A pressure-resistant glass and its preparation method

Abstract

This invention discloses a pressure-resistant glass and its preparation method, relating to the field of special glass technology. In preparing the pressure-resistant glass, this invention uses an anorthite crystalline phase as the main component and a wollastonite crystalline phase as a secondary component, and adds zinc, barium, boron, sodium, antimony, and titanium elements to prepare a pressure-resistant microcrystalline glass. A modified sol is prepared by mixing tetraethyl orthosilicate, zirconium oxychloride octahydrate, and 3-glycidyl etheroxypropyltrimethoxysilane and then adding hydrochloric acid and stirring. An organosilane modified solution is prepared by mixing hydroxyl-terminated polysiloxane, trimethylethoxysilane, methyltriethoxysilane, and octadecyltriethoxysilane and then reacting them with hydrochloric acid solution. The modified sol and organosilane modified solution are mixed, coated onto the surface of the pressure-resistant microcrystalline glass, and then cured to obtain the pressure-resistant glass. The pressure-resistant glass prepared by this invention has the advantages of high compressive strength, hydrophobicity, wear resistance, and high surface hardness.

Description

Technical Field

[0001] This invention relates to the field of special glass technology, specifically to a pressure-resistant glass and its preparation method. Background Technology

[0002] Glass is ubiquitous in our daily lives and has played an indispensable role in the progress of human civilization and social change. As a common building material, glass has wide applications in aerospace, energy, construction, and automotive industries. As one of the common inorganic non-metallic materials, glass is generally made by melting a mixture of various inorganic minerals, such as quartz sand, boric acid, barium carbonate, barite, feldspar, and limestone, all of which are common raw materials for glass.

[0003] However, when glass is used as a building material, its compressive strength significantly impacts its performance. Furthermore, due to its thin surface stress layer, it is prone to penetrating cracks caused by friction, dust, cleaning, and impacts from hard particles during daily use. This leads to a sharp decrease in overall strength and reduces its service life. Therefore, these issues need to be addressed to expand its application range and extend its service life. Summary of the Invention

[0004] The purpose of this invention is to provide a pressure-resistant glass and its preparation method to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A pressure-resistant glass, wherein the pressure-resistant glass is prepared by mixing a modified sol and an organosilane modified solution, coating the mixture onto the surface of a pressure-resistant microcrystalline glass, and then curing it at high temperature;

[0007] The modified sol is prepared by mixing tetraethyl orthosilicate, zirconium oxychloride octahydrate and 3-glycidyl etheroxypropyltrimethoxysilane, and then adding hydrochloric acid solution and stirring.

[0008] The organosilane modified solution is prepared by mixing hydroxyl-terminated polysiloxane, trimethylethoxysilane, methyltriethoxysilane, and octadecyltriethoxysilane and then reacting them with hydrochloric acid solution.

[0009] The composition of the pressure-resistant microcrystalline glass is as follows: silicon dioxide, 41wt%–43wt%; calcium oxide, 22.96wt%–23.65wt%; aluminum oxide, 19.04wt%–20.35wt%; zinc oxide, 2.8wt%–3.6wt%; barium oxide, 4.2wt%–5.4wt%; boron trioxide, 0.8wt%–1.2wt%; sodium oxide, 2wt%–3wt%; antimony trioxide, 0.4wt%–0.6wt%; titanium dioxide, 2.8wt%–3.2wt%.

[0010] The pressure-resistant microcrystalline glass is produced by weighing the corresponding raw materials according to the formula, mixing and ball milling, drying, sieving, melting, casting, annealing, cutting and polishing, and then heat-treating at high temperature for a period of time before cooling.

[0011] As an optimization, the calcium oxide is added in the form of calcium carbonate;

[0012] The barium oxide was added in the form of barium carbonate;

[0013] The boron trioxide is added in the form of boric acid;

[0014] The sodium oxide is added in the form of sodium carbonate;

[0015] The aluminum oxide is added in the form of aluminum hydroxide.

[0016] As an optimization, the mass ratio of silicon dioxide to calcium oxide is 1:(0.55~0.56).

