Machinable and chemically toughenable fluorine glass-ceramic

Abstract

The present invention is directed to a kind of machinable glass ceramic which can be chemically toughened. The machinable and chemically toughenable glass ceramic, which comprises, as represented by weight percentage based on the following compositions, 25-75 wt % of SiO.sub.2, 6-30 wt % of Al.sub.2O.sub.3, 0.1-30 wt % of Na.sub.2O, 0-15 wt % of K.sub.2O, 0-30 wt % of B.sub.2O.sub.3, 4-35 wt % of MgO, 0-4 wt % of CaO, 1-20 wt % of F, 0-10 wt % of ZrO.sub.2, 0.1-10 wt % of P.sub.2O.sub.5, 0-1 wt % of CeO.sub.2 and 0-1 wt % of SnO.sub.2, wherein P.sub.2O.sub.5+Na.sub.2O>3 wt %, and Al.sub.2O.sub.3+Na.sub.2O+P.sub.2O.sub.5>17 wt %. Mica crystalline phase can be formed in the glass ceramic and the glass ceramic can be chemically toughened by one step, two steps or multiple steps with depth of K-ion layer of at least 15 m and surface compress stress of at least 300 MPa. The profile on depth of the ion exchange layer follows the complementary error function. Hardness can be improved by at least 20% after chemical toughening. The dimension deviation ratio is less than 0.06% by ion-exchanging.

Claims

1. A fluorine mica glass-ceramic, comprising: SiO.sub.2: 25-75 wt %; Al.sub.2O.sub.3: 6-30 wt %; Na.sub.2O: 3-30 wt %; K.sub.2O: 0-15 wt %; B.sub.2O.sub.3: 0.1-30 wt %; MgO: 4-35 wt %; CaO: 0-4 wt %; F: 1-20 wt %; ZrO.sub.2: 0-10 wt %; P.sub.2O.sub.5: 1-10 wt %; CeO.sub.2: 0-1 wt %; SnO.sub.2: 0-1 wt %, wherein P.sub.2O.sub.5+Na.sub.2O>5 wt %, and Al.sub.2O.sub.3+Na.sub.2O+P.sub.2O.sub.5>17 wt %, and, wherein the glass ceramic has a microstructure comprising: 1). a glass matrix, and 2) at least one crystalline phase with the formula of (K,Na).sub.1xMg.sub.3(Al,B,P).sub.1xSi.sub.3+xO.sub.10F.sub.2, where x is 0 to 1,the glass ceramic is machinable and can be ion exchanged to achieve compress stress CS >300 MPa, and Dol >15 m.

2. The fluorine mica glass-ceramic according to claim 1, comprising the following composition, as calculated from batches based on oxides: SiO.sub.2: 30-70 wt %; Al.sub.2O.sub.3: 7-29 wt %; Na.sub.2O: 3-15 wt %; K.sub.2O: 0.5-12 wt %; B.sub.2O.sub.3: 0.1-20 wt %; MgO: 4-25 wt %; CaO: 0-2 wt %; F: 1-15 wt %; P.sub.2O.sub.5: 1-9 wt %; ZrO.sub.2: 0-8 wt %; CeO.sub.2: 0-0.5 wt %; SnO.sub.2: 0-0.5 wt %.

3. The fluorine mica glass-ceramic according to claim 1, comprising the following composition, as calculated from batches based on oxides: SiO.sub.2: 35-65 wt %; Al.sub.2O.sub.3: 8-27 wt %; Na.sub.2O: 3-15 wt %; K.sub.2O: 1-11 wt %; B.sub.2O.sub.3: 1-20 wt %; MgO: 4-20 wt %; CaO: 0-1.5 wt %; F: 2-12 wt %; P.sub.2O.sub.5: 1-8 wt %; ZrO.sub.2: 0-6 wt %; CeO.sub.2: 0-0.3 wt %; SnO.sub.2: 0-0.3 wt %.

4. The fluorine mica glass-ceramic according to claim 1, comprising the following compositions, as calculated from batches based on oxides: SiO.sub.2: 40-65 wt %; Al.sub.2O.sub.3: 8-26 wt %; Na.sub.2O: 3-14 wt %; K.sub.2O: 2-10 wt %; B.sub.2O.sub.3: 1-17 wt %; MgO: 4-17 wt %; CaO: 0-1 wt %; F: 5-10 wt %; P.sub.2O.sub.5: 1-7 wt %; ZrO.sub.2: 0-6 wt %; CeO.sub.2: 0-0.2 wt %; SnO.sub.2: 0-0.2 wt %.

5. The fluorine mica glass-ceramic according to claim 1, wherein the fluorine mica glass-ceramic has a porosity of 0%, has greater than 40 Vol. % of crystalline phase and interlock crystallization structure can be formed, wherein the mica crystalline size is 5-100 m, with an aspect ratio of <0.5.

6. The fluorine mica glass-ceramic according to claim 1, having a CTE <20 ppm/K in the temperature range of 20300 C. and a Poisson's ratio of <0.3.

7. The fluorine mica glass-ceramic according to claim 1, having a maximum thermal shock resistance T>300 C., thermal conductivity lower than 1.8 W/m C. and maximum usage temperature higher than 800 C.

8. The fluorine mica glass-ceramic according to claim 1, having the thermal shock resistance parameter R of higher than 180 W/m.sup.2.

9. The fluorine mica glass-ceramic according to claim 1, having a compress stress higher than 300 MPa, a mechanical strength higher than 350 MPa, fracture modulus higher than 100 MPa, Young's modulus higher than 65 GPa, and bending strength higher than 94 MPa.

