Antibacterial UTG glass and preparation method thereof

Abstract

The invention discloses antibacterial UTG glass and a preparation method thereof, and belongs to the technical field of antibacterial glass. According to the preparation method disclosed by the invention, Na < + > in a salt bath solution and Li < + > in the glass are subjected to ion exchange through primary strengthening, the intrinsic strength of the antibacterial UTG glass is improved, then trace Ag < + > in the salt bath solution and Li < + > in the glass are subjected to ion exchange through secondary strengthening, and the antibacterial effect of a glass surface layer is enhanced; the antibacterial UTG glass obtained by the preparation method has the advantages of antibacterial performance and strength performance; the antibacterial UTG glass prepared by the preparation method can achieve a long-acting antibacterial effect under the condition of long-time application.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial glass, and in particular relates to an antibacterial UTG glass and a preparation method thereof. Background Art

[0002] With the development and innovation of 5G technology, foldable screen mobile phones have been successfully introduced into the market and have become an emerging mobile phone development trend. Ultra-thin flexible glass (UTG glass) with a thickness of less than 100 microns is widely used in foldable screen mobile phones due to its advantages of ultra-thinness, bendability, good resilience, flexibility, wear resistance, and high strength. However, bacteria, viruses and other microorganisms are commonly found on the surface of mobile phones. With the widespread application of touch interactive technology, humans have more frequent contact with the screens of touch products. If these microorganisms enter our bodies, they will cause bacterial and viral infections and endanger human life and health.

[0003] At present, there are two ways to improve the antibacterial properties of conventional glass. The first is the coating method, which uses PVD technology to coat a film with antibacterial properties on the glass surface to achieve an antibacterial effect. This method is simple, but the antibacterial film has poor wear resistance and is easy to fall off, and there is a risk of scratching and abrasion. Once the non-antibacterial part of the glass surface is exposed, the antibacterial effect will be greatly reduced; the second is the ion exchange method, which uses the antibacterial ions in the fortified salt solution to exchange with the alkali metal ions in the glass network structure, so that the antibacterial ions enter the glass surface to achieve an antibacterial effect. This method will cause the intrinsic strength of the glass to decrease, and it is difficult to ensure the light transmittance of the glass during production. There are problems such as discoloration when the environmental conditions such as temperature, humidity and light change drastically. So far, there has been little research on antibacterial UTG glass, and UTG glass cannot have both antibacterial and strength properties at the same time. Summary of the invention

[0004] The object of the present invention is to provide an antibacterial UTG glass and a preparation method thereof, so as to solve the technical problem that the existing antibacterial methods have poor antibacterial effect.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: The invention discloses an antibacterial UTG glass. The raw materials of the antibacterial UTG glass include, by molar ratio, 42%-48% SiO2, 22%-28% Al2O3, 9%-15% Y2O3, 5%-11% Li2O, 2%-8% B2O3, 0-5% MgO, 0.5%-3% ZnO, 0-3% P2O5, 0-3% ZrO2 and 0.1%-2% AgNO3.

[0006] Furthermore, the thickness of the antibacterial UTG glass is 30-100 μm, the minimum bending radius is not greater than 1 mm, the number of static bending times is not less than 300,000 times, and the pen impact height is not less than 45 cm.

[0007] Furthermore, the antibacterial UTG glass has an antibacterial rate of not less than 99.9%, a transmittance of not less than 90%, and a thermal conductivity of not less than 750 kgf / mm 2 Vickers hardness of not less than 1.2Mpa•m 1 / 2 The fracture toughness is not less than 125 GPa and the elastic modulus is not less than 125 GPa.

[0008] The present invention also discloses a method for preparing the antibacterial UTG glass, comprising the following steps: Weighing raw materials, melting the raw materials and forming them into UTG glass; The UTG glass is sequentially subjected to pretreatment, preheating, primary strengthening, secondary strengthening and cooling treatment to obtain the antibacterial UTG glass.

[0009] Furthermore, the forming method is a down-draw method, a slit down-draw method or a melting method.

[0010] Furthermore, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and water in sequence; the temperature of the ultrasonic cleaning is 30-60° C. and the frequency is 40-120 kHz.

[0011] Furthermore, the preheating temperature is 300-420°C.

