A wear-resistant microcrystalline panel with a rough texture on the surface and a preparation method thereof

Abstract

The present application relates to the technical field of microcrystalline glass, and particularly relates to a wear-resistant microcrystalline panel with rough texture on the surface and a preparation method thereof. The preparation method provided by the present application comprises the following steps: immersing a microcrystalline glass panel into an etching solution for high-temperature etching, taking out and cleaning after the etching is completed, and obtaining a wear-resistant microcrystalline panel with rough texture on the surface; the etching solution is a molten mixture of an alkaline substance and boron oxide, the alkaline substance is one or more of potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, calcium oxide and zinc oxide, and the content of the boron oxide in the molten mixture is 15-40 wt%; the arithmetic roughness of the surface of the wear-resistant microcrystalline panel is 2-6 mu m, and the root mean square slope is 5-12 degrees. The preparation method provided by the present application can form a texture with suitable arithmetic roughness and root mean square slope on the surface of the microcrystalline panel, and significantly improve the wear resistance of the microcrystalline panel.

Description

Technical Field

[0001] This invention relates to the field of microcrystalline glass technology, and in particular to a wear-resistant microcrystalline panel with a rough texture on its surface and its preparation method. Background Technology

[0002] Low-expansion microcrystalline glass possesses excellent high-temperature resistance, low expansion, and high strength properties, and is primarily used in the field of cover panels for household appliances, serving as user interfaces. Due to its extremely high viscosity at high temperatures, low-expansion microcrystalline glass panels (hereinafter referred to as microcrystalline panels) are generally produced using a calendering method. The resulting raw microcrystalline panel blanks have roller marks on their surface that are unacceptable to users, requiring further grinding and polishing to achieve a mirror finish, commonly known as "polished panels." Polished panels have a smooth and aesthetically pleasing surface with a Mohs hardness of 5, but the surface is still highly susceptible to micro-scratches that are difficult to heal. Over long-term use, this severely impacts the user experience. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a wear-resistant microcrystalline panel with a rough texture on the surface and a method for preparing the same, so as to enhance the wear resistance of the microcrystalline panel.

[0004] This invention provides a method for preparing a wear-resistant microcrystalline panel with a rough textured surface, comprising the following steps:

[0005] The microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cleaned to obtain a wear-resistant microcrystalline panel with a rough texture on the surface.

[0006] The average linear thermal expansion coefficient of the microcrystalline glass panel is less than 20ppm / K at 40~700℃;

[0007] The etching solution is a molten mixture of an alkaline substance and boron oxide. The alkaline substance is one or more of potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and zinc oxide. The content of boron oxide in the molten mixture is 15-40 wt%.

[0008] The high-temperature etching temperature is higher than the melting point of the molten mixture but lower than the glass transition temperature of the microcrystalline glass panel; the high-temperature etching time is 1~30 min;

[0009] The arithmetic roughness of the wear-resistant microcrystalline panel surface is 2~6μm, and the root mean square slope is 5~12°.

[0010] Preferably, to avoid the wear-resistant microcrystalline panel after etching having roller marks that are visible to the naked eye, the surface arithmetic roughness of the microcrystalline glass panel is ≤0.4μm.

[0011] Preferably, the alkaline substance is potassium hydroxide.

[0012] Preferably, the boron oxide content in the molten mixture is 18-25 wt%.

[0013] Preferably, the high-temperature etching temperature is 550~700℃.

[0014] Preferably, the high-temperature etching temperature is 580~630℃.

[0015] Preferably, the high-temperature etching time is 3 to 8 minutes.

[0016] Preferably, to avoid or delay the high-temperature deterioration of the etching solution, the CO2 partial pressure of the environment in which the etching solution is located is lower than 3 Pa during the high-temperature etching process.

[0017] Preferably, the cleaning method is water washing and / or acid washing.

[0018] Preferably, the material of the microcrystalline glass panel is lithium aluminum silicon microcrystalline glass.