10. The fluorine mica glass-ceramic according to claim 1, having a dielectric constant in the range of 5.5-9 at 25 C. and 1 KHZ, and a loss tangent of <0.002 at 25 C. and 1 MHz.

11. The fluorine mica glass-ceramic according to claim 1, wherein the fluorine mica glass-ceramic exhibits an Hv hardness higher than 200 kg/mm.sup.2.

12. The fluorine mica glass-ceramic according to claim 1, having a chemical toughening temperature from 300 C..sup.500 C., a chemical toughening time of 0.1.sup.16h in a pure KNO.sub.3 salt bath.

13. The fluorine mica glass-ceramic according to claim 1, with a depth of K ion layer >15 m, and a compress stress >300 MPa.

14. The fluorine mica glass-ceramic according to claim 1, wherein the hardness of chemically toughened machinable glass ceramic can be improved by higher than 20% after chemical toughening.

15. The fluorine mica glass-ceramic according to claim 1, having a dimension deviation ratio of the fluorine mica glass ceramic that is less than 0.06%, which is caused by chemical toughening.

16. The fluorine mica glass-ceramic according to claim 1, having widths and depths of scratches that are reduced by higher than 10% after chemical toughening.

17. The fluorine mica glass-ceramic according to claim 1, that is chemically toughened by three steps.

18. The fluorine mica glass-ceramic according to claim 17, wherein the first step produces a Dol.sub.1, and the Dol.sub.1 varies according to a first function; the second step produces a Dole, and the Dole varies according to a second function, and wherein the first function is different from the second function; and the third step produces Dol.sub.3, and the Dol.sub.3 varies according to a third function, and wherein the third function is different from the first function and the second function.

19. The fluorine mica glass-ceramic according to claim 18, wherein the first function is a first complementary error function.

20. The fluorine mica glass-ceramic according to claim 18, wherein the second function is a second complementary error function.

21. The fluorine mica glass-ceramic according to claim 18, wherein for the first step, a chemical toughening temperature is 300 C..sup.500 C., a chemical toughening time is 0.1.sup.16h in a pure KNO.sub.3 salt bath.

22. The fluorine mica glass-ceramic according to claim 18, wherein for the second step, a heat treatment temperature is 200.sup.600 C. and a treatment time is 0.1.sup.10h.

23. The fluorine mica glass-ceramic according to claim 18, wherein for the third step, a chemical toughening temperature is 300 C..sup.500 C., a chemical toughening time is 0.01.sup.16h in a pure KNO.sub.3 salt bath.

24. The fluorine mica glass-ceramic according to claim 1, wherein the fluorine mica glass-ceramic can be chemically toughened by multiple steps, to achieve a depth of K ion layer >40 m, and a compress stress >300 MPa.

25. The fluorine mica glass-ceramic according to claim 1, wherein the hardness of machinable glass ceramic can be improved by higher than 30% after multiple chemical toughening steps.

26. The fluorine mica glass-ceramic according to claim 1, wherein the dimension deviation ratio of the machinable glass ceramic is less than 0.06% after multiple chemical toughening steps.

27. The fluorine mica glass-ceramic according to claim 1, wherein the widths and depths of scratches can be reduced by higher than 15% after multiple chemical toughening steps.

28. The fluorine mica glass-ceramic according to claim 1, which can be chemical toughened by AgNO.sub.3 to get the antimicrobial properties and can be colorized by kinds of coloring ions (e.g. Cu.sup.2+, Fe.sup.2+, Co.sup.3+, Ni.sup.4+ and Cr.sup.3+).

29. The fluorine mica glass-ceramic according to claim 1, wherein the fluorine mica glass-ceramic, which can be chemically toughened, can be used for providing insulation and tighten performance in high-end equipment, holders in the equipment, or a backside cover/frame on electronic products.

30. A fluorine mica glass-ceramic, comprising: SiO.sub.2: 25-75 wt %; Al.sub.2O.sub.3: 6-30 wt %; Na.sub.2O: 3-30 wt %; K.sub.2O: 0-15 wt %; B.sub.2O.sub.3: 0.1-30 wt %; MgO: 4-35 wt %; CaO: 0-4 wt %; F: 1-20 wt %; ZrO.sub.2: 0-10 wt %; P.sub.2O.sub.5: 0.1-10 wt %; CeO.sub.2: 0-1 wt %; SnO.sub.2: 0-1 wt %, wherein P.sub.2O.sub.5+Na.sub.2O>3 wt %, and Al.sub.2O.sub.3+Na.sub.2O+P.sub.2O.sub.5>17 wt %, wherein the fluorine mica glass-ceramic has a porosity of 0%, has greater than 40 Vol. % of crystalline phase and interlock crystallization structure can be formed, wherein the mica crystalline size is 5-100 m, with an aspect ratio of <0.5, and wherein the glass ceramic has a microstructure comprising: 1). a glass matrix, and 2) at least one crystalline phase with the formula of (K,Na).sub.1xMg.sub.3(Al,B,P).sub.1xSi.sub.3+xO.sub.10F.sub.2, where x is 0 to 1,the glass ceramic is machinable and can be ion exchanged to achieve compress stress CS >300 MPa, and Dol >15 m.

