Compression-resistant glass and preparation method thereof

Abstract

The invention discloses compression-resistant glass and a preparation method thereof, and relates to the technical field of special glass. When the compression-resistant glass is prepared, an anorthite crystal phase is used as a main material, a wollastonite crystal phase is used as an auxiliary material, and zinc, barium, boron, sodium, antimony and titanium elements are added, so that the compression-resistant glass ceramic is prepared; the preparation method comprises the following steps: mixing tetraethoxysilane, zirconium oxychloride octahydrate and 3-glycidyl ether oxypropyl trimethoxy silane, adding hydrochloric acid, and stirring to obtain modified sol; the preparation method comprises the following steps: mixing hydroxyl-terminated polysiloxane, trimethyl ethyoxyl silane, methyl triethyoxyl silane and octadecyl triethyoxyl silane, adding a hydrochloric acid solution, and reacting to prepare an organosilane modified solution; mixing the modified sol and the organosilane modified solution, coating the surface of the compression-resistant microcrystalline glass with the mixture, and curing to obtain the compression-resistant glass. The compressive glass prepared by the invention has the advantages of high compressive strength, hydrophobicity, wear resistance and high surface hardness.

Description

Technical Field

[0001] The present invention relates to the technical field of special glass, in particular to a pressure-resistant glass and a preparation method thereof. Background Art

[0002] Glass is ubiquitous in our daily lives, playing an indispensable role in the advancement of human civilization and social change. As a common building material, glass is widely used in aerospace, energy, construction, and automotive industries. As one of the most common inorganic non-metallic materials, glass is typically made by melting a mixture of various inorganic minerals, such as quartz sand, boric acid, barium carbonate, barite, feldspar, and limestone.

[0003] However, when glass is used as a building material, its compressive strength affects its effectiveness. Furthermore, due to its thin surface stress layer, it often develops through-cracks and scratches due to friction, dust, cleaning, and impact from hard particles during daily use. This leads to a sharp decrease in overall strength and shortens its service life. Therefore, in order to expand its application range and extend its service life, these issues need to be addressed. Summary of the Invention

[0004] The object of the present invention is to provide a pressure-resistant glass and a preparation method thereof, so as 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, which is prepared by mixing a modified sol and an organic silane modified solution, coating the mixture on the surface of a pressure-resistant micro-ceramic glass, and then curing the mixture at a high temperature;

[0007] The modified sol is prepared by mixing ethyl orthosilicate, zirconium oxychloride octahydrate and 3-glycidyloxypropyltrimethoxysilane, adding hydrochloric acid solution and stirring;

[0008] The organosilane modified solution is prepared by mixing hydroxyl-terminated polysiloxane, trimethylethoxysilane, methyltriethoxysilane and octadecyltriethoxysilane and then adding hydrochloric acid solution for reaction;

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

[0010] The compression-resistant microcrystalline glass is prepared by weighing corresponding raw materials according to the formula components, mixing and ball-milling, drying, sieving and then melting, casting and then annealing, cutting and polishing, and then performing high-temperature heat treatment again for a period of time and then cooling.

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

[0012] The barium oxide is 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 comprises the following steps:

[0018] (1) weighing raw materials according to the formula components and adding them into a ball mill, then adding pure water and zirconium balls and ball milling, drying and passing through a 120-mesh sieve, adding them into a crucible to melt, casting them into a mold and pressing them into shape, annealing, cooling, cutting and polishing, and then placing them into a muffle furnace for heat preservation and cooling to obtain a pressure-resistant microcrystalline glass;

[0019] (2) 2-3 parts of ethyl 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-glycidyloxypropyltrimethoxysilane were mixed uniformly by weight, stirred at 200-300 r / min for 30-40 minutes at room temperature, 1-1.2 parts of hydrochloric acid solution were added, and stirring was continued for 20-22 hours to prepare a modified sol;

