High performance glass ceramics and method for producing high-performance glass ceramics
The invention relates to a glass ceramic comprising article, wherein the integral, non-post-processed and non-reworked glass ceramic comprising article comprises at least three different types of microstructures. The microstructures differ in the number and/or size of the crystallites contained per unit volume, and/or in the composition of the crystallites, and/or in the composition of the residual glass phases. The different microstructures are characterized by different relative ion content profiles across a cross-section perpendicular to the transition areas. The relative ion content profiles are determined from intensities which are determined using secondary ion mass spectrometry, and each of the three different types of microstructures preferably has different intensity plateaus for individual ions, wherein the individual ions are components of the main crystal phases.
1. A glass ceramic comprising article, comprising:
an integral, non-post-processed and non-reworked glass ceramic comprising at least three different microstructures;
wherein said at least three different microstructures differ in a property selected from the group consisting of a number of crystallites contained per unit volume, a size of the crystallites contained per unit volume, a composition of the crystallites, and a composition of residual glass phases; and
wherein the at least three different microstructures comprise different relative ion content profiles across a cross-section perpendicular to transition areas, the relative ion content profiles being determined from intensities determined by secondary ion mass spectrometry, each of the at least three different microstructures having different intensity plateaus for individual ions, the individual ions being components of main crystal phases.
2. The glass ceramic comprising article as claimed in claim 1 , further comprising transitions between the at least three different microstructures, wherein the transitions reproduce a morphology of an interface to the environment of the glass ceramic comprising article, and wherein the at least three different microstructures are arranged successively from a periphery to an inside of the glass ceramic comprising article.
3. The glass ceramic comprising article as claimed in claim 2 , wherein the interface of the glass ceramic comprising article to the environment comprises an outer zone that exhibits a predominantly amorphous first microstructure with a crystallite content being not more than 10 vol. %.
4. The glass ceramic comprising article as claimed in claim 3 , further comprising a second microstructure adjacent to the first microstructure, the second microstructure having a crystallite content from 10 to 80 vol. %.
5. The glass ceramic comprising article as claimed in claim 4 , further comprising a third microstructure adjacent to the second microstructure, the third microstructure having a crystallite content of more than 80 vol. %.
6. The glass ceramic comprising article as claimed in claim 1 , wherein the glass ceramic comprising article exhibits an impact resistance of more than 15 cm fracture height in a ball drop test, wherein given values correspond to 5% fractile of Weibull distribution and relate to a sample size of 200×200×4 mm onto which a 535 g steel ball falls.
7. The glass ceramic comprising article as claimed in claim 1 , wherein the glass ceramic comprising article exhibits a resistance to acids of class 1 or class 2 according to DIN 12 116.
8. The glass ceramic comprising article as claimed in claim 6 , wherein the glass ceramic comprising article, following a 30 minute attack of concentrated sulfuric acid at a temperature of 370° C., exhibits a fracture height in a subsequently performed ball drop test of more than 15 cm.
9. The glass ceramic comprising article as claimed in claim 1 , wherein the glass ceramic comprising article has a composition selected from the ranges of:
60-73.0 wt. % Si 0 2 ,
15-25.0 wt. % Al 2 O 3 ,
2.2-5.0 wt.% Li 2 O,
0-5.0 wt. % CaO+SrO+BaO,
0-5.0 wt. % Ti 0 2 ,
0-5.0 wt. % Zr 0 2 ,
0-4.0 wt. % ZnO,
0-3.0 wt. % Sb 2 O 3 ,
0-3.0 wt. % MgO,
0-3.0 wt. % SnO 2 ,
0-2.0 wt. % P 2 O 5 ,
0-1.5 wt. % As 2 O 3 , and
0-1.2 wt. % Na 2 O+K 2 O, wherein the respective contents are within the specified ranges of:
0-1.0 wt. % Na 2 O,
0-0.5 wt. % K 2 O, and
0-1.0 wt. % of coloring oxides.
