Zirconium-silicon-based glass ceramic having ultra-high toughness and bending strength, and preparation method therefor

Abstract

The present invention belongs to the technical field of glass ceramics. Disclosed are a zirconium-silicon-based glass ceramic having ultra-high toughness and bending strength and a preparation method therefor. Said zirconium-silicon-based glass ceramic comprises the following components in molar percentages: 1-15% of X, 25-70% of ZrO2 and 25-70% of SiO2, wherein the X represents an oxide of a metal having a +1 to +5 valence. A precipitation process is used for preparing a high-purity nanoscale zirconium-silicon-based amorphous powder doped with a cation (e.g. K2O, MgO, Al2O3, Y2O3, CeO2 and Ta2O5); and the nanoscale amorphous powder is sintered to obtain the zirconium-silicon-based glass ceramic. A novel zirconium-silicon-based nanocrystalline glass ceramic system which is tough and is resistant to damage is developed by alloying the zirconium-silicon-based glass ceramic with alloying elements having various valences and cation radii.

Description

Zirconium-silicon-based glass-ceramics with ultra-high toughness and bending strength and a method for preparing the same TECHNICAL FIELD

[0001] The present application relates to the technical field of glass-ceramics, and particularly relates to a zirconium-silicon-based glass-ceramics with ultra-high toughness and bending strength and a method for preparing the same. BACKGROUND

[0002] Dental glass-ceramics are an important type of oral repair materials, and are widely used in the production of restorations such as crowns, bridges, inlays, veneers, etc. Glass-ceramics were first developed in the 1960s and applied in dentistry. After years of research and technological development, they have become a mainstream restoration material on a par with metal and resin-based materials. The main feature of glass-ceramics is its unique aesthetic effect and excellent biocompatibility. Its translucency and similar optical properties to natural teeth make the appearance of the restoration in the mouth very close to natural teeth. This feature makes glass-ceramics particularly suitable for the restoration of the anterior aesthetic area. In addition, the color of the glass-ceramic material can be finely adjusted according to the color of the patient's teeth to achieve the desired aesthetic effect.

[0003] In addition to aesthetic properties, the chemical properties of glass-ceramics also make them an excellent restoration material. Its main components often include silicon dioxide, aluminum oxide, potassium oxide, sodium oxide, etc., which have good chemical compatibility with human tissues. This material does not cause immune reactions or allergies, has good biocompatibility, and its surface is smooth and not prone to accumulation of dental plaque, which is conducive to long-term maintenance of oral health.

[0004] In terms of mechanical properties, dental glass-ceramics can achieve relatively high strength through different strengthening processes such as crystal precipitation and heat treatment. Common types of glass-ceramics include materials containing feldspar, alumina, lithium disilicate, phosphate crystals, etc. Each type of glass-ceramic has different physical properties and can meet different restoration needs. For example, lithium disilicate glass-ceramics are widely used in posterior tooth restoration due to their high strength and toughness.

[0005] However, despite the many advantages of glass-ceramics, their brittleness still limits their application in high-load areas, and low toughness limits the wider application of glass-ceramic materials. Enhancing the toughness of glass-ceramics remains a major challenge, and even with all-ceramic materials, plane slip is almost impossible due to their inherent properties. With the increasing demand for material performance, modern dental technology also presents new challenges to glass-ceramics, including improving their mechanical properties without sacrificing aesthetic effects, and improving efficiency and reducing waste during processing.

[0006] Currently, the strength of glass-ceramics can be improved in the following ways: (1) Crystal precipitation strengthening: Introducing crystalline phases (such as lithium disilicate crystals or phosphate crystals) into the glass matrix, and promoting the crystallization of the crystals in the matrix through heat treatment process. These micron or nanoscale crystals can prevent the propagation of cracks, thereby enhancing the crack resistance of the material. (2) Toughening mechanism: The common toughening mechanisms in the study include crack blunting and crack deflection. When the crack propagates to the interface between the crystal and the matrix, the crack path will be deflected or blocked, reducing the crack propagation speed and thus improving the toughness of the material. (3) Particle or fiber reinforcement: By introducing other phases (such as zirconia particles or fibers) into the glass-ceramics, the fracture toughness of the material can be effectively enhanced. These reinforcing phases can provide stress dispersion at stress concentration points, thereby reducing the formation and propagation of microcracks. However, the enhancement results of these mechanisms are limited, and the current glass-ceramics still cannot meet the clinical requirements. Therefore, new methods and mechanisms are needed. SUMMARY

[0007] The purpose of the present application is to provide a zirconium-silicon-based glass ceramic with ultra-high toughness and bending strength and a preparation method thereof, which solves the problem of poor toughness of existing glass ceramic materials.

[0008] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0009] The present application provides a zirconium-silicon-based glass ceramic with ultra-high toughness and bending strength, which comprises the following components in mole percentage:

[0010] X 1-15%, ZrO2 25-70%, SiO2 25-70%;

[0011] Wherein, X is a metal oxide with +1 to +5 valence.

[0012] Preferably, in the above-mentioned zirconium-silicon-based glass ceramic with ultra-high toughness and bending strength, X is K2O, MgO, Al2O3, Y2O3, CeO2 or Ta2O5.

[0013] The present application also provides a preparation method of a zirconium-silicon-based glass ceramic with ultra-high toughness and bending strength, comprising the following steps:

[0014] Mixing the precursor of X, the zirconium-based precursor, the silicon-based precursor and the alcohol solution to obtain a mixed solution;

[0015] Adding an alkaline solution to the mixed solution to react, and then aging after the reaction to obtain nano-gel particles;

[0016] Calcining the nano-gel particles to obtain a powder;

[0017] The powder is sintered to obtain the zirconium-silicon-based glass ceramic.

[0018] Preferably, in the above method for preparing the zirconium-silicon-based glass ceramic with super-high toughness and bending strength, the precursor of X is potassium chloride, potassium nitrate, potassium isopropoxide, magnesium chloride, magnesium nitrate, aluminum chloride, aluminum nitrate, aluminum isopropoxide, yttrium chloride, yttrium nitrate, yttrium triisopropoxide, cerium chloride, cerium nitrate hexahydrate, cerium tetraisopropoxide, tantalum nitrate, tantalum penta-isopropoxide or tantalum chloride.

[0019] The zirconium-based precursor is zirconium n-propylate, zirconium dichloride or zirconium nitrate.

