Transparent anti-cracking microcrystalline glass and preparation method thereof

Abstract

The invention belongs to the field of preparation of microcrystalline glass, and particularly relates to transparent anti-cracking microcrystalline glass and a preparation method thereof. The invention provides a preparation method of transparent anti-cracking microcrystalline glass. The preparation method comprises the following steps: S1, preparing a glass substrate; S2, coating a polymer layer; S3, depositing metal oxide particles; high-strength and impact-resistant chemical materials such as polyphenylene sulfide, aluminum-titanium oxide, silicon nitride and graphene are creatively adopted, a multi-layer composite structure is formed in the glass ceramic, the impact resistance, penetration resistance and toughness of the glass are remarkably improved, and the problem that in the prior art, glass ceramic is fragile under high impact is solved. The composite structure not only has good practical application value, but also opens up a new direction for research and application of glass materials.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of glass-ceramics, and particularly relates to a transparent crack-resistant glass-ceramics and a preparation method thereof. Background Art

[0002] Glass-ceramics, also known as glass ceramics, are a new type of inorganic non-metallic material. Based on glass, through specific heat treatment processes or other technical means, a large number of uniformly distributed tiny crystals are formed in the glass, thus combining the advantages of both glass and ceramics. This material combines the characteristics of glass, ceramics, and some natural stones, and has excellent physical properties such as high strength, high temperature resistance, and low coefficient of thermal expansion. With the progress of technology and the development of emerging industries, such as the aerospace, electronic information, and LED lighting fields, the demand for high-performance materials is increasing continuously. The application fields of glass-ceramics will be further broadened, and the demand is also expected to continue to grow. However, although the existing glass-ceramics have high hardness and strength, they are still prone to cracking or generating cracks when facing external impacts. Especially when the impact force is large, the glass is easy to be penetrated.

[0003] Therefore, how to enhance the impact resistance of glass-ceramics and prevent objects from penetrating is a difficult problem in the current technology, and it is very necessary to invent a transparent crack-resistant glass-ceramics. Summary of the Invention

[0004] Aiming at the above existing technical problems, the present invention aims to provide a transparent crack-resistant glass-ceramics and a preparation method thereof. The preparation method of this transparent crack-resistant glass-ceramics is to innovatively adopt high-strength and impact-resistant chemical materials such as polyphenylene sulfide, aluminum titanium oxide, silicon nitride, and graphene to form a multi-layer composite structure in the glass-ceramics, significantly improving the impact resistance, penetration resistance, and toughness of the glass, and solving the problem that the existing glass-ceramics are fragile under high impact. This composite structure not only has good practical application value but also opens up a new direction for the research and application of glass materials.

[0005] The present invention discloses a preparation method of a transparent crack-resistant glass-ceramics, including the following preparation steps:

[0006] S1 Preparation of glass matrix: Add raw materials silicon dioxide, sodium oxide, calcium oxide, magnesium oxide, aluminum oxide, and zirconium oxide to a ball mill for mixing, and then add the mixed raw materials to a high-temperature furnace for heating and melting. After the raw materials are completely melted, pour the glass liquid into a molding die for cooling and molding to obtain a glass matrix;

[0007] S2 Coating of polymer layer: Dissolve polyphenylene sulfide in a solvent to form a uniform coating solution, and use the dipping method to uniformly coat the coating solution on the surface of the glass matrix, and then form a polymer layer on the surface of the glass matrix through heat treatment;

[0008] S3 Metal oxide particle deposition: Titanium-aluminum oxide nanoparticles are uniformly deposited on the surface of the polymer layer by chemical vapor deposition to obtain a composite layer;

[0009] S4 Embedding of nano-ceramic layer: Silicon nitride nano-ceramic particles are embedded into the composite layer obtained in step S3 to obtain a nano-ceramic layer;

[0010] S5 Preparation of graphene toughening layer: Graphene nanosheets are mixed with an ethanol solvent to obtain a slurry. The slurry is coated on the surface of the nano-ceramic layer by spin coating and then heat-treated to obtain a graphene toughening layer;

[0011] S6 Heat treatment of composite structure: The glass substrate coated in steps S2 to S5 is returned to a high-temperature furnace for high-temperature heat treatment. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0012] Preferably, in the S1 glass substrate preparation step, the melting temperature of the high-temperature furnace is 1500-1700 °C, and the melting time is 2-4 h.