[0020] (3) By weight, 3 to 4 parts of hydroxy-terminated polysiloxane, 1 to 1.2 parts of trimethylethoxysilane, 0.8 to 1 parts of methyltriethoxysilane, 1.2 to 1.5 parts of octadecyltriethoxysilane, 30 to 40 parts of anhydrous ethanol, and 1 to 1.2 parts of hydrochloric acid solution were mixed uniformly, and stirred at 60 to 65° C. and 300 to 400 r / min for 2 to 3 hours to prepare an organosilane modified solution;

[0021] (4) The modified sol and the organosilane modified solution are mixed evenly in a volume ratio of (2-3):1, stirred at 200-300 r / min for 15-20 min at room temperature, coated on the surface of the pressure-resistant microcrystalline glass, first cured at 100-120°C for 10-15 min, and then cured at 300-350°C for 15-20 min to obtain the pressure-resistant glass.

[0022] As an optimization, the compression-resistant microcrystalline glass in step (1) is prepared by weighing raw materials according to the formula components and adding them into a ball mill, then adding pure water and zirconium balls, the mass ratio of raw materials, pure water and zirconium balls being 1:1:3, ball milling at 120-150 rpm for 3-4 hours, drying at 110-120°C for 10-12 hours, passing through a 120-mesh sieve, adding to a crucible, heating to 1100-1200°C at a heating rate of 5°C / min and keeping warm for 1.5-2 hours, then continuing to heat to 1500°C, melting for 2-2.5 hours, casting in a mold and pressing into shape, placing in a muffle furnace and annealing at 650°C for 1 hour, naturally cooling to room temperature, cutting and polishing, then placing in a muffle furnace, heating to 1120°C at a heating rate of 10°C / min and keeping warm for 1 hour, and cooling to room temperature with the furnace.

[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 solutions in step (2) and step (3) are both 36 wt% hydrochloric acid aqueous solutions.

[0025] As an optimization, the viscosity of the hydroxy-terminated polysiloxane in step (3) is 20,000 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 present invention has the following beneficial effects:

[0027] When preparing the pressure-resistant glass, the present invention first weighs the corresponding raw materials according to the formula components, mixes and mills them, dries, sieves and then melts them, casts them into shape and then anneals them, cuts and polishes them, heat-treats them again at high temperature for a period of time and then cools them to obtain the pressure-resistant microcrystalline glass; ethyl orthosilicate, zirconium oxychloride octahydrate and 3-glycidyloxypropyltrimethoxysilane are mixed, and then hydrochloric acid solution is added and stirred to obtain a modified sol; terminal hydroxyl polysiloxane, trimethylethoxysilane, methyltriethoxysilane and octadecyltriethoxysilane are mixed, and then hydrochloric acid solution is added to react to obtain an organosilane modified solution; the modified sol and the organosilane modified solution are mixed, coated on the surface of the pressure-resistant microcrystalline glass, and then cured at high temperature to obtain the pressure-resistant glass.

[0028] First, after a high proportion of calcium and aluminum elements are introduced into calcium aluminosilicate glass, after crystallization, wollastonite is no longer the main crystal phase, but calcium feldspar is precipitated as the main crystal phase, with wollastonite as the auxiliary. At the same time, zinc and barium elements are introduced to improve the melting crystallization process. Zinc oxide can improve the fluidity of the glass and thus reduce the crystallization temperature, while barium oxide can promote the crystallization behavior of the glass and reduce the softening temperature of the glass; titanium dioxide is added as a nucleating agent; sodium oxide is added as a network adjuster, which can reduce the melting temperature, viscosity and crystallization temperature; antimony trioxide is used as a clarifier; and boron trioxide plays a role in improving the melting process; after precipitating calcium feldspar as the main crystal phase, the relative crystallinity is improved by adjusting the element ratio to obtain a compressive microcrystalline glass with high compressive strength, among which the mass ratio of silicon dioxide to calcium oxide is optimally 1:(0.55~0.56), which can effectively improve the compressive strength.

