Water-resistant and acid-alkali-resistant Na-Ca glass, preparation method thereof and application of water-resistant and acid-alkali-resistant Na-Ca glass in preparation of bathroom mirror

Abstract

The invention discloses a preparation method of water-resistant and acid-alkali-resistant Na-Ca glass, which comprises the following steps: S1, by taking Na-Ca glass as a substrate, depositing a layer of amorphous ZrO2 film on the Na-Ca glass by a reactive magnetron sputtering method; and S2, carrying out plasma treatment on the Na-Ca glass with the amorphous ZrO2 thin film to crystallize the amorphous ZrO2 thin film so as to obtain the water-resistant and acid-alkali-resistant Na-Ca glass. According to the preparation method of the water-resistant and acid-alkali-resistant Na-Ca glass disclosed by the invention, a layer of uniform and compact ZrO2 crystal film can be obtained on the surface of the Na-Ca glass, and the film is smooth in surface, low in roughness and good in chemical stability and physical durability.

Description

Technical Field

[0001] The invention relates to the technical field of glass processing, and in particular to a water-resistant, acid-resistant and alkali-resistant Na-Ca glass, a preparation method thereof and an application of the glass in preparing a bathroom mirror. Background Art

[0002] Glass is widely used as a material for making mirrors and windows because of its transparency and durability. High-purity quartz glass is a material with excellent acid and water resistance, but its high glass transition point leads to high processing costs. In order to overcome the problem of high processing costs of high-purity quartz glass, an appropriate amount of impurities such as alkali metal elements are generally added to the glass material to adjust the performance. At present, most flat glass used for building materials and general purposes is Na-Ca glass, in which 10-20wt% of Na is added to lower the glass transition point. 2 O and CaO for improving chemical resistance.

[0003] Although Na-Ca glass is a glass material widely used in industry and has excellent performance, the addition of additives to improve manufacturing and processing convenience during its preparation significantly reduces the water resistance of Na-Ca glass, and a large amount of dirt easily adheres to the surface. Therefore, when Na-Ca glass is used for a long time in an environment containing a large amount of water vapor or water, such as a bathroom or shower room, the surface of the Na-Ca glass will fog and turn white.

[0004] Therefore, it is necessary to provide a high-performance glass with water-resistant, acid-resistant and alkali-resistant functions. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing water-resistant, acid-resistant and alkali-resistant Na-Ca glass, which can obtain a uniform and dense ZrO layer on the surface of the Na-Ca glass. 2 The film has a smooth surface, low roughness, and good chemical stability and physical durability.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] In a first aspect, the present invention provides a method for preparing water-resistant, acid-resistant and alkali-resistant Na-Ca glass, comprising the following steps:

[0008] S1. Using Na-Ca glass as substrate, a layer of amorphous ZrO was deposited on the Na-Ca glass by reactive magnetron sputtering. 2 film;

[0009] S2. With the amorphous ZrO 2The thin film of Na-Ca glass is plasma treated to make the amorphous ZrO 2 The film is crystallized to obtain the water-resistant, acid-resistant and alkali-resistant Na-Ca glass.

[0010] Na-Ca glass has been added with Na as an additive to improve the convenience of manufacturing and processing. 2 O and CaO cause the water resistance of Na-Ca glass to be significantly reduced, and a large amount of dirt is easily attached to the surface. When used for a long time in an environment containing a large amount of water vapor or water, such as a bathroom or shower room, the surface of Na-Ca glass will fog and turn white.

[0011] By applying a dense and strong protective layer on the surface of Na-Ca glass, water or water vapor can be effectively isolated, thereby protecting the Na-Ca glass. 2 ) has good chemical stability, not only has good water resistance, but also has good acid and alkali resistance, so it is a good material for preparing Na-Ca glass protective film.

[0012] Magnetron sputtering is a commonly used method for preparing micro-scale oxide films. By adjusting the sputtering parameters, a relatively uniform and dense crystalline film can be obtained on the substrate. However, the crystalline ZrO prepared by magnetron sputtering 2 The film has a large roughness and poor flatness. This is because during the magnetron sputtering process, some columnar crystals grow abnormally and penetrate the entire film layer, thus affecting the protective effect of the film on the Na-Ca glass.