[0013] Preferably, in the S2 polymer layer coating step, the solvent is ethanol, and the concentration of the coating solution formed by polyphenylene sulfide is 10-20%.

[0014] Preferably, in the S3 metal oxide particle deposition step, the chemical vapor deposition uses a low-pressure CVD reactor, and the pressure of the low-pressure CVD reactor is 10-100 Pa; the deposition temperature is 300-800 °C; the deposition time is 5-10 min.

[0015] Preferably, in the S3 metal oxide particle deposition step, the oxidant used in the chemical vapor deposition is oxygen; the metal precursors are titanium tetrachloride and trimethylaluminum.

[0016] Preferably, in the S3 metal oxide particle deposition step, the flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:(0.8-1.2).

[0017] Preferably, in the S3 metal oxide particle deposition step, the gas flow rate of the oxygen is 20-200 sccm.

[0018] Preferably, in the S3 metal oxide particle deposition step, the surface of the polymer is subjected to plasma treatment.

[0019] Preferably, in the S6 composite structure heat treatment step, the temperature of the high-temperature heat treatment is 300-500 °C, and the time of the high-temperature heat treatment is 1-3 h.

[0020] A transparent crack-resistant microcrystalline glass, which is a transparent crack-resistant microcrystalline glass prepared by any one of the above transparent crack-resistant microcrystalline glass preparation methods.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The present invention provides a transparent crack-resistant microcrystalline glass and a preparation method thereof. By innovatively introducing a polyphenylene sulfide polymer layer, aluminum-titanium oxide particles, a silicon nitride nanoceramic layer, and a graphene toughening layer, the impact resistance of the microcrystalline glass is significantly improved. Especially under high-energy impact, it can effectively disperse the impact force and prevent the glass from cracking or penetrating. The hardness and anti-penetration performance of the metal oxide and ceramic layers in the composite structure greatly enhance the protection ability of the glass. The combination of the graphene toughening layer and the ceramic layer endows the glass with good toughness while ensuring high strength, avoiding brittle fracture. The transparent microcrystalline glass prepared by the present invention can be widely used in building exterior wall glass, smartphone screens, the aerospace field, and protective layers for other high-end products. Detailed implementation manners

[0023] The following embodiments are provided to better further understand the present invention. They are not limited to the best implementation manner, and do not limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with those of other prior arts falls within the protection scope of the present invention.

[0024] For those not specifying specific experimental steps or conditions in the embodiments, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For reagents or instruments without indicating the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0025] Embodiment 1: A preparation method of a transparent crack-resistant microcrystalline glass, comprising the following steps:

[0026] S1 Preparation of the glass substrate: 70% of silica, 10% of sodium oxide, 10% of calcium oxide, 3% of magnesium oxide, 3% of aluminum oxide, and 4% of zirconium oxide as raw materials are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1500 °C, and the melting time is 2 h. After the raw materials are completely melted, the glass liquid is poured into a forming mold and cooled to 500 °C for forming. After forming, it is placed in a temperature control furnace for annealing to obtain the glass substrate.

[0027] S2 Coating of the polymer layer: Polyphenylene sulfide is dissolved in an ethanol solvent to form a uniform coating solution with a concentration of 10%. The coating solution is uniformly coated on the surface of the glass substrate by impregnation, and then a polymer layer is formed on the surface of the glass substrate after heat treatment at 120 °C for 30 min.