[0012] Furthermore, in terms of molar ratio, the salt bath used in the primary strengthening includes 100% NaNO3; the temperature of the primary strengthening is 380-500°C, and the time is 30-420min.

[0013] Furthermore, the salt bath used in the secondary strengthening includes 98%-99.9% NaNO3 and 0.1%-2% AgNO3 in terms of molar ratio; the temperature of the secondary strengthening is 380-450°C, and the time is 2-30 minutes.

[0014] In terms of molar ratio, the salt bath used in the secondary strengthening includes 98%-99.9% NaNO3 and 0.1%-2% AgNO3; the temperature of the secondary strengthening is 380-450°C and the time is 2-30 minutes.

[0015] The temperature is lowered to 70-100°C at a rate of 2-10°C / min.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention discloses an antibacterial UTG glass. In the design of raw material components, a trace amount of Ag with antibacterial effect is introduced. + and Zn 2+, so that the glass as a whole has an antibacterial effect, and at the same time, a trace amount of Ag with antibacterial effect is introduced into the secondary strengthening salt solution + , which enhances the antibacterial effect of the glass surface. It not only ensures that the UTG glass surface has antibacterial effect, but also ensures that the Ag inside the glass is effectively protected under long-term use. + and Zn 2+ It has a sustained release effect and achieves a long-lasting antibacterial effect.

[0017] The present invention also discloses a method for preparing the antibacterial UTG glass, which combines the glass components and strengthens the Na in the salt bath solution. + Li in glass + Ion exchange is performed to improve the intrinsic strength of the antibacterial UTG glass, and then secondary strengthening is performed to reduce the trace amount of Ag in the salt solution. + With Li in glass + Ion exchange is carried out to enhance the antibacterial effect of the glass surface; the antibacterial UTG glass obtained by this preparation method has the advantages of both antibacterial performance and strength performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a process flow chart of the preparation of the antibacterial UTG glass of the present invention; Figure 2 The transmittance curve of the antibacterial UTG glass prepared by the present invention from 200nm to 1200nm wavelength; Figure 3 This is a graph showing the 12-hour antibacterial effect of the antibacterial UTG glass prepared by the present invention on Staphylococcus aureus. DETAILED DESCRIPTION

[0019] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0020] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0021] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0022] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0023] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0024] like Figure 1 As shown, the present invention provides a method for preparing antibacterial UTG glass, comprising the following steps: S1: In terms of molar percentage, 42% to 48% SiO2, 22% to 28% Al2O3, 9% to 15% Y2O3, 5% to 11% Li2O, 2% to 8% B2O3, 0% to 5% MgO, 0.5% to 3% ZnO, 0% to 3% P2O5, 0% to 3% ZrO2 and 0.1% to 2% AgNO3 are used. Raw materials are weighed; the raw materials are melted and then formed to obtain UTG glass; S2: The UTG glass is sequentially pretreated, preheated, strengthened once, strengthened twice, and cooled to room temperature to obtain the target antibacterial UTG glass.

[0025] Preferably, the thickness of the UTG glass is preferably 30-100 μm.

[0026] Preferably, the forming method includes an overflow down-draw method, a slot down-draw method or a melting method.

[0027] Preferably, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in sequence, the temperature is 30-60°C, and the frequency of ultrasonic cleaning is 40-120kHz; ultrasonic cleaning of the glass using alkaline solution, acid solution and pure water can effectively remove surface dirt, improve the surface wettability of the glass, and effectively enhance the ion exchange capacity during the chemical strengthening process.

[0028] Preferably, the preheating temperature is 300-400°C; the purpose of preheating is to shorten the temperature difference between the glass and the molten salt during chemical strengthening, reduce the tensile stress caused by the temperature difference, and further avoid defect generation, while the control of the target temperature can solve the problem of deformation caused by tensile stress.

[0029] Preferably, the salt bath during the primary strengthening comprises 100% NaNO3 in terms of molar ratio, the primary strengthening temperature is 380-500°C, and the primary strengthening time is 30-420 min.+ Therefore, the salt bath uses 100% NaNO3 to react with Li in the glass. + Ion exchange is carried out to achieve the purpose of improving the strength performance of antibacterial UTG glass.