31. A fluorine mica glass-ceramic, comprising: SiO.sub.2: 25-75 wt %; Al.sub.2O.sub.3: 6-30 wt %; Na.sub.2O: 3-30 wt %; K.sub.2O: 0-15 wt %; B.sub.2O.sub.3: 0.1-30 wt %; MgO: 4-35 wt %; CaO: 0-4 wt %; F: 1-20 wt %; ZrO.sub.2: 0-10 wt %; P.sub.2O.sub.5: 0.1-10 wt % CeO.sub.2: 0-1 wt %; SnO.sub.2: 0-1 wt %, wherein P.sub.2O.sub.5+Na.sub.2O>5 wt %, and Al.sub.2O.sub.3+Na.sub.2O+P.sub.2O.sub.5>17 wt %, and, wherein the glass ceramic has a microstructure comprising: 1). a glass matrix, and 2) at least one crystalline phase with the formula of (K,Na).sub.1x Mg.sub.3(Al,B,P).sub.1xSi.sub.3+xO.sub.10F.sub.2, where x is 0 to 1,the glass ceramic is machinable and can be ion exchanged to achieve compress stress CS >300 MPa, and Dol >15 m, wherein the fluorine mica glass-ceramic exhibits an Hv hardness higher than 200 kg/mm.sup.2.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1 to 4 show XRD and SEM of the machinable glass ceramic (mica is formed)) according to one embodiment of the present disclosure during different stages of its production: FIG. 1, SEM and XRD on phase separation to form a body-centered cubic form of chondrodite; FIG. 2, SEM and XRD of norbergite; FIG. 3, SEM and XRD on epitaxial manner; and FIG. 4, SEM on phlogopite phase, exhibiting an interlock crystallization structure or a morphology of preferred lateral direction or cabbage-head shape.

(2) FIG. 5 shows depth of K.sup.+ layer by chemical toughening the machinable glass ceramic according to one embodiment of the present disclosure.

(3) FIG. 6 shows depth of K.sup.+ layer by 3 steps chemical toughening the machinable glass ceramic according to one embodiment of the present disclosure.

(4) FIG. 7 shows the results of Hardness comparison before and after chemical toughening the machinable glass ceramic according to one embodiment of the present disclosure.

(5) FIG. 8 shows the schematic diagram of the scratch test.

(6) FIG. 9 shows the cross section of scratched samples (under 750 gf Moha hardness class 7) of the machinable glass ceramic according to one embodiment of the present disclosure: (a) before chemical toughening, (b) after chemical toughening. As evident from this figure, the width of scratch is reduced from 169 m to 15 m after chemical toughening, and the depth of scratch is reduced from 84 m to 35 m; and shows results of anti-scratching tests on the machinable glass ceramic according to one embodiment of the present disclosure before and after chemical toughing compared with the glass ceramic of the prior art, wherein the samples are scratched by or those (hardness is 6) under 1500 g pressure load, the machinable glass ceramic of the present disclosure exhibits better anti-scratching performances than the glass ceramic of the prior art, with the width of scratch being reduced from 1347 m (FIG. 9(c)) to 199 m (FIG. 9(d)), and the machinable glass ceramic of the present disclosure after the chemical toughing exhibits no scratch (FIG. 9(e)).

(7) FIG. 10 shows the comparative results of Hk hardness of the machinable glass ceramic according to one embodiment of the present disclosure before and after chemical toughing compared with the glass ceramic of the prior art.

(8) FIG. 11 shows the comparative results of 3P (three-point bending) strength of the machinable glass ceramic according to one embodiment of the present disclosure before and after chemical toughing compared with the glass ceramic of the prior art.

DETAILED DESCRIPTION OF THE DISCLOSURE

(9) In the present disclosure, the expression consist of is intended to mean than in addition to inevitable impurities, only the compositions as listed are comprised, that is to say, no additional compositions are introduced intentionally.

(10) In the glass ceramic composition according to the present disclosure, SiO.sub.2 is the largest constituent of the glass ceramic composition and therefore, it is the largest primary constituent of the glass network. SiO.sub.2 is important for the resistance of the glass ceramic on the one hand that can be increased with an increasing amount of SiO.sub.2. A higher content of SiO.sub.2 may increase the durability and mechanical strength of the glass ceramic, but it is also important to the melting capabilities on the other hand, wherein the formability may be diminished with higher concentrations of more than 75 mol %. Therefore, it is advantageous in the technical solutions of the present disclosure that the amount of SiO.sub.2 is limited within the following ranges: 25-75 wt. %, preferably 30-70 wt. %, particularly preferably 35-65 wt. %, in particular 40-65 wt. %.

(11) Al.sub.2O.sub.3 is also an important constituent for the glass ceramic composition according to the present disclosure since it may facilitate the ion exchange on the glass surface. A larger exchange depth of the ion exchange is favorable for the scratch-tolerance of the glass. In addition, it is an essential component for improving the chemical stability. Also, it may increase hardness of the glass. But, on the other hand, if the amount of Al.sub.2O.sub.3 is too high, the melting temperature may increase and the resistance to acids may decrease. Therefore, it is advantageous in the technical solutions of the present disclosure that the amount of Al.sub.2O.sub.3 is limited within the following ranges: 6-30 wt. %, preferably 7-29 wt. %, more preferably 8-27 wt. %, in particular 8-26 wt. %.