[0029] Secondly, ethyl orthosilicate and zirconium oxychloride octahydrate form a mixed sol of silica and zirconium dioxide under acidic conditions. Zirconium dioxide has high hardness and can improve the wear resistance of the final coating when used in conjunction with silica as a sol; terminal hydroxyl polysiloxane, trimethylethoxysilane, methyltriethoxysilane, and octadecyltriethoxysilane are hydrolyzed and condensed under acid catalysis to form hydrophobic and flexible polysiloxane chains. Among them, the addition of long carbon chain siloxane and the introduction of terminal hydroxyl polysiloxane can effectively improve the wear resistance and hydrophobicity.

[0030] Finally, the modified sol is mixed with the organosilane modified solution and then coated on the pressure-resistant microcrystalline glass. After high-temperature curing, a 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 is mixed with the modified sol, a certain coupling reaction occurs with the hydroxyl groups on the surface of silica and zirconium dioxide, thereby wrapping the silica and zirconium dioxide in the polysiloxane chain segments. The two are tightly combined, which greatly improves the wear resistance. DETAILED DESCRIPTION

[0031] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts 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] The coating thickness of all the following examples and comparative examples is 50 nm ± 5 nm, except for the hardness test sample which is 250 nm ± 15 nm.

[0034] Example 1:

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

[0036] The formula components used in the pressure-resistant micro-ceramic glass are: silicon dioxide, 41wt%; calcium oxide, 22.96wt%; aluminum oxide, 19.04wt%; zinc oxide, 3.6wt%; barium oxide, 5.4wt%; boron trioxide, 1.2wt%; sodium oxide, 3wt%; antimony trioxide, 0.6wt%; titanium dioxide, 3.2wt%;

[0037] (1) Weighing raw materials according to the formula components and adding them into 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, ball milling at 120 rpm for 4 hours, drying at 110 ° C for 12 hours, passing through a 120 mesh sieve, adding to a crucible, heating to 1100 ° C at a heating rate of 5 ° C / min and keeping warm for 2 hours, then continuing to heat to 1500 ° C, melting for 2 hours, casting in a mold and pressing into shape, placing in a muffle furnace and annealing at 650 ° C for 1 hour, cooling naturally to room temperature, cutting and polishing, and then placing in a muffle furnace, heating to 1120 ° C at a heating rate of 10 ° C / min and keeping warm for 1 hour, and cooling to room temperature with the furnace to obtain pressure-resistant microcrystalline glass;

[0038] (2) 2 parts by mass of ethyl orthosilicate, 3 parts of zirconium oxychloride octahydrate, 6 parts of pure water, 20 parts of anhydrous ethanol, and 0.05 parts of 3-glycidoxypropyltrimethoxysilane were mixed uniformly, stirred at room temperature at 200 r / min for 40 minutes, and 1 part of a 36 wt% aqueous hydrochloric acid solution was added, and stirring was continued for 22 hours to prepare a modified sol;

[0039] (3) By weight, 3 parts of hydroxy-terminated polysiloxane, 1 part of trimethylethoxysilane, 0.8 parts of methyltriethoxysilane, 1.2 parts of octadecyltriethoxysilane, 30 parts of anhydrous ethanol, and 1 part of a 36 wt % hydrochloric acid aqueous solution were mixed uniformly, and stirred at 60° C. and 300 rpm for 3 h to prepare an organosilane modified solution;

[0040] (4) The modified sol and the organosilane modified solution were mixed evenly in a volume ratio of 2:1, stirred at 200 r / min for 20 min at room temperature, coated on the surface of the pressure-resistant microcrystalline glass, first cured at 100°C for 15 min, and then cured at 300°C for 20 min to obtain the pressure-resistant glass.