[0017] A method for preparing pressure-resistant glass includes the following preparation steps:

[0018] (1) Weigh the raw materials according to the formula and add them to the ball mill jar. Then add pure water and zirconium balls and ball mill. Dry and pass through a 120-mesh sieve. Add to a crucible to melt, pour into a mold and press into shape. Anneal, cool, cut and polish, then put into a muffle furnace for heat preservation and cooling to obtain pressure-resistant microcrystalline glass.

[0019] (2) By mass, 2-3 parts of tetraethyl orthosilicate, 3-4 parts of zirconium oxychloride octahydrate, 6-7 parts of pure water, 20-25 parts of anhydrous ethanol, and 0.05-0.07 parts of 3-glycidyl etheroxypropyltrimethoxysilane are mixed evenly and stirred at 200-300 r / min for 30-40 min at room temperature. Then, 1-1.2 parts of hydrochloric acid solution are added and stirring is continued for 20-22 h to obtain the modified sol.

[0020] (3) By mass, 3-4 parts of terminal hydroxyl polysiloxane, 1-1.2 parts of trimethylethoxysilane, 0.8-1 parts of methyltriethoxysilane, 1.2-1.5 parts of octadecyltriethoxysilane, 30-40 parts of anhydrous ethanol, and 1-1.2 parts of hydrochloric acid solution are mixed evenly and stirred at 60-65℃ and 300-400r / min for 2-3h to obtain organosilane modified solution;

[0021] (4) Mix the modified sol and organosilane modified solution at a volume ratio of (2-3):1, stir at 200-300 r / min for 15-20 min at room temperature, apply to the surface of the pressure-resistant microcrystalline glass, first cure at 100-120℃ for 10-15 min, then cure at 300-350℃ for 15-20 min to obtain the pressure-resistant glass.

[0022] As an optimization, the pressure-resistant microcrystalline glass in step (1) is prepared by weighing the raw materials according to the formula components and adding them to a ball mill jar, then adding pure water and zirconium balls. The mass ratio of raw materials, pure water and zirconium balls is 1:1:3. The mixture is ball-milled at 120-150 rpm for 3-4 hours, dried at 110-120℃ for 10-12 hours, passed through a 120-mesh sieve, added to a crucible, heated to 1100-1200℃ at a heating rate of 5℃ / min and held for 1.5-2 hours, then heated to 1500℃ and melted for 2-2.5 hours. The mixture is then cast into a mold and pressed into shape, placed in a muffle furnace and annealed at 650℃ for 1 hour. After naturally cooling to room temperature, it is cut and polished, then placed in a muffle furnace and heated to 1120℃ at a heating rate of 10℃ / min and held for 1 hour. Finally, it is cooled to room temperature with the furnace to obtain the final product.

[0023] As an optimization, the raw materials in step (1) include silicon dioxide, calcium carbonate, aluminum hydroxide, zinc oxide, barium carbonate, boric acid, sodium carbonate, antimony trioxide, and titanium dioxide.

[0024] As an optimization, the hydrochloric acid solution in steps (2) and (3) is a 36wt% hydrochloric acid aqueous solution.

[0025] As an optimization, the viscosity of the hydroxyl-terminated polysiloxane in step (3) is 20000 mpa·s, the model is RTV-6200, and it was purchased from Guangzhou Jibisheng Technology Industry Co., Ltd.

[0026] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0027] In preparing pressure-resistant glass, the present invention first weighs the corresponding raw materials according to the formula components, mixes and ball-mills, dries, sieves, melts, casts and molds, anneals, cuts and polishes, and then heat-treats at high temperature for a period of time before cooling to obtain pressure-resistant microcrystalline glass; a modified sol is prepared by mixing tetraethyl orthosilicate, zirconium oxychloride octahydrate, and 3-glycidyl etheroxypropyltrimethoxysilane and adding hydrochloric acid solution; an organosilane modified solution is prepared by mixing hydroxyl-terminated polysiloxane, trimethylethoxysilane, methyltriethoxysilane, and octadecyltriethoxysilane and adding hydrochloric acid solution; the modified sol and organosilane modified solution are mixed, coated on the surface of the pressure-resistant microcrystalline glass, and cured at high temperature to obtain pressure-resistant glass.