[0030] Preferably, the salt bath during secondary strengthening includes 98%-99.9% NaNO3 and 0.1%-2% AgNO3 in terms of molar ratio. The secondary strengthening temperature is 380-450°C, and the secondary strengthening time is 2-30 minutes. A trace amount of Ag with antibacterial effect is introduced into the salt bath solution of the secondary strengthening. + , and Li in glass + Carry out ion exchange to enhance the antibacterial effect of the glass surface.

[0031] Preferably, the temperature is lowered to 70-100°C at a cooling rate of 2-10°C / min.

[0032] The invention also discloses antibacterial UTG glass prepared by the preparation method.

[0033] Preferably, the antimicrobial UTG glass has an elastic modulus of not less than 125 GPa. Preferably, the antibacterial UTG glass has a thermal conductivity of not less than 1.2 Mpa•m 1 / 2 fracture toughness.

[0034] Preferably, the antibacterial UTG glass has a strength of not less than 750 kgf / mm 2 Vickers hardness.

[0035] Preferably, the antibacterial UTG glass has a transmittance of not less than 90%.

[0036] Preferably, the minimum bending radius of the antibacterial UTG glass is no more than 1 mm.

[0037] Preferably, the antibacterial UTG glass is statically bent no less than 300,000 times.

[0038] Preferably, the pen impact height of the antibacterial UTG glass is not less than 45 cm.

[0039] Preferably, the antibacterial UTG glass has an antibacterial rate of not less than 99.9%.

[0040] The raw materials used in the antibacterial UTG glass disclosed in the present invention, SiO2 is the core component for forming the glass structure, and is a component that plays the role of the skeleton of the glass structure; if its content is too low, there is a problem of weakening the structure of the glass, and if its content is too high, the melting temperature of the glass will be too high, and it will be difficult to form, thereby reducing the operability during the quenching process; therefore, the range of SiO2 is 42%~48%.

[0041] Al2O3 is a component that forms the glass network structure. The aluminum-oxygen tetrahedron and silicon-oxygen tetrahedron formed by it interpenetrate into a network structure. If the content is too low, the thermal stability, chemical stability, mechanical strength and hardness will be reduced. However, if the content is too high, the melting temperature of the glass will be too high, making it difficult to form, and thus reducing the operability during the quenching process. Therefore, the range of Al2O3 is 22%~28%. Y2O3 is used to increase the elastic modulus of glass, reduce the high-temperature viscosity and melting temperature of glass, and transform between different non-bridging oxygen structural units. If the content is too low, the mechanical strength such as the elastic modulus will be reduced. If the content is too high, the tendency of crystallization will increase. Therefore, the range of Y2O3 is 9%~15%.

[0042] Li2O is an alkali metal oxide, which acts as a non-crosslinked network modifier in the glass composition, can reduce the softening point of the basic glass composition, and participate in chemical strengthening. If the content is too low, the chemical strengthening effect is not good, but if the content is too high, the viscosity is too low, making the composition fluid, thus failing to form a basic glass, and increasing the tendency of crystallization; therefore, the range of Li2O is 5%~11%.

[0043] B2O3 is used to reduce the viscosity of the glass and can also serve as a flux to help lower the softening point of the resulting glass; therefore, the range of B2O3 is 2% to 8%.

[0044] MgO is an alkaline earth metal oxide that reduces the melting point of glass and improves the chemical stability of glass. Therefore, the range of MgO is 0~5%.

[0045] ZnO is an alkaline earth metal oxide that can improve the chemical stability of glass and has a certain antibacterial ability; therefore, the range of ZnO is 0.5%~3%.

[0046] P2O5 makes the glass structure loose, which is beneficial to increasing the ion exchange depth of the glass. Therefore, the range of P2O5 is 0~3%.

[0047] ZrO2 is a network former or intermediate in the base glass, which can significantly reduce the devitrification and phenomenon during glass forming and lower the liquidus temperature, and is used to increase the chemical durability and fracture toughness of the glass; therefore, the range of ZrO2 is 0~3%.

[0048] AgNO3 can provide Ag + , Ag + It has broad-spectrum antibacterial properties and is used to improve the antibacterial ability of glass. Therefore, the range of AgNO3 is 0.1%~2%.

