High-strength glass-ceramics and method for preparing the same

Abstract

The present invention relates to high-strength microcrystalline glass and a preparation method thereof, belonging to the technical field of composite materials; the present invention uses broken glass, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, boron nitride, barium oxide, zirconium oxide, and modified carbon fiber as raw materials to prepare a high-strength microcrystalline glass, and the present invention also discloses the formula of each raw material; the high-strength microcrystalline glass of the present invention uses modified carbon fiber as the reinforcing phase to solve the problem that the microcrystalline glass itself is brittle and easy to break, and the modified carbon fiber of the present invention has good compatibility with the microcrystalline glass substrate, so the prepared microcrystalline glass has excellent mechanical properties, and the impact toughness can reach up to 3.91 KJ / cm 3 , the compressive strength can reach up to 371.28 MPa, and the flexural strength can reach up to 46.93 MPa. In addition, the modified carbon fiber of the present invention can also improve the thermal stability of the microcrystalline glass and solve the yield influence caused by thermal stress.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and specifically relates to high-strength glass ceramics and a preparation method thereof. Background Art

[0002] Glass ceramics, also known as ceramic glass or crystallized glass, are a type of composite material. They originated in the United States and then rapidly developed in Japan. The research on glass ceramics in China began in the 1980s, and after decades of research, the production process has basically matured. Glass ceramics are polycrystalline solids obtained through the devitrification of glass. They have an aesthetically pleasing overall appearance and are easy to process. Their microstructures are uniform, dense, pore-free, and have a smooth surface. This structure significantly improves the softening temperature, thermal stability, chemical stability, and mechanical strength of glass ceramics. Currently, they have been widely used in many fields such as construction, aerospace, optics, and electronics.

[0003] Although glass ceramics have good mechanical strength, due to their structure, glass ceramics are still a brittle material and are prone to fracture when subjected to strong impact and loading. In the prior art, composite fiber materials such as carbon fiber and basalt fiber are commonly used to enhance the toughness of glass ceramics. However, there are still problems with the compatibility between fiber materials and glass ceramics. In the crystallization and firing processes of glass ceramic plates with composite fiber materials, millimeter-level gaps and bubbles may be generated underneath, and these bubbles and gaps will further reduce the mechanical strength of the substrate. How to improve the toughness of glass ceramics without affecting the mechanical strength of the glass ceramics themselves has become an urgent problem to be solved at the present stage. Summary of the Invention

[0004] The purpose of the present invention is to provide high-strength glass ceramics and a preparation method thereof to solve the problems mentioned in the above background art.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] High-strength glass ceramics, comprising the following raw materials in parts by mass: 52 - 59 parts of cullet, 4 - 6 parts of titanium dioxide, 9 - 11 parts of spodumene, 13 - 17 parts of potassium carbonate, 2 - 2.5 parts of lanthanum oxide, 3 - 4 parts of boron nitride, 2 - 3 parts of barium oxide, 1.5 - 2 parts of zirconium oxide, 4 - 5 parts of modified carbon fiber;

[0007] The preparation method of the high-strength glass ceramics includes the following steps:

[0008] First step: Weigh each raw material according to the parts by mass, mix cullet, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, barium oxide, and zirconium oxide evenly, and then place them into a glass kiln and heat to melt into a glass melt;

[0009] Step 2: Crush the modified carbon fiber, and spray and thoroughly mix the boron nitride and the modified carbon fiber powder into the glass melt under a nitrogen-protected gas stream to obtain a modified carbon fiber glass melt;

[0010] Step 3: Add the modified carbon fiber glass melt obtained in Step 2 into a preheated graphite mold, and anneal to obtain a crude glass;

[0011] Step 4: Nucleate and crystallize the crude glass obtained in Step 3 to obtain a high-strength glass-ceramic.

[0012] Further, the temperature condition for heating and melting the glass melt in the glass furnace in Step 1 is 1400 - 1500 °C, and the melting time condition is 4 - 6 h.

[0013] Further, the particle size specification of the modified carbon fiber powder in Step 2 is 20 - 40 μm.