[0020] The silicon-based precursor is tetraethyl orthosilicate, ethyl silicate, tetramethoxysilane or tetraisopropoxysilane.

[0021] The alcohol solution is propanol or anhydrous ethanol.

[0022] Preferably, in the above method for preparing the zirconium-silicon-based glass ceramic with super-high toughness and bending strength, the ratio of the zirconium-based precursor to the alcohol solution is 0.5:1 to 1:10.

[0023] Preferably, in the above method for preparing the zirconium-silicon-based glass ceramic with super-high toughness and bending strength, the mixing temperature is 20 to 50℃, the mixing time is 0.5 to 2h, and the mixing speed is 500 to 1500rpm.

[0024] Preferably, in the above method for preparing the zirconium-silicon-based glass ceramic with super-high toughness and bending strength, the alkaline solution is an ammonia solution or a sodium hydroxide solution.

[0025] The concentration of the alkaline solution is 0.1 to 2mol / L.

[0026] The volume ratio of the alcohol solution to the alkaline solution is 1 to 8:1.

[0027] Preferably, in the above method for preparing the zirconium-silicon-based glass ceramic with super-high toughness and bending strength, the aging temperature is 20 to 90℃, and the aging time is 0.5 to 72h.

[0028] Preferably, in the above method for preparing the zirconium-silicon-based glass ceramic with super-high toughness and bending strength, the calcination conditions are as follows: the initial temperature is 20 to 30℃, the final temperature is 400 to 700℃, the rate of increasing the temperature from the initial temperature to the final temperature is 0.5 to 5℃ / min, and the holding time at the final temperature is 30 to 180min.

[0029] Preferably, in the preparation method of the zirconium-silicon-based glass ceramic with super-high toughness and bending strength, the sintering method is pressureless sintering, hot-press sintering, hot isostatic sintering or rapid sintering.

[0030] The rapid sintering is spark plasma sintering or rapid hot-press sintering.

[0031] Compared with the prior art, the application has the following beneficial effects:

[0032] In the application, the ZrO2-SiO2 glass ceramic is alloyed with alloying elements (K + (138pm), Mg 2+ (89pm), Al 3+ (54pm), Ce 4+ (97pm) and Ta 5+ (74pm) with different valence states and cation radii, and a new type of tough and damage-resistant zirconium-silicon-based nanocrystalline glass ceramic system is developed. High-purity nanoscale zirconium-silicon-based amorphous powder doped with cations (K2O, MgO, Al2O3, CeO2, Ta2O5) is prepared by a precipitation method; and the zirconium-silicon-based glass ceramic is obtained by sintering the nanoscale amorphous powder. This method introduces a new strategy: instead of weakening the nanointerface in the glass ceramic, the nanointerface is further strengthened by alloying different elements, so as to strengthen the brittle inorganic material. This prevents the formation of a single main crack and creates an intermediate stage between strengthening and weakening.

[0033] The application can realize a material formula containing up to 25-70% (molar ratio) of zirconia. The average grain size of the sintered material is less than about 100 nm, and the minimum can be less than 50 nm, and the obtained material shows excellent mechanical properties.

[0034] The zirconium-silicon-based glass ceramic prepared by the application embeds spherical nanocrystalline ZrO2 balls in an amorphous SiO2 matrix, and the doping elements (K, Mg, Al, Ce, Ta) are segregated in the interface layer, wherein the content of ZrO2 is more than 50% (volume ratio), and the bending strength of the material is more than about 500 MPa, and the highest is more than 900 MPa, and the fracture toughness is more than about 4 MPa, and the highest can be more than 12 MPa. BRIEF DESCRIPTION OF DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description.

[0036] Figure 1 is a graph of mechanical properties of zirconium silicate-based glass-ceramics and lithium silicate glass-ceramics of Examples 1-5; (a) toughness and flexural strength of zirconium silicate-based glass-ceramics of Examples 1-5; (b) nano-hardness and elastic modulus of zirconium silicate-based glass-ceramics of Examples 1-5; (c) flexural strength and toughness of lithium silicate glass-ceramics, inset in (c) is a comparison of indentation traces of lithium silicate glass-ceramics and zirconium silicate-based glass-ceramics 5MgO-65Zr02-30Si02 of Example 2 under 1 kgf applied load; (d) SEM images of fracture surface of zirconium silicate-based glass-ceramics 5MgO-65Zr02-30Si02 of Example 2, inset in (d) is a higher magnification SEM image of fracture surface of 5MgO-65Zr02-30Si02; (e) appearance of lithium silicate glass-ceramics and zirconium silicate-based glass-ceramics 5MgO-65Zr02-30Si02 of Example 2 after 30 kgf applied load; (f) representative SEM images of indentation crack tip of zirconium silicate-based glass-ceramics 5MgO-65Zr02-30Si02 of Example 2; (g) representative SEM images of indentation crack tip of 5MgO-65Zr02-30Si02 after etching with hydrofluoric acid (HF);

[0037] Figure 2 is a SEM image of indentation traces of lithium silicate glass-ceramics and zirconium silicate-based glass-ceramics of Examples 1-5 under 1 kgf, 5 kgf, and 10 kgf load; the scale bars in the SEM images of indentation traces of lithium silicate glass-ceramics under 1 kgf, 5 kgf, and 10 kgf load are 70 μm, 100 μm, 100 μm, respectively; the scale bars in the SEM images of indentation traces of zirconium silicate-based glass-ceramics of Examples 1-5 under 1 kgf, 5 kgf, and 10 kgf load are 70 μm, 70 μm, 100 μm, respectively;

[0038] Figure 3 is a SEM image of indentation traces of zirconium silicate-based glass-ceramics 5MgO-65Zr02-30Si02 of Example 2 under 30 kgf load;

[0039] Figure 4 is STEM-HAADF images and corresponding STEM-EDS elemental maps of zirconium-silicon-based glass-ceramics produced in Examples 1-5; where (a) is a STEM-HAADF image of 5K20-65Zr02-30Si02, (b) is a STEM-HAADF image of 5MgO-65Zr02-30Si02, (c) is a STEM-HAADF image of 5AI2O3-65Zr02-30Si02, (d) is a STEM-HAADF image of 5Ce02-65Zr02-30Si02, (e) is a STEM-HAADF image of 5Ta205-65Zr02-30Si02, (f) is a STEM-EDS elemental map of 5K20-65Zr02-30Si02, (g) is a STEM-EDS elemental map of 5MgO-65Zr02-30Si02, (h) is a STEM-EDS elemental map of 5AI2O3-65Zr02-30Si02, (i) is a STEM-EDS elemental map of 5Ce02-65Zr02-30Si02, (j) is a STEM-EDS elemental map of 5Ta205-65Zr02-30Si02;