[0041] Example 2:

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

[0043] The formula components used in the pressure-resistant micro-ceramic glass are: silicon dioxide, 42wt%; calcium oxide, 23.31wt%; aluminum oxide, 19.69wt%; zinc oxide, 3.2wt%; barium oxide, 4.8wt%; boron trioxide, 1wt%; sodium oxide, 2.5wt%; antimony trioxide, 0.5wt%; titanium dioxide, 3wt%;

[0044] (1) Weighing raw materials according to the formula components and adding them into a ball mill, then adding pure water and zirconium balls, the mass ratio of raw materials, pure water and zirconium balls is 1:1:3, ball milling at 135 rpm for 3.5 hours, drying at 115 ° C for 11 hours, passing through a 120 mesh sieve, adding to a crucible, heating to 1150 ° C at a heating rate of 5 ° C / min and keeping warm for 1.5 hours, then continuing to heat to 1500 ° C, melting for 2.2 hours, casting in a mold and pressing into shape, placing in a muffle furnace and annealing at 650 ° C for 1 hour, cooling naturally to room temperature, cutting and polishing, and then placing in a muffle furnace, heating to 1120 ° C at a heating rate of 10 ° C / min and keeping warm for 1 hour, cooling to room temperature with the furnace to obtain pressure-resistant microcrystalline glass;

[0045] (2) 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-glycidyloxypropyltrimethoxysilane were mixed uniformly by weight, stirred at 250 r / min for 35 minutes at room temperature, and 1.1 parts of a 36 wt% aqueous hydrochloric acid solution were added, and stirring was continued for 21 hours to prepare a modified sol;

[0046] (3) 3.5 parts by mass of hydroxy-terminated polysiloxane, 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 a 36 wt % aqueous hydrochloric acid solution were mixed uniformly, and stirred at 62° C. and 350 rpm for 2.5 h to prepare an organosilane-modified solution;

[0047] (4) The modified sol and the organosilane modified solution were mixed evenly in 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, first cured at 110°C for 12 min, and then cured at 325°C for 18 min to obtain the pressure-resistant glass.

[0048] Example 3:

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

[0050] The formula components used in the pressure-resistant micro-ceramic glass are: silicon dioxide, 43wt%; calcium oxide, 23.65wt%; aluminum oxide, 20.35wt%; zinc oxide, 2.8wt%; barium oxide, 4.2wt%; boron trioxide, 0.8wt%; sodium oxide, 2wt%; antimony trioxide, 0.4wt%; titanium dioxide, 2.8wt%;

[0051] (1) Weighing raw materials according to the formula components and adding them into a ball mill, then adding pure water and zirconium balls, the mass ratio of raw materials, pure water and zirconium balls is 1:1:3, ball milling at 150 rpm for 3 hours, drying at 120 ° C for 10 hours, passing through a 120 mesh sieve, adding to a crucible, heating to 1200 ° C at a heating rate of 5 ° C / min and keeping warm for 1.5 hours, then continuing to heat to 1500 ° C, melting for 2.5 hours, casting in a mold and pressing into shape, placing in a muffle furnace and annealing at 650 ° C for 1 hour, cooling naturally to room temperature, cutting and polishing, and then placing in a muffle furnace, heating to 1120 ° C at a heating rate of 10 ° C / min and keeping warm for 1 hour, and cooling to room temperature with the furnace to obtain pressure-resistant microcrystalline glass;

[0052] (2) 3 parts of ethyl orthosilicate, 4 parts of zirconium oxychloride octahydrate, 7 parts of pure water, 25 parts of anhydrous ethanol, and 0.07 parts of 3-glycidoxypropyltrimethoxysilane were mixed uniformly by weight, stirred at 300 rpm for 30 minutes at room temperature, and 1.2 parts of a 36 wt% aqueous hydrochloric acid solution were added, and stirring was continued for 20 hours to prepare a modified sol;

[0053] (3) By weight, 4 parts of hydroxy-terminated 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 a 36 wt % hydrochloric acid aqueous solution were mixed uniformly, and stirred at 65° C. and 400 rpm for 2 h to prepare an organosilane modified solution;

[0054] (4) The modified sol and the organosilane modified solution were mixed evenly in a volume ratio of 3:1, stirred at 300 r / min for 15 min at room temperature, coated on the surface of the pressure-resistant microcrystalline glass, first cured at 120°C for 10 min, and then cured at 350°C for 15 min to obtain the pressure-resistant glass.