[0028] S3 Metal Oxide Particle Deposition: The surface of the polymer layer obtained in step S2 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 10 Pa and the temperature is 300 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidant oxygen is introduced for metal oxide particle precipitation. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:0.8, and the gas flow rate of oxygen is 20 sccm. After 5 minutes of metal oxide particle precipitation, a composite layer is obtained.

[0029] S4 Embedding of Nano-Ceramic Layer: Silicon nitride nano-ceramic particles are embedded into the composite layer obtained in step S3 to obtain a nano-ceramic layer.

[0030] S5 Preparation of Graphene Toughening Layer: Graphene nanosheets and ethanol solvent are ultrasonically oscillated and mixed to obtain a slurry, and the mass fraction of graphene nanosheets is 0.1%. The slurry is coated on the surface of the nano-ceramic layer by spin coating method with a spin coating speed of 1500 rpm. After spin coating for 30 s, it is dried. After drying for 1 h, heat treatment is carried out to obtain a graphene toughening layer.

[0031] S6 Heat Treatment of Composite Structure: The glass substrate coated through steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 300 °C, and the time of the high-temperature heat treatment is 1 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0032] Example 2: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0033] S1 Glass Substrate Preparation: 70% of raw material silica, 10% of sodium oxide, 10% of calcium oxide, 3% of magnesium oxide, 3% of aluminum oxide, and 4% of zirconium oxide are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1550 °C, and the melting time is 2.5 h. After the raw materials are completely melted, the glass liquid is poured into a molding die and cooled to 500 °C for molding. After molding, it is placed in a temperature control furnace for annealing to obtain a glass substrate.

[0034] S2 Polymer Layer Coating: Polyphenylene sulfide is dissolved in ethanol solvent to form a uniform coating solution with a concentration of 12%. The coating solution is uniformly coated on the surface of the glass substrate by impregnation, and then heat-treated at 120 °C for 30 min to form a polymer layer on the surface of the glass substrate.

[0035] S3 Metal Oxide Particle Deposition: The surface of the polymer layer obtained in step S2 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 30 Pa and the temperature is set to 350 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidant oxygen is introduced for metal oxide particle precipitation. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:0.9, and the gas flow rate of oxygen is 70 sccm. After 6 minutes of metal oxide particle precipitation, a composite layer is obtained.

[0036] S4 Embedding of Nano-Ceramic Layer: Silicon nitride nano-ceramic particles are embedded into the composite layer obtained in step S3 to obtain a nano-ceramic layer.

[0037] S5 Preparation of Graphene Toughening Layer: Graphene nanosheets and ethanol solvent are ultrasonically oscillated and mixed to obtain a slurry. The mass fraction of graphene nanosheets is 0.2%. The slurry is coated on the surface of the nano-ceramic layer by spin coating at a controlled spin coating speed of 1500 rpm. After spin coating for 30 s, it is dried. After drying for 1 h, heat treatment is carried out to obtain a graphene toughening layer.

[0038] S6 Heat Treatment of Composite Structure: The glass substrate coated through steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 350 °C, and the time of the high-temperature heat treatment is 1.5 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0039] Example 3: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0040] S1 Glass Substrate Preparation: 70% of raw material silicon dioxide, 10% of sodium oxide, 10% of calcium oxide, 3% of magnesium oxide, 3% of aluminum oxide, and 4% of zirconium oxide are added to a ball mill for mixing. Then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1600 °C, and the melting time is 3 h. After the raw materials are completely melted, the glass liquid is poured into a forming mold and cooled to 500 °C for forming. After forming, it is placed in a temperature control furnace for annealing to obtain a glass substrate.

[0041] S2 Polymer Layer Coating: Polyphenylene sulfide is dissolved in ethanol solvent to form a uniform coating solution. The concentration of the coating solution is 14%. The coating solution is uniformly coated on the surface of the glass substrate by impregnation, and then after heat treatment at 120 °C for 30 min, a polymer layer is formed on the surface of the glass substrate.