[0040] Figure 5 is STEM-HAADF images of zirconium-silicon-based glass-ceramics produced in Examples 1-3 at scales of 100 nm and 50 nm; where (a), (b) are STEM-HAADF images of zirconium-silicon-based glass-ceramics produced in Example 1 at scales of 100 nm and 50 nm, respectively, (c), (d) are STEM-HAADF images of zirconium-silicon-based glass-ceramics produced in Example 2 at scales of 100 nm and 50 nm, respectively, (e), (f) are STEM-HAADF images of zirconium-silicon-based glass-ceramics produced in Example 3 at scales of 100 nm and 50 nm, respectively;

[0041] Figure 6 is STEM-HAADF images of zirconium-silicon-based glass-ceramics produced in Examples 4, 5 at scales of 100 nm and 50 nm; where (a), (b) are STEM-HAADF images of zirconium-silicon-based glass-ceramics produced in Example 4 at scales of 100 nm and 50 nm, respectively, (c), (d) are STEM-HAADF images of zirconium-silicon-based glass-ceramics produced in Example 5 at scales of 100 nm and 50 nm, respectively;

[0042] Figure 7 is a picture of characterization of the zirconium-silicon-based glass ceramic in Examples 1-5, wherein (a) is an XRD pattern of the zirconium-silicon-based glass ceramic in Examples 1-5, (b) is a grain size of the zirconium-silicon-based glass ceramic in Examples 1-5, (c) is a low magnification STEM-HAADF image of 5MgO-65ZrO2-30SiO2 in Example 2, (d)-(f) are high magnification STEM-HAADF images of 5MgO-65ZrO2-30SiO2 in Example 2, and (g) is a ZrO2 particle distribution in 5MgO-65ZrO2-30SiO2 in Example 2;

[0043] Figure 8 is an XRD pattern of the zirconium-silicon-based glass ceramic in Examples 1-10. DETAILED DESCRIPTION

[0044] The present application provides a zirconium-silicon-based glass ceramic with super-high toughness and bending strength, comprising the following components in mole percentage:

[0045] X 1-15%, ZrO2 25-70%, SiO2 25-70%;

[0046] X is a metal oxide with valence of +1 to +5.

[0047] In the present application, X is preferably K2O, MgO, Al2O3, Y2O3, CeO2 or Ta2O5, further preferably K2O, MgO, Al2O3 or CeO2, and more preferably MgO or CeO2.

[0048] In the present application, the mole percentage of X is preferably 1-15%, further preferably 4-10%, and more preferably 5-8%.

[0049] In the present application, the mole percentage of ZrO2 is preferably 25-70%, further preferably 41-64%, and more preferably 52-63%.

[0050] In the present application, the mole percentage of SiO2 is preferably 25-70%, further preferably 31-55%, and more preferably 32-35%.

[0051] The present application also provides a preparation method of a zirconium-silicon-based glass ceramic with super-high toughness and bending strength, comprising the following steps:

[0052] Mixing a precursor of X, a zirconium-based precursor, a silicon-based precursor and an alcohol solution to obtain a mixed solution;

[0053] Adding an alkaline solution to the mixed solution for reaction, and aging after the reaction to obtain nano-gel particles;

[0054] Calcining the nano-gel particles to obtain a powder;

[0055] sintering the powder to obtain a zirconium-silicon-based glass ceramic.

[0056] In the present application, the precursor of X is preferably potassium chloride, potassium nitrate, potassium isopropoxide, magnesium chloride, magnesium nitrate, aluminum chloride, aluminum nitrate, aluminum isopropoxide, yttrium chloride, yttrium nitrate, yttrium triisopropoxide, cerium chloride, cerium nitrate hexahydrate, tetraisopropoxy cerium, tantalum nitrate, pentaisopropoxy tantalum or tantalum chloride.

[0057] In the present application, the zirconium-based precursor is preferably zirconium n-propylate, zirconium dichloride or zirconium nitrate.

[0058] In the present application, the silicon-based precursor is preferably tetraethyl orthosilicate, ethyl silicate, tetramethoxysilane or tetraisopropoxysilane.

[0059] In the present application, the alcohol solution is preferably 1-propanol or anhydrous ethanol, more preferably 1-propanol.

[0060] In the present application, the volume ratio of the zirconium-based precursor to the alcohol solution is preferably 0.5:1 to 1:10, further preferably 1:1 to 1:6, more preferably 1:1.5 to 1:4.

[0061] In the present application, the specific process of mixing is as follows:

[0062] First, the precursor of X is added to the alcohol solution, and stirred at 550 rpm at 40℃ until the precursor of X is completely dissolved, then the zirconium-based precursor and the silicon-based precursor are added for mixing.

[0063] In the present application, the temperature of mixing is preferably 20 to 50℃, further preferably 25 to 45℃, more preferably 30 to 40℃; the time of mixing is preferably 0.5 to 2h, further preferably 0.75 to 1.5h, more preferably 1 to 1.25h; the rotation speed of mixing is preferably 500 to 1500rpm, further preferably 550 to 900rpm, more preferably 600 to 650rpm.

[0064] In the present application, the alkaline solution is preferably an ammonia solution or a sodium hydroxide solution;

[0065] The concentration of the alkaline solution is preferably 0.1 to 2mol / L, further preferably 0.5 to 1.3mol / L, more preferably 1 to 1.2mol / L;

[0066] The volume ratio of the alcohol solution to the alkaline solution is preferably 1 to 8:1, further preferably 4 to 7:1, more preferably 5 to 6:1.

[0067] In the present application, the adding process of the alkaline solution is: adding the alkaline solution in batches under stirring condition;

[0068] The rate of the stirring is preferably 500-1200 rpm, further preferably 600-1000 rpm, and more preferably 700-900 rpm.

[0069] The number of the batches is preferably 17-50, further preferably 20-45, and more preferably 25-35. The adding of the alkaline solution is to initiate the hydrolysis, polymerization and precipitation of the sol.