[0049] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0050] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0051] Example 1 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.3% SiO2, 26.7% Al2O3, 10% Y2O3, 10% Li2O, 2% B2O3, 1.5% MgO, 1% ZnO, 1.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 300°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 380°C, strengthening time is 420min), secondary strengthening (salt bath NaNO3:AgNO3 is 98:2, strengthening temperature is 380°C, strengthening time is 30min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0052] Example 2 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.3% SiO2, 26.7% Al2O3, 10% Y2O3, 10% Li2O, 2% B2O3, 1.5% MgO, 1% ZnO, 1.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 320°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 400°C, strengthening time is 300min), secondary strengthening (salt bath NaNO3:AgNO3 is 98.5:1.5, strengthening temperature is 395°C, strengthening time is 25min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0053] Example 3 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.3% SiO2, 26.7% Al2O3, 10% Y2O3, 10% Li2O, 2% B2O3, 1.5% MgO, 1% ZnO, 1.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 340°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 420°C, strengthening time is 240min), secondary strengthening (salt bath NaNO3:AgNO3 is 99:1, strengthening temperature is 400°C, strengthening time is 20min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0054] Example 4 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.3% SiO2, 26.7% Al2O3, 10% Y2O3, 10% Li2O, 2% B2O3, 1.5% MgO, 1% ZnO, 1.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0055] Example 5 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.3% SiO2, 26.7% Al2O3, 10% Y2O3, 10% Li2O, 2% B2O3, 1.5% MgO, 1% ZnO, 1.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 370°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 460°C, strengthening time is 120min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.5:0.5, strengthening temperature is 420°C, strengthening time is 10min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0056] Example 6 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.3% SiO2, 26.7% Al2O3, 10% Y2O3, 10% Li2O, 2% B2O3, 1.5% MgO, 1% ZnO, 1.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 390°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 480°C, strengthening time is 50min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.7:0.3, strengthening temperature is 435°C, strengthening time is 5min), then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0057] Example 7 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.3% SiO2, 26.7% Al2O3, 10% Y2O3, 10% Li2O, 2% B2O3, 1.5% MgO, 1% ZnO, 1.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 400°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 500°C, strengthening time is 30min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.9:0.1, strengthening temperature is 450°C, strengthening time is 2min), then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0058] Example 8 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 42% SiO2, 28% Al2O3, 12% Y2O3, 10.5% Li2O, 4% B2O3, 2% MgO, 0.5% ZnO, 0.5% P2O5 and 0.5% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0059] Example 9 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 43.5% SiO2, 26.5% Al2O3, 11% Y2O3, 9% Li2O, 3.5% B2O3, 5% MgO, 0.5% ZnO, 0.5% ZrO2 and 0.5% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0060] Example 10 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45% SiO2, 25% Al2O3, 13% Y2O3, 5% Li2O, 5% B2O3, 1% MgO, 1% ZnO, 1% P2O5, 3% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0061] Embodiment 11 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 45.5% SiO2, 24% Al2O3, 12% Y2O3, 8% Li2O, 3.5% B2O3, 1.5% MgO, 0.5% ZnO, 3% P2O5 and 2% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0062] Example 12 A method for preparing antibacterial UTG glass comprises the following steps: S1: In terms of molar percentage, raw materials are weighed according to 46% SiO2, 22.5% Al2O3, 11% Y2O3, 6% Li2O, 8% B2O3, 1.5% MgO, 2.4% ZnO, 0.5% P2O5, 2% ZrO2 and 0.1% AgNO3; the raw materials are melted and then formed into UTG glass by a melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0063] Example 13 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 47% SiO2, 22% Al2O3, 15% Y2O3, 5% Li2O, 5.5% B2O3, 3% ZnO, 0.5% P2O5, 1% ZrO2 and 1% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0064] Embodiment 14 A method for preparing antibacterial UTG glass comprises the following steps: S1: weigh raw materials according to molar percentage, 48% SiO2, 22% Al2O3, 9% Y2O3, 11% Li2O, 6% B2O3, 2.5% MgO, 0.5% ZnO, 0.5% P2O5 and 0.5% AgNO3; melt the raw materials and then form them into UTG glass by melting method; S2: Pre-treating, preheating, primary strengthening, secondary strengthening, and cooling the UTG glass to room temperature in sequence to obtain the target antibacterial UTG glass; Among them, the pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and pure water in turn, the temperature is 30°C, the frequency of ultrasonic cleaning is 60kHz; the preheating temperature is 360°C; primary strengthening (salt bath is 100% NaNO3, strengthening temperature is 440°C, strengthening time is 180min), secondary strengthening (salt bath NaNO3:AgNO3 is 99.2:0.8, strengthening temperature is 410°C, strengthening time is 15min), and then cooled to 100°C at a cooling rate of 2°C / min, and finally naturally cooled to ambient temperature to obtain the target antibacterial UTG glass.