[0028] Firstly, after introducing a high proportion of calcium and aluminum elements into calcium aluminum silicate glass, its crystallization process no longer uses wollastonite as the main crystalline phase, but rather anorthite as the main crystalline phase, with wollastonite as a secondary phase. Simultaneously, zinc and barium elements are introduced to improve the melting and crystallization process. Zinc oxide improves the glass's fluidity, thereby lowering the crystallization temperature, while barium oxide promotes the glass's crystallization behavior and lowers its softening temperature. Titanium dioxide is added as a nucleating agent; sodium oxide is added as a network modifier, which can reduce the melting temperature, viscosity, and crystallization temperature; antimony trioxide is used as a clarifying agent; and boron trioxide improves the melting process. After anorthite is precipitated as the main crystalline phase, the relative crystallinity is increased by adjusting the element ratios, resulting in a high-compressive-strength microcrystalline glass. The optimal mass ratio of silicon dioxide to calcium oxide is 1:(0.55–0.56), which effectively improves the compressive strength.

[0029] Secondly, tetraethyl orthosilicate and zirconium oxychloride octahydrate form a mixed sol of silica and zirconium dioxide under acidic conditions. Zirconium dioxide has high hardness, and when used in conjunction with silica as a sol, it can improve the wear resistance of the final coating. Hydroxyl-terminated polysiloxanes, trimethylethoxysilanes, methyltriethoxysilanes, and octadecyltriethoxysilanes undergo hydrolysis and condensation under acid catalysis to form hydrophobic and flexible polysiloxane chains. The addition of long-chain siloxanes and the introduction of hydroxyl-terminated polysiloxanes can effectively improve the wear resistance and hydrophobicity.

[0030] Finally, the modified sol and organosilane modified solution are mixed and coated onto the pressure-resistant microcrystalline glass. After high-temperature curing, pressure-resistant glass with wear resistance, high hardness, and hydrophobic surface is formed. The polysiloxane chain has hydrophobic properties. At the same time, after the organosilane modified solution and the modified sol are mixed, they also undergo a certain coupling reaction with the hydroxyl groups on the surface of silica and zirconium dioxide, thereby wrapping silica and zirconium dioxide in the polysiloxane chain segments. The two are tightly bonded, which greatly improves the wear resistance. Detailed Implementation

[0031] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] The raw materials used in all the following examples and comparative examples are silicon dioxide, calcium carbonate, aluminum hydroxide, zinc oxide, barium carbonate, boric acid, sodium carbonate, antimony trioxide, and titanium dioxide.

[0033] In all the following examples and comparative examples, the coating thickness is 50nm ± 5nm, except for the hardness test sample which is 250nm ± 15nm.

[0034] Example 1:

[0035] A method for preparing pressure-resistant glass, the method comprising the following preparation steps:

[0036] The formulation components of the pressure-resistant microcrystalline glass are: silicon dioxide, 41 wt%; calcium oxide, 22.96 wt%; aluminum oxide, 19.04 wt%; zinc oxide, 3.6 wt%; barium oxide, 5.4 wt%; boron oxide, 1.2 wt%; sodium oxide, 3 wt%; antimony trioxide, 0.6 wt%; and titanium dioxide, 3.2 wt%.

[0037] (1) Weigh the raw materials according to the formula and add them to the ball mill jar. Then add pure water and zirconium balls. The mass ratio of raw materials, pure water and zirconium balls is 1:1:3. Ball mill at 120 rpm for 4 hours, dry at 110℃ for 12 hours, pass through a 120-mesh sieve, add to a crucible, heat to 1100℃ at a heating rate of 5℃ / min and hold for 2 hours, then continue to heat to 1500℃ and melt for 2 hours. Cast into a mold and press into shape. Place in a muffle furnace and anneal at 650℃ for 1 hour. After naturally cooling to room temperature, cut and polish. Place in a muffle furnace and heat to 1120℃ at a heating rate of 10℃ / min and hold for 1 hour. Cool to room temperature with the furnace to obtain pressure-resistant microcrystalline glass.

[0038] (2) By mass, 2 parts of tetraethyl orthosilicate, 3 parts of zirconium oxychloride octahydrate, 6 parts of pure water, 20 parts of anhydrous ethanol, and 0.05 parts of 3-glycidyl etheroxypropyltrimethoxysilane are mixed evenly and stirred at 200 r / min for 40 min at room temperature. Then, 1 part of 36 wt% hydrochloric acid aqueous solution is added and stirring is continued for 22 h to obtain the modified sol.