[0070] In the present application, the temperature of the reaction is preferably 20-50℃, further preferably 22-40℃, and more preferably 25-30℃; and the time of the reaction is preferably 8-15 min, further preferably 9-14 min, and more preferably 10-12 min.

[0071] In the present application, the temperature of the aging is preferably 20-90℃, further preferably 35-75℃, and more preferably 40-55℃; and the time of the aging is preferably 0.5-72 h, further preferably 1-48 h, and more preferably 1.5-36 h.

[0072] In the present application, after the aging, the obtained product is dried, and then ball-milled.

[0073] The temperature of the drying is preferably 50-120℃, further preferably 65-110℃, and more preferably 70-90℃; and the time of the drying is preferably 1-48 h, further preferably 5-36 h, and more preferably 8-24 h.

[0074] The time of the ball-milling is preferably 30-150 min, further preferably 40-90 min, and more preferably 55-60 min.

[0075] In the present application, the conditions of the calcination are: the initial temperature is preferably 20-30℃, further preferably 22-28℃, and more preferably 24-25℃; the final temperature is preferably 400-700℃, further preferably 450-630℃, and more preferably 520-600℃; the rate of increasing from the initial temperature to the final temperature is preferably 0.5-5℃ / min, further preferably 1-4℃ / min, and more preferably 1.5-3.5℃ / min; and the time of keeping at the final temperature is preferably 30-180 min, further preferably 40-150 min, and more preferably 60-120 min. The purpose of the calcination is to burn off the residual chemicals.

[0076] In this invention, the sintering method is preferably pressureless sintering, hot pressing sintering, hot isostatic pressing sintering, or rapid sintering, and more preferably rapid sintering;

[0077] The rapid sintering is preferably spark plasma sintering or rapid hot pressing sintering, and more preferably spark plasma sintering.

[0078] In this invention, the sintering method is spark plasma sintering, and the sintering process is as follows:

[0079] Under a pressure of 40–100 MPa, the temperature is raised from a first temperature of 350–400°C to a second temperature of 700–1000°C at a first heating rate of 80–150°C / min, and then raised to a third temperature of 1050–1250°C at a second heating rate of 20–50°C / min. The temperature is held for 3–7 minutes. After the holding period, the temperature is lowered to a fourth temperature of 700–800°C at a rate of 20–40°C / min.

[0080] The pressure is preferably 40-100 MPa, more preferably 50-85 MPa, and even more preferably 60-75 MPa;

[0081] The preferred first temperature is 350-400°C, more preferably 366-380°C, and even more preferably 370-375°C;

[0082] The second temperature is preferably 700–1000°C, more preferably 730–980°C, and even more preferably 800–900°C;

[0083] The first heating rate is preferably 80-150℃ / min, more preferably 83-138℃ / min, and even more preferably 95-125℃ / min;

[0084] The third temperature is preferably 1050-1250°C, more preferably 1130-1200°C, and even more preferably 1145-1150°C;

[0085] The second heating rate is preferably 20-50℃ / min, more preferably 25-43℃ / min, and even more preferably 30-38℃ / min;

[0086] Keep warm for 3 to 7 minutes, more preferably 4 to 6 minutes, and even more preferably 5 minutes;

[0087] The cooling rate is 20–40 °C / min, more preferably 22–37 °C / min, and even more preferably 25–30 °C / min;

[0088] The fourth temperature is preferably 700-800°C, further preferably 720-780°C, and more preferably 730-750°C. By pressure-assisted sintering, a ZrO2-SiO2 nanoglass-ceramic is obtained, in which spherical ZrO2 nanocrystalline grains with a grain size in the range of 10-100 nm are embedded in an amorphous SiO2 matrix. Tetragonal ZrO2 grains are embedded in an amorphous SiO2 matrix, while the doping elements are segregated at the interface between the ZrO2 grains and the ZrO2 grains / glass matrix.

[0089] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0090] Embodiment 1

[0091] A preparation method of a zirconium-silicon-based glass ceramic 5K2O-65ZrO2-30SiO2 with super-high toughness and bending strength, comprising the following steps:

[0092] 2.53 g of potassium chloride was mixed with 250 mL of 1-propanol, and stirred at a speed of 550 rpm at 40°C until the potassium chloride was completely dissolved, then 46 mL of tetraethyl orthosilicate and 200 mL of zirconium n-propylate were added for mixing, and the stirring was continued at a speed of 550 rpm at 30°C for 0.5 h to obtain a mixed solution;

[0093] 50 mL of 0.1 mol / L ammonia solution was added to the mixed solution at a stirring speed of 500 rpm (added in batches, 2 mL each time), and then stirred at a speed of 500 rpm at 25°C for 10 min. After stirring, the obtained product was dried at 80°C for 48 h, and then ball-milled for 45 min to obtain gel particles;

[0094] The gel particles were heated at a rate of 1°C / min to 600°C at 25°C, and calcined at 600°C for 1 h to obtain a powder;

[0095] The powder was subjected to spark plasma sintering (SPS-825, Fuji Electronic Industrial Co., Ltd., Japan); the sintering process was as follows: heated from 400°C to 900°C at a rate of 125°C / min under a pressure of 60 MPa, then further heated to 1150°C at a rate of 38°C / min, kept for 5 min, and then cooled to 800°C at a rate of 30°C / min to obtain a zirconium-silicon-based glass ceramic 5K2O-65ZrO2-30SiO2, denoted as 5K-65Zr-30Si.

[0096] Example 2

[0097] A method for preparing a zirconium-silicon-based glass ceramic 5MgO-65ZrO2-30SiO2 with super-high toughness and bending strength, comprising the following steps:

[0098] 3.24 g of magnesium chloride was mixed with 250 mL of 1-propanol, stirred at a speed of 550 rpm at 40 °C until the potassium chloride was completely dissolved, then 46 mL of tetraethyl orthosilicate and 200 mL of zirconium n-propyl alcohol were added for mixing, and the stirring was continued at a speed of 550 rpm at 30 °C for 0.5 h to obtain a mixed solution;

[0099] 50 mL of 0.1 mol / L ammonia solution was added to the mixed solution at a stirring speed of 500 rpm (added in batches, 2 mL each time), then stirred at a speed of 500 rpm at 25 °C for 10 min, and after the stirring was completed, the obtained product was dried at 80 °C for 48 h, and then ball-milled for 45 min to obtain gel particles;

[0100] The gel particles were heated at a rate of 1 °C / min from 25 °C to 600 °C, and calcined at 600 °C for 1 h to obtain a powder;

[0101] The powder was subjected to spark plasma sintering (SPS-825, Fuji Electronic Industrial Co., Ltd., Japan); the sintering process: heated from 400 °C to 900 °C at a rate of 125 °C / min under a pressure of 60 MPa, then further heated to 1150 °C at a rate of 38 °C / min, kept for 5 min, and then cooled to 800 °C at a rate of 30 °C / min to obtain a zirconium-silicon-based glass ceramic 5MgO-65ZrO2-30SiO2, denoted as 5Mg-65Zr-30Si.