[0055] Comparative Example 1:

[0056] The method for preparing the pressure-resistant glass of Comparative Example 1 differs from that of Example 2 in that the composition is modified to: 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%; and titanium dioxide, 3 wt%. The remaining steps are the same as those of Example 2.

[0057] Comparative Example 2:

[0058] The method for preparing the pressure-resistant glass of Comparative Example 2 differs from that of Example 2 in that the composition is modified to: 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 %; and titanium dioxide, 3 wt %. The remaining steps are the same as those of Example 2.

[0059] Comparative Example 3:

[0060] The method for preparing the pressure-resistant glass of Comparative Example 3 differs from that of Example 2 in step (2), which is modified as follows: 2.5 parts of tetraethyl orthosilicate, 6.5 parts of pure water, 22.5 parts of anhydrous ethanol, and 0.06 parts of 3-glycidoxypropyltrimethoxysilane are uniformly mixed, stirred at 250 rpm for 35 minutes at room temperature, and 1.1 parts of a 36 wt% aqueous hydrochloric acid solution are added, followed by continued stirring for 21 hours to obtain a modified sol. The remaining steps are the same as those of Example 2.

[0061] Comparative Example 4:

[0062] The method for preparing the pressure-resistant glass of Comparative Example 4 differs from that of Example 2 in that step (2) is omitted and step (4) is modified as follows: anhydrous ethanol and the organosilane-modified solution are uniformly mixed in a volume ratio of 2.5:1, stirred at 250 rpm for 18 minutes at room temperature, applied to the surface of the pressure-resistant micro-ceramic glass, and cured at 110°C for 12 minutes and then at 325°C for 18 minutes to produce the pressure-resistant glass. The remaining steps are the same as those of Example 2.

[0063] Comparative Example 5:

[0064] The method for preparing the pressure-resistant glass of Comparative Example 5 differs from that of Example 2 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 a 36 wt % aqueous hydrochloric acid solution are uniformly mixed, and stirred at 62° C. and 350 rpm for 2.5 hours to prepare an organosilane-modified solution. The remaining steps are the same as those of Example 2.

[0065] Comparative Example 6:

[0066] The method for preparing the pressure-resistant glass of Comparative Example 6 differs from that of Example 2 in step (3), which is modified as follows: 3.5 parts by weight of hydroxy-terminated polysiloxane, 1.1 parts of trimethylethoxysilane, 0.9 parts of methyltriethoxysilane, 35 parts of anhydrous ethanol, and 1.1 parts of a 36 wt % aqueous hydrochloric acid solution are uniformly mixed, and stirred at 62° C. and 350 rpm for 2.5 hours to prepare an organosilane-modified solution. The remaining steps are the same as those of Example 2.

[0067] Comparative Example 7:

[0068] The method for preparing the pressure-resistant glass of Comparative Example 7 differs from that of Example 2 in that step (3) is omitted, and step (4) is modified as follows: the modified sol and anhydrous ethanol are uniformly mixed in a volume ratio of 2.5:1, stirred at 250 rpm for 18 minutes at room temperature, applied to the surface of the pressure-resistant micro-ceramic glass, and cured at 110°C for 12 minutes and then at 325°C for 18 minutes to produce the pressure-resistant glass. The remaining steps are the same as those of Example 2.

[0069] Test Example 1:

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

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

[0072] Hardness: The surface hardness of the prepared compressive glass was tested using a Nano Indenter G200 nanoindenter. The test surface was the coated surface. Each group of samples was tested 5 times in parallel, 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] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 7 in Table 1, it can be found that the pressure-resistant glass prepared by the present invention has good compressive strength and hardness.