[0039] (3) By mass fraction, 3 parts of terminal hydroxyl polysiloxane, 1 part of trimethylethoxysilane, 0.8 parts of methyltriethoxysilane, 1.2 parts of octadecyltriethoxysilane, 30 parts of anhydrous ethanol, and 1 part of 36wt% hydrochloric acid aqueous solution are mixed evenly and stirred at 60℃ and 300r / min for 3h to obtain organosilane modified solution;

[0040] (4) Mix the modified sol and organosilane modified solution at a volume ratio of 2:1, stir at 200 r / min for 20 min at room temperature, coat the mixture onto the surface of the pressure-resistant microcrystalline glass, cure at 100℃ for 15 min, and then cure at 300℃ for 20 min to obtain the pressure-resistant glass.

[0041] Example 2:

[0042] A method for preparing pressure-resistant glass, the method comprising the following preparation steps:

[0043] The formulation components of the pressure-resistant microcrystalline glass are: silicon dioxide, 42 wt%; calcium oxide, 23.31 wt%; aluminum oxide, 19.69 wt%; zinc oxide, 3.2 wt%; barium oxide, 4.8 wt%; boron oxide, 1 wt%; sodium oxide, 2.5 wt%; antimony trioxide, 0.5 wt%; and titanium dioxide, 3 wt%.

[0044] (1) Weigh the raw materials according to the formula and add them to the ball mill jar. Then add pure water and zirconium balls. The mass ratio of raw materials, pure water and zirconium balls is 1:1:3. Ball mill at 135 rpm for 3.5 h, dry at 115℃ for 11 h, pass through a 120 mesh sieve, add to a crucible, heat to 1150℃ at a heating rate of 5℃ / min and hold for 1.5 h, then continue to heat to 1500℃ and melt for 2.2 h. Cast into a mold and press to form. Place in a muffle furnace and anneal at 650℃ for 1 h. After naturally cooling to room temperature, cut and polish. Place in a muffle furnace and heat to 1120℃ at a heating rate of 10℃ / min and hold for 1 h. Cool to room temperature with the furnace to obtain pressure-resistant microcrystalline glass.

[0045] (2) By mass, 2.5 parts of tetraethyl orthosilicate, 3.5 parts of zirconium oxychloride octahydrate, 6.5 parts of pure water, 22.5 parts of anhydrous ethanol, and 0.06 parts of 3-glycidyl etheroxypropyltrimethoxysilane were mixed evenly and stirred at 250 r / min for 35 min at room temperature. Then, 1.1 parts of 36 wt% hydrochloric acid aqueous solution were added and stirring was continued for 21 h to obtain the modified sol.

[0046] (3) By mass fraction, 3.5 parts of terminal hydroxyl polysiloxane, 1.1 parts of trimethylethoxysilane, 0.9 parts of methyltriethoxysilane, 1.35 parts of octadecyltriethoxysilane, 35 parts of anhydrous ethanol, and 1.1 parts of 36wt% hydrochloric acid aqueous solution are mixed evenly and stirred at 62℃ and 350r / min for 2.5h to obtain organosilane modified solution;

[0047] (4) Mix the modified sol and organosilane modified solution at a volume ratio of 2.5:1, stir at 250 r / min for 18 min at room temperature, coat the mixture onto the surface of the pressure-resistant microcrystalline glass, cure at 110℃ for 12 min, and then cure at 325℃ for 18 min to obtain the pressure-resistant glass.

[0048] Example 3:

[0049] A method for preparing pressure-resistant glass, the method comprising the following preparation steps:

[0050] The formulation components of the pressure-resistant microcrystalline glass are: silicon dioxide, 43 wt%; calcium oxide, 23.65 wt%; aluminum oxide, 20.35 wt%; zinc oxide, 2.8 wt%; barium oxide, 4.2 wt%; boron oxide, 0.8 wt%; sodium oxide, 2 wt%; antimony trioxide, 0.4 wt%; and titanium dioxide, 2.8 wt%.