[0102] Example 3

[0103] A method for preparing a zirconium-silicon-based glass ceramic 5Al2O3-65ZrO2-30SiO2 with super-high toughness and bending strength, comprising the following steps:

[0104] 6.94 g of isopropoxy aluminum was mixed with 250 mL of 1-propanol, stirred at a speed of 550 rpm at 40 °C until the potassium chloride was completely dissolved, then 46 mL of tetraethyl orthosilicate and 200 mL of zirconium n-propyl alcohol were added for mixing, and the stirring was continued at a speed of 550 rpm at 30 °C for 0.5 h to obtain a mixed solution;

[0105] The mixed solution was stirred at 500 rpm, and 50 mL of 0.1 mol / L ammonia solution was added (added in batches, 2 mL each time) at 25 °C and 500 rpm for 10 min. After stirring, the reaction was aged at 60 °C for 72 h. The product was dried at 80 °C for 48 h, and then ball-milled for 45 min to obtain gel particles;

[0106] The gel particles were heated at 1 °C / min to 600 °C at 25 °C, and calcined at 600 °C for 1 h to obtain a powder;

[0107] The powder was subjected to spark plasma sintering (SPS-825, Fuji Electronic Industrial Co., Ltd., Japan); the sintering process was as follows: heated from 400 °C to 900 °C at a rate of 125 °C / min under a pressure of 60 MPa, and then further heated to 1150 °C at a rate of 38 °C / min, and kept for 5 min, and then cooled to 800 °C at a rate of 30 °C / min to obtain a zirconium-silicon-based glass ceramic 5Al2O3-65ZrO2-30SiO2, denoted as 5Al-65Zr-30Si.

[0108] Example 4

[0109] A method for preparing a zirconium-silicon-based glass ceramic 5CeO2-65ZrO2-30SiO2 with super-high toughness and bending strength, comprising the following steps:

[0110] 14.76 g of cerium nitrate hexahydrate was mixed with 250 mL of 1-propanol, and stirred at 550 rpm at 40 °C until the potassium chloride was completely dissolved. Then 46 mL of tetraethyl orthosilicate and 200 mL of zirconium n-propylate were added for mixing, and the stirring was continued at 550 rpm at 30 °C for 0.5 h to obtain a mixed solution.

[0111] The mixed solution was stirred at 500 rpm, and 50 mL of 0.1 mol / L ammonia solution was added (added in batches, 2 mL each time) at 25 °C and 500 rpm for 10 min. After stirring, the reaction was aged at 60 °C for 72 h. The product was dried at 80 °C for 48 h, and then ball-milled for 45 min to obtain gel particles;

[0112] The gel particles were heated at 1 °C / min to 600 °C at 25 °C, and calcined at 600 °C for 1 h to obtain a powder;

[0113] The powder was subjected to spark plasma sintering (SPS-825, Fuji Electronic Industrial Co., Ltd.); the sintering process: heating from 400℃ to 900℃ at a rate of 125℃ / min under a pressure of 60MPa, then further heating to 1150℃ at a rate of 38℃ / min, holding for 5min, and then cooling to 800℃ at a rate of 30℃ / min, to obtain a zirconium-silicon-based glass ceramic 5CeO2-65ZrO2-30SiO2, denoted as 5Ce-65Zr-30Si.

[0114] Example 5

[0115] A method for preparing a zirconium-silicon-based glass ceramic 5Ta2O5-65ZrO2-30SiO2 with super-high toughness and bending strength, comprising the following steps:

[0116] 12.18g of tantalum chloride was mixed with 250mL of 1-propanol, stirred at a speed of 550rpm at 40℃ until the potassium chloride was completely dissolved, then 46mL of tetraethyl orthosilicate and 200mL of zirconium n-propyl alcohol were added for mixing, and the stirring was continued at a speed of 550rpm at 30℃ for 0.5h to obtain a mixed solution;

[0117] 50mL of 0.1mol / L ammonia solution was added to the mixed solution at a stirring speed of 500rpm (added in batches, 2mL each time), then stirred at a speed of 500rpm at 25℃ for 10min, and then aged at 60℃ for 72h, and then dried at 80℃ for 48h, and then ball-milled for 45min to obtain gel particles;

[0118] The gel particles were heated at a rate of 1℃ / min to 600℃, and calcined at 600℃ for 1h to obtain a powder;

[0119] The powder was subjected to spark plasma sintering (SPS-825, Fuji Electronic Industrial Co., Ltd.); the sintering process: heating from 400℃ to 900℃ at a rate of 125℃ / min under a pressure of 60MPa, then further heating to 1150℃ at a rate of 38℃ / min, holding for 5min, and then cooling to 800℃ at a rate of 30℃ / min, to obtain a zirconium-silicon-based glass ceramic 5Ta2O5-65ZrO2-30SiO2, denoted as 5Ta-65Zr-30Si.

[0120] Example 6

[0121] A method for preparing a zirconium-silicon-based glass ceramic 5K2O-60ZrO2-35SiO2, 10K2O-60ZrO2-30SiO2 with super-high toughness and bending strength, consistent with Example 1, except that:

[0122] For preparing 5K2O-60ZrO2-35SiO2(5K-60Zr-35Si), the amount of potassium chloride is 2.76g, the amount of tetraethyl orthosilicate is 58.1 mL, and the amount of zirconium n-propylate is 200 mL;

[0123] For preparing 10K2O-60ZrO2-30SiO2(10K-60Zr-30Si), the amount of potassium chloride is 5.52g, the amount of tetraethyl orthosilicate is 49.8 mL, and the amount of zirconium n-propylate is 200 mL.