[0019] Preferably, the composition of the lithium aluminum silicon microcrystalline glass includes SiO2, Al2O3, Li2O, TiO2, ZrO2 and P2O5.

[0020] This invention provides a wear-resistant microcrystalline panel with a rough textured surface, which is prepared according to the preparation method described in the above technical solution.

[0021] Compared with existing technologies, this invention provides a wear-resistant microcrystalline panel with a rough textured surface and its preparation method. The preparation method provided by this invention includes the following steps: immersing a microcrystalline glass panel in an etching solution for high-temperature etching; removing and cleaning the panel after etching to obtain a wear-resistant microcrystalline panel with a rough textured surface; the average linear thermal expansion coefficient of the microcrystalline glass panel at 40~700℃ is less than 20ppm / K; the etching solution is a molten mixture of an alkaline substance and boron oxide, wherein the alkaline substance is one or more of potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and zinc oxide, and the boron oxide content in the molten mixture is 15~40wt%; the high-temperature etching temperature is higher than the melting point temperature of the molten mixture but lower than the glass transition temperature of the microcrystalline glass panel; the high-temperature etching time is 1~30min; the arithmetic roughness of the wear-resistant microcrystalline panel surface is 2~6μm, and the root mean square slope is 5~12°. The preparation method provided by this invention can form a texture with suitable arithmetic roughness and root mean square slope on the surface of the microcrystalline panel, significantly improving the wear resistance of the microcrystalline panel. Detailed Implementation

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] This invention provides a method for preparing a wear-resistant microcrystalline panel with a rough textured surface, comprising the following steps:

[0024] The microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cleaned to obtain a wear-resistant microcrystalline panel with a rough texture on the surface.

[0025] The average linear thermal expansion coefficient of the microcrystalline glass panel is less than 20ppm / K at 40~700℃;

[0026] The etching solution is a molten mixture of an alkaline substance and boron oxide; wherein the alkaline substance is one or more selected from potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and zinc oxide, preferably potassium hydroxide; the content of boron oxide in the molten mixture is 15-40 wt%.

[0027] The high-temperature etching temperature is higher than the melting point of the molten mixture and lower than the glass transition temperature (Tg) of the microcrystalline glass panel; the high-temperature etching time is 1~30 min;

[0028] The arithmetic roughness of the wear-resistant microcrystalline panel surface is 2~6μm, and the root mean square slope is 5~12°.

[0029] In the preparation method provided by the present invention, in order to avoid the wear-resistant microcrystalline panel after etching having roller marks that are visible to the naked eye, the surface arithmetic roughness of the microcrystalline glass panel is preferably ≤0.4μm, specifically 0.2μm, 0.1μm, 0.08μm, 0.04μm, 0.01μm or 0.004μm; the surface root mean square slope of the microcrystalline glass panel is preferably ≤0.6°, specifically 0.1°, 0.2°, 0.3°, 0.4°, 0.5° or 0.6°.

[0030] In the preparation method provided by the present invention, the material of the microcrystalline glass panel includes, but is not limited to, lithium aluminum silicon microcrystalline glass; the composition of the lithium aluminum silicon microcrystalline glass preferably includes SiO2, Al2O3, Li2O, TiO2, ZrO2 and P2O5, and more preferably includes flux and clarifying agent; wherein, the content of SiO2 is preferably 65~75 mol%, more preferably 71 mol%; the content of Al2O3 is preferably 10~15 mol%, more preferably 13 mol%; the content of Li2O is preferably 8~12 mol%, more preferably 10 mol%; the content of TiO2 is preferably 2~3 mol%, more preferably 2.4 mol%; the content of ZrO2 is preferably 0.4~0.8 mol%, more preferably 0.6 mol%; the content of P2O5 is preferably 0.3~0.4 mol%, more preferably 0.35 mol%; the content of flux is preferably 2~3 mol%, more preferably 2.3 mol%; and the content of clarifying agent is preferably 0.2~0.4 mol%, more preferably 0.3 mol%.