[0042] S3 Metal Oxide Particle Deposition: The surface of the polymer layer obtained in step S2 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 50 Pa and the temperature is 400 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidizing agent oxygen is introduced for metal oxide particle precipitation. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:1, and the gas flow rate of oxygen is 110 sccm. After 7 minutes of metal oxide particle precipitation, a composite layer is obtained.

[0043] S4 Embedding of Nano-Ceramic Layer: Silicon nitride nano-ceramic particles are embedded into the composite layer obtained in step S3 to obtain a nano-ceramic layer.

[0044] S5 Preparation of Graphene Toughening Layer: Graphene nanosheets are ultrasonically oscillated and mixed with an ethanol solvent to obtain a slurry. The mass fraction of graphene nanosheets is 0.3%. The slurry is coated on the surface of the nano-ceramic layer by spin coating at a controlled spin coating speed of 1500 rpm. After spin coating for 30 s, it is dried. After drying for 1 h, heat treatment is carried out to obtain a graphene toughening layer.

[0045] S6 Heat Treatment of Composite Structure: The glass substrate coated through steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 400 °C, and the time of the high-temperature heat treatment is 2 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0046] Example 4: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0047] S1 Glass Substrate Preparation: 70% silica, 10% sodium oxide, 10% calcium oxide, 3% magnesium oxide, 3% aluminum oxide, and 4% zirconium oxide as raw materials are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1650 °C, and the melting time is 3.5 h. After the raw materials are completely melted, the glass liquid is poured into a molding die and cooled to 500 °C for molding. After molding, it is placed in a temperature control furnace for annealing to obtain a glass substrate.

[0048] S2 Polymer Layer Coating: Polyphenylene sulfide is dissolved in an ethanol solvent to form a uniform coating solution. The concentration of the coating solution is 17%. The coating solution is uniformly coated on the surface of the glass substrate by impregnation, and then after heat treatment at 120 °C for 30 min, a polymer layer is formed on the surface of the glass substrate.

[0049] S3 Metal Oxide Particle Deposition: The surface of the polymer layer obtained in step S2 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 70 Pa and the temperature is 450 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidant oxygen is introduced for metal oxide particle precipitation. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:1.1, and the gas flow rate of oxygen is 160 sccm. After 8 minutes of metal oxide particle precipitation, a composite layer is obtained.

[0050] S4 Embedding of Nano-Ceramic Layer: Silicon nitride nano-ceramic particles are embedded into the composite layer obtained in step S3 to obtain a nano-ceramic layer.

[0051] S5 Preparation of Graphene Toughening Layer: Graphene nanosheets and an ethanol solvent are ultrasonically oscillated and mixed to obtain a slurry, and the mass fraction of graphene nanosheets is 0.4%. The slurry is coated on the surface of the nano-ceramic layer by spin coating at a spin coating speed of 1500 rpm. After spin coating for 30 s, it is dried, and after drying for 1 h, heat treatment is carried out to obtain a graphene toughening layer.

[0052] S6 Heat Treatment of Composite Structure: The glass substrate coated through steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 450 °C, and the time of the high-temperature heat treatment is 2.5 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0053] Example 5: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0054] S1 Glass Substrate Preparation: 70% silica, 10% sodium oxide, 10% calcium oxide, 3% magnesium oxide, 3% aluminum oxide, and 4% zirconium oxide as raw materials are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1700 °C, and the melting time is 4 h. After the raw materials are completely melted, the glass liquid is poured into a molding die and cooled to 500 °C for molding. After molding, it is placed in a temperature control furnace for annealing to obtain a glass substrate.

[0055] S2 Polymer Layer Coating: Polyphenylene sulfide is dissolved in an ethanol solvent to form a uniform coating solution with a concentration of 20%. The coating solution is uniformly coated on the surface of the glass substrate by dipping, and then after heat treatment at 120 °C for 30 min, a polymer layer is formed on the surface of the glass substrate.