[0124] Example 7

[0125] A method for preparing zirconium-silicon-based glass ceramic 5MgO-60ZrO2-35SiO2, 10MgO-60ZrO2-30SiO2 with super-high toughness and bending strength, which is consistent with Example 1, except that:

[0126] For preparing 5MgO-60ZrO2-35SiO2(5Mg-60Zr-35Si), the amount of magnesium chloride is 3.52g, the amount of tetraethyl orthosilicate is 58.1 mL, and the amount of zirconium n-propylate is 200 mL;

[0127] For preparing 10MgO-60ZrO2-30SiO2(10Mg-60Zr-30Si), the amount of magnesium chloride is 7.05g, the amount of tetraethyl orthosilicate is 49.8 mL, and the amount of zirconium n-propylate is 200 mL.

[0128] Example 8

[0129] A method for preparing zirconium-silicon-based glass ceramic 5Al2O3-60ZrO2-35SiO2, 10Al2O3-60ZrO2-30SiO2 with super-high toughness and bending strength, which is consistent with Example 1, except that:

[0130] For preparing 5Al2O3-60ZrO2-35SiO2(5Al-60Zr-35Si), the amount of isopropoxy aluminum is 7.56g, the amount of tetraethyl orthosilicate is 58.1 mL, and the amount of zirconium n-propylate is 200 mL;

[0131] For preparing 10Al2O3-60ZrO2-30SiO2(10Al-60Zr-30Si), the amount of isopropoxy aluminum is 15.12g, the amount of tetraethyl orthosilicate is 49.8 mL, and the amount of zirconium n-propylate is 200 mL.

[0132] Example 9

[0133] A method for preparing zirconium-silicon-based glass ceramics 5CeO2-60ZrO2-35SiO2, 10CeO2-60ZrO2-30SiO2 with super-high toughness and bending strength, consistent with Example 1, the difference lies in:

[0134] When preparing 5CeO2-60ZrO2-35SiO2(5Ce-60Zr-35Si), the amount of cerium nitrate hexahydrate is 16.07g, the amount of tetraethyl orthosilicate is 58.1mL, and the amount of zirconium n-propyl alcohol is 200mL;

[0135] When preparing 10CeO2-60ZrO2-30SiO2(10Ce-60Zr-30Si), the amount of cerium nitrate hexahydrate is 32.13g, the amount of tetraethyl orthosilicate is 49.8mL, and the amount of zirconium n-propyl alcohol is 200mL.

[0136] Example 10

[0137] A method for preparing zirconium-silicon-based glass ceramics 5Ta2O5-60ZrO2-35SiO2, 10Ta2O5-60ZrO2-30SiO2 with super-high toughness and bending strength, consistent with Example 1, the difference lies in:

[0138] When preparing 5Ta2O5-60ZrO2-35SiO2(5Ta-60Zr-35Si), the amount of tantalum chloride is 13.25g, the amount of tetraethyl orthosilicate is 58.1mL, and the amount of zirconium n-propyl alcohol is 200mL;

[0139] When preparing 10Ta2O5-60ZrO2-30SiO2(10Ta-60Zr-30Si), the amount of tantalum chloride is 26.51g, the amount of tetraethyl orthosilicate is 49.8mL, and the amount of zirconium n-propyl alcohol is 200mL.

[0140] Mechanical property test:

[0141] The elastic modulus and nano-hardness were measured using a nano-indenter (UltraNano Indenter, CSM Instruments, Switzerland) with a load of 8000μN at a rate of 8000μN / min, 20 indents were made on each sample, and three samples were selected for testing in each group; the fracture toughness was measured using a micro-indenter based on the indentation method, with a load of 8000μN at a rate of 8000μN / min, 5 indents were made at different positions on each sample, the micro-hardness was measured, and the micro-indenter and SEM were used to observe the diagonal line (α) of the indentation and the crack length (l) from the edge of the diagonal line, respectively. The NiiharaK method was used to calculate the fracture toughness for Palmqvist cracks.

[0142] Piston-three ball tests were performed on polished samples supported by three balls distributed on a circle with a radius of 3.445 mm. An autograph (Autograph AGS-H; Shimadzu, Japan) was used. Biaxial flexural strength was calculated according to the ISO 6872 standard.

[0143] The toughness and flexural strength of the zirconia-silica-based glass-ceramics 5K2O-65ZrO2-30SiO2, 5MgO-65ZrO2-30SiO2, 5Al2O3-65ZrO2-30SiO2, 5CeO2-65ZrO2-30SiO2, 5Ta2O5-65ZrO2-30SiO2 produced in Examples 1-5 are shown in Figure 1(a). As can be seen from Figure 1(a), 5MgO-65ZrO2-30SiO2exhibited significantly higher toughness, 12.39 ± 1.34 MPa·m 1 / 2 , followed by 5CeO2-65ZrO2-30SiO2(11.52 ± 1.63 MPa·m 1 / 2 ), 5Al2O3-65ZrO2-30SiO2(8.19 ± 1.49 MPa·m 1 / 2 ), 5Ta2O5-65ZrO2-30SiO2(6.94 ± 0.86 MPa·m 1 / 2 ) and 5K2O-65ZrO2-30SiO2(5.54 ± 0.35 MPa·m 1 / 2 ); 5K2O-65ZrO2-30SiO2exhibited the highest flexural strength, 910 ± 52 MPa, followed by 5CeO2-65ZrO2-30SiO2, 5Ta2O5-65ZrO2-30SiO2, 5MgO-65ZrO2-30SiO2and 5Al2O3-65ZrO2-30SiO2.

[0144] The nano-hardness and elastic modulus of the zirconia-silica based glass-ceramics 5K2O-65ZrO2-30SiO2, 5MgO-65ZrO2-30SiO2, 5Al2O3-65ZrO2-30SiO2, 5CeO2-65ZrO2-30SiO2, 5Ta2O5-65ZrO2-30SiO2 produced in Examples 1-5 are shown in Figure 1 (b). As can be seen from Figure 1 (b), 5MgO-65ZrO2-30SiO2 shows the highest nano-hardness and elastic modulus values of 11.86 ± 0.89 GPa and 203.55 ± 13.98 GPa, respectively; in contrast, 5CeO2-65ZrO2-30SiO2 shows the lowest hardness of 9.88 ± 0.65 GPa, while 5K2O-65ZrO2-30SiO2 has the lowest elastic modulus of 127.99 ± 7.69 GPa.