[0031] In the preparation method provided by this invention, the average linear thermal expansion coefficient of the microcrystalline glass panel at 40~700℃ is preferably less than 20ppm / K, more preferably 0.5~1ppm / K, specifically 0.5ppm / K, 0.6ppm / K, 0.7ppm / K, 0.8ppm / K, 0.9ppm / K, or 1ppm / K. If the thermal expansion coefficient is too high, there is a risk of the panel exploding after immersion in a high-temperature etching solution.

[0032] In the preparation method provided by this invention, the high-temperature etching time is 1~30 min, preferably 3~8 min, specifically 3 min, 4 min, 5 min, 6 min, 7 min or 8 min. In this invention, excessively long high-temperature etching time will lead to adverse effects such as excessive etching, difficulty in cleaning the surface, decreased panel performance, and a sharp increase in cost; while etching time of less than 1 min is insufficient to form the desired surface texture.

[0033] In the preparation method provided by this invention, the microcrystalline glass panel exhibits superior acid resistance but slightly inferior alkali resistance. Especially at high temperatures, molten alkaline substances can easily damage the surface of the microcrystalline glass, forming etching textures. By adjusting the etching temperature and etching time, the range of surface arithmetic roughness and root mean square slope after etching can be adjusted. However, both are synchronous; increasing the arithmetic roughness also leads to an increase in the root mean square slope. This invention has found that improving the roughness of the microcrystalline panel (such as arithmetic roughness and root mean square slope) helps improve the wear resistance of the microcrystalline glass. When the surface arithmetic roughness of the microcrystalline panel is 2~6 μm and the root mean square slope is 5~12°, the wear resistance of the microcrystalline panel reaches an excellent level. This is because the polycrystalline multiphase composite structure of the microcrystalline glass, through the etching reaction, removes the residual glass phase and some silica components from the surface, increasing the alumina ratio and exhibiting a strong ability to resist scratches. Furthermore, the uneven structure makes it difficult for scratches to form continuous lines, and the alternating light and dark surface texture also reduces the visibility of scratches. However, excessively high arithmetic roughness and root mean square slope bring many problems. First, excessive etching results in excessive arithmetic roughness, making the surface of the microcrystalline panel appear sharp and unsmooth, significantly reducing the visual effect. Second, an excessively high root mean square slope makes it difficult to clean solid residues after etching, which solidify on the surface and form white impurities, creating appearance defects. Third, excessive etching leads to uncontrollable microcrack expansion and significant strength reduction. Surprisingly, this invention has discovered that the relationship between arithmetic roughness and root mean square slope can be reversed using a smoothing agent. That is, while increasing, maintaining, or slightly decreasing the arithmetic roughness, the root mean square slope is significantly reduced, smoothing the sharp contours of the microcrystalline panel surface and adjusting both arithmetic roughness and root mean square slope to the desired range. The smoothing agent is boron oxide.

[0034] In the preparation method provided by this invention, the content of boron oxide in the molten mixture is 15-40 wt%, preferably 18-25 wt%, specifically 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, or 25 wt%. In this invention, a boron oxide content higher than 40 wt% easily leads to delamination and peeling of the microcrystalline glass surface; a content lower than 15% makes it difficult to achieve a smoothing effect.

[0035] In the preparation method provided by this invention, the high-temperature etching temperature directly affects the etching effect. The preferred high-temperature etching temperature is 550~700℃, more preferably 580~630℃, and specifically can be 580℃, 590℃, 600℃, 610℃, 620℃, or 630℃. This invention has found that increasing the etching temperature can effectively improve the etching reaction efficiency; simultaneously, since the melting point of boron oxide is 450℃, temperatures above 550℃ are more conducive to the implementation of this method. Furthermore, this invention has found that excessively high etching temperatures are detrimental.

[0036] In the preparation method provided by the present invention, in order to avoid or delay the high-temperature deterioration of the etching solution, the CO2 partial pressure of the environment in which the etching solution is located during the high-temperature etching process is preferably lower than 3 Pa.