[0014] Further, the preheating temperature of the graphite mold in Step 3 is 450 - 550 °C, the annealing temperature is 400 - 500 °C, and the annealing time condition is 3 - 4 h.

[0015] Further, the nucleation temperature of the crude glass in Step 4 is 500 - 700 °C, the nucleation time condition is 3 - 6 h, the crystallization temperature is 700 - 900 °C, and the crystallization time condition is 4 - 8 h.

[0016] Further, the modified carbon fiber is prepared by the following steps:

[0017] Step 1: Wind the carbon fiber around a glass frame, then place the glass frame wound with the carbon fiber into a supercritical extraction reactor, add acetone into the reactor, then close the reactor, wash for 25 - 40 min, and then place it in an oven at 50 °C for heating and drying for 12 h to obtain surface-treated carbon fiber;

[0018] Step 2: Mix the surface-treated carbon fiber and a nitric acid solution in a flask, turn on the magnetic stirrer, and react at 40 - 70 °C for 3 - 4 h. After the reaction ends, perform vacuum filtration. The obtained solid is washed with acetone and then placed in an oven at 50 °C for heating and drying for 12 h to obtain surface-oxidized carbon fiber;

[0019] Step 3: Mix dodecafluoroheptanol and a sodium hydroxide solution in a three-necked flask, install a condenser and a thermometer, turn on the magnetic stirrer, and use a high-pressure dropping pump to drop epichlorohydrin into the three-necked flask under nitrogen protection. After the dropping is completed, react at 70 - 90 °C for 4 - 6 h. After the reaction ends, wash with deionized water 3 times. After separating the organic layer with a separatory funnel, perform rotary evaporation to obtain Intermediate 1;

[0020] Step 4: Mix intermediate 1, 3-aminopropyltriethoxysilane, and chloroform in a three-necked flask. Install a condenser and a thermometer, start magnetic stirring, and react at a temperature of 50-70 °C for 12-15 h. After the reaction is completed, rotary evaporation is carried out to obtain intermediate 2;

[0021] Step 5: Mix surface-oxidized carbon fiber, intermediate 2, N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and chloroform in a three-necked flask. Install a condenser and a thermometer, start magnetic stirring, and react at a temperature of 40-50 °C for 18-24 h. After the reaction is completed, vacuum filtration is carried out. The obtained solid is washed 3 times with acetone, and then placed in an oven at 50 °C and heated for 12 h to dry, obtaining modified carbon fiber;

[0022] Further, in Step 1, the pressure parameter condition of the supercritical extraction reactor is 8-12 MPa, and the temperature parameter condition is 35-45 °C.

[0023] Further, in Step 2, the nitric acid solution used is an aqueous nitric acid solution with a molar concentration of 8 mol / L, and the dosage ratio of the surface-treated carbon fiber to nitric acid is 3 g:60 mL.

[0024] Further, in Step 3, the sodium hydroxide solution used is an aqueous sodium hydroxide solution with a molar concentration of 6 mol / L, and the dosage ratio of dodecafluoroheptanol, sodium hydroxide solution, and epichlorohydrin is 0.1 mol:50-80 mL:0.11-0.13 mol.

[0025] Further, in Step 4, the dosage ratio of intermediate 1, 3-aminopropyltriethoxysilane, and chloroform used is 0.08 mol:0.09-0.11 mol:80-120 mL.

[0026] Further, in Step 5, the dosage ratio of surface-oxidized carbon fiber, intermediate 2, N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and chloroform used is 3 g:0.3-0.5 g:0.9-1 g:2.1-2.4 g:60-80 mL.