[0051] (1) Weigh the raw materials according to the formula and add them to the ball mill jar. Then add pure water and zirconium balls. The mass ratio of raw materials, pure water and zirconium balls is 1:1:3. Ball mill at 150 rpm for 3 hours, dry at 120℃ for 10 hours, pass through a 120-mesh sieve, add to a crucible, heat to 1200℃ at a heating rate of 5℃ / min and hold for 1.5 hours, then continue to heat to 1500℃ and melt for 2.5 hours. Cast into a mold and press to form. Place in a muffle furnace and anneal at 650℃ for 1 hour. After naturally cooling to room temperature, cut and polish. Place in a muffle furnace and heat to 1120℃ at a heating rate of 10℃ / min and hold for 1 hour. Cool to room temperature with the furnace to obtain pressure-resistant microcrystalline glass.

[0052] (2) By mass fraction, 3 parts of tetraethyl orthosilicate, 4 parts of zirconium oxychloride octahydrate, 7 parts of pure water, 25 parts of anhydrous ethanol, and 0.07 parts of 3-glycidyl etheroxypropyltrimethoxysilane are mixed evenly and stirred at 300 r / min for 30 min at room temperature. Then, 1.2 parts of 36 wt% hydrochloric acid aqueous solution are added and stirring is continued for 20 h to obtain the modified sol.

[0053] (3) By mass fraction, 4 parts of terminal hydroxyl polysiloxane, 1.2 parts of trimethylethoxysilane, 1 part of methyltriethoxysilane, 1.5 parts of octadecyltriethoxysilane, 40 parts of anhydrous ethanol, and 1.2 parts of 36wt% hydrochloric acid aqueous solution are mixed evenly and stirred at 65℃ and 400r / min for 2h to obtain organosilane modified solution;

[0054] (4) Mix the modified sol and organosilane modified solution at a volume ratio of 3:1, stir at 300 r / min for 15 min at room temperature, coat the mixture onto the surface of the pressure-resistant microcrystalline glass, cure at 120℃ for 10 min, and then cure at 350℃ for 15 min to obtain the pressure-resistant glass.

[0055] Comparative Example 1:

[0056] The preparation method of the pressure-resistant glass in Comparative Example 1 differs from that in Example 2 in that the formulation components are different. The formulation components are modified as follows: silicon dioxide, 44.13 wt%; calcium oxide, 21.18 wt%; aluminum oxide, 19.69 wt%; zinc oxide, 3.2 wt%; barium oxide, 4.8 wt%; boron trioxide, 1 wt%; sodium oxide, 2.5 wt%; antimony trioxide, 0.5 wt%; titanium dioxide, 3 wt%. The remaining steps are the same as in Example 2.

[0057] Comparative Example 2:

[0058] The preparation method of the pressure-resistant glass in Comparative Example 2 differs from that in Example 2 in that the formulation components are different. The formulation components are modified as follows: silicon dioxide, 40.07 wt%; calcium oxide, 25.24 wt%; aluminum oxide, 19.69 wt%; zinc oxide, 3.2 wt%; barium oxide, 4.8 wt%; boron trioxide, 1 wt%; sodium oxide, 2.5 wt%; antimony trioxide, 0.5 wt%; titanium dioxide, 3 wt%. The remaining steps are the same as in Example 2.

[0059] Comparative Example 3:

[0060] The difference between the preparation method of the pressure-resistant glass in Comparative Example 3 and Example 2 lies in step (2). Step (2) is modified as follows: 2.5 parts by mass of tetraethyl orthosilicate, 6.5 parts by mass of pure water, 22.5 parts by mass of anhydrous ethanol, and 0.06 parts by mass of 3-glycidyl etheroxypropyltrimethoxysilane are mixed evenly and stirred at 250 r / min for 35 min at room temperature. Then, 1.1 parts by mass of 36 wt% hydrochloric acid aqueous solution are added, and stirring is continued for 21 h to obtain the modified sol. The remaining steps are the same as in Example 2.

[0061] Comparative Example 4:

[0062] The difference between the preparation method of the pressure-resistant glass in Comparative Example 4 and Example 2 is that step (2) is omitted, and step (4) is modified as follows: anhydrous ethanol and organosilane modified solution are mixed evenly at a volume ratio of 2.5:1, stirred at 250 r / min for 18 min at room temperature, coated on the surface of pressure-resistant microcrystalline glass, cured at 110℃ for 12 min, and then cured at 325℃ for 18 min to obtain pressure-resistant glass. The remaining steps are the same as in Example 2.