[0056] S3 Metal Oxide Particle Deposition: The surface of the polymer layer obtained in step S2 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 100 Pa and the temperature is 500 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidant oxygen is introduced for metal oxide particle precipitation. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:1.1, and the gas flow rate of oxygen is 200 sccm. After 10 min of metal oxide particle precipitation, a composite layer is obtained.

[0057] S4 Embedding of Nano-Ceramic Layer: Silicon nitride nano-ceramic particles are embedded into the composite layer obtained in step S3 to obtain a nano-ceramic layer.

[0058] S5 Preparation of Graphene Toughening Layer: Graphene nanosheets and ethanol solvent are mixed by ultrasonic oscillation to obtain a slurry, and the mass fraction of graphene nanosheets is 0.5%. The slurry is coated on the surface of the nano-ceramic layer by spin coating method with a spin coating speed of 1500 rpm. After spin coating for 30 s, it is dried. After drying for 1 h, heat treatment is carried out to obtain a graphene toughening layer.

[0059] S6 Heat Treatment of Composite Structure: The glass substrate coated after steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 500 °C, and the time of the high-temperature heat treatment is 3 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0060] Example 6: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0061] S1 Glass Substrate Preparation: 70% of raw material silica, 10% of sodium oxide, 10% of calcium oxide, 3% of magnesium oxide, 3% of aluminum oxide, and 4% of zirconium oxide are added to a ball mill for mixing. Then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1700 °C, and the melting time is 4 h. After the raw materials are completely melted, the glass liquid is poured into a molding die and cooled to 500 °C for molding. After molding, it is annealed in a temperature control furnace to obtain a glass substrate.

[0062] S2 Polymer Layer Coating: Polyphenylene sulfide is dissolved in ethanol solvent to form a uniform coating solution. The concentration of the coating solution is 20%. The coating solution is uniformly coated on the surface of the glass substrate by dipping, and then after heat treatment at 120 °C for 30 min, a polymer layer is formed on the surface of the glass substrate.

[0063] S3 Metal Oxide Particle Deposition: The surface of the polymer layer obtained in step S2 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 100 Pa and the temperature is set to 500 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidant oxygen is introduced for metal oxide particle precipitation. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:1.1, and the gas flow rate of oxygen is 200 sccm. After 10 minutes of metal oxide particle precipitation, a composite layer is obtained.

[0064] S4 Embedding of Nanoceramic Layer: Silicon nitride nanoceramic particles are embedded into the composite layer obtained in step S3 to obtain a nanoceramic layer.

[0065] S5 Heat Treatment of Composite Structure: The glass substrate coated through steps S2 to S4 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 500 °C, and the time of the high-temperature heat treatment is 3 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0066] Example 7: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0067] S1 Glass Substrate Preparation: 70% of raw material silicon dioxide, 10% of sodium oxide, 10% of calcium oxide, 3% of magnesium oxide, 3% of aluminum oxide, and 4% of zirconium oxide are added to a ball mill for mixing. Then, the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1700 °C, and the melting time is 4 h. After the raw materials are completely melted, the glass liquid is poured into a molding die and cooled to 500 °C for molding. After molding, it is placed in a temperature control furnace for annealing to obtain a glass substrate.

[0068] S2 Polymer Layer Coating: Polyphenylene sulfide is dissolved in an ethanol solvent to form a uniform coating solution. The concentration of the coating solution is 20%. The coating solution is uniformly coated on the surface of the glass substrate by means of impregnation, and then a polymer layer is formed on the surface of the glass substrate after heat treatment at 120 °C for 30 min.

[0069] S3 Metal Oxide Particle Deposition: The surface of the polymer layer obtained in step S2 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 100 Pa and the temperature is set to 500 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidant oxygen is introduced for metal oxide particle precipitation. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:1.1, and the gas flow rate of oxygen is 200 sccm. After 10 minutes of metal oxide particle precipitation, a composite layer is obtained.