[0027] Advantages of the present invention:

[0028] 1) The present invention uses broken glass, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, barium oxide, zirconium oxide, boron nitride, and modified carbon fiber as raw materials to prepare a high-strength glass-ceramic. In the present invention, several raw materials such as broken glass, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, barium oxide, and zirconium oxide are first mixed and melted into a glass melt, and then the modified carbon fiber powder and boron nitride are dispersed in the glass melt by using protective nitrogen. After several steps of annealing, nucleation, and crystallization, a high-strength glass-ceramic is obtained. In the formula of the present invention, broken glass is recycled, and titanium dioxide is also added to regulate the crystallization process of the glass, reducing energy consumption, being economical and environmentally friendly. Moreover, modified carbon fiber powder with good tensile strength and boron nitride with good thermal conductivity are added to the formula. The prepared glass has good toughness, high strength, and good thermal conductivity, and can be widely used in the fields of aerospace, optics, and microelectronics.

[0029] 2) The present invention uses carbon fiber as the raw material, and uses supercritical carbon dioxide to clean the surface slurry of the carbon fiber to obtain surface-treated carbon fiber. Then, the surface-treated carbon fiber is oxidized with a nitric acid solution to oxidize the hydroxyl groups on the surface of the carbon fiber into carboxyl groups, obtaining surface-oxidized carbon fiber. At the same time, the present invention uses 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoroheptanol as the raw material, and undergoes a nucleophilic substitution reaction with epichlorohydrin under alkaline conditions and nitrogen protection to obtain intermediate 1 with surface epoxidation. Then, the epoxy group of intermediate 1 reacts with the amino group of 3-aminopropyltriethoxysilane to undergo an amidation reaction to obtain intermediate 2 containing an organosilicon structure. Finally, the amino group of intermediate 2 reacts with the carboxyl group of the surface-oxidized carbon fiber under the catalysis of the N-hydroxysuccinimide / 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride system to undergo an amidation reaction to obtain a modified carbon fiber grafted with a fluoroalkyl long chain and an organosilicon structure. Carbon fiber is a high-performance fiber material, and its tensile strength is 7-9 times that of steel materials, and it has good chemical stability. The present invention first cleans the surface slurry of the carbon fiber by supercritical carbon dioxide and uses acetone as an additive. As a polar solvent, acetone can improve the solubility of supercritical carbon dioxide in polar substances, and the interaction between the two can achieve a better cleaning effect, making the cleaned carbon fiber have better reactivity. The modified carbon fiber contains an organosilicon structure, which can not only repair the surface defects of the carbon fiber to make the carbon fiber have better single-filament tensile strength, but also form effective chemical bond connections at the interface between the modified carbon fiber and silica, making the combination of the modified carbon fiber and the glass-ceramic matrix more sufficient and enhancing the mechanical properties of the interface. Moreover, the modified carbon fiber also has a large number of carbon-fluorine bonds, and the carbon-fluorine bonds have a large bond energy and are not easily corroded by acids and bases. When used in glass-ceramics, it can also provide better heat resistance and thermal stability.

[0030] 3) The preparation process of the high-strength microcrystals of the present invention is economical, environmentally friendly, the reinforcing phase has good compatibility with the microcrystalline glass substrate, the resulting finished glass has high strength, good toughness, is not prone to fracture, and has good thermal conductivity and heat resistance, and is less affected by the yield and fatigue of thermal stress, and can be widely used in the fields of aerospace, optics, and microelectronics. Detailed implementation manners

[0031] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0032] Example 1

[0033] A modified carbon fiber includes the following preparation steps:

[0034] Step 1: Wind the carbon fiber around a frame, then place the frame wound with the carbon fiber into a supercritical extraction reactor, add acetone to the reactor, then close the reactor, control the pressure parameter to 8 MPa, control the temperature parameter to 35 °C, wash for 25 min, and then heat and dry at a temperature of 50 °C for 12 h to obtain surface-treated carbon fiber;

[0035] Step 2: Mix 3 g of the surface-treated carbon fiber and 60 mL of a nitric acid aqueous solution with a molar concentration of 8 mol / L in a container, stir evenly, and react at a temperature of 40 °C for 3 h. After the reaction ends, perform vacuum filtration. The obtained solid is washed with acetone and then heated and dried at a temperature of 50 °C for 12 h to obtain surface-oxidized carbon fiber;