[0013] In view of the technical problem that some zirconium oxide crystals grow abnormally during magnetron sputtering, the present invention first controls the sputtering parameters to deposit amorphous ZrO on a Na-Ca glass substrate. 2 The amorphous ZrO film is then treated by plasma treatment. 2 film, causing it to crystallize, thus avoiding the ZrO 2 The problem of abnormal crystal growth and penetration of the thin film layer, and the obtained crystallized ZrO 2 The film surface is smooth and has low roughness.

[0014] Furthermore, in step S1, during the reactive magnetron sputtering, the temperature of the substrate is controlled to be below 60° C. During magnetron sputtering, if the substrate temperature is low, the film is likely to form an amorphous structure, and the deposited atoms quickly lose kinetic energy and condense on the surface, so that the formed surface is relatively smooth and dense.

[0015] During the magnetron sputtering process, high-speed particles will continuously hit the substrate and deposit on the substrate, causing the substrate temperature to continue to rise. Therefore, an external cooling device is required to cool the substrate to control the substrate temperature below 60° C. In some embodiments, the substrate temperature can be controlled to be 20° C., 30° C., 40° C., 50° C., 60° C., etc.

[0016] Furthermore, in step S1, the present invention uses a reactive magnetron sputtering method to deposit amorphous ZrO 2 The film is completed in a high vacuum magnetron sputtering device. The target material of the magnetron sputtering is preferably metal zirconium with a purity of more than 99%, and the reaction atmosphere used is an atmosphere containing oxygen.

[0017] Furthermore, in step S1, during the reactive magnetron sputtering, the atmosphere used is a mixed atmosphere of oxygen and argon; wherein the total flow rate of the mixed atmosphere is controlled at 10 to 60 sccm, for example, 10 sccm, 20 sccm, 30 sccm, 40 sccm, 50 sccm, 60 sccm, etc.

[0018] In some embodiments of the present invention, the flow ratio of oxygen to argon is 1:2 to 5, for example, 1:2, 1:3, 1:4, 1:5, etc. When the oxygen concentration is higher than 1:2, polycrystalline ZrO is easily obtained on the substrate. 2 film, and at the same time the roughness of the film increases and the flatness decreases; when the oxygen concentration is lower than 1:5, the reaction will be incomplete, resulting in a partially metallized Zr film on the substrate.

[0019] Further, in step S1, during the reactive magnetron sputtering, the distance between the target and the Na-Ca glass substrate is preferably controlled to be 50-100 mm, for example, 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, 100 mm, etc. The sputtering power is controlled to be between 30 and 100 W, for example, 30 W, 40 W, 50 W, 60 W, 70 W, 80 W, 90 W, 100 W, etc.

[0020] Furthermore, in step S1, the amorphous ZrO deposited on the substrate 2 The thickness of the film is between 50 and 150 nm, for example, 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, etc.

[0021] Further, in step S2, the plasma treatment is oxygen plasma treatment, and the power of the oxygen plasma treatment is preferably 10 to 30 W, for example, 10 W, 20 W, 30 W, etc.; the treatment time is preferably 6 to 24 h, for example, 6 h, 8 h, 10 h, 12 h, 15 h, 16 h, 18 h, 20 h, 22 h, 24 h, etc.

[0022] The amorphous ZrO 2 If the film is not further densified and crystallized, it is impossible to obtain a protective film with high chemical stability and strong durability. The conventional treatment method is high-temperature heat treatment (generally above 300°C) to make the amorphous ZrO 2 Crystallization occurs to form crystalline ZrO 2 However, high temperature heat treatment will lead to grain coarsening in the film and partial ZrO 2 On the other hand, excessive grain growth will lead to the appearance of gaps between the film and the substrate due to the presence of residual thermal stress; in addition, high-temperature heat treatment will also cause the sodium and other elements contained in the Na-Ca glass to diffuse into the ZrO 2 In thin films, it hinders the crystallization process.