10. The glass ceramic comprising article as claimed in claim 9 , wherein a first microstructure of the at least three microstructures is depleted in Li and Mg ions and is enriched in Na and K ions, as compared to second and third microstructures of the at least three microstructures.
11. The glass ceramic comprising article as claimed in claim 10 , wherein the second microstructure is enriched in Li and Mg ions as compared to the first microstructure, while being depleted in Na and K ions as compared to the first microstructure.
12. The glass ceramic comprising article as claimed in claim 11 , wherein the third microstructure is enriched in Li and Mg ions as compared to the first and second microstructures, and is depleted in Na and K ions as compared to the first and second microstructures.
13. The glass ceramic comprising article as claimed in claim 10 , wherein the first microstructure has a peripheral area that is enriched in gahnite mixed crystals, and/or a non-peripheral area that is depleted in gahnite mixed crystals.
14. The glass ceramic comprising article as claimed in claim 10 , wherein the first and second microstructures have a thickness of not more than 10 μm.
15. The glass ceramic comprising article as claimed in claim 10 , wherein at least the third microstructure includes a main crystalline phase of keatite mixed crystals and a second crystalline phase of high quartz mixed crystals, a ratio between the high quartz mixed crystal phase and the keatite mixed crystal phase increasing towards a surface of the glass ceramic comprising article.
16. A method for producing a glass ceramic comprising article, comprising:
transforming at least one precursor article , at least partially, to a glass ceramic comprising article,
wherein either a first precursor article of glass is ceramized to the glass ceramic comprising article; or
at least a first crystalline phase of a second precursor article is further ceramized to a second crystalline phase of the glass ceramic comprising article; and
wherein the first or second precursor article is heated to a maximum temperature so that a temperature distribution between a top and a bottom of the first or second precursor article deviates by not more than ±1 K from an average temperature at least during an exothermic period of phase transition,
wherein the maximum temperature is achieved with a heat-up rate that is above 10 K/min, and
the maximum temperature being maintained for not more than two minutes.
17. The method as claimed in claim 16 , wherein the heat-up rate that is run to achieve the maximum temperature is between 14 and 36 K/min.
18. The method as claimed in claim 17 , wherein at least 80% of a volume change experienced by said first or second precursor article during ceramization to the first or second crystalline phase of the glass ceramic comprising article is completed within a time window comprising one to six minutes.
19. A glass ceramic comprising article which is produced by the method as claimed in claim 16 .
20. The glass ceramic comprising article as claimed in claim 1 , wherein the glass ceramic comprising article is configured for use as a device selected from the group consisting of a support plate, an oven liner, a furnace lining, chemically resistant laboratory equipment, an oven pane for incinerators, a heat shield for shielding hot environments, a cover for reflectors, flood lights, video projectors, data projectors, or photocopiers, night vision devices, a cover for heating elements, a cooking or frying surface cover, a heater cover, a wafer substrate, a translucent article with UV protection, and a facade plate.
21. A method for producing a glass ceramic comprising article, comprising:
transforming at least one precursor article having a top and a bottom to a glass ceramic by heating the at least one precursor article to a maximum temperature so that a temperature distribution between the top and the bottom deviates by not more than ±1 K from an average temperature at least during an exothermic period of phase transition, wherein the maximum temperature is achieved with a heat-up rate that is above 10 K/min; and
maintaining the maximum temperature for not more than two minutes so that the glass ceramic has at least three different microstructures that differ in a property selected from the group consisting of a number of crystallites contained per unit volume, a size of the crystallites contained per unit volume, a composition of the crystallites, and a composition of residual glass phases and the at least three different microstructures comprise different relative ion content profiles across a cross-section perpendicular to transition areas, the relative ion content profiles being determined from intensities determined by secondary ion mass spectrometry, each of the at least three different microstructures having different intensity plateaus for individual ions, the individual ions being components of main crystal phases.