[0036] Step 3: Mix 0.1 mol of dodecafluoroheptanol and 50 mL of a sodium hydroxide aqueous solution with a molar concentration in a container, stir evenly, and then dropwise add 0.11 mol of epichlorohydrin to the container under nitrogen protection. After the dropping is completed, react at a temperature of 70 °C for 4 h. After the reaction ends, wash with deionized water 3 times. After separating the organic layer with a separatory funnel, perform rotary evaporation to obtain Intermediate 1;

[0037] Step 4: Mix 0.08 mol of Intermediate 1, 0.09 mol of 3-aminopropyltriethoxysilane, and 80 mL of chloroform in a three-necked flask, install a condenser and a thermometer, start magnetic stirring, and react at a temperature of 50 - 70 °C for 12 - 15 h. After the reaction ends, perform rotary evaporation to obtain Intermediate 2;

[0038] Step 5: Mix 3 g of surface-oxidized carbon fiber, 0.3 g of intermediate 2, 0.9 g of N-hydroxysuccinimide, 2.1 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 60 mL of chloroform in a container. After stirring evenly, react at 40 °C for 18 h. After the reaction ends, perform vacuum filtration. Wash the obtained solid with acetone three times, and then dry it by heating at 50 °C for 12 h to obtain a modified carbon fiber.

[0039] Example 2

[0040] A modified carbon fiber, comprising the following preparation steps:

[0041] Step 1: Wind the carbon fiber around a frame, then place the frame with the wound carbon fiber into a supercritical extraction reactor. Add acetone to the reactor, then close the reactor. Control the pressure parameter to be 10 MPa and the temperature parameter to be 40 °C. After cleaning for 37.5 min, dry it by heating at 50 °C for 12 h to obtain surface-treated carbon fiber.

[0042] Step 2: Mix 3 g of surface-treated carbon fiber and 60 mL of nitric acid aqueous solution with a molar concentration of 8 mol / L in a container. After stirring evenly, react at 55 °C for 3.5 h. After the reaction ends, perform vacuum filtration. Wash the obtained solid with acetone, and then dry it by heating at 50 °C for 12 h to obtain surface-oxidized carbon fiber.

[0043] Step 3: Mix 0.1 mol of dodecafluoroheptanol and 65 mL of sodium hydroxide aqueous solution with a molar concentration in a container. After stirring evenly, dropwise add 0.12 mol of epichlorohydrin to the container under nitrogen protection. After the addition is complete, react at 80 °C for 5 h. After the reaction ends, wash it with deionized water three times. After separating the organic layer with a separatory funnel, perform rotary evaporation to obtain intermediate 1.

[0044] Step 4: Mix 0.08 mol of intermediate 1, 0.1 mol of 3-aminopropyltriethoxysilane, and 100 mL of chloroform in a three-necked flask. Install a condenser and a thermometer, turn on magnetic stirring, and react at 60 °C for 13.5 h. After the reaction ends, perform rotary evaporation to obtain intermediate 2.

[0045] Step 5: Mix 3 g of surface-oxidized carbon fiber, 0.4 g of intermediate 2, 0.95 g of N-hydroxysuccinimide, 2.25 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 70 mL of chloroform in a container. After stirring evenly, react at 45 °C for 21 h. After the reaction ends, perform vacuum filtration. Wash the obtained solid with acetone three times, and then dry it by heating at 50 °C for 12 h to obtain a modified carbon fiber.

[0046] Example 3

[0047] A modified carbon fiber, comprising the following preparation steps:

[0048] Step 1: Wind the carbon fiber around a frame, then place the frame with the wound carbon fiber into a supercritical extraction reactor, add acetone to the reactor, close the reactor, control the pressure parameter at 12 MPa, control the temperature parameter at 45 °C, wash for 40 min, and then heat and dry at 50 °C for 12 h to obtain surface-treated carbon fiber;

[0049] Step 2: Mix 3 g of the surface-treated carbon fiber and 60 mL of a nitric acid aqueous solution with a molar concentration of 8 mol / L in a container, stir evenly, react at 70 °C for 4 h, after the reaction ends, perform vacuum filtration, wash the obtained solid with acetone, and then heat and dry at 50 °C for 12 h to obtain surface-oxidized carbon fiber;