[0077] By comparing the data in the table, the data of Comparative Examples 1 to 2 show that when the calcium-silicon ratio changes, whether it becomes larger or smaller, the crystallinity of the compressive microcrystalline glass changes, resulting in a decrease in compressive strength. When the calcium content is low, it cannot be completely crystallized, and the proportion of wollastonite crystal phase is higher, resulting in a decrease in compressive strength. When the calcium content is high, the crystals grow excessively and squeeze each other, destroying the crystal structure, resulting in a decrease in compressive strength; the data of Comparative Example 3 show that the addition of zirconium oxychloride octahydrate to the modified sol forms zirconium dioxide, which has a good hardness improvement effect; the data of Comparative Example 4 show that the coating surface formed after the modified sol and the organosilane modified solution are mixed has good bonding, which can effectively improve the surface hardness. When the modified sol is not added, the hardness of the coating surface formed by the simple organosilane modified solution is greatly reduced.

[0078] Test Example 2:

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

[0080] Water contact angle test: The prepared pressure-resistant glass was left at room temperature for 12 hours and then cleaned. Water droplets were added to the coated surface of the pressure-resistant glass using the sessile drop method and the water contact angle was measured using a contact angle meter. Five 5μL water droplets were added to different locations on the specimen using a 50μL microsyringe, and the average of the droplets was taken as the contact angle. Five specimens were tested per group, and the average was recorded.

[0081] Wear test: Place the prepared compressive glass on the workbench of a reciprocating linear wear tester, set the instrument friction speed to 60 cycles / min, and the load to 120g / cm 2 Rub the coated surface of the pressure-resistant glass. After every 1000 rubs, perform a water contact angle test according to the water contact angle test method. Stop rubbing when the water contact angle is less than 80° and record the number of rubs. Test each set of samples five times in parallel, and record the minimum value.

[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] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 7 in Table 2, it can be found that the pressure-resistant glass prepared by the present invention has good hydrophobicity and wear resistance.

[0086] By comparing the data in the table, the data of Comparative Example 3 shows that the addition of zirconium oxychloride octahydrate forms zirconium dioxide with high hardness on the surface of the pressure-resistant glass, effectively improves the surface morphology, improves the hydrophobic effect, and also effectively improves the wear resistance; the data of Comparative Example 4 shows that the zirconium dioxide and silicon dioxide composite formed by the modified sol effectively improves the wear resistance, contributes to the improvement of the surface morphology, and improves the hydrophobic effect; the data of Comparative Example 5 shows that the addition of terminal hydroxyl polysiloxane in the organosilane modified solution greatly improves the hydrophobic effect and wear resistance. The terminal hydroxyl polysiloxane serves as a skeleton and connects the remaining modified siloxanes under the action of acid to form a composite with better effect. The silane layer of the result, and the long chain of the terminal hydroxyl polysiloxane can effectively wrap zirconium dioxide and silicon dioxide, fully exerting the reinforcing effect of the filling particles; the data of comparative example 6 show that the introduction of octadecyltriethoxysilane effectively improves the hydrophobic effect, and at the same time has a certain improvement effect on the wear resistance; the data of comparative example 7 show that the organic silane modified solution forms a polysiloxane protective layer after being coated on the surface of the pressure-resistant glass, and at the same time has good compatibility with the zirconium dioxide and silicon dioxide formed by the modified sol, and can give full play to the effects of the two, effectively improving the surface hydrophobicity. Since the water contact angle of the sample in comparative example 7 is too low, the friction test was not carried out.