(12) B.sub.2O.sub.3 exerts a very positive influence on the scratch-tolerance of the glass ceramic or glass ceramic article, respectively. Also, it is favorable to the melting properties of the glass ceramic. But, it may negatively influence the ion exchange. Therefore, it is significantly important for the glass ceramic or glass ceramic article of the disclosure to appropriately adjust the amount of B.sub.2O.sub.3 to achieve desirable balance among scratch-tolerance, melting property and ion-exchanging performance. The inventors have found that it is advantageous in the technical solutions of the present disclosure that the amount of B.sub.2O.sub.3 is limited within the following ranges: 0-30 wt. %, preferably 0.1-20 wt. %, particularly preferably 1-20 wt. %, in particular 2-17 wt. %.

(13) The glass ceramic composition also comprises alkali oxides R.sub.2O, wherein R.sub.2O is at least one of Na.sub.2O and K.sub.2O since the glass ceramic composition is substantially free of Li. The glass composition in accordance to the disclosure also comprises alkaline earth oxides RO, wherein RO is at least one of MgO, CaO, SrO, ZnO and BaO. RO as well as R.sub.2O are network transformers and therefore favorable to the melting properties of the glass ceramic.

(14) The existence of Sodium ions, Potassium ions and P.sub.2O.sub.5 is of high importance to the ion exchange; a glass ceramic without alkali oxides is not suitable for chemical toughening. Potassium ions are advantageous for the improvement in the exchange depth. Therefore, K.sub.2O may be present to a specific amount within the glass ceramic composition. It has been found that a higher content of Na.sub.2O is also favorable for forming processes, in particular for floating or down-drawing. If the content of Na.sub.2O and K.sub.2O is too high, however, the glass viscosity may decrease. Therefore, the content of alkali oxides is carefully matched with the content of alkaline earth oxides.

(15) The existence of alkaline earth oxides RO may improve the melting behavior by stabilizing the glass ceramic. MgO may not greatly affect the ion exchange by moderate use, wherein heavier constituents CaO, SrO or BaO as well as ZnO may influence the ion-exchange more, especially, if the content increases up to 4 wt. %. In some preferred embodiments of the present disclosure, the glass ceramic composition and the articles produced therefrom contains no alkaline earth oxides CaO, SrO, BaO and ZnO.

(16) In embodiments of the present disclosure, the amount of Na.sub.2O is 0.1-30 wt. %, preferably 0.5-15 wt. %, particularly preferably 1-15 wt. %, in particular 3-14 wt. %; the amount of K.sub.2O is 0-15 wt. %, preferably 0.5-12 wt. %, particularly preferably 1-11 wt. %, in particular 2-10 wt. %; the amount of P.sub.2O.sub.5 is 0.1-10 wt. %, preferably 0.5-9 wt. %, particularly preferably 1-8 wt. %, in particular 1-7 wt. %; the amount of MgO is 4-35 wt. %, preferably 4-25 wt. %, particularly preferably 4-20 wt. %, in particular 4-17 wt. %; the amount of CaO is 0-4 wt. %, preferably 0-2 wt. %, particularly preferably 0-1.5 wt. %, in particular 0-1 wt. %.

(17) In addition, as a composition involving various constituents, its properties are not equal to simple addition of respective constituents thereof, and are directed to interaction of respective constituents or the like. This is a very complicated issue and constitutes characteristic of chemistry science as a laboratory course. By means inventive labor, the inventors have surprisingly found that the technical problems addressed by the present disclosure can be advantageously resolved, i.e. the glass ceramic composition is able to be used for producing the machinable glass ceramic and articles thereof with excellent chemical toughening performances when P.sub.2O.sub.5+Na.sub.2O>3 wt. % and Al.sub.2O.sub.3+Na.sub.2O+P.sub.2O.sub.5>17 wt. %.

(18) According to the present disclosure, Al.sub.2O.sub.3 and P.sub.2O.sub.5 are also important constituents for glass ceramic composition since they may facilitate the ion exchange on the glass ceramic surface. A larger exchange depth of the ion exchange is favorable for the strength and the scratch-tolerance of the glass ceramic. The inventors have surprisingly found that the strength of the machinable glass ceramic can be advantageously improved by limiting that the sum of amount of Al.sub.2O.sub.3, Na.sub.2O and P.sub.2O.sub.5 is higher than 16 wt. %, in particular higher than 17 wt. % (i.e. Al.sub.2O.sub.3+Na.sub.2O+P.sub.2O.sub.5>17 wt. %). Preferably, the sum of amount of Al.sub.2O.sub.3, Na.sub.2O and P.sub.2O.sub.5 is higher than 18 wt. %, more preferably higher than 20 wt. %, for example, higher than 22 wt. %.

(19) According to the present disclosure, as calculated from batches based on oxides, the sum of amount of Al.sub.2O.sub.3, Na.sub.2O and P.sub.2O.sub.5 is no more than 70 wt. %, preferably no more than 60 wt. %, more preferably no more than 50 wt. %, in particular no more than 46 wt. %.

(20) The existence of Sodium ions and Potassium ions is of high importance to the ion exchange of the glass ceramic of the present disclosure. A glass ceramic without alkali oxides is not suitable for chemical toughening. Potassium ions are advantageous for the exchange depth. Therefore, K.sub.2O may be present to a specific amount within the glass ceramic composition. By means inventive labor, the inventors have surprisingly found that ion exchange can be carried out advantageously when the sum of amount of P.sub.2O.sub.5 and Na.sub.2O is higher than 3 wt. % (i.e. P.sub.2O.sub.5+Na.sub.2O>3 wt. %). Preferably, the sum of amount of P.sub.2O.sub.5 and Na.sub.2O is higher than 5 wt. %, more preferably at least 6 wt. %.