[0050] Step 3: Mix 0.1 mol of dodecafluoroheptanol and 80 mL of a sodium hydroxide aqueous solution with a molar concentration in a container, stir evenly, dropwise add 0.13 mol of epichlorohydrin to the container under nitrogen protection, after the addition is complete, react at 90 °C for 6 h, after the reaction ends, wash 3 times with deionized water, separate the organic layer with a separatory funnel, and then perform rotary evaporation to obtain intermediate 1;

[0051] Step 4: Mix 0.08 mol of intermediate 1, 0.11 mol of 3-aminopropyltriethoxysilane, and 120 mL of chloroform in a three-necked flask, install a condenser and a thermometer, start magnetic stirring, react at 70 °C for 15 h, after the reaction ends, perform rotary evaporation to obtain intermediate 2;

[0052] Step 5: Mix 3 g of the surface-oxidized carbon fiber, 0.5 g of intermediate 2, 1 g of N-hydroxysuccinimide, 2.4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 80 mL of chloroform in a container, stir evenly, react at 50 °C for 24 h, after the reaction ends, perform vacuum filtration, wash the obtained solid 3 times with acetone, and then heat and dry at 50 °C for 12 h to obtain a modified carbon fiber.

[0053] Example 4

[0054] A high-strength glass-ceramics, comprising the following raw materials in parts by mass: 52 parts of cullet, 4 parts of titanium dioxide, 9 parts of spodumene, 13 parts of potassium carbonate, 2 parts of lanthanum oxide, 3 parts of boron nitride, 2 parts of barium oxide, 1.5 parts of zirconium oxide, and 4 parts of the modified carbon fiber obtained in Example 1;

[0055] The preparation method of the high-strength glass-ceramics, comprising the following steps:

[0056] Step 1: Weigh each raw material according to the mass parts. Mix crushed glass, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, barium oxide, and zirconium oxide evenly and then put them into a glass kiln. Heat them at 1400 °C for 4 h to melt into glass liquid;

[0057] Step 2: Crush the modified carbon fiber obtained in Example 1 into powder with a particle size of 20 μm, and spray boron nitride and the modified carbon fiber powder into it through a nitrogen-protected air flow and mix them evenly to obtain modified carbon fiber glass liquid;

[0058] Step 3: Add the modified carbon fiber glass liquid obtained in the second step into a graphite mold with a preheating temperature of 450 °C, cool it down to 400 °C, anneal and keep it warm for 3 h to obtain crude glass;

[0059] Step 4: Keep the crude glass obtained in the third step at 500 °C for 3 h for nucleation and at 700 °C for 4 h for crystallization to obtain a kind of high-strength glass-ceramics.

[0060] Example 5

[0061] A kind of high-strength glass-ceramics, comprising the following raw materials in mass parts: 52 parts of crushed glass, 6 parts of titanium dioxide, 9 parts of spodumene, 13 parts of potassium carbonate, 2.5 parts of lanthanum oxide, 3 parts of boron nitride, 3 parts of barium oxide, 2 parts of zirconium oxide, and 4 parts of the modified carbon fiber obtained in Example 2;

[0062] The preparation method of the high-strength glass-ceramics comprises the following steps:

[0063] Step 1: Weigh each raw material according to the mass parts. Mix crushed glass, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, barium oxide, and zirconium oxide evenly and then put them into a glass kiln. Heat them at 1450 °C for 5 h to melt into glass liquid;

[0064] Step 2: Crush the modified carbon fiber obtained in Example 2 into powder with a particle size of 30 μm, and spray boron nitride and the modified carbon fiber powder into it through a nitrogen-protected air flow and mix them evenly to obtain modified carbon fiber glass liquid;

[0065] Step 3: Add the modified carbon fiber glass liquid obtained in the second step into a graphite mold with a preheating temperature of 500 °C, cool it down to 450 °C, anneal and keep it warm for 3.5 h to obtain crude glass;

[0066] Step 4: Keep the crude glass obtained in the third step at 600 °C for 4.5 h for nucleation and at 800 °C for 6 h for crystallization to obtain a kind of high-strength glass-ceramics.