[0037] In the preparation method provided by this invention, after etching, the panel can be cleaned after cooling to below 150°C; the cleaning method includes, but is not limited to, water washing and / or acid washing. In this invention, the water washing method includes, but is not limited to, rinsing with clean water, with water pressure within a common pressure range, such as 0.6~6MPa, and water quality being common municipal water quality. In this invention, the acid washing method includes, but is not limited to, immersion cleaning in an acidic solution; wherein, the acidic solution can be one or any combination of dilute hydrochloric acid solution (concentrated hydrochloric acid volume ratio less than 30%), dilute sulfuric acid solution, nitric acid, and phosphoric acid, or other solutions providing H... + The solution can quickly remove residual alkaline substances and reaction products from the surface; hydrofluoric acid can also be added to the acidic solution, with the amount of hydrofluoric acid added ranging from 1 to 20% wt. Hydrogen fluoride has a strong affinity for silicate substances and can quickly dissolve solid substances on the microcrystalline surface, further extending the soaking time of the acidic solution containing hydrofluoric acid, resulting in a microcrystalline panel with a softer surface.

[0038] This invention has found that the scratch resistance of microcrystalline glass is closely related to its surface texture. Low roughness, especially on mirror-like surfaces such as polished panels, results in extremely poor abrasion resistance and is prone to numerous scratches during daily use. In this invention, abrasion resistance is evaluated using the following methods:

[0039] Take quartz sand of 200 mesh or finer and spread it evenly on the surface of the microcrystalline panel. Place a 100mm × 100mm × 10mm wooden or plastic board on it, and place a 10kg object on the board. Move the board back and forth 5 times, counting each round trip as one round, with each one-way trip being 100mm. The surface scratches are graded as follows:

[0040] a. Poor, the surface has a large number of scratches, with more than 20 scratches;

[0041] b. Qualified, the surface has scratches, but there are no more than 3 scratches longer than 3cm;

[0042] c. Good, with scratches on the surface, which are short and shallow, and no scratches longer than 3cm;

[0043] d. Excellent, scratches longer than 1cm are difficult to observe on the surface.

[0044] This invention has found that increasing surface roughness is beneficial for improving the scratch resistance of microcrystalline panels. An arithmetic roughness of not less than 2 μm and a root mean square slope of not less than 5° can achieve superior wear resistance. This is because a texture meeting these conditions can form densely packed bumps on the panel surface, effectively suppressing the penetration of scratches and reducing their visual visibility. However, an arithmetic roughness higher than 6 μm and a root mean square slope higher than 12° will lead to difficulties in cleaning during the finishing process and in removing oil stains and residues during use, increasing the burden on users.

[0045] In this invention, surface roughness is detected using a Mitutuyo SJ401, with λc=2.5mm, repeated 5 times.

[0046] In this invention, the wear-resistant microcrystalline panel prepared by the method of this invention also has an anti-glare effect.

[0047] In this invention, the wear-resistant microcrystalline panel prepared by the method of this invention has excellent surface appearance quality. The appearance quality can be evaluated using the following methods:

[0048] a. Poor, with more than 3 white spots on the surface that are larger than 1.2 mm in diameter;

[0049] b. Qualified; no white impurities with a diameter greater than 1.2mm on the surface, and fewer than 2 white impurities with a diameter greater than 0.8mm.

[0050] c. Excellent, with no obvious white impurities or rainbow-colored stripes on the surface.

[0051] In this invention, the wear-resistant microcrystalline panel prepared by the method of this invention has good bending strength. The bending strength can be tested by the following method: prepare no less than 10 long strip samples of 50mm×120mm×4mm with smooth edges, use the three-point bending method, with a span of 100mm and a load application rate of 5mm / min, and take the average value as the bending strength.

[0052] For clarity, the following examples and comparative models will be used to provide a detailed description.