[0145] Figure 1 (c) is a plot of the flexural strength and toughness of lithium disilicate glass-ceramics, and the inset of Figure 1 (c) is a comparison of the indentation marks of lithium disilicate glass-ceramics and zirconia-silica based glass-ceramics 5MgO-65ZrO2-30SiO2 produced in Example 2 under a 1 kgf applied load. As can be seen from Figure 1 (c), the classic radial cracks starting from the corners of the Vickers indentation are clearly visible, and lithium disilicate glass-ceramics show significantly longer cracks, while no cracks are visible for the 5MgO-65ZrO2-30SiO2 sample.

[0146] Figure 1 (d) is a SEM image of the fracture surface of zirconia-silica based glass-ceramics 5MgO-65ZrO2-30SiO2 produced in Example 2, and the inset of Figure 1 (d) is a higher magnification SEM image of the fracture surface of 5MgO-65ZrO2-30SiO2. As can be seen from Figure 1 (d), the fracture surface of 5MgO-65ZrO2-30SiO2 shows nanoscale particles and voids, indicating that the fracture occurred along the interface, showing a shell-like fracture behavior.

[0147] Figure 1 (e) is the appearance of lithium disilicate glass-ceramics and 5MgO-65ZrO2-30SiO2 after a 30 kgf applied load. As can be seen from Figure 1 (e), the lithium disilicate glass-ceramics fractured during the test, while 5Mg-65Zr-30Si remained intact.

[0148] Figure 1 (f) is a representative SEM image of the indentation crack tip of zirconia-silica based glass-ceramics 5MgO-65ZrO2-30SiO2 produced in Example 2, revealing intergranular cracks progressing along the ZrO2 grain boundaries.

[0149] Figure 1 (g) is a representative indentation crack tip SEM image of 5MgO-65Zr02-30Si02 after hydrofluoric acid (HF) etching (10% HF solution etching for 90 s), crack deflection, bridging and branching were observed, revealing crack deflection and crack bridging.

[0150] The above observations suggest that micro and macro cracks propagate along the interface rather than within the glass matrix and the crystalline grains.

[0151] Material Characterization:

[0152] Phase composition was confirmed by X-ray diffraction (XRD) using a Bruker D8 double diffractometer in the range of 10-80° 2-theta with a scan rate of 2° / min. The grain size of Zr02nanocrystals was calculated using the Scherrer equation, and the (101) plane of tetragonal Zr02was selected for the calculation. The morphology of the glass-ceramics was analyzed by scanning electron microscopy (SEM, Merlin, Zeiss, Germany). To resolve the Zr02grains, the samples were etched in a HF bath to remove the Si02phase before observation. The microstructure and elemental distribution were further examined by transmission electron microscopy (TEM, FEI Company, Netherlands) and electron energy loss spectroscopy (EELS) with a GIF quantum filter (Gatan, Inc., Pleasanton, CA, USA).

[0153] Figure 2 is a SEM image of indentation traces of lithium silicate glass-ceramics and zirconium-silicon based glass-ceramics 5K20-65Zr02-30Si02, 5MgO-65Zr02-30Si02, 5Al203-65Zr02-30Si02, 5Ce02-65Zr02-30Si02, 5Ta205-65Zr02-30Si02 prepared in Examples 1-5 under 1 kgf, 5 kgf and 10 kgf load, wherein the scale bar in the SEM image of indentation traces of lithium silicate glass-ceramics under 1 kgf, 5 kgf and 10 kgf load is 70 pm, 100 pm, 100 pm, respectively; the scale bar in the SEM image of indentation traces of zirconium-silicon based glass-ceramics in Examples 1-5 under 1 kgf, 5 kgf and 10 kgf load is 70 pm, 70 pm, 100 pm, respectively. As can be seen from Figure 2, the crack is significantly shorter in the magnesium-doped sample 5MgO-65Zr02-30Si02 than in the potassium-doped sample 5K20-65Zr02-30Si02. The crack length increases with increasing load.

[0154] Figure 3 is an SEM image of indentation marks of the zirconium-silicon based glass-ceramics 5MgO-65ZrO2-30SiO2 of Example 2 under a load of 30 kgf. As can be seen from Figure 3, the length of the cracks is less than 100 microns even under a load of 30 kgf. In comparison, for lithium-silicate glass-ceramics, the samples all cracked under a load of 30 kgf.

[0155] The mechanical properties of the zirconium-silicon based glass-ceramics of Examples 1-10 are shown in Table 1.

[0156] Table 1 Mechanical properties of the zirconium-silicon based glass-ceramics of Examples 1-10

[0157] Figure 4 is a STEM-HAADF image and corresponding STEM-EDS elemental mapping of the zirconium-silicon based glass-ceramics 5K2O-65ZrO2-30SiO2, 5MgO-65ZrO2-30SiO2, 5Al2O3-65ZrO2-30SiO2, 5CeO2-65ZrO2-30SiO2, 5Ta2O5-65ZrO2-30SiO2 produced in Examples 1-5.

[0158] Figures 5, 6 are STEM-HAADF images of the zirconium-silicon based glass-ceramics 5K2O-65ZrO2-30SiO2, 5MgO-65ZrO2-30SiO2, 5Al2O3-65ZrO2-30SiO2, 5CeO2-65ZrO2-30SiO2, 5Ta2O5-65ZrO2-30SiO2 produced in Examples 1-5 at a scale of 100 nm, 50 nm.

[0159] As can be seen from Figures 4, 5, 6, two different phases of different contrast can be clearly observed, with the elliptical crystalline phase uniformly distributed in a darker matrix. In the STEM-HAADF imaging mode, the annular detector collects scattered electrons, indicating that the brightness of the micrograph depends on the atomic number Z. Thus, the brighter elliptical shapes correspond to ZrO2nanocrystals. The STEM-EDS results also confirm that the brighter ZrO2nanocrystalline phase is uniformly embedded in the darker SiO2amorphous phase. The doping elements show different distributions, with a core-shell structure observed in the Mg 2+ , Al 3+ and Ce 4+ elemental mapping, indicating that the doping elements strongly segregate at the ZrO2grain boundaries and ZrO2-SiO2interfaces. K + and Ta 5+ are mainly dissolved in the ZrO2grains with a small amount of segregation at the interfaces.