(21) According to the present disclosure, as calculated from batches based on oxides, the sum of amount of P.sub.2O.sub.5 and Na.sub.2O is no more than 40 wt. %, preferably no more than 30 wt. %, more preferably no more than 25 wt. %, in particular no more than 21 wt. %.

(22) In some preferred embodiments of the present disclosure, the fluorine mica glass-ceramic composition which can be chemically toughened optionally contains ZrO.sub.2, CeO.sub.2 and SnO.sub.2. ZrO.sub.2 can be used a nucleating agent to improve harness and strength of the materials. CeO.sub.2 and SnO.sub.2 function as fining agents.

(23) In some preferred embodiments of the present disclosure, the amount of ZrO.sub.2 is 0-10 wt. %, preferably 0-8 wt. %, in particular 0-6 wt. %. For example, in some illustrative embodiments of the present disclosure, the amount of ZrO.sub.2 is 0-0.11 wt. %. In some preferred embodiments of the present disclosure, the amount of CeO.sub.2 is 0-1 wt. %, preferably 0-0.5 wt. %, more preferably 0-0.3 wt. %, in particular 0-0.2 wt. %. For example, in some illustrative embodiments of the present disclosure, the amount of CeO.sub.2 is 0-0.01 wt. %. In some preferred embodiments of the present disclosure, the amount of SnO.sub.2 is 0-1 wt. %, preferably 0-0.5 wt. %, more preferably 0-0.3 wt. %, in particular 0-0.2 wt. %. For example, in some illustrative embodiments of the present disclosure, the amount of SnO.sub.2 is 0-0.11 wt. %. In some preferred embodiments of the present disclosure, the amounts of ZrO.sub.2, CeO.sub.2 and CeO.sub.2 can be 0-6 wt. %, 0-0.01 wt. % and 0-0.11 wt. %, respectively.

(24) In some preferred embodiments of the present disclosure, the glass-ceramic composition is a fluorine mica glass-ceramic composition, wherein F is present in an amount of 1-20 wt. %, preferably 1-15 wt. %, particularly preferably 2-12 wt. %, in particular 5-10 wt. %.

(25) According to the present disclosure, mica crystalline phase can be formed in the fluorine mica glass-ceramic composition of the present disclosure and the machinable glass ceramic produced therefrom, and the glass ceramic can be chemically toughened, for example by ion exchanging. Mica is classified as a phyllosilicate; its basic structure feature is a composite sheet in which a layer of octahedrally-coordinate cations is sandwiched between two identical layers of linked (Si, Al)O.sub.4 tetrahedra. The general formula of the mica structure can be found in Dana's new Mineralogy, R. V. Gaines et al., eds. (John Wiley & Sons, New York, 1997), and the structure can be written as:
A.sub.0-5R.sub.2-3T.sub.4O.sub.10X.sub.2,

(26) wherein,

(27) A=a large monovalent or bivalent ion (e.g. Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+), or a partial vacancy (partial vacancy denoted by subscript .sub.( )),

(28) R=an octahedrally-coordinated cation (e.g. Li.sup.+, Mg.sup.2+, Fe.sup.2+, Mn.sup.2+, Zn.sup.2+, Al.sup.3+, Fe.sup.3+, Mn.sup.3+, V.sup.3+),

(29) T=a tetrahedrally-coordinated cation (predominantly Si.sup.4+, with Al.sup.3+ and B.sup.3+), and

(30) X=is an anion (predominantly OH.sup. in minerals, but F.sup. in glass-ceramics. X may also be partially O.sup.2).

(31) Micas are extremely common in rocks, and numerous classification system exist for them. In glass-ceramics, micas are typically classified as alkaline (containing alkali ions) and non-alkaline (containing no monovalent ions), and as trisilicic (wherein T.sub.4 is (Si.sub.3Al)) and tetrasilicic (Si.sub.4). These compositional parameters can be varied to produce desired properties in a glass-ceramic. The machinable glass ceramic is based on mica crystalline phase formed.

(32) The crystallization begins lower than 650 C. when a metastable phase forms in the magnesium-rich matrix at the interfaces of the aluminosilicate droplets (e.g. KAlSi.sub.2O.sub.6). These crystals have been identified as a body-centered cubic form of chondrodite, Mg.sub.3Si.sub.4O.sub.10F.sub.2. At approximately higher than 750 C., the chondrodite phase recrystallizes to small platy crystals of norbergite, Mg.sub.3Si.sub.4O.sub.10F.sub.2. Then phlogopite KMg.sub.3AlSi.sub.3O.sub.12F.sub.2 crystals are found to grow epitaxially on these earlier crystals, resulting in the interlocked house-of-cards structures from 900 C. to 1200 C.; alternatively, fluoromica crystal with preferred lateral direction or cabbage-head shape can be formed in the fluorine mica glass-ceramic and the size of crystal grains of the fluoromica crystal is >5 m, >10 m, or >15 m.

(33) The toughening process could be done by immersing glass ceramic into a salt bath which containing monovalent ions to exchange with alkali ions inside glass. The monovalent ions in the salt bath has radius larger than alkali ions inside glass. A compressive stress to the glass is built up after ion-exchange due to larger ions squeezing in the glass network. After the ion-exchange, the strength and flexibility of glass ceramic are surprisingly and significantly improved. In addition, the DoL and the CS induced by chemical toughening could increase scratch resistance of glass ceramic so that toughened glass ceramic would not get scratched easily.