[0023] In the present invention, the amorphous ZrO on the substrate can be made by plasma treatment without high temperature heat treatment. 2 The film transforms into a dense, uniform crystalline ZrO 2 Since no high temperature heat treatment is performed, ZrO 2 The excessive growth of grains also avoids the formation of gaps between the film and the substrate due to the existence of residual thermal stress; in addition, it also avoids the diffusion of sodium elements in Na-Ca glass and hinders the crystallization process.

[0024] Due to the plasma treatment, amorphous ZrO 2 Crystallization occurs slowly, so if the treatment time is too short, for example, less than 6 hours, only part of the ZrO 2 Crystallization occurs, but the film as a whole remains amorphous.

[0025] Furthermore, step S2 also includes a step of heating the Na-Ca glass after the plasma treatment. The heat treatment at a lower temperature can accelerate the amorphous ZrO 2The transformation speed is accelerated to promote crystallization, and at the same time, it will not cause excessive growth of grains and diffusion of sodium in Na-Ca glass. The heating temperature is preferably 180-220°C, for example, 180°C, 190°C, 200°C, 210°C, 220°C, etc. The heating time is preferably 0.5-3h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, etc.

[0026] The second aspect of the present invention provides water-resistant, acid-resistant and alkali-resistant Na-Ca glass prepared by the method.

[0027] The third aspect of the present invention provides the use of the water-resistant, acid-resistant and alkali-resistant Na-Ca glass in the preparation of bathroom mirrors.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] In the preparation method of the water-resistant and acid-alkali-resistant Na-Ca glass provided by the present invention, firstly, amorphous ZrO is deposited on a Na-Ca glass substrate by reactive magnetron sputtering. 2 The amorphous ZrO film is then treated by plasma treatment. 2 The film is crystallized to obtain a dense and strong ZrO layer on the surface of Na-Ca glass. 2 The protective layer can effectively isolate water or water vapor, thereby protecting the Na-Ca glass and improving the water resistance and acid and alkali resistance of the Na-Ca glass. The water-resistant and acid-resistant Na-Ca glass can be used for a long time in an environment containing a large amount of water vapor or water, and the surface will not fog or turn white, so it can be used to prepare bathroom mirrors. DETAILED DESCRIPTION

[0030] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0031] Example 1

[0032] This embodiment provides a method for preparing water-resistant, acid-resistant and alkali-resistant Na-Ca glass, comprising the following steps:

[0033] S1. Provide a Na-Ca glass with a length of 60 mm, a width of 60 mm, and a thickness of 5 mm, place it in alcohol for ultrasonic cleaning for 5 minutes, then rinse it with deionized water, and then dry it for use.

[0034] S2. Use the dried Na-Ca glass as substrate and place it in a high vacuum magnetron sputtering device; use 99.999% pure zirconium as target and control the distance between the target and substrate to be 80 mm. The vacuum degree in the vacuum chamber is 5×10 -4 Pa, a mixed atmosphere of oxygen and argon is introduced into the vacuum chamber, and the total flow rate of the mixed atmosphere is controlled to be 50sscm, and the flow ratio of oxygen and argon is 1:3. The power of reactive sputtering is controlled to be 50W, and the temperature of the substrate is controlled below 50℃ by cooling equipment; after sputtering, a layer of ZrO with a thickness of 80nm is deposited on the Na-Ca glass 2 film.

[0035] S3. Place the Na-Ca glass in a plasma generating device and perform oxygen plasma treatment. The generating power of the oxygen plasma is 20 W and the treatment time is 20 h.

[0036] Example 2

[0037] This embodiment provides a method for preparing water-resistant, acid-resistant and alkali-resistant Na-Ca glass, comprising the following steps:

[0038] S1. Provide a Na-Ca glass with a length of 60 mm, a width of 60 mm, and a thickness of 5 mm, place it in alcohol for ultrasonic cleaning for 5 minutes, then rinse it with deionized water, and then dry it for use.

[0039] S2. Use the dried Na-Ca glass as substrate and place it in a high vacuum magnetron sputtering device; use 99.999% pure zirconium as target and control the distance between the target and substrate to be 80 mm. The vacuum degree in the vacuum chamber is 5×10 -4 Pa, a mixed atmosphere of oxygen and argon is introduced into the vacuum chamber, and the total flow rate of the mixed atmosphere is controlled to be 50sscm, and the flow ratio of oxygen and argon is 1:3. The power of reactive sputtering is controlled to be 50W, and the temperature of the substrate is controlled below 50℃ by cooling equipment; after sputtering, a layer of ZrO with a thickness of 80nm is deposited on the Na-Ca glass 2 film.

[0040] S3. Place the Na-Ca glass in a plasma generating device and perform oxygen plasma treatment. The generating power of the oxygen plasma is 20 W and the treatment time is 8 hours.

[0041] S4. The Na-Ca glass after plasma treatment is subjected to low-temperature heat treatment at a temperature of 220° C. for 2 hours.

[0042] Example 3

[0043] This embodiment provides a method for preparing water-resistant, acid-resistant and alkali-resistant Na-Ca glass, comprising the following steps:

[0044] S1. Provide a Na-Ca glass with a length of 60 mm, a width of 60 mm, and a thickness of 5 mm, place it in alcohol for ultrasonic cleaning for 5 minutes, then rinse it with deionized water, and then dry it for use.

[0045] S2. Use the dried Na-Ca glass as substrate and place it in a high vacuum magnetron sputtering device; use 99.999% pure zirconium as target and control the distance between the target and substrate to be 80 mm. The vacuum degree in the vacuum chamber is 5×10 -4 Pa, a mixed atmosphere of oxygen and argon is introduced into the vacuum chamber, and the total flow rate of the mixed atmosphere is controlled to be 50sscm, and the flow ratio of oxygen and argon is 1:4. The power of reactive sputtering is controlled to be 80W, and the temperature of the substrate is controlled below 50℃ by cooling equipment; after sputtering, a layer of ZrO with a thickness of 80nm is deposited on the Na-Ca glass 2 film.

[0046] S3. Place the Na-Ca glass in a plasma generating device and perform oxygen plasma treatment. The generating power of the oxygen plasma is 30 W and the treatment time is 16 h.

[0047] Comparative Example 1

[0048] This comparative example provides a method for preparing Na-Ca glass, comprising the following steps:

[0049] S1. Provide a Na-Ca glass with a length of 60 mm, a width of 60 mm, and a thickness of 5 mm, place it in alcohol for ultrasonic cleaning for 5 minutes, then rinse it with deionized water, and then dry it for use.

[0050] S2. Use the dried Na-Ca glass as substrate and place it in a high vacuum magnetron sputtering device; use 99.999% pure zirconium as target and control the distance between the target and substrate to be 80 mm. The vacuum degree in the vacuum chamber is 5×10 -4 Pa, a mixed atmosphere of oxygen and argon is introduced into the vacuum chamber, and the total flow rate of the mixed atmosphere is controlled to be 50sscm, and the flow ratio of oxygen and argon is 1:3. The power of reactive sputtering is controlled to be 50W, and the temperature of the substrate is controlled below 50℃ by cooling equipment; after sputtering, a layer of ZrO with a thickness of 80nm is deposited on the Na-Ca glass 2 film.

[0051] S3. The Na-Ca glass is subjected to high temperature heat treatment at a temperature of 550° C. for a treatment time of 1 hour.

[0052] Comparative Example 2

[0053] This comparative example provides a method for preparing Na-Ca glass, comprising the following steps:

[0054] S1. Provide a Na-Ca glass with a length of 60 mm, a width of 60 mm, and a thickness of 5 mm, place it in alcohol for ultrasonic cleaning for 5 minutes, then rinse it with deionized water, and then dry it for use.

[0055] S2. Use the dried Na-Ca glass as substrate and place it in a high vacuum magnetron sputtering device; use 99.999% pure zirconium as target and control the distance between the target and substrate to be 80 mm. The vacuum degree in the vacuum chamber is 5×10 -4 Pa, a mixed atmosphere of oxygen and argon was introduced into the vacuum chamber, and the total flow rate of the mixed atmosphere was controlled to be 50sscm, and the flow ratio of oxygen and argon was 1:3. The power of the reactive sputtering was controlled to be 50W, and the temperature of the substrate was 400℃; after sputtering, a layer of ZrO with a thickness of 80nm was deposited on the Na-Ca glass 2 film.

[0056] S3. Place the Na-Ca glass in a plasma generating device and perform oxygen plasma treatment. The generating power of the oxygen plasma is 20 W and the treatment time is 20 h.

[0057] Comparative Example 3

[0058] This comparative example provides a method for preparing Na-Ca glass, comprising the following steps:

[0059] S1. Provide a Na-Ca glass with a length of 60 mm, a width of 60 mm, and a thickness of 5 mm, place it in alcohol for ultrasonic cleaning for 5 minutes, then rinse it with deionized water, and then dry it for use.

[0060] S2. Use the dried Na-Ca glass as substrate and place it in a high vacuum magnetron sputtering device; use 99.999% pure zirconium as target and control the distance between the target and substrate to be 80 mm. The vacuum degree in the vacuum chamber is 5×10 -4 Pa, a mixed atmosphere of oxygen and argon is introduced into the vacuum chamber, and the total flow rate of the mixed atmosphere is controlled to be 50sscm, and the flow ratio of oxygen and argon is 3:1. The power of reactive sputtering is controlled to be 50W, and the temperature of the substrate is controlled below 50℃ by cooling equipment; after sputtering, a layer of ZrO with a thickness of 80nm is deposited on the Na-Ca glass 2 film.

[0061] S3. Place the Na-Ca glass in a plasma generating device and perform oxygen plasma treatment. The generating power of the oxygen plasma is 20 W and the treatment time is 20 h.

[0062] Performance Testing

[0063] The Na-Ca glass samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were taken and the ZrO 2 The film is scanned with a scanning range of 3μm×3μm, and the root mean square roughness R of the scanning area is calculated. q , the results are shown in Table 1.

[0064] Table 1

[0065] Group Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 <![CDATA[R q (nm)]]> 0.281 0.315 0.254 0.646 0.697 0.512

[0066] Please refer to Table 1. In Example 1, the ZrO on the substrate surface 2 The root mean square roughness R of the film q The thickness of the amorphous ZrO can be deposited on the substrate by controlling the substrate temperature to below 50°C and the flow ratio of oxygen to argon in the mixed atmosphere to 1:3. 2 The film can be made into amorphous ZrO 2 The film is transformed into a uniform and dense crystalline ZrO 2 Since it has not been subjected to high temperature heat treatment, it avoids the grain coarsening and partial ZrO 2 The excessive growth of grains results in the formation of crystalline ZrO 2 The film surface is relatively smooth and has low roughness.

[0067] Compared with Example 1, in Example 2, after the oxygen plasma treatment, a low-temperature heat treatment at 220° C. is performed. The low-temperature heat treatment can promote the 2 The crystallization of ZrO on the surface of the substrate in Example 2 can greatly shorten the time of oxygen plasma treatment. 2 The root mean square roughness R of the film q The thickness of ZrO is 0.315 nm, which is slightly higher than that of Example 1. This indicates that the heat treatment temperature of 220°C does not cause a large amount of ZrO 2 Excessive grain growth.

[0068] Example 3 Compared with Example 1, the ratio of oxygen to argon in the mixed atmosphere was changed from 1:3 to 1:4. From the results, the ZrO 2 The root mean square roughness R of the film q It also remains at a low level of only 0.254nm.

[0069] In Comparative Example 1, ZrO is deposited on the substrate. 2 After the film is formed, it is directly subjected to high temperature heat treatment without plasma treatment. Due to the high heat treatment temperature, reaching 550°C, although this temperature can make the non-static ZrO 2 Crystallization occurs, but it also leads to grain coarsening and partial ZrO 2 The excessive growth of grains and penetration of the film caused a significant increase in roughness. 2 The root mean square roughness R of the film q It reached 0.646 nm, which was significantly higher than that in Example 1.

[0070] In Comparative Example 2, during magnetron sputtering, the substrate temperature was controlled to be 400°C. At this substrate temperature, the deposited ZrO 2 Crystallization will occur directly, and some columnar crystals will grow abnormally and penetrate the entire film layer, resulting in poor surface flatness and high roughness of the film. 2 The root mean square roughness R of the film q It reached 0.697 nm, which was significantly higher than that in Example 1.

[0071] In comparative example 3, during magnetron sputtering, the flow ratio of oxygen to argon in the mixed atmosphere was controlled to be 3:1. A higher oxygen ratio would result in a higher ZrO 2 The film has a polycrystalline structure, which will increase the roughness of the film and deteriorate the surface flatness. 2 The root mean square roughness R of the film q It reached 0.512 nm, which was significantly higher than that in Example 1.

[0072] In summary, the present invention successfully deposits a uniform and dense ZrO layer on the surface of Na-Ca glass. 2 The crystal film has a smooth surface, low roughness, good chemical stability and physical durability, and can well protect Na-Ca glass. The water-resistant, acid-resistant and alkali-resistant Na-Ca glass can be used for a long time in an environment containing a large amount of water vapor or water without fogging or whitening on the surface, so it can be used to prepare bathroom mirrors.

[0073] In summary, although the present invention has been disclosed as above in terms of preferred embodiments, the above preferred embodiments are not intended to limit the present invention. A person skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be based on the scope defined in the claims.

Claims

1. A method for preparing water-resistant, acid-resistant and alkali-resistant Na-Ca glass, characterized in that: The following steps are involved: S1. Using Na-Ca glass as a substrate, a layer of amorphous ZrO2 film is deposited on the Na-Ca glass by reactive magnetron sputtering; S2. Plasma treatment is performed on the Na-Ca glass with the amorphous ZrO2 film to crystallize the amorphous ZrO2 film, thereby obtaining the water-resistant, acid-resistant and alkali-resistant Na-Ca glass.

2. The method for preparing a water-resistant, acid-resistant and alkali-resistant Na-Ca glass according to claim 1, characterized in that: In step S1, during the reactive magnetron sputtering process, the temperature of the substrate is controlled to be below 60°C.

3. The method for preparing a water-resistant, acid-resistant and alkali-resistant Na-Ca glass according to claim 1, characterized in that: In step S1, during the reactive magnetron sputtering, the atmosphere used is a mixed atmosphere of oxygen and argon; wherein the flow ratio of oxygen to argon in the mixed atmosphere is 1:2-5.

4. The method for preparing a water-resistant, acid-resistant and alkali-resistant Na-Ca glass according to claim 3, characterized in that: In step S1, during the reactive magnetron sputtering, metal zirconium with a purity of more than 99% is used as a target material, and the sputtering power is between 30 and 100W.

5. The method for preparing a water-resistant, acid-resistant and alkali-resistant Na-Ca glass according to claim 1, characterized in that: In step S1, the thickness of the ZrO2 film deposited on the substrate is 50-150 nm.

6. The method for preparing a water-resistant, acid-resistant and alkali-resistant Na-Ca glass according to claim 1, characterized in that: In step S2, the plasma treatment is oxygen plasma treatment, the power of the oxygen plasma treatment is 10 to 30 W, and the treatment time is 6 to 24 hours.

7. The method for preparing a water-resistant, acid-resistant and alkali-resistant Na-Ca glass according to claim 1, characterized in that: Step S2 also includes a step of heating the Na-Ca glass after the plasma treatment; the heating temperature is 180 to 220° C., and the heating time is 0.5 to 3 hours.

8. The water-resistant, acid-resistant and alkali-resistant Na-Ca glass prepared according to the method according to any one of claims 1 to 7.

9. Use of the water-resistant, acid-resistant and alkali-resistant Na-Ca glass according to claim 8 in the preparation of bathroom mirrors.