[0087] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method 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 in 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 a modified sol and an organic silane modified solution, coating the mixture on the surface of the pressure-resistant micro-ceramic glass, and then curing the mixture at high temperature. The modified sol is prepared by mixing ethyl orthosilicate, zirconium oxychloride octahydrate and 3-glycidyloxypropyltrimethoxysilane, adding hydrochloric acid solution and stirring; The organosilane modified solution is prepared by mixing hydroxyl-terminated polysiloxane, trimethylethoxysilane, methyltriethoxysilane and octadecyltriethoxysilane and then adding hydrochloric acid solution for reaction; The formula components of the pressure-resistant microcrystalline glass are: silicon dioxide, 41wt% to 43wt%; calcium oxide, 22.96wt% to 23.65wt%; aluminum oxide, 19.04wt% to 20.35wt%; zinc oxide, 2.8wt% to 3.6wt%; barium oxide, 4.2wt% to 5.4wt%; boron trioxide, 0.8wt% to 1.2wt%; sodium oxide, 2wt% to 3wt%; antimony trioxide, 0.4wt% to 0.6wt%; titanium dioxide, 2.8wt% to 3.2wt%; The compression-resistant microcrystalline glass is prepared by weighing corresponding raw materials according to the formula components, mixing and ball-milling, drying, sieving and then melting, casting and then annealing, cutting and polishing, and then performing high-temperature heat treatment again for a period of time and then 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 is 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 the silicon dioxide to the calcium oxide is 1:(0.55-0.56).

4. A method for preparing pressure-resistant glass, characterized in that: The method comprises the following preparation steps: (1) weighing raw materials according to the formula components and adding them into a ball mill, then adding pure water and zirconium balls and ball milling, drying and passing through a 120-mesh sieve, adding them into a crucible to melt, casting them into a mold and pressing them into shape, annealing, cooling, cutting and polishing, and then placing them into a muffle furnace for heat preservation and cooling to obtain a pressure-resistant microcrystalline glass; (2) 2-3 parts of ethyl 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-glycidyloxypropyltrimethoxysilane were mixed uniformly by weight, stirred at 200-300 r / min for 30-40 minutes at room temperature, 1-1.2 parts of hydrochloric acid solution were added, and stirring was continued for 20-22 hours to prepare a modified sol; (3) By weight, 3 to 4 parts of hydroxy-terminated polysiloxane, 1 to 1.2 parts of trimethylethoxysilane, 0.8 to 1 parts of methyltriethoxysilane, 1.2 to 1.5 parts of octadecyltriethoxysilane, 30 to 40 parts of anhydrous ethanol, and 1 to 1.2 parts of hydrochloric acid solution were mixed uniformly, and stirred at 60 to 65° C. and 300 to 400 r / min for 2 to 3 hours to prepare an organosilane modified solution; (4) The modified sol and the organosilane modified solution are mixed evenly in a volume ratio of (2-3):1, stirred at 200-300 r / min for 15-20 min at room temperature, coated on the surface of the pressure-resistant microcrystalline glass, first cured at 100-120°C for 10-15 min, and then cured at 300-350°C 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 compression-resistant microcrystalline glass in step (1) is prepared by weighing raw materials according to the formula components and adding them into a ball mill, then adding pure water and zirconium balls, wherein the mass ratio of the raw materials, pure water and zirconium balls is 1:1:3, ball milling at 120-150 rpm for 3-4 hours, drying at 110-120°C for 10-12 hours, passing through a 120-mesh sieve, adding to a crucible, heating to 1100-1200°C at a heating rate of 5°C / min and keeping warm for 1.5-2 hours, then continuing to heat to 1500°C, melting for 2-2.5 hours, casting in a mold and pressing into shape, placing in a muffle furnace and annealing at 650°C for 1 hour, naturally cooling to room temperature, cutting and polishing, and then placing in a muffle furnace, heating to 1120°C at a heating rate of 10°C / min and keeping warm for 1 hour, and cooling to room temperature with the furnace.

6. The method for preparing pressure-resistant glass according to claim 4, characterized in that: 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.

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

8. The method for preparing pressure-resistant glass according to claim 4, characterized in that: The viscosity of the hydroxy-terminated polysiloxane in step (3) is 20,000 mPa·s.