated multipurpose horizontal X-ray diffractometer SmartLab manufactured by Rigaku corporation). The scan mode was 20/0 measurement, the scan type was a continuous scan, the scattering and divergent slit width was 1°, the light-receiving slit width was 0.2°, the measurement range was 10 to 60°, the measurement step was 0.1°, and the scan speed was 5°/min. The type of major crystalline phase and the crystal grain size were evaluated using analysis software installed on the instrument package.

[0110] The coefficient of thermal expansion was evaluated, using a crystallized glass sample processed with a length of 20 mm and a diameter of 3.8 mm, from its average coefficients of linear thermal expansion measured in a temperature range of 20 to 200° C., a temperature range of 20 to 380° C., and a temperature range of 20 to 750° C. A dilatometer manufactured by NETZSCH was used for the measurement.

[0111] The liquidus temperature was evaluated in the following manner. First, glass powder sized between 300 micrometers and 500 micrometers was filled in a platinum boat with approximately 120×20×10 mm, the boat was put into an electric furnace, and the glass powder was melted at 1600° C. for 30 minutes in the furnace. Thereafter, the boat was moved into an electric furnace having a linear temperature gradient and placed therein for 20 hours to precipitate devitrification. The measurement sample was air cooled to room temperature, the devitrification precipitated at the interface between the platinum boat and the glass was observed, and the temperature at the portion where the devitrification was precipitated was calculated as a liquidus temperature from the temperature gradient graph of the electric furnace. Furthermore, the obtained liquidus temperature was interpolated into the high-temperature viscosity curve of the glass and the viscosity in the viscosity curve corresponding to the liquidus temperature was determined as a liquidus viscosity. The primary phases of the glasses shown in the tables were analyzed using X-ray diffraction, composition analysis, and so on (with a scanning electron microscope S-3400N Type II manufactured by Hitachi High-Tech Corporation and EMAX ENERGY EX-250X manufactured by Horiba, Ltd.).

[0112] The density was measured by the Archimedes's method.

[0113] The strain point and the annealing point were evaluated by the fiber elongation method. The fiber sample was made by hand-drawing from the crystallizable glass.

[0114] The high-temperature viscosity was evaluated by the platinum ball pulling-up method. In making the evaluation, a mass of glass sample was crushed to an appropriate size and loaded into an alumina-made crucible so as not to entrain air bubbles as much as possible. Subsequently, the alumina crucible was heated to turn the sample into a melt, the measured values of the glass viscosity at a plurality of temperatures were determined, the constant of the Vogel-Fulcher equation was calculated, a viscosity curve was created, and the temperature at each viscosity was calculated from the viscosity curve.

[0115] The Young's modulus, the modulus of rigidity, and the Poisson's ratio were measured, using a plate-like sample (40 mm×20 mm×2 mm) surface-polished with a polishing solution containing 1200 mesh alumina powder dispersed therein, with a free resonance elastic modulus measurement device (JE-RT3 manufactured by Nihon Techno-Plus Corporation) in a room temperature environment.

[0116] The evaluation on breakage was made by considering a crystallized glass having been visually confirmed to have no breakage as “good” and considering a crystallized glass having been visually confirmed to have a breakage as “poor”.

[0117] The evaluation on transparency was made by considering a crystallized glass having been found to be visually transparent as “good” and considering a crystallized glass having been found not to be visually transparent as “poor”.

[0118] As is obvious from Tables 1 to 8, each of the crystallized glasses of Samples Nos. 1 to 16 had a (3-quartz solid solution precipitated as a major crystalline phase and showed a high transmittance in a ultraviolet to infrared range and a low coefficient of thermal expansion. Furthermore, the crystallized glasses were confirmed to have no breakage and were transparent.

INDUSTRIAL APPLICABILITY

[0119] The Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to the present invention has a high permeability to light in a ultraviolet to infrared range and a low thermal expansion and is therefore suitable for semiconductor substrates. Furthermore, the Li.sub.2O-Al.sub.2O.sub.3-SiO.sub.2-based crystallized glass according to the present invention is also suitable for front windows of oil stoves, wood stoves and the like, substrates for high-technology products, such as color filter substrates and image sensor substrates, setters for firing electronic components, light diffuser plates, furnace core tubes for producing semiconductors, masks for producing semiconductors, optical lenses, dimension measurement members, communication members, construction members, chemical reaction containers, electromagnetic cooker top plates, heat-resistant plates and utensils, heat-resistant covers, fire door windows, members for astrometric telescopes, and members for space optics.