(34) The most used salt for chemical toughening is Na.sup.+-containing or K.sup.+-containing melted salt or mixture thereof. The commonly used salts are NaNO.sub.3, KNO.sub.3, NaCl, KCl, K.sub.2SO.sub.4, Na.sub.2SO.sub.4, Na.sub.2CO.sub.3, and K.sub.2CO.sub.3. Additives like NaOH, KOH and other sodium salts or potassium salts could be also used for better controlling the speed of ion-exchange, CS and DoL during chemical toughening. Ag.sup.+-containing or Cu.sup.2+-containing salt bath could be used to add anti-microbial function to glass ceramic.

(35) In addition, the machinable glass ceramic can be chemically toughened by three steps, to increase the DoL to higher than 40 m. The first step is to chemically toughen the glass, and the chemical-toughened layer exhibits a profile conforming to standard complementary error function. As for the samples shown in FIG. 6, the first step of chemical toughing is carried out by immersion for 0.5-6 h in a KNO.sub.3 salt bath at temperatures lower than the stress temperature of the glass ceramic, and the resulted DoL conforms to typical complementary error function profile.

(36) As used herein, the terms error function and Erf refer to the function which is twice the integral of a normalized Gaussian function between 0 and x/2, and the terms complementary error function and Erfc are equal to one minus the error function; i.e., Erfc(x)=1Erf (x).

(37) K ion concentration for the first step is modeled by error-function:
C(x)=1(1C.sub.0)erf(x/2Dt)(1)

(38) wherein C.sub.0 is the K ion concentration in the internal glass ceramic, D is the diffusion coefficient, t is the diffusion time.

(39) In the second step, the ion exchanged glass ceramic samples are heat treated at a temperature below the strain point of the glass ceramic for a desired period to promote diffusion of potassium to extend the depth of the DoL, while at the same time relaxing the surface compressive stress in the samples. The samples shown in FIG. 6, are heat treated below strain point for 0.1-10 h, which results in an extension of the DoL beyond the DoL achieved in the first step. The choice of heat treatment temperature and time depends on the rate of stress relaxation and rate of diffusion for a given glass ceramic composition at a given temperature.

(40) Samples of K ion concentration for the second step are modeled:
C(x)=N/(Dt).Math.e.sup.x{circumflex over ()}2/4Dt(2)

(41) wherein N is the K ion content of the glass ceramic, D is the diffusion coefficient, t is the diffusion time.

(42) In the third step, a second ion-exchange for short period reestablishes the surface DoL. In FIG. 6, the second ion-exchange at temperature below the strain point of the glass ceramic for 2-200 minutes results in that the total DoL increases from 25 m to 53 m.

(43) Samples of K ion concentration for the third step 3 are modeled by error-function:
C(x)=1(1C.sub.0)erf(x/2Dt)+N/(Dt).Math.e.sup.x{circumflex over ()}2/4Dt(3)

(44) The thermal shock resistance of glass ceramic is especially the most important factor for the glass ceramic, because the thermal shocking resistance determines economical availability of said toughened glass ceramic with high quality. This is also why the composition of raw glass ceramic sheet is carefully designed for each type of glass ceramic which has been already described in the past paragraphs.

(45) The robustness of a material to thermal shock is characterized by the thermal shock resistance parameter:

(46) $R=\frac{\left(1-\right)}{E}$

(47) wherein R is the thermal shock resistance; is CTE; is the thermal conductivity; a is the maximal tension the material can resist, E is the Young's modulus and is Poisson ratio. Higher value for R represents greater resistance to thermal shock and high tolerance to temperature gradient and thermal loading. Accordingly, thermal stress resistance of the glass ceramic is determined by maximum thermal loading T from the following equation:

(48) $T\frac{2\left(1-\right)}{E}$

(49) With no doubt glass ceramic with higher R would certainly has higher thermal loading tolerance and hence has greater resistance to thermal shock.

(50) For the practical applications, R should be higher than 180 W/m.sup.2, preferred higher than 200 W/m.sup.2, preferred higher than 250 W/m.sup.2. And T should be higher than 300 C., preferred higher than 350 C., preferred higher than 400 C.

(51) CTE is the key factor to fulfill the requirement of R and T mentioned above for the thermal shock resistance of glass ceramic. The glass ceramic with lower CTE and Young's modulus has higher thermal shock resistance and are less prone to breakage caused by temperature gradient and has an advantage of reducing uneven distribution of thermal stress in chemical toughening process and other high temperature. CTE should be lower than 20*10.sup.6/K, preferred lower than 18*10.sup.6/K, preferred lower than 16*10.sup.6/K, preferred lower than 10*10.sup.6/K, preferred lower than 9*10.sup.6/K.

(52) R is calculated to evaluate the thermal shock resistance of glass ceramic without thermal shock experiment, and the accordance with experimental data is generally good. However, the thermal shocking resistance of glass will also be affected by other factors, e.g. the shape of the sample, the thickness and processing history.

(53) T is calculated from intrinsic parameters to evaluate the temperature gradient resistance of glass ceramic material without temperature difference experiment, and the accordance with experimental data is also generally good. However, the resistance to temperature difference is also highly depended on the specific conditions such as the size of glass sample, thickness of glass, and processing history of glass ceramic.

Examples

(54) The disclosure is explained and illustrated in greater detail by the following examples, without wishing to restrict it thereby in any manner.

(55) In general, molten mother glass is casted into desired shapes and then gradually cooled to below transformation temperature for forming. And then a two-step process is adopted to carry out crystallization: in the first step, the glass articles are heated up to about T.sub.g, for example, 750-850 C., and then heat treatment for a suitable period, for example 1-6 hours, so as to ensure production of crystal nucleus in the glass liquid; and in the second step, the system is heated up to a temperature between 850 C. and 1100 C. and incubated for a suitable period, for example 1-8 hours, so as to ensure growth of crystal.