[0053] In the following embodiments and comparative examples of the present invention, the surface arithmetic roughness of the microcrystalline glass panel used is 0.1 μm, the root mean square slope is 0.2°, the bending strength is 106 MPa, and the average linear thermal expansion coefficient from 40 to 700°C is 0.6 ppm / K. The material of the microcrystalline glass panel is lithium aluminum silicon-based microcrystalline glass, the main crystalline phase is a high quartz phase, the crystallinity is 77%, the Tg point temperature is greater than 750°C, and the main components are shown in Table 1.

[0054] Table 1. Composition of Glass-Crystal

[0055]

[0056] Example 1

[0057] A microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cooled to below 150°C, then rinsed with a water gun to obtain a wear-resistant microcrystalline panel with a rough texture. The etching solution is a molten mixture of KOH and boron oxide, with the boron oxide content in the molten mixture being 15wt%. The high-temperature etching temperature is 600°C, the CO2 partial pressure of the etching solution environment is 2Pa, and the etching time is 5min. The arithmetic roughness of the wear-resistant microcrystalline panel surface is 3.11μm, and the root mean square slope is 8.9°.

[0058] The wear-resistant microcrystalline panel prepared in this embodiment has excellent wear resistance; the surface reaction products can be easily removed by rinsing with a water gun, resulting in excellent surface quality; the bending strength is 108 MPa, which is close to that of the polished panel before treatment.

[0059] Example 2

[0060] A microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cooled to below 150°C, then rinsed with a water gun to obtain a wear-resistant microcrystalline panel with a rough texture. The etching solution is a molten mixture of KOH and boron oxide, with the boron oxide content in the molten mixture being 15wt%. The high-temperature etching temperature is 630°C, the CO2 partial pressure of the etching solution environment is 2Pa, and the etching time is 5min. The arithmetic roughness of the wear-resistant microcrystalline panel surface is 3.87μm, and the root mean square slope is 9.3°.

[0061] The wear-resistant microcrystalline panel prepared in this embodiment has excellent wear resistance; the surface reaction products can be easily removed by rinsing with a water gun, resulting in excellent surface quality; and the flexural strength is 102 MPa.

[0062] A comparison of Example 2 and Example 1 shows that the surface arithmetic roughness and root mean square slope of the wear-resistant microcrystalline panel increase with increasing etching temperature, but the wear resistance, surface quality, and bending strength remain at a good level.

[0063] Example 3

[0064] A microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cooled to below 150°C, then rinsed with a water gun to obtain a wear-resistant microcrystalline panel with a rough texture. The etching solution is a molten mixture of KOH and boron oxide, with the boron oxide content in the molten mixture being 20wt%. The high-temperature etching temperature is 600°C, the CO2 partial pressure of the etching solution environment is 2Pa, and the etching time is 5min. The arithmetic roughness of the wear-resistant microcrystalline panel surface is 2.91μm, and the root mean square slope is 6.7°.

[0065] The wear-resistant microcrystalline panel prepared in this embodiment has excellent wear resistance; the surface reaction products can be easily removed by rinsing with a water gun, resulting in excellent surface quality; and the flexural strength is 105 MPa.

[0066] A comparison of Example 3 and Example 1 shows that increasing the boron oxide content in the molten mixture reduces the surface arithmetic roughness and root mean square slope of the prepared wear-resistant microcrystalline panel.

[0067] Comparative Example 1

[0068] The microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cooled to below 150°C, then soaked in 1+1 dilute hydrochloric acid for 30 minutes to obtain a wear-resistant microcrystalline panel with a rough texture. The etching solution is a KOH melt. The high-temperature etching temperature is 600°C, the CO2 partial pressure of the etching solution environment is 2 Pa, and the etching time is 5 minutes. The arithmetic roughness of the wear-resistant microcrystalline panel surface is 3.29 μm, and the root mean square slope is 15.3°.

[0069] The wear-resistant microcrystalline panel prepared in this comparative example has excellent wear resistance; however, the surface has agglomerated white residue that is difficult to clean, resulting in poor surface quality; the flexural strength is 77 MPa.