[0065] The obtained antibacterial UTG glass is subjected to various performance tests or treatments. The treatment methods, test methods and judgment criteria are as follows: Transmittance test: analytik jena SPECORD 50 visible spectrophotometer; place the sample vertically in the optical path of the spectrophotometer, and measure the light transmittance of the sample to air at a wavelength of 550mm. The current customer standard is that the transmittance is not less than 90%.

[0066] Vickers hardness and fracture toughness test: HVS-1000Z Vickers hardness tester.

[0067] Surface hardness test: pencil hardness test.

[0068] Bending strength test: Shangzhun universal material testing machine RS-N8000; During the bending strength test, a special fixture is used to clamp the glass, and the instrument steps forward from top to bottom until the product is crushed. The bending radius of the product when it is crushed is recorded. This is a destructive test. The current customer standard is that a radius less than 1mm is OK.

[0069] Static bending test: Fix the two ends of the long side of the product on the bending fatigue tester, set the reciprocating frequency of the tester to 30 times / min, and when the product reaches the bending radius, move the plate back to the starting position, complete one bending fatigue test, and then cycle the sample back and forth. The current customer standard is that if the static bending times are greater than 300,000 times without breaking, it is recorded as OK, otherwise it is recorded as NG.

[0070] Pen drop impact test: SA-8220V fully automatic pen drop impact tester; pen drop weight: 8.6g, M&G 0.5mm pen core, hollow fixture, test starting from 5cm, raising 1cm each time and repeating the test until it breaks.

[0071] Antibacterial test: UTG glass was tested for 12 hours using Staphylococcus aureus and Gram-negative Escherichia coli (model: E.coli, ATCC No.25922). The bactericidal ability of different samples can be determined by the number of surviving colonies on the culture medium.

[0072] The antibacterial UTG glasses of Examples 1 to 14 were tested for transmittance, elastic modulus, fracture toughness, Vickers hardness, surface hardness, 300,000 static bending, pen drop impact, etc. The test results are shown in Table 1: Table 1 Antibacterial UTG glass performance test data of Example 1 to Example 14

[0073] It can be seen from the data in Table 1 that the antibacterial UTG glass prepared by the present invention not only has an antibacterial rate of 99.9% or above, but also exhibits excellent performance in terms of transmittance, elastic modulus, fracture toughness, Vickers hardness, surface hardness, 300,000 static bendings, and pen impact.

[0074] Figure 2 This is the transmittance curve of the antibacterial UTG glass prepared in the present invention from a wavelength of 200nm to 1200nm. It can be seen that the transmittance of the antibacterial UTG glass prepared in the present invention is not less than 90% at a wavelength of 550nm, showing excellent transmittance.

[0075] Figure 3 This is a 12-hour antibacterial effect diagram of the antibacterial UTG glass prepared by the present invention on Staphylococcus aureus. It can be seen that the antibacterial UTG glass prepared by the present invention exhibits excellent antibacterial effect.

[0076] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. An antibacterial UTG glass, characterized in that: In terms of molar ratio, the raw materials of the antibacterial UTG glass include: 42%~48% SiO2, 22%~28% Al2O3, 9%~15% Y2O3, 5%~11% Li2O, 2%~8% B2O3, 0~5% MgO, 0.5%~3% ZnO, 0~3% P2O5, 0~3% ZrO2 and 0.1%~2% AgNO3.

2. The antibacterial UTG glass according to claim 1, characterized in that: The antibacterial UTG glass has a thickness of 30-100 μm, a minimum bending radius of no more than 1 mm, a static bending number of no less than 300,000 times, and a pen impact height of no less than 45 cm.

3. The antibacterial UTG glass according to claim 1, characterized in that: The antibacterial UTG glass has an antibacterial rate of not less than 99.