(56) Samples for SEM test are firstly subjected to acid corrosion treatment for 5-30 minutes, and then morphology and size of the crystal are measured by means of JSM-6380 SEM.

(57) The X-ray diffraction patterns are measured by means of an XRD instrument of DX-2007. Vickers hardness is characterized by HXD-1000.

(58) With the specific composition as illustrated (such as those as shown in Examples 1-12), one skilled in the art is able to select any starting materials to meet the composition as defined. In addition the processes as described above, one skilled in the art is able to select any additional suitable methods or process conditions for processing the glass-ceramic composition to produce the machinable glass ceramic without an inventive step.

(59) In one illustrative embodiment of the present disclosure, lapping and polishing of both sides of the glass ceramic article can be performed, wherein the Hv hardness of the glass ceramic article is higher than 250 kgf/mm.sup.2, preferably higher than 260 kgf/mm.sup.2 and more preferably higher than 270 kgf/mm.sup.2. Then the glass ceramic article can be chemically toughened in molten pure KNO.sub.3 at a temperature of 390 to 450 C., the chemical toughening time could be from 1 to 10 hours, preferably from 400 to 430 C. for 5 to 8 hours, and more preferably at 420 C. for 6 hours, so that the glass ceramic article is toughened. A high strength and Dol can be achieved with a compress strength of more than 350 MPa and a DoL of more than 15 m.

(60) FIGS. 1 to 4 show XRD and SEM of the machinable glass ceramic (mica is formed)) according to one embodiment of the present disclosure during different stages of its production. Specifically, crystallization begins lower than 650 C. when a metastable phase forms in the magnesium-rich matrix at the interfaces of the aluminosilicate droplets (KAlSi.sub.2O.sub.6). These crystals have been identified as a body-centered cubic form of chondrodite, Mg.sub.3Si.sub.4O.sub.10F.sub.2 (see FIG. 1, by example of Example 1). At approximately higher than 750 C., the chondrodite phase recrystallizes to small platy crystals of norbergite, Mg.sub.3Si.sub.4O.sub.10F.sub.2 (see FIG. 2, by example of Example 1). Then phlogopite KMg.sub.3AlSi.sub.3O.sub.12F.sub.2 crystals are found to grow epitaxially on these earlier crystals (see FIG. 3), resulting in the interlocked house-of-cards structures from 900 C. to 1200 C. (see FIG. 4 (upper)) or the morphology of cabbage-head shape (see FIG. 4 (middle)).

(61) By example of Example 1, FIG. 5 shows depth of K.sup.+ layer by chemical toughening the machinable glass ceramic. In FIG. 5, the horizontal ordinate stands for the distance from cross-section (m), and the vertical coordinate stands for the concentration of K ions. FIG. 6 shows depth of K.sup.+ layer by 3 steps chemical toughening the machinable glass ceramic. Compared with FIG. 5, the Dol increases from 25 m to 53 m.

(62) Table 1 below presents the data of composition and performances (Dol, Hv hardness and strength) of Examples 1-12 of the present disclosure:

(63) TABLE-US-00001 TABLE 1 data of composition and performances of Examples 1-12 composition/wt. % Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 SiO.sub.2 45.96 45.96 43.10 53.47 59.14 64.38 Al.sub.2O.sub.3 16.26 16.26 19.25 18.18 17.11 13.90 Na.sub.2O 3 7 5.35 9.62 10.69 11.76 K.sub.2O 9.25 7.25 9.62 7.49 6.42 5.35 MgO 14.12 12.12 8.56 9.62 10.69 12.83 ZrO.sub.2 0.11 0.11 0.11 0.11 CeO.sub.2 0.01 0.01 0.01 0.01 SnO.sub.2 0.11 0.11 0.11 0.11 F 6.13 6.13 6.42 7.49 8.56 9.62 P.sub.2O.sub.5 3 3 2.14 3.21 2.14 1.07 B.sub.2O.sub.3 2.28 2.28 5.35 6.42 7.49 8.56 Al.sub.2O.sub.3 + Na.sub.2O + P.sub.2O.sub.5 22.26 26.26 26.74 31.01 29.94 26.74 Na.sub.2O + P.sub.2O.sub.5 6 10 7.49 12.83 12.83 12.83 Dol/m (one step ion 20 25 28.00 30.00 32.00 33.00 exchanging) Hv/(kg/mm.sup.2) 260 265 278 300 316 320 (one step ion exchanging) strength 160 165 168 170 172 180 (3-point bending) (one step ion exchanging) (MPa) Dol/m 66 68 70 73 75 80 (three steps chemical toughening) Hv/(kg/mm.sup.2) 350 380 450 (three steps chemical toughening) 3-point bending 250 300 strength (three steps chemical toughening) (MPa) CTE/ppm/K 8.76 8.54 8.22 8.01 7.56 7.21 /W/mK 1.47 1.47 1.45 1.46 1.45 1.42 0.29 0.29 0.28 0.28 0.28 0.27 R/W/m 253 288 289 293 295 300 T/ C. 355 420 450 458 460 465 Dimension deviation 0.03% 0.03% 0.04% 0.04% 0.05% 0.05% ratio by ion exchanging Example Example Example Example Example Example composition wt. % 7 8 9 10 11 12 SiO.sub.2 58.71 62.90 61.22 41.93 44.45 45 Al.sub.2O.sub.3 8.39 11.74 13.42 16.77 25.16 25.9 Na.sub.2O 5.03 6.71 8.39 10.06 13.42 5 K.sub.2O 8.39 6.71 5.03 3.35 2.52 5 MgO 4.19 5.87 7.55 10.90 16.77 12 ZrO.sub.2 0.10 0.10 0.10 0.10 0.10 CeO.sub.2 0.01 0.01 0.01 0.01 0.01 SnO.sub.2 0.10 0.10 0.10 0.10 0.10 F 5.03 5.87 6.29 7.55 6.71 5 P.sub.2O.sub.5 3.35 4.19 5.03 5.87 6.71 1 B.sub.2O.sub.3 6.71 10.06 11.74 13.42 16.77 1 Al.sub.2O.sub.3 + Na.sub.2O + P.sub.2O.sub.5 16.77 22.64 26.84 32.71 45.29 31.9 Na.sub.2O + P.sub.2O.sub.5 8.39 10.90 13.42 15.93 20.13 6 Dol/m (one step ion 25.00 28.00 30.00 25.00 19.00 20 exchanging) Hv/(kg/mm.sup.2) 255 265 270 276 258 280 (one step ion exchanging) strength 175 188 190 176 168 170 (3-point bending) (one step ion exchanging) (MPa) Dol/m 70 75 68 65 60 70 (three steps chemical toughening) Hv/(kg/mm2) 350 380 400 420 350 360 (three steps chemical toughening 3-point bending 280 300 310 strength (three steps chemical toughening) (MPa) CTE/ppm/K 5.67 6.76 8.56 9.87 10.02 9.7 /W/mK 1.48 1.46 1.45 1.46 1.45 1.45 0.28 0.28 0.29 0.27 0.28 0.27 R/W/m 350 420 336 402 380 390 T/ C. 650 800 667 750 680 760 Dimension deviation 0.03% 0.02% 0.04% 0.04% 0.04% 0.04% ratio by ion exchanging