[0070] Preparation of S4 graphene toughening layer: Graphene nanosheets and ethanol solvent are ultrasonically oscillated and mixed to obtain a slurry, and the mass fraction of graphene nanosheets is 0.5%; The slurry is coated on the surface of the composite layer by spin coating at a spin coating speed of 1500 rpm, dried after spin coating for 30 s, and heat treated for 1 h to obtain the graphene toughening layer.

[0071] S5 Heat treatment of composite structure: The glass substrate coated in steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 500 °C, and the time of the high-temperature heat treatment is 3 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0072] Example 8: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0073] S1 Preparation of glass substrate: 70% silica, 10% sodium oxide, 10% calcium oxide, 3% magnesium oxide, 3% aluminum oxide, and 4% zirconium oxide are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1700 °C, and the melting time is 4 h. After the raw materials are completely melted, the glass liquid is poured into a forming mold and cooled to 500 °C for forming. After forming, it is placed in a temperature control furnace for annealing to obtain the glass substrate.

[0074] S2 Coating of polymer layer: Polyphenylene sulfide is dissolved in ethanol solvent to form a uniform coating solution with a concentration of 20%. The coating solution is uniformly coated on the surface of the glass substrate by impregnation, and then heat treated at 120 °C for 30 min to form a polymer layer on the surface of the glass substrate.

[0075] S3 Embedding of nano-ceramic layer: Silicon nitride nano-ceramic particles are embedded into the polymer layer obtained in step S2 to obtain the nano-ceramic layer.

[0076] S4 Preparation of graphene toughening layer: Graphene nanosheets and ethanol solvent are ultrasonically oscillated and mixed to obtain a slurry, and the mass fraction of graphene nanosheets is 0.5%; The slurry is coated on the surface of the nano-ceramic layer by spin coating at a spin coating speed of 1500 rpm, dried after spin coating for 30 s, and heat treated for 1 h to obtain the graphene toughening layer.

[0077] S5 Heat treatment of composite structure: The glass substrate coated in steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The temperature of the high-temperature heat treatment is 500 °C, and the time of the high-temperature heat treatment is 3 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0078] Example 9: A method for preparing transparent crack-resistant microcrystalline glass, comprising the following steps:

[0079] Preparation of S1 glass matrix: 70% of raw material silica, 10% of sodium oxide, 10% of calcium oxide, 3% of magnesium oxide, 3% of aluminum oxide and 4% of zirconium oxide are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1700 °C and the melting time is 4 h. After the raw materials are completely melted, the glass liquid is poured into a forming mold and cooled to 500 °C for forming. After forming, it is placed in a temperature control furnace for annealing to obtain the glass matrix.

[0080] S2 Deposition of metal oxide particles: The surface of the glass matrix obtained in step S1 is subjected to plasma treatment, and then it is placed in a low-pressure CVD reactor. The pressure is set to 100 Pa and the temperature is 500 °C. After introducing metal precursors titanium tetrachloride and trimethylaluminum, an oxidant oxygen is introduced for the precipitation of metal oxide particles. The flow rate ratio of titanium tetrachloride to trimethylaluminum is 1:1.1, and the gas flow rate of oxygen is 200 sccm. After 10 min of precipitation of metal oxide particles, a composite layer is obtained.

[0081] S3 Embedding of nano-ceramic layer: Silicon nitride nano-ceramic particles are embedded into the composite layer obtained in step S3 to obtain the nano-ceramic layer.

[0082] S4 Preparation of graphene toughening layer: Graphene nanosheets and ethanol solvent are ultrasonically oscillated and mixed to obtain a slurry, and the mass fraction of graphene nanosheets is 0.5%. The slurry is coated on the surface of the nano-ceramic layer by spin coating method with a spin coating speed of 1500 rpm. After spin coating for 30 s, it is dried. After drying for 1 h, heat treatment is carried out to obtain the graphene toughening layer.