[0070] A comparison of Comparative Example 1 and Example 1 shows that it is difficult to achieve a balance between the wear resistance and surface quality of the microcrystalline panel when using pure potassium hydroxide for etching; moreover, the deep etching results in microcracks that severely affect the bending strength of the microcrystalline panel.

[0071] Comparative Example 2

[0072] The microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cooled to below 150°C, then soaked in 1+1 dilute hydrochloric acid for 30 minutes to obtain a wear-resistant microcrystalline panel with a rough texture. The etching solution is a KOH melt. The high-temperature etching temperature is 500°C, the CO2 partial pressure of the etching solution environment is 2 Pa, and the etching time is 5 minutes. The arithmetic roughness of the wear-resistant microcrystalline panel surface is 1.79 μm, and the root mean square slope is 10.7°.

[0073] The wear-resistant microcrystalline panel prepared in this comparative example shows scratches on its surface, indicating good wear resistance; the surface solid products are easy to clean, resulting in excellent surface quality; and the flexural strength is 103 MPa.

[0074] A comparison of Comparative Example 2 and Example 1 shows that it is difficult to achieve a balance between the wear resistance and surface quality of the microcrystalline panel when using pure potassium hydroxide for etching.

[0075] Comparative Example 3

[0076] The microcrystalline glass panel is immersed in an etching solution for high-temperature etching; wherein the etching solution is a molten mixture of KOH and boron oxide, and the content of boron oxide in the molten mixture is 50wt%; the high-temperature etching temperature is 650℃, the CO2 partial pressure of the etching solution environment is 2Pa, and the etching time is 5min.

[0077] The results showed that the excessive boron oxide content in the etching solution caused delamination and peeling on the surface of the microcrystalline panel.

[0078] For a more intuitive comparison, the key conditions, parameters and effects of Examples 1-3 and Comparative Examples 1-3 are summarized in Table 2.

[0079] Table 2 Comparison of High-Temperature Etching Effects

[0080]

[0081] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a wear-resistant microcrystalline panel with a rough textured surface, characterized in that, The arithmetic roughness of the wear-resistant microcrystalline panel surface is 2~6μm, and the root mean square slope is 5~12°; The preparation method includes the following steps: The microcrystalline glass panel is immersed in an etching solution for high-temperature etching. After etching, it is removed and cleaned to obtain a wear-resistant microcrystalline panel with a rough texture on the surface. The average linear thermal expansion coefficient of the microcrystalline glass panel is less than 20ppm / K at 40~700℃; The etching solution is a molten mixture of an alkaline substance and boron oxide. The alkaline substance is one or more of potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, calcium oxide, and zinc oxide. The content of boron oxide in the molten mixture is 18-25 wt%. The high-temperature etching temperature is 550~700℃; the high-temperature etching temperature is higher than the melting point temperature of the molten mixture and lower than the glass transition temperature of the microcrystalline glass panel; the CO2 partial pressure of the etching solution environment during the high-temperature etching process is lower than 3Pa; the high-temperature etching time is 1~30min.

2. The preparation method according to claim 1, characterized in that, The surface arithmetic roughness of the microcrystalline glass panel is ≤0.4μm.

3. The preparation method according to claim 1, characterized in that, The high-temperature etching time is 3-8 minutes.

4. The preparation method according to claim 1, characterized in that, The cleaning method is water washing and / or acid washing.

5. The preparation method according to claim 1, characterized in that, The microcrystalline glass panel is made of lithium aluminum silicon microcrystalline glass.

6. The preparation method according to claim 5, characterized in that, The lithium aluminum silicon-based microcrystalline glass comprises SiO2, Al2O3, Li2O, TiO2, ZrO2, and P2O5.

7. A wear-resistant microcrystalline panel with a rough textured surface, characterized in that, Prepared according to the preparation method according to any one of claims 1 to 6.

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