[0067] Example 6

[0068] A high-strength microcrystalline glass, comprising the following raw materials in parts by mass: 59 parts of cullet, 4 parts of titanium dioxide, 11 parts of spodumene, 17 parts of potassium carbonate, 2 parts of lanthanum oxide, 4 parts of boron nitride, 2 parts of barium oxide, 1.5 parts of zirconium oxide, and 5 parts of modified carbon fiber obtained in Example 3;

[0069] The preparation method of the high-strength microcrystalline glass comprises the following steps:

[0070] The first step: Weigh each raw material according to the parts by mass, mix cullet, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, barium oxide, and zirconium oxide evenly and then put them into a glass kiln, and heat them at a temperature of 1500 °C for 6 h to melt into a glass melt;

[0071] The second step: Crush the modified carbon fiber obtained in Example 3 into powders with a particle size of 40 μm, and spray and mix boron nitride and the modified carbon fiber powders evenly through a nitrogen-protected gas stream to obtain a modified carbon fiber glass melt;

[0072] The third step: Add the modified carbon fiber glass melt obtained in the second step into a graphite mold with a preheating temperature of 550 °C, cool it to 500 °C, anneal and keep it warm for 4 h to obtain a crude glass;

[0073] The fourth step: Keep the crude glass obtained in the third step warm at a temperature of 700 °C for 6 h for nucleation and keep it warm at a temperature of 900 °C for 8 h for crystallization to obtain a high-strength microcrystalline glass.

[0074] Comparative Example 1

[0075] Replace the raw material "modified carbon fiber obtained in Example 3" used in Example 6 with ordinary carbon fiber, and keep the other conditions and steps unchanged.

[0076] Comparative Example 2

[0077] This comparative example is the microcrystalline glass sold by Dongguan Mingda Glass Co., Ltd.

[0078] Conduct mechanical property tests on a high-strength microcrystalline glass in Examples 4-6 and Comparative Example 1 and the microcrystalline glass sold by Dongguan Mingda Glass Co., Ltd. in Comparative Example 2. The test results are shown in Table 1:

[0079] Table 1

[0080] Project Flexural strength (MPa) Compressive strength (MPa) <![CDATA[Impact toughness (KJ / cm 3 )]]> Example 4 44.81 357.39 3.49 Example 5 46.93 371.28 3.91 Example 6 41.69 351.19 3.26 Comparative Example 1 26.95 327.29 2.34 Comparative Example 2 32.45 303.24 2.67

[0081] As can be seen from Table 1, the high-strength glass-ceramics of Examples 4-6 are superior to the commercially available glass-ceramics in terms of compressive strength, flexural strength, and impact toughness. Although the high-strength glass-ceramics of Comparative Example 1 are still superior to the commercially available glass-ceramics in terms of compressive strength, their flexural strength and impact toughness are poor. This may be due to the poor compatibility between the carbon fiber powder and the glass-ceramic matrix, resulting in the presence of bubbles or gaps and a decrease in mechanical properties. Based on Table 1, it can be concluded that the modified carbon fiber of the present invention can effectively improve the mechanical properties of glass-ceramics. The glass-ceramics of the present invention have excellent mechanical properties and are not prone to fracture, and can be widely used in the fields of aerospace, optics, and microelectronics.

[0082] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications, supplements, or use similar methods to replace the specific embodiments described, as long as they do not deviate from the invention or exceed the scope defined by this claim book, they should fall within the protection scope of the present invention.