[0083] S5 Heat treatment of composite structure: The glass matrix coated in steps S2 - S5 is returned to a high-temperature furnace for high-temperature heat treatment. The high-temperature heat treatment temperature is 500 °C and the high-temperature heat treatment time is 3 h. After the heat treatment is completed, transparent crack-resistant microcrystalline glass is obtained.

[0084] Example 10: A method for preparing microcrystalline glass, comprising the following steps:

[0085] Preparation of microcrystalline glass: 70% of raw material silica, 10% of sodium oxide, 10% of calcium oxide, 3% of magnesium oxide, 3% of aluminum oxide and 4% of zirconium oxide are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. The melting temperature is 1700 °C and the melting time is 4 h. After the raw materials are completely melted, the glass liquid is poured into a forming mold and cooled to 500 °C for forming. After forming, it is placed in a temperature control furnace for annealing to obtain the microcrystalline glass.

[0086] The microcrystalline glass prepared in Examples 1 - 10 is subjected to performance testing, and the test results are shown in the following table:

[0087]

[0088] As can be seen from the above table data, Examples 1-5 screened the condition parameters of each step in the preparation method. Among them, the transparent crack-resistant glass-ceramics in Example 5 have the highest compressive strength of 380 MPa, the strongest impact toughness of 7.5 J, the smallest thermal expansion coefficient of 2.8×10-6 / °C, perform optimally in terms of cold and heat resistance, can withstand more cold-heat cycles of 25 times, and have the highest transparency of 94%.

[0089] In Example 6, the step of preparing the graphene toughening layer was removed during the preparation of the transparent crack-resistant glass-ceramics. From the test data of Example 6 in the above table, removing the graphene toughening layer has a greater impact on the impact toughness of the transparent crack-resistant glass-ceramics. This is because the tensile strength and fracture toughness of graphene are very high. Therefore, the graphene toughening layer formed on the surface of the glass-ceramics can significantly improve the crack resistance of the glass. Graphene can effectively inhibit the initiation and propagation of cracks, so that the glass will not undergo brittle fracture even when subjected to external force impact; the good interfacial bonding between the graphene layer and the ceramic layer helps to improve the overall mechanical properties of the glass and avoid delamination and cracking caused by weak interfaces; the unique structure and properties of graphene can effectively absorb and disperse external impact energy, reduce the probability of the glass cracking under multiple impacts or repeated loads, and improve its fatigue resistance.

[0090] In Example 7, the step of embedding the nano-ceramic layer was removed during the preparation of the transparent crack-resistant glass-ceramics. Removing the nano-ceramic layer has a greater impact on the compressive strength of the transparent crack-resistant glass-ceramics; Example 8 is the step of removing the deposition of metal oxide particles during the preparation of the transparent crack-resistant glass-ceramics. When removing the metal oxide particle deposition layer, it also has a greater impact on the compressive strength of the transparent crack-resistant glass-ceramics. This is because silicon nitride has excellent mechanical properties, especially its compressive strength and flexural strength under high temperature and high pressure conditions, which can effectively improve the crack resistance of the glass-ceramics. Aluminum-titanium oxide particles, as hard fillers, can significantly improve the compressive strength of the glass-ceramics, making it not easy to crack when subjected to external forces. Aluminum-titanium oxide particles can promote the formation of the ceramic phase in the step of embedding the S4 nano-ceramic layer and improve the overall crack resistance of the glass.

[0091] In Example 9, the step of coating the polymer layer was removed during the preparation of the transparent crack-resistant glass-ceramics. Removing the polymer layer coating has a greater impact on the impact toughness of the transparent crack-resistant glass-ceramics. This is because the polyphenylene sulfide polymer layer can effectively disperse external impact forces or stresses and reduce the propagation of cracks. Especially when subjected to greater external forces, PPS can buffer and absorb energy to prevent cracks from further expanding.