(64) As evident from Table 1, the glass ceramic according to the present disclosure is able to achieve DoL of 20 m or higher, Hv hardness of 250 kg/mm.sup.2 or higher, and strength of 160 MPa or higher.

(65) FIG. 7 shows the results of Hardness comparison before and after chemical toughening the machinable glass ceramic of Example 1. As shown in FIG. 7, the Hv hardness of the glass ceramic according to the present disclosure after chemical toughing is significantly improved, compared to that before chemical toughing.

(66) FIG. 8 shows the schematic diagram of the scratch test. As shown in this figure, an indenter is arranged vertically to the glass ceramic sample to keep the both in contact, a certain load is applied to the indenter in vertical direction, and then a tangential force is applied to the glass ceramic sample to make a displacement. Taking Example 1 as the testing target, the glass ceramic is sampled before and after chemical toughing, and the samples are respectively subjected to scratching tests under the same testing conditions.

(67) FIG. 9 shows the cross-section of scratched samples (under 750 gf) of the machinable glass ceramic of Example 1 of the present disclosure: (a) before chemical toughening, (b) after chemical toughening. As shown in this figure, the width of scratch is reduced from 169 m to 15 m after chemical toughening, and the depth of scratch is reduced from 84 m to 35 m, indicating that the glass ceramic according to the present disclosure is able to be chemically toughened and thus achieve significant improvement over the prior art with respect to the anti-scratching performance.

(68) By example of ACA-2483 with the composition of Example 12 and the chemically toughened ACA-2483 (referred to as ACA2483CT hereinafter), FIG. 9 further shows results of anti-scratching tests on the machinable glass ceramic according to one embodiment of the present disclosure (MIGC) before and after chemical toughing compared with the glass ceramic of the prior art. The samples are scratched by or those (hardness is 6) under 1500 g pressure load, the machinable glass ceramic of the present disclosure, e.g. ACA-2483, exhibits better anti-scratching performances than the sample MACOR (commercially available from Corning, also referred to as CorningMACOR), with the width of scratch being reduced from 1347 m (MACOR, FIG. 9(c)) to 199 m (ACA-2483, FIG. 9(d)), and the sample ACA-2483 exhibits no scratch (FIG. 9(e)). That is to say, the anti-scratching performances of ACA-2483 are further improved significantly after the chemical toughing. Therefore, compared with MACOR, the machinable glass ceramic according to the present disclosure exhibits significantly improved anti-scratching performances, and the hardness and the strength are further improved by the chemical toughing.

(69) By example of ACA-2483 and ACA2483CT, FIG. 10 shows the comparative results of Hk hardness of the machinable glass ceramic according to the present disclosure with the glass ceramic of the prior art. ACA-2483 and ACA2483CT exhibits the cabbage-head shape as shown in FIG. 4. As seen from FIG. 10, in comparison with MACOR, the Hk hardness of ACA-2483 is significantly improved, and after the chemical toughing, the Hk hardness of ACA-2483CT is further improved.

(70) By example of ACA-2483 and ACA2483CT, FIG. 11 shows the comparative results of 3P (three-point bending) strength of the machinable glass ceramic according to the present disclosure compared with the glass ceramic of the prior art. As shown in FIG. 11, the 3P strength of ACA-2483 is lower than that of MACOR; whereas after the chemical toughing, the 3P strength of ACA-2483CT is significantly improved and is comparable to that of MACOR.

(71) The abovementioned comparison definitely demonstrates that the present disclosure has achieved significant improvement over the prior art.