CN116730635A - Preparation method of chemically strengthened glass - Google Patents
Preparation method of chemically strengthened glass Download PDFInfo
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- CN116730635A CN116730635A CN202310649800.5A CN202310649800A CN116730635A CN 116730635 A CN116730635 A CN 116730635A CN 202310649800 A CN202310649800 A CN 202310649800A CN 116730635 A CN116730635 A CN 116730635A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
本发明提供一种化学强化玻璃的制备方法，将玻璃升温后浸入380℃‑420℃的含有M+离子的熔盐中强化得到化学强化玻璃；将化学强化玻璃降温至室温后升温至300℃‑350℃，通入加热的气体与玻璃表面的M+离子反应，离子反应后降温至室温再清洗玻璃以脱除M盐制得化学强化玻璃，所述加热气体的温度为300℃‑350℃。本发明可以将玻璃表面压应力提高至790MPa‑842Mpa以上，将玻璃翘曲降到0.15mm以下。The invention provides a method for preparing chemically strengthened glass. The glass is heated and then immersed in molten salt containing M + ions at 380°C-420°C to strengthen it to obtain chemically strengthened glass; the chemically strengthened glass is cooled to room temperature and then heated to 300°C- At 350°C, heated gas is introduced to react with M + ions on the glass surface. After the ion reaction, the temperature is cooled to room temperature and the glass is washed to remove M salts to obtain chemically strengthened glass. The temperature of the heated gas is 300°C-350°C. This invention can increase the compressive stress on the glass surface to more than 790MPa-842Mpa and reduce the glass warpage to less than 0.15mm.
Description
Technical Field
The invention relates to the technical field of glass, in particular to a preparation method of chemically strengthened glass.
Background
In order to increase the strength of the glass article, the glass article is typically chemically strengthened. The chemical strengthening method is to exchange the ions with larger radius in molten salt with the ions with smaller radius in glass at the temperature of about 400 ℃, and to form compressive stress on the surface layer of the glass by utilizing the difference of alkali ion volumes, so as to improve the strength of the glass. However, as the ion exchange time increases or the ion exchange depth increases, the warpage continues to increase. When the warpage of the glass product exceeds a certain value, the problem of poor lamination in the glass panel assembling process can be caused.
Current methods for reducing warp during float glass production include: the method for reducing the warpage of chemically strengthened glass is needed because the method for removing the tin surface through physical polishing, controlling the sodium oxide content of the air surface and the tin surface of the glass on a production line, passivating the glass surface in a tin bath and polishing the finished product back is high in cost.
Disclosure of Invention
The invention aims to provide a preparation method of chemically strengthened glass, which is characterized in that the chemically strengthened glass reacts with molten salt at a specific temperature by the method of the invention, and then gas and M on the surface of the glass are introduced at the specific temperature + And after the ion reaction, the M salt is removed by cleaning, so that the warping of the glass can be effectively reduced.
In the present invention, the term "glass article" refers to various articles manufactured and manufactured using glass as a main material for production, daily life or industrial use.
In the present invention, the term "chemically strengthened glass" refers to a glass in which a compressive stress layer is formed on the surface of the glass by a chemical method such as ion exchange to improve the strength and abrasion resistance of the glass.
In the present invention, the term "cover glass" refers to a glass plate that is generally used as a protective screen for mobile electronic devices, such as smart phones and tablet computers, and can protect the electronic devices from dropping, scratches and other external damage.
In the present invention, the term "high alumina cover glass" is an aluminosilicate glass containing a high concentration of aluminum element.
In the present invention, the term "strengthening" is equivalent to tempering, and means changing the chemical composition of the surface of glass to increase the strength of the glass.
In the present invention, the term "chemically strengthened" means that the glass is immersed in molten salt and M + Ion exchange is performed to form surface stress on the surface of the glass to enhance the strengthening of the glass.
In the present invention, the term "M + The ion "refers to a cation in the molten salt.
In the present invention, the term "Msalt" means M + Salts formed after the ions react with the gas.