[0092] Example 10 is ordinary glass-ceramics without any composite structure, and its various properties are inferior to those of Examples 1-5.

[0093] Obviously, the above embodiments are merely examples for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or alterations can be made based on the above description. It is not necessary and impossible to enumerate all implementation manners here. And the obvious changes or alterations derived therefrom still fall within the protection scope of the present invention.

Claims

1. A method for preparing transparent crack-resistant microcrystalline glass, characterized in that: The following steps are involved: S1 Preparation of glass matrix: raw materials of silicon dioxide, sodium oxide, calcium oxide, magnesium oxide, aluminum oxide and zirconium oxide are added to a ball mill for mixing, and then the mixed raw materials are added to a high-temperature furnace for heating and melting. After the raw materials are completely melted, the glass liquid is poured into a molding mold for cooling and molding to obtain a glass matrix; S2 polymer layer coating: polyphenylene sulfide is dissolved in a solvent to form a uniform coating liquid, the coating liquid is uniformly coated on the surface of the glass substrate by dipping, and then a polymer layer is formed on the surface of the glass substrate through heat treatment; S3 metal oxide particle deposition: using chemical vapor deposition method to uniformly deposit titanium aluminum oxide nanoparticles on the surface of the polymer layer to obtain a composite layer; S4 embedding of nano-ceramic layer: embedding silicon nitride nano-ceramic particles into the composite layer obtained in step S3 to obtain a nano-ceramic layer; S5 preparation of graphene toughening layer: mixing graphene nanosheets with ethanol solvent to obtain slurry, coating the slurry on the surface of the nano-ceramic layer by spin coating, and then heat treating to obtain the graphene toughening layer; S6 Composite structure heat treatment: The glass substrate coated in steps S2 to S5 is returned to the high temperature furnace for high temperature heat treatment, and a transparent anti-cracking microcrystalline glass is obtained after the heat treatment is completed.

2. The method for preparing a transparent anti-crack glass-ceramic according to claim 1, characterized in that: In the S1 glass substrate preparation step, the melting temperature of the high temperature furnace is 1500-1700° C., and the melting time is 2-4 hours.

3. The method for preparing a transparent anti-crack glass-ceramic according to claim 1, characterized in that: In the S2 polymer layer coating step, the solvent is ethanol, and the concentration of the coating solution formed by polyphenylene sulfide is 10-20%.

4. The method for preparing a transparent anti-crack glass-ceramic according to claim 1, characterized in that: In the S3 metal oxide particle deposition step, the chemical vapor deposition uses a low-pressure CVD reactor, the pressure of the low-pressure CVD reactor is 10-100 Pa; the deposition temperature is 300-800° C.; and the deposition time is 5-10 min.

5. The method for preparing a transparent anti-crack glass-ceramic according to claim 1, characterized in that: In the S3 metal oxide particle deposition step, the oxidant used in the chemical vapor deposition is oxygen; the metal precursors are titanium tetrachloride and trimethylaluminum.

6. The method for preparing a transparent anti-crack glass-ceramic according to claim 5, characterized in that: In the S3 metal oxide particle deposition step, the flow ratio of titanium tetrachloride to trimethylaluminum is 1:(0.8-1.2).

7. The method for preparing a transparent anti-crack glass-ceramic according to claim 5, characterized in that: In the S3 metal oxide particle deposition step, the gas flow rate of oxygen is 20-200 sccm.

8. The method for preparing a transparent anti-crack glass-ceramic according to claim 1, characterized in that: In the S3 metal oxide particle deposition step, the polymer surface is plasma treated.

9. The method for preparing a transparent anti-crack glass-ceramic according to claim 1, characterized in that: In the S6 composite structure heat treatment step, the temperature of the high temperature heat treatment is 300-500° C., and the time of the high temperature heat treatment is 1-3 hours.

10. Transparent anti-crack glass-ceramics prepared by the method for preparing transparent anti-crack glass-ceramics as claimed in any one of claims 1 to 9.

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