[0160] The XRD patterns of the zirconia-silica-based glass-ceramics 5K2O-65ZrO2-30SiO2, 5MgO-65ZrO2-30SiO2, 5Al2O3-65ZrO2-30SiO2, 5CeO2-65ZrO2-30SiO2, 5Ta2O5-65ZrO2-30SiO2 prepared in Examples 1-5 are shown in Figure 7(a).

[0161] The XRD patterns of the zirconia-silica-based glass-ceramics prepared in Examples 1-10 are shown in Figure 8.

[0162] As can be seen from Figure 7(a) and Figure 8, two crystalline phases were identified from the diffraction patterns of all samples, tetragonal ZrO2 (t-ZrO2) and monoclinic ZrO2 (m-ZrO2). The monoclinic phase occurs due to the phase transition of the tetragonal phase during cooling and the heterovalent doping elements with larger or smaller radii can contribute to the stability of t-ZrO2 against monoclinic distortion, since the relaxed oxygen atoms show a strong attraction to the oxygen vacancies induced by the doping elements; this process in turn leads to a distortion of the structure and thus to a decrease in the tetragonality of the crystal.

[0163] The grain size results of the zirconia-silica-based glass-ceramics 5K2O-65ZrO2-30SiO2, 5MgO-65ZrO2-30SiO2, 5Al2O3-65ZrO2-30SiO2, 5CeO2-65ZrO2-30SiO2, 5Ta2O5-65ZrO2-30SiO2 prepared in Examples 1-5 are shown in Figure 7(b). Since the doping elements segregate at the interface, it can control the grain growth behavior during sintering, because of the difficulty of nucleation (impurity drag force). Figure 7(b) illustrates the grain size of the glass-ceramics (GC) doped with different elements. The K2O-doped ZrO2-SiO2 GC shows the smallest grain size of 25.8 ± 8.1 nm. With the increase of valence, the grain size increases, reaching the highest value of 48.6 ± 17.7 nm for the Ta2O5-doped ZrO2-SiO2 GC.

[0164] Figure 7(c) is a low magnification STEM-HAADF image of 5MgO-65ZrO2-30SiO2 in Example 2. As can be seen from Figure 7(c), the ZrO2 particles mainly present an elliptical shape.

[0165] The ZrO2 particle distribution in 5MgO-65ZrO2-30SiO2 was calculated from Figure 7(c) and the results are shown in Figure 7(g). As can be seen from Figure 7(g), the ZrO2 particle size follows a Gaussian distribution.

[0166] Fig. 7 (d)-(f) are high magnification STEM-HAADF images of 5MgO-65ZrO2-30SiO2of Example 2. The triple junction between three grains and the grain boundary between the grains are shown in Fig. 7 (d) and (e), (f), respectively, and the thickness of the grain boundary is less than 1 nm.

[0167] The above description is only preferred embodiments of the present application, it should be pointed out that, for those skilled in the art, without departing from the principles of the present application, can make a number of improvements and refinements, these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A zirconia-silica based glass-ceramic having super-toughness and bending strength, characterized in that, The zirconium-silicon-based glass ceramic comprises the following components in mole percentage: X 1-15%, ZrO2 25-70%, SiO2 25-70%; The X is a metal oxide with valence of +1 to +5.

2. The zirconia-silica based glass-ceramic with super-toughness and bending strength according to claim 1, characterized in that, The X is K2O, MgO, Al2O3, Y2O3, CeO2 or Ta2O5.

3. Process for the production of zirconosilicate-based glass-ceramics with super- toughness and bending strength according to claim 1 or 2, characterized in that, The method comprises the following steps: Mixing a precursor of X, a zirconium-based precursor, a silicon-based precursor and an alcohol solution to obtain a mixed solution; Adding an alkaline solution to the mixed solution to react, and then aging after the reaction to obtain nanogel particles; Calcining the nanogel particles to obtain a powder; Sintering the powder to obtain a zirconium-silicon-based glass ceramic.

4. The method of making zirconium-silicon based glass-ceramics with super-toughness and bending strength according to claim 2, characterized in that, The precursor of X is potassium chloride, potassium nitrate, potassium isopropoxide, magnesium chloride, magnesium nitrate, aluminum chloride, aluminum nitrate, aluminum isopropoxide, yttrium chloride, yttrium nitrate, yttrium triisopropoxide, cerium chloride, cerium nitrate hexahydrate, cerium tetraisopropoxide, tantalum nitrate, tantalum penta-isopropoxide or tantalum chloride; The zirconium-based precursor is zirconium n-propylate, zirconium dichloride or zirconium nitrate; The silicon-based precursor is tetraethyl orthosilicate, ethyl silicate, tetramethoxysilane or tetraisopropoxysilane; The alcohol solution is 1-propanol or anhydrous ethanol.

5. The method of making zirconium-silicon based glass-ceramics with super-toughness and bending strength according to claim 4, characterized in that, The volume ratio of the silicon-based precursor to the alcohol solution is 0.5:1 to 1:

10.

6. The method of making zirconium-silicon based glass-ceramics with super-toughness and bending strength according to claim 5, characterized in that, The mixing temperature is 20-50°C, the mixing time is 0.5-2h, and the mixing speed is 500-1500rpm.

7. The method of producing a zirconium-silicon based glass-ceramic with super-high toughness and bending strength according to claim 5 or 6, characterized in that, The alkaline solution is an ammonia solution or a sodium hydroxide solution; The concentration of the alkaline solution is 0.1-2mol / L; The volume ratio of the alcohol solution to the alkaline solution is 1-8:

1.

8. The method of making zirconium-silicon based glass-ceramics with super-high toughness and bending strength according to claim 7, characterized in that, The aging temperature is 20-90°C, and the aging time is 0.5-72h.

9. The method of making zirconium-silicon based glass-ceramics with super-high toughness and bending strength according to claim 8, characterized in that, The calcination conditions are as follows: the initial temperature is 20-30°C, the final temperature is 400-700°C, the rate of increasing the temperature from the initial temperature to the final temperature is 0.5-5°C / min, and the holding time at the final temperature is 30-180min.

10. The method of making a zirconia-silica based glass-ceramic having super-toughness and bending strength according to claim 9, characterized in that, The sintering method is pressureless sintering, hot-pressing sintering, hot-isostatic-pressing sintering or rapid sintering; The rapid sintering is spark plasma sintering or rapid hot-pressing sintering.

Images