[0063] Comparative Example 5:

[0064] The difference between the preparation method of the pressure-resistant glass in Comparative Example 5 and Example 2 lies in step (3). Step (3) is modified as follows: 1.1 parts by mass of trimethylethoxysilane, 0.9 parts by mass of methyltriethoxysilane, 1.35 parts by mass of octadecyltriethoxysilane, 35 parts by mass of anhydrous ethanol, and 1.1 parts by mass of 36 wt% hydrochloric acid aqueous solution are mixed evenly and stirred at 62°C and 350 r / min for 2.5 h to obtain an organosilane modified solution. The remaining steps are the same as in Example 2.

[0065] Comparative Example 6:

[0066] The difference between the preparation method of the pressure-resistant glass in Comparative Example 6 and Example 2 lies in step (3). Step (3) is modified as follows: 3.5 parts by mass of terminal hydroxyl polysiloxane, 1.1 parts by mass of trimethylethoxysilane, 0.9 parts by mass of methyltriethoxysilane, 35 parts by mass of anhydrous ethanol, and 1.1 parts by mass of 36 wt% hydrochloric acid aqueous solution are mixed evenly and stirred at 62°C and 350 r / min for 2.5 h to obtain an organosilane modified solution. The remaining steps are the same as in Example 2.

[0067] Comparative Example 7:

[0068] The difference between the preparation method of the pressure-resistant glass in Comparative Example 7 and Example 2 is that step (3) is omitted, and step (4) is modified as follows: the modified sol and anhydrous ethanol are mixed evenly at a volume ratio of 2.5:1, stirred at 250 r / min for 18 min at room temperature, coated on the surface of the pressure-resistant microcrystalline glass, cured at 110℃ for 12 min, and then cured at 325℃ for 18 min to obtain the pressure-resistant glass. The remaining steps are the same as in Example 2.

[0069] Test Example 1:

[0070] Mechanical property testing: The compressive strength and hardness of the prepared pressure-resistant glass are tested to evaluate its mechanical properties. The specific testing methods are as follows:

[0071] Compressive strength: The compressive strength of the prepared glass was determined using an electronic universal testing machine in accordance with the test method of GB / T 13465.3-2014. The sample size was 14.5mm×14.5mm×7.5mm, the compression rate was 5mm / min, and each group of samples was tested in parallel 5 times. The average value was recorded.

[0072] Hardness: The surface hardness of the prepared pressure-resistant glass was tested using a Nano Indenter G200 nanoindenter. The test surface was the coated surface. Each group of samples was tested in parallel 5 times, and the average value was recorded.

[0073] The results are shown in Table 1.

[0074] Table 1

[0075] Compressive strength / MPa Hardness / GPa Example 1 364.57 15.9 Example 2 372.48 16.2 Example 3 368.55 16.0 Comparative Example 1 204.69 16.2 Comparative Example 2 287.72 16.1 Comparative Example 3 370.58 12.4 Comparative Example 4 369.81 2.59 Comparative Example 5 371.54 16.0 Comparative Example 6 370.22 16.1 Comparative Example 7 368.75 15.9

[0076] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-7 in Table 1 shows that the pressure-resistant glass prepared by the present invention has good compressive strength and hardness.

[0077] Comparing the data in the table, Comparative Examples 1 and 2 show that when the calcium-silicon ratio changes, whether it increases or decreases, the crystallinity of the compressive-resistant microcrystalline glass changes, leading to a decrease in compressive strength. When the calcium content is low, complete crystallization is impossible, resulting in a higher proportion of wollastonite crystal phase and a decrease in compressive strength. When the calcium content is high, excessive crystal growth and mutual compression damage the crystal structure, leading to a decrease in compressive strength. Comparative Example 3 shows that the addition of zirconium oxychloride octahydrate to the modified sol forms zirconium dioxide, which has a good hardness-enhancing effect. Comparative Example 4 shows that the coating surface formed by mixing the modified sol with the organosilane modified solution has good adhesion and can effectively improve surface hardness. When no modified sol is added, the hardness of the coating surface formed by the organosilane modified solution alone is greatly reduced.