Claims

1. High-strength glass-ceramics, characterized in that: The raw materials include the following parts by weight: 52-59 parts of cullet, 4-6 parts of titanium dioxide, 9-11 parts of spodumene, 13-17 parts of potassium carbonate, 2-2.5 parts of lanthanum oxide, 3-4 parts of boron nitride, 2-3 parts of barium oxide, 1.5-2 parts of zirconium oxide, and 4-5 parts of modified carbon fiber; Wherein, the modified carbon fiber is made by the following steps: Step 1: Wind the carbon fiber on a frame, then place the frame wrapped with the carbon fiber into a supercritical extraction reactor, add acetone into the reactor, then close the reactor, and wash for 25-40 minutes to obtain surface-treated carbon fiber; Step 2: Mix the surface treated carbon fiber and nitric acid solution in a container, stir evenly, and react at a temperature of 40-70° C. for 3-4 hours to obtain surface oxidized carbon fiber; Step 3: dodecafluoroheptanol and sodium hydroxide solution are mixed in a container, stirred evenly, and then epichlorohydrin is added dropwise to the container under nitrogen protection. After the addition is complete, the mixture is reacted at 70-90° C. for 4-6 hours to obtain intermediate 1; Step 4: Mix the intermediate 1, 3-aminopropyltriethoxysilane and chloroform in a container, stir evenly, and react at a temperature of 50-70° C. for 12-15 hours to obtain the intermediate 2; Step 5: Mix the surface oxidized carbon fiber, intermediate 2, N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and chloroform in a container, stir evenly, and react at a temperature of 45-50° C. for 18-24 hours to obtain modified carbon fiber.

2. The high-strength microcrystalline glass according to claim 1, characterized in that: In step 1, the pressure parameter condition of the supercritical extraction reactor is 8-12 MPa, and the temperature parameter condition is 35-45°C.

3. The high-strength microcrystalline glass according to claim 1, characterized in that: The nitric acid solution used in step 2 is an aqueous nitric acid solution with a molar concentration of 8 mol / L, and the amount ratio of the surface treated carbon fiber to the nitric acid is 3 g:60 mL.

4. The high-strength microcrystalline glass according to claim 1, characterized in that: The sodium hydroxide solution used in step 3 is a sodium hydroxide aqueous solution with a molar concentration of 6 mol / L, and the amount ratio of the used dodecafluoroheptanol, sodium hydroxide solution and epichlorohydrin is 0.1 mol:50-80 mL:0.11-0.13 mol.

5. The high-strength glass-ceramics according to claim 1, characterized in that: The amount ratio of the intermediate 1, 3-aminopropyltriethoxysilane and chloroform used in step 4 is 0.08 mol: 0.09-0.11 mol: 80-120 mL.

6. The high-strength glass-ceramics according to claim 1, characterized in that: The amount ratio of the surface oxidized carbon fiber, intermediate 2, N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and chloroform used in step 5 is 3g:0.3-0.5g:0.9-1g:2.1-2.4g:60-80mL.

7. The method for preparing high-strength glass-ceramics according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1: Weigh each raw material by mass, mix the broken glass, titanium dioxide, spodumene, potassium carbonate, lanthanum oxide, barium oxide and zirconium oxide evenly, place them in a glass kiln, and heat and melt them into glass liquid; Step 2: crush the modified carbon fiber, and spray boron nitride and modified carbon fiber powder into the powder through a nitrogen protective gas flow and mix them evenly to obtain a modified carbon fiber glass liquid; Step 3: adding the modified carbon fiber glass liquid obtained in the second step into the preheated graphite mold and annealing to obtain the rough glass; Step 4: Nucleate and crystallize the crude glass obtained in the third step to obtain high-strength microcrystalline glass.

8. The method for preparing high-strength glass-ceramics according to claim 7, characterized in that: In the first step, the temperature condition for heating and melting the glass liquid in the glass kiln is 1400-1500° C., and the melting time condition is 4-6 hours. In the second step, the particle size specification of the modified carbon fiber powder is 20-40 μm.

9. The method for preparing high-strength glass-ceramics according to claim 7, characterized in that: In the third step, the preheating temperature of the graphite mold is 450-550°C, the annealing temperature is 400-500°C, and the annealing time is 3-4h.

10. The method for preparing high-strength glass-ceramics according to claim 7, characterized in that: In the fourth step, the nucleation temperature of the crude glass is 500-700° C., the nucleation time condition is 3-6 hours, the crystallization temperature is 700-900° C., and the crystallization time condition is 4-8 hours.