In the present invention, the term "stress layer thickness" refers to the depth of ion exchange between ions in glass and ions in molten salt, also known as stress layer depth.
In order to achieve the above object, the present invention provides a method for preparing chemically strengthened glass, comprising the steps of:
s1, immersing glass which is heated to 380-420 ℃ and contains M + Strengthening in the molten salt of the ions;
s2, cooling the glass reinforced by the S1 fused salt, then heating to 300-350 ℃, and introducing heated gas and M on the surface of the fused salt reinforced glass + And (3) carrying out ion reaction, cleaning glass after the reaction to remove M salt, wherein the temperature of the heating gas is 300-350 ℃.
In some embodiments, the S1 molten salt strengthened glass has a surface stress in the range of 201Mpa to 292Mpa, e.g., 201Mpa, 220Mpa, 240Mpa, 260Mpa, 280Mpa, 292Mpa, and any combination thereof, and a stress layer thickness in the range of 37-45 μm, e.g.
37 μm, 39 μm, 41 μm, 43 μm, 45 μm, and any combination thereof.
In some embodiments, S2 is M with the glass surface by a heated gas + Ion reaction to form M salt, and washing to eliminate M salt to obtain K on glass surface + Concentration increases and K in the glass is increased by removing M salts by cleaning the glass + Concentration of heated gas M with glass surface + The ion reaction exchange layer is controlled to be less than 5um, and the surface compressive stress of the glass is increased to 790-842 Mpa in the set cooling process after the reaction.
In some embodiments, the temperature of the reaction of the S2 glass with the heated gas must not be higher than the temperature in S1, more specifically must not be higher than 350 ℃, further controlled in the range of 340 ℃ to 300 ℃, such as 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ and any combination thereof, and the cooling rate of the glass after the reaction with the heated gas ions is in the range of 8 ℃/min to 15 ℃/min, such as 10 ℃, 12 ℃, 14 ℃,15 ℃ and any combination thereof, and further cleaning the glass is not effective in preventing the glass from cracking or cooling.
In some embodiments, step S1 comprises M + The ionic molten salt contains: 15mol% to 35mol% of lithium ions, 20mol% to 35mol% of sodium ions, and 30mol% to 65mol% of potassium ions.
In some embodiments, step S1 comprises M + The ionic molten salt contains: 20mol% to 30mol% lithium ions, 25mol% to 35mol% sodium ions and/or 40mol% to 50mol% potassium ions.
In some embodiments, step S1 comprises M + The ionic molten salt contains: 30mol% lithium ions, 25mol% sodium ions and/or 45mol% potassium ions.
In some embodiments, step S1 comprises M + The anions in the molten salt of ions are nitrate ions.
In some embodiments, step S1 comprises M + The ionic molten salt contains: 15-35 mol% of lithium nitrate, 20-35 mol% of sodium nitrate and 30-65 mol% of potassium nitrate.
In some embodiments, step S1 comprises M + The ionic molten salt contains: 20mol% to 30mol% lithium nitrate, 25mol% to 35mol% sodium nitrate and/or 40mol% to 50mol% potassium nitrate.
In some embodiments, step S1 comprises M + The ionic molten salt contains: 30mol% lithium nitrate, 25mol% sodium nitrate and/or 45mol% potassium nitrate.
In some embodiments, the glass is a cover glass. In some embodiments, the cover glass is an aluminum cover glass.
In some embodiments, the high aluminum cover glass is prepared using float fusion forming.
In some embodiments, the cover glass is edging, chamfering, and annealing.
In some embodiments, the strengthening time in S1 is 3.5h-6h, e.g., 3.5h
Ranges of 4h, 4.5h, 5h, 5.5h, 6h, and any combination thereof.
In some embodiments, the temperature rise rate in S1 is 8℃to 15℃per minute, e.g., 8 ℃
Ranges of/min, 10 ℃/min, 12 ℃/min, 14 ℃/min, 15 ℃/min, and any combination thereof.
In some embodiments, the chemically strengthened glass prepared in S2 is cooled to room temperature.
In some embodiments, the chemically strengthened glass temperature reduction rate in S2 is in the range of 8 ℃/min to 15 ℃/min, such as 8 ℃/min, 10 ℃/min, 12 ℃/min, 14 ℃/min, 15 ℃/min, and any combination thereof. .
In some embodiments, the temperature rise rate in S2 is 8℃to 15℃per minute, e.g., 8 ℃
Ranges of/min, 10 ℃/min, 12 ℃/min, 14 ℃/min, 15 ℃/min, and any combination thereof. In some embodiments, the flow rate of the heating gas is: 50mL/min-150mL/min, such as a range of 50mL/min, 70mL/min, 90mL/min, 110mL/min, 130mL/min, 150mL/min, and any combination thereof.
In some embodiments, the heated gas is M with the glass surface + The ion reaction time is 10min-40min, such as 10min, 20min,30min, 40min, and any combination thereof.
In some embodiments, the post-ion reaction cooling in S2 is cooling the post-ion reaction glass to room temperature;
in some embodiments, the cooling rate of the glass after the ion reaction in S2 is 8 ℃/min to 15 ℃/min.
In some embodiments, washing the glass in S2 is washing the glass in water.
In some embodiments, cleaning the glass in S2 is ultrasonic cleaning the glass at room temperature for 10 minutes.
In some embodiments, the gas in step S2 is one or more of carbon dioxide, sulfur dioxide gas.
In some embodiments, the gas in step S2 is sulfur dioxide gas.
In some embodiments, the sulfur dioxide gas is a high purity sulfur dioxide gas.
In some embodiments, the glass in S1 is warmed to 330 ℃ to 400 ℃.
In some embodiments, the glass in S1 is warmed to 350 ℃.
In some embodiments, the high-aluminum cover glass is a high-aluminum cover glass sheet.
In some embodiments, the high aluminum cover glass sheet is 0.30mm to 1.0mm thick, such as 0.30mm thick
Ranges of 0.5mm,0.7mm,0.9mm and any combination thereof, ranges of 100mm to 300mm long, such as 100mm,150mm,200mm,250mm and any combination thereof, ranges of 50mm to 150mm wide, such as 50mm,80mm,100mm,130mm and any combination thereof.
In some embodiments, S1 may first warm the glass to a temperature close to the molten salt temperature and then place the glass sheet in the molten salt.
In some embodiments, after the S2 glass is reacted with the gas, the glass can be removed and cooled and then sonicated with water at room temperature to remove the M salts from the surface.
In some embodiments, the high aluminum cover glass sheet is 0.7mm thick, 150mm long and 75mm wide.
In some embodiments, the glass article in S1 is warmed to 330 ℃ to 400 ℃.
In some embodiments, the glass article in S1 is chemically strengthened after being heated to 350 ℃.
In some embodiments, the method comprises the steps of:
s1, heating the high-aluminum cover plate glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the high-aluminum cover plate glass sheet into a glass sheet containing M at 400 DEG C + Strengthening for 5 hours in ion molten salt to obtain chemically strengthened glass, wherein the molten salt contains: 30mol% lithium nitrate, 25mol% sodium nitrate and/or 45mol% potassium nitrate;
s2, cooling the chemically strengthened glass prepared in the step S1 to room temperature at a cooling rate of 15 ℃/min, and then introducing sulfur dioxide gas at a heating rate of 15 ℃/min to a high temperature of 330 ℃, wherein the gas temperature is 330 ℃, and the gas flow rate is as follows: and (3) maintaining the temperature for 20 minutes at 100mL/min, removing M salt on the surface of the sample after cleaning, and drying the sample.
In some embodiments, the present invention provides a chemically strengthened glass.
In some embodiments, the invention provides the use of a chemically strengthened glass in an electronic consumer product, automotive glass, architectural glass, medical device, lighting fixture, optical instrument product.
In some embodiments, the invention provides an application of chemically strengthened glass in an electronic consumer product with touch control function and display function.
In some embodiments, the electronic product is one or more of a capacitive touch screen mobile phone, a tablet computer, a digital camera, a GPS, various query terminals, various self-service terminals, an ATM, a jukebox, and a large screen touch electronic whiteboard.
The inventors found that by M in molten salt + The surface stress of the glass after the ion is chemically strengthened is 201Mpa-292Mpa, and the thickness of the stress layer is 37 μm-45 μm. By heating the gas with M on the glass surface + Ion reaction to form M salt, washing to eliminate M salt and K on the surface of glass + The ion concentration increases, thereby reducing the warpage of the chemically strengthened glass.
The invention has the advantages that:
through the technical scheme, the surface compressive stress of the chemically strengthened glass is improved, wherein the surface compressive stress of the chemically strengthened glass is improved to be more than 790Mpa-842Mpa, and the warpage of a chemically strengthened glass sample can be reduced to be less than 0.15 mm.
Detailed Description
Embodiments of the present invention are described in further detail below with reference to examples. The following detailed description of embodiments is provided to illustrate the principles of the invention and not to limit the scope of the invention, which may be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein, but rather should be construed as including all technical solutions falling within the scope of the appended claims.
These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. It should be noted that: the relative arrangement of parts and steps, the composition of materials, numerical expressions and numerical values set forth in these embodiments should be construed as exemplary only and not limiting unless otherwise specifically stated.
In the description of the present invention, unless otherwise indicated, the meaning of "plurality of" means greater than or equal to two;
all terms used herein have the same meaning as understood by one of ordinary skill in the art to which the present invention pertains, unless specifically defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the techniques, methods, and apparatus should be considered part of the specification.
The glass of the invention adopts commercial high-alumina cover glass sheets, and is purchased from panda cover glass held by the Dongxu group, and the model is as follows: 228;
according to the invention, the glass is placed on a sample holder, which is then placed in an oven to raise the temperature.
According to the invention, the sample holder is made of a shaped and heat-resistant material.
The sample rack of the invention adopts stainless steel material, can be a vertical or side-standing separation bracket, and is characterized by good heat resistance and stable shape. The glass can be stored in the sample rack in a standing or side-standing mode, and the samples cannot influence each other during the heating and cooling processes. This way, the heating and cooling effect of the cover glass can be ensured.
According to the invention, the glass has been subjected to edging, chamfering and annealing before starting step S1.
The glass is therefore edged, chamfered and annealed prior to chemical strengthening.
According to the invention, before starting step S1, the dimensions and thickness of the individual glasses are identical.
According to the invention, before starting step S1, the glass is placed in an upright stainless steel sample holder. All samples were the same size and thickness, had been subjected to edging, chamfering and annealing, and were free of fusion defects. The samples are placed apart in an upright manner on a sample holder, and then the entire sample holder is placed in an oven.
The invention is illustrated in further detail by the following examples.
Glass sizes used in examples and comparative examples were 150mm 75mm 0.7mm.
Example 1
Example 1 provides a method for preparing chemically strengthened glass comprising the steps of:
101. heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 30mol% lithium nitrate, 25mol% sodium nitrate and 45mol% potassium nitrate.
102. Cooling the chemically strengthened glass prepared in the step 101 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to a high temperature of 330 ℃, heating sulfur dioxide gas is introduced, the gas temperature is 330 ℃, and the gas flow rate is as follows: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, cleaning, removing M salt on the surface of the sample, and drying the sample to obtain the cover plate glass with low warpage.
Example 2
Example 2 provides a method for preparing chemically strengthened glass comprising the steps of:
201. heating the cover glass sheet to 400 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet into the solution containing M at 420 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 30mol% lithium nitrate, 25mol% sodium nitrate and 45mol% potassium nitrate.
202. Cooling the chemically strengthened glass prepared in 201 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, and introducing sulfur dioxide gas when the temperature is increased to a high temperature of 330 ℃, wherein the gas temperature is 330 ℃, and the gas flow rate is as follows: 100mL/min, keeping the temperature for 20 minutes, cooling the glass to room temperature at a cooling rate of 15 ℃/min, and then cleaning the glass with water to remove M on the surface of the sample + And (5) ion and drying the sample.
Example 3
Example 3 provides a method for preparing chemically strengthened glass comprising the steps of:
301. heating the cover glass sheet to 330 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 380 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 30mol% lithium nitrate, 25mol% sodium nitrate and 45mol% potassium nitrate.
302. Cooling the chemically strengthened glass prepared in 301 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, and introducing sulfur dioxide gas when the temperature is increased to a high temperature of 330 ℃, wherein the gas temperature is 330 ℃, and the gas flow rate is as follows: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 4
Example 4 provides a method of making a chemically strengthened glass comprising the steps of:
401. heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 30mol% lithium nitrate, 25mol% sodium nitrate and 45mol% potassium nitrate.
402. Cooling the chemically strengthened glass prepared by 401 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to 300 ℃, sulfur dioxide gas is introduced, the gas temperature is 300 ℃, and the gas flow rate is: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 5
Example 5 provides a method of making a chemically strengthened glass comprising the steps of:
501. heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 30mol% lithium nitrate, 25mol% sodium nitrate and 45mol% potassium nitrate.
502. Cooling the chemically strengthened glass prepared by 501 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to a high temperature of 350 ℃, sulfur dioxide gas is introduced, the gas temperature is 350 ℃, and the gas flow rate is: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 6
Example 6 provides a method of making chemically strengthened glass comprising the steps of:
601. heating the high-aluminum cover plate glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the high-aluminum cover plate glass sheet into a glass sheet containing M at 400 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes:35mol% lithium nitrate, 35mol% sodium nitrate, 30mol% potassium nitrate.
602. Cooling the chemically strengthened glass prepared by 601 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to a high temperature of 330 ℃, sulfur dioxide gas is introduced, the gas temperature is 330 ℃, and the gas flow rate is: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 7
Example 7 provides a method of making a chemically strengthened glass comprising the steps of:
701. heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 15mol% lithium nitrate, 20mol% sodium nitrate, 65mol% potassium nitrate.
702. Cooling the chemically strengthened glass prepared by 701 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to a high temperature of 330 ℃, sulfur dioxide gas is introduced, the gas temperature is 330 ℃, and the gas flow rate is: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 8
Example 8 provides a method of making a chemically strengthened glass comprising the steps of:
801. heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 6h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 35mol% lithium nitrate, 20mol% sodium nitrate, 45mol% potassium nitrate.
802. Cooling the chemically strengthened glass prepared by 801 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to a high temperature of 330 ℃, sulfur dioxide gas is introduced, the gas temperature is 330 ℃, and the gas flow rate is: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 9
Example 9 provides a method of making chemically strengthened glass comprising the steps of:
901. heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 3.5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 35mol% lithium nitrate, 20mol% sodium nitrate, 45mol% potassium nitrate.
902. Cooling the chemically strengthened glass prepared in 901 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to a high temperature of 330 ℃, sulfur dioxide gas is introduced, the gas temperature is 330 ℃, and the gas flow rate is: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 10
Example 10 provides a method of making chemically strengthened glass comprising the steps of:
1001. heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 35mol% lithium nitrate, 20mol% sodium nitrate, 45mol% potassium nitrate.
1002. Cooling the chemically strengthened glass prepared by 1001 to room temperature at a cooling rate of 15 ℃/min, then placing the chemically strengthened glass in an oven for heating, wherein the heating rate is 15 ℃/min, and when the temperature is raised to a high temperature of 330 ℃, sulfur dioxide gas is introduced, the gas temperature is 330 ℃, and the gas flow rate is: and (3) maintaining the temperature for 40 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Example 11
Example 11 provides a method of making chemically strengthened glass comprising the steps of:
1101. heating the cover plate glass sheet at 15 ℃/minAfter the temperature is raised to 350 ℃, the mixture is immersed into 400 ℃ and contains M + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 35mol% lithium nitrate, 20mol% sodium nitrate, 45mol% potassium nitrate.
1102. Cooling the chemically strengthened glass prepared in 1101 to room temperature at a cooling rate of 15 ℃/min, heating in an oven at a heating rate of 15 ℃/min, and introducing sulfur dioxide gas when the temperature is raised to a high temperature of 330 ℃, wherein the gas temperature is 330 ℃, and the gas flow rate is as follows: and (3) maintaining the temperature for 10 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Comparative example 1
Comparative example 1 provides a method of making a glass article comprising the steps of:
c101, heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 30mol% lithium nitrate, 25mol% sodium nitrate and 45mol% potassium nitrate.
And C102, cooling the chemically strengthened glass prepared by the C101 to room temperature at a cooling rate of 15 ℃/min, heating in an oven at a heating rate of 15 ℃/min, and introducing sulfur dioxide gas when the temperature is raised to a high temperature of 400 ℃, wherein the gas temperature is 330 ℃, and the gas flow rate is as follows: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Comparative example 2
Comparative example 2 provides a method of making a glass article comprising the steps of:
c201, inserting the cover plate glass sheet on a sample frame, heating to 330 ℃ at a heating rate of 15 ℃/min, introducing sulfur dioxide gas into the oven, keeping the temperature of 330 ℃ and keeping the temperature for 20 minutes.
C202, heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in the solution containing M at 450 DEG C + Strengthening in ion molten salt for 5h to obtain chemically strengthened glass containing M + The molten salt of the ion includes:taking out the cover plate glass to cool the cover plate glass, cooling the cover plate glass to room temperature at a cooling rate of 15 ℃/min, and then cleaning the cover plate glass by using water at room temperature for ultrasonic for 10 minutes.
Comparative example 3
Comparative example 3 provides a method of making a glass article comprising the steps of:
c301, heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in the solution containing M at 400 DEG C + Strengthening for 5h in ionic molten salt to obtain chemically strengthened glass, wherein the molten salt contains 100mol% of lithium nitrate, M + The ion is lithium nitrate.
And C302, cooling the chemically strengthened glass prepared in the step C301 to room temperature at a cooling rate of 15 ℃/min, heating in an oven at a heating rate of 15 ℃/min, and introducing sulfur dioxide gas when the temperature is raised to a high temperature of 330 ℃, wherein the gas temperature is 330 ℃, and the gas flow rate is as follows: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, then cleaning the glass with water to remove M salt on the surface of the sample, and drying the sample.
Comparative example 4
Comparative example 4 provides a method of making a glass article comprising the steps of:
heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet at 400 ℃ to contain M + Strengthening in ion molten salt for 5 hr to obtain chemically strengthened glass containing M + The molten salt of the ion includes: 30mol% lithium nitrate, 25mol% sodium nitrate and 45mol% potassium nitrate. Taking out, cooling the glass to room temperature at a cooling rate of 15 ℃/min, removing M salt on the surface of the sample by using water at room temperature through ultrasonic for 10 minutes, and drying the sample.
Comparative example 5
Comparative example 5 provides a method of making a glass article comprising the steps of:
inserting a cover plate glass sample on a sample frame, heating to 330 ℃ at a heating rate of 15 ℃/min, and introducing sulfur dioxide gas at a gas temperature of 330 ℃ at a gas flow rate of: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, cooling the glass to room temperature at a cooling rate of 15 ℃/min, cleaning the cover plate glass by using water through ultrasonic for 10 minutes, and drying the sample.
Comparative example 6
Comparative example 6 provides a method of making a glass article comprising the steps of:
c601, heating the cover glass sheet to 350 ℃ at a heating rate of 15 ℃/min, and immersing the cover glass sheet in a solution containing M at 400 DEG C + And (3) strengthening the glass in the ionic molten salt for 5 hours to obtain the chemically strengthened glass, wherein the molten salt contains 3mol% of lithium nitrate, 20mol% of sodium nitrate and 77mol% of potassium nitrate.
And C602, cooling the chemically strengthened glass prepared in the step C601 to room temperature at a cooling rate of 15 ℃/min, heating in an oven at a heating rate of 15 ℃/min, and introducing sulfur dioxide gas when the temperature is raised to a high temperature of 330 ℃, wherein the gas temperature is 330 ℃, and the gas flow rate is as follows: and (3) maintaining the temperature for 20 minutes at a constant temperature of 100mL/min, and cooling to room temperature at a speed of 30 ℃/min, so that the glass is subjected to self-explosion and fragmentation.
The reaction parameters in the glass article manufacturing methods of the respective examples and comparative examples are shown in table 1.
TABLE 1 examples 1-11, comparative examples 1-6 reaction parameters
The glass articles provided in examples 1-11 and comparative examples 1-6 were tested as follows:
the surface stress CS (unit is Mpa) and the stress layer thickness DOL (unit is mu m) of the chemically strengthened glass are measured by adopting an FSM-6000X dual-band glass surface stress meter, and the testing method comprises the following steps: after FSM-6000X dual-band glass surface stress meter and software are opened, glass products of examples 1-11 and comparative examples 1-6 are respectively placed stably after immersion liquid is dripped on the prism surface on the stress meter, test data are obtained after thickness, photoelastic coefficient and refractive index test parameters of a sample are input, and the test data are recorded, wherein the test results are shown in Table 2.
The center drop impact height (in cm) of the sample was measured by using an ultra-thin glass impact strength test method GB/T39814-2021, and the test results are shown in Table 2.
TABLE 2 results of test of surface stress, stress layer thickness, ball drop impact height for examples 1-11, comparative examples 1-6
As can be seen from the data in Table 2, the surface stress CS after tempering in examples 1-11 is 201-292MPa, the stress layer thickness after tempering is 37-45 μm, the surface stress CS of the glass after introducing gas is 790-842 MPa, the stress layer thickness after introducing gas is 37-45 μm, the center drop ball impact resistance height (unit is cm) of the test sample is tested by adopting the ultra-thin glass impact resistance test method GB/T39814-2021, the impact resistance height (cm) after 0.7T strengthening is 130g is 45-60cm, the surface stress after introducing gas is 400MPa after S2 in comparative example 1 is heated to 400 ℃, and the temperature is lower than that in examples 1-11. In comparative example 2, gas is introduced first, then tempering is performed, the surface stress and stress layer thickness of the glass are both 0, then the glass is tempered, the surface stress is 820MPa, the impact resistance is reduced, and meanwhile, the warping degree of the product is higher than that of examples 1-11. Comparative example 3 molten salt contains 100mol% of lithium nitrate, M + The ion is lithium nitrate, and the surface stress after the gas is introduced is as follows: 926MPa, the stress layer thickness is 44um, and the impact resistance height of the product is greatly reduced. Comparative example 4 only tempered glass, after tempering, had a surface stress, and the stress layer thickness was similar to that of examples 1 to 11, however, since no gas was introduced, the impact resistance height was greatly reduced. In comparative example 5, only gas was introduced, and the effect of secondary control was not achieved, and the glass warpage was not improved. Comparative example 6 lost its properties due to the self-explosion and chipping of the glass caused by the too fast cooling rate.
The warp test method was performed according to GB/T31958-2015.5.3.8, and the warp (in mm) of the sample was tested using a feeler gauge, and the test results are shown in Table 3.
TABLE 3 results of warp test for examples 1-11, comparative examples 1-6
As can be seen from the data in table 2, the chemically strengthened glass prepared in examples 1 to 11 can reduce warpage of glass, and the temperature of the gas introduced in comparative example 1 is 400 ℃ as compared with that in example 1, and the warpage in comparative example 1 is: the warpage of 0.25mm was higher than that of example 1, indicating that the temperature of the gas introduced had an effect on the degree of warpage of the glass. Comparative example 2 is to first introduce gas into the glass and then to temper the glass, and the warpage is 0.28mm, which means that the steps of ventilation and tempering affect the warpage sequentially. The molten salts in examples 1 to 11 contain 15 to 40mol% of lithium ions, the molten salt in comparative example 3 contains 100mol% of lithium nitrate, and the warpage is 0.27mm after gas is introduced; the glass of comparative example 4 was only tempered and warped by 0.12, whereas the impact height after 0.7T strengthening was only 5cm, which is much lower than 48-60cm in examples 1-11. In comparative example 5, only gas was introduced, the warpage was unchanged, however, the surface stress was 0MPa and the stress layer thickness was 0. Mu.m, and the drop resistance was greatly reduced. Comparative example 6 molten salt contained 3mol% of lithium nitrate, and after gas was introduced, the warp was 0.30mm, and the glass was broken by rapid cooling, and it was found that ions exceeding the range of the examples of the present invention caused an increase in warp. From the data of the above examples and comparative examples, it is understood that the method of the present invention can improve the stress of glass, improve the drop resistance, and reduce the warpage of glass.
Thus, various embodiments of the present invention have been described in detail. In order to avoid obscuring the concepts of the invention, some details known in the art have not been described. How to implement the inventive solutions herein will be fully apparent to those skilled in the art from the above description.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the invention. It will be understood by those skilled in the art that the foregoing embodiments may be modified and equivalents substituted for elements thereof without departing from the scope and spirit of the invention. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict.
Claims (10)
1. A method for preparing chemically strengthened glass, comprising the steps of:
s1, heating glass, immersing the glass at 380-420 ℃ and containing M + Strengthening in the molten salt of the ions;
s2, cooling the glass reinforced by the molten salt, heating to 300-350 ℃, and then introducing heated gas and M on the surface of the glass reinforced by the molten salt + And (3) carrying out ion reaction, cooling after the ion reaction, and cleaning glass to remove M salt, wherein the temperature of the heating gas is 300-350 ℃.
2. The method according to claim 1, wherein the glass after molten salt strengthening has a surface stress of 201Mpa to 292Mpa and a stress layer thickness of 37 μm to 45 μm.
3. The method according to claim 1, wherein M is contained in step S1 + The molten salt of the ion includes: 15mol% to 35mol% lithium ions, 20mol% to 35mol% sodium ions and/or 30mol% to 65mol% potassium ions; preferably, M is contained in the step S1 + The ion molten salt comprises: 20mol% to 30mol% lithium ions, 25mol% to 35mol% sodium ions and/or 40mol% to 50mol% potassium ions.
4. The method of manufacturing according to claim 1, wherein the glass is a cover glass.
5. The method of manufacturing according to claim 4, wherein the cover glass is a high-alumina cover glass, and the high-alumina cover glass is manufactured by float fusion molding.
6. The process of claim 1, wherein the strengthening time in S1 is3.5-6 h, and/or the heating rate in S1 is 8-15 ℃/min, and/or the chemically-strengthened glass in S2 is cooled to room temperature; and/or, the cooling rate of the chemically strengthened glass in the step S2 is 8 ℃/min-15 ℃/min; and/or, the heating rate in the step S2 is 8 ℃/min-15 ℃/min; and/or, the flow rate of the heating gas is: 50-150 mL/min; and/or M of the heated gas and the glass surface in S2 + The ion reaction time is 10min-40min; and/or, cooling the glass after the ion reaction in S2 to room temperature; and/or the cooling rate of the glass after the ion reaction in the step S2 is 8 ℃/min-15 ℃/min, and/or the glass is cleaned in water in the step S2.
7. The method according to claim 1, wherein the gas in the step S2 is one or more of carbon dioxide and sulfur dioxide.
8. The method of claim 1, wherein the glass in S1 is heated to 330 ℃ to 400 ℃.
9. A chemically strengthened glass prepared by the method of any one of claims 1-8.
10. Use of the chemically strengthened glass of claim 9 in electronic consumer products, automotive glass, architectural glass, medical devices, lighting fixtures, optical instrument products.
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