[0078] Test Example 2:

[0079] Hydrophobicity and Abrasion Resistance Testing: The water contact angle and abrasion resistance cycles of the prepared pressure-resistant glass are tested to evaluate its hydrophobicity and abrasion resistance. The specific test methods are as follows:

[0080] Water contact angle test: The prepared pressure-resistant glass was placed at room temperature for 12 hours and the surface was cleaned. Water droplets were added to the coated surface of the pressure-resistant glass using the seat drop method, and the water contact angle was measured using a contact angle meter. Five 5μL water droplets were added to different positions of the sample using a 50μL microsyringe, and the average value was taken as the contact angle. Five samples were tested in each group, and the average value was recorded.

[0081] Abrasion resistance test: The prepared pressure-resistant glass was placed on the working table of a reciprocating linear abrasion tester, and the instrument friction speed was set to 60 cycles / min and the load to 120 g / cm. 2 The coated surface of the pressure-resistant glass was rubbed, and the water contact angle was tested according to the water contact angle test method after every 1000 rubs, until the water contact angle was less than 80° and the number of rubs was recorded. Each group of samples was tested in parallel 5 times, and the minimum value was recorded.

[0082] The results are shown in Table 2.

[0083] Table 2

[0084] Water contact angle Wear times Example 1 108.54° 15000 Example 2 109.84° 16000 Example 3 109.23° 16000 Comparative Example 1 109.67° 16000 Comparative Example 2 109.72° 16000 Comparative Example 3 104.34° 13000 Comparative Example 4 100.23° 10000 Comparative Example 5 98.37° 12000 Comparative Example 6 95.48° 14000 Comparative Example 7 65.96° /

[0085] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-7 in Table 2 shows that the pressure-resistant glass prepared by the present invention has good hydrophobicity and wear resistance.

[0086] Comparing the data in the table, Comparative Example 3 shows that the addition of zirconium oxychloride octahydrate forms a high-hardness zirconium dioxide on the pressure-resistant glass surface, effectively improving the surface morphology, enhancing hydrophobicity, and also effectively improving wear resistance. Comparative Example 4 shows that the zirconium dioxide-silica composite formed by the modified sol effectively improves wear resistance and contributes to surface morphology improvement, enhancing hydrophobicity. Comparative Example 5 shows that the addition of hydroxyl-terminated polysiloxanes in the organosilane-modified solution significantly improves both hydrophobicity and wear resistance. The hydroxyl-terminated polysiloxanes act as a framework, connecting other modified siloxanes under acidic conditions to form a more effective... The silane layer of the fruit, along with the long chains of the terminal hydroxyl polysiloxane, can effectively encapsulate zirconium dioxide and silica, fully leveraging the reinforcing effect of the filler particles. Data from Comparative Example 6 shows that the introduction of octadecyltriethoxysilane effectively improves the hydrophobic effect and also enhances the wear resistance. Data from Comparative Example 7 shows that after the organosilane modified solution is coated on the pressure-resistant glass surface, a polysiloxane protective layer is formed. It also has good compatibility with the zirconium dioxide and silica formed by the modified sol, fully leveraging the effects of both and effectively improving the surface hydrophobic properties. Due to the low water contact angle of the sample in Comparative Example 7, a friction test was not conducted.

[0087] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A pressure-resistant glass, characterized in that, The pressure-resistant glass is prepared by mixing modified sol and organosilane modified solution, coating it onto the surface of pressure-resistant microcrystalline glass, and then curing it at high temperature. The modified sol is prepared by mixing tetraethyl orthosilicate, zirconium oxychloride octahydrate and 3-glycidyl etheroxypropyltrimethoxysilane, and then adding hydrochloric acid solution and stirring. The organosilane modified solution is prepared by mixing hydroxyl-terminated polysiloxane, trimethylethoxysilane, methyltriethoxysilane, and octadecyltriethoxysilane and then reacting them with hydrochloric acid solution. The composition of the pressure-resistant microcrystalline glass is as follows: silicon dioxide, 41wt%–43wt%; calcium oxide, 22.96wt%–23.65wt%; aluminum oxide, 19.04wt%–20.35wt%; zinc oxide, 2.8wt%–3.6wt%; barium oxide, 4.2wt%–5.4wt%; boron trioxide, 0.8wt%–1.2wt%; sodium oxide, 2wt%–3wt%; antimony trioxide, 0.4wt%–0.6wt%; titanium dioxide, 2.8wt%–3.2wt%. The pressure-resistant microcrystalline glass is produced by weighing the corresponding raw materials according to the formula, mixing and ball milling, drying, sieving, melting, casting, annealing, cutting and polishing, and then heat-treating at high temperature for a period of time before cooling.

2. The pressure-resistant glass according to claim 1, characterized in that, The calcium oxide is added in the form of calcium carbonate; The barium oxide was added in the form of barium carbonate; The boron trioxide is added in the form of boric acid; The sodium oxide is added in the form of sodium carbonate; The aluminum oxide is added in the form of aluminum hydroxide.

3. The pressure-resistant glass according to claim 1, characterized in that, The mass ratio of silicon dioxide to calcium oxide is 1:(0.55-0.56).

4. A method for preparing pressure-resistant glass, characterized in that, The preparation steps include the following: (1) Weigh the raw materials according to the formula and add them to the ball mill jar. Then add pure water and zirconium balls and ball mill. Dry and pass through a 120-mesh sieve. Add to a crucible to melt, pour into a mold and press into shape. Anneal, cool, cut and polish, then put into a muffle furnace for heat preservation and cooling to obtain pressure-resistant microcrystalline glass. (2) By mass, 2-3 parts of tetraethyl orthosilicate, 3-4 parts of zirconium oxychloride octahydrate, 6-7 parts of pure water, 20-25 parts of anhydrous ethanol, and 0.05-0.07 parts of 3-glycidyl etheroxypropyltrimethoxysilane are mixed evenly and stirred at 200-300 r / min for 30-40 min at room temperature. Then, 1-1.2 parts of hydrochloric acid solution are added and stirring is continued for 20-22 h to obtain the modified sol. (3) By mass, 3-4 parts of terminal hydroxyl polysiloxane, 1-1.2 parts of trimethylethoxysilane, 0.8-1 parts of methyltriethoxysilane, 1.2-1.5 parts of octadecyltriethoxysilane, 30-40 parts of anhydrous ethanol, and 1-1.2 parts of hydrochloric acid solution are mixed evenly and stirred at 60-65℃ and 300-400r / min for 2-3h to obtain organosilane modified solution; (4) Mix the modified sol and organosilane modified solution at a volume ratio of (2-3):1, stir at 200-300 r / min for 15-20 min at room temperature, apply to the surface of the pressure-resistant microcrystalline glass, first cure at 100-120℃ for 10-15 min, then cure at 300-350℃ for 15-20 min to obtain the pressure-resistant glass.

5. The method for preparing pressure-resistant glass according to claim 4, characterized in that, The pressure-resistant microcrystalline glass described in step (1) is made by weighing the raw materials according to the formula and adding them to a ball mill jar, then adding pure water and zirconium balls. The mass ratio of raw materials, pure water and zirconium balls is 1:1:

3. The mixture is ball-milled at 120-150 rpm for 3-4 hours, dried at 110-120℃ for 10-12 hours, passed through a 120-mesh sieve, added to a crucible, heated to 1100-1200℃ at a heating rate of 5℃ / min and held for 1.5-2 hours, then heated to 1500℃ and melted for 2-2.5 hours. The mixture is then cast into a mold and pressed into shape, placed in a muffle furnace and annealed at 650℃ for 1 hour. After naturally cooling to room temperature, it is cut and polished, then placed in a muffle furnace and heated to 1120℃ at a heating rate of 10℃ / min and held for 1 hour. Finally, it is cooled to room temperature with the furnace to obtain the final product.

6. The method for preparing a pressure-resistant glass according to claim 4, characterized in that, The raw materials mentioned in step (1) include silicon dioxide, calcium carbonate, aluminum hydroxide, zinc oxide, barium carbonate, boric acid, sodium carbonate, antimony trioxide, and titanium dioxide.

7. The method for preparing pressure-resistant glass according to claim 4, characterized in that, The hydrochloric acid solutions mentioned in steps (2) and (3) are both 36wt% hydrochloric acid aqueous solutions.

8. The method for preparing pressure-resistant glass according to claim 4, characterized in that, The viscosity of the hydroxyl-terminated polysiloxane in step (3) is 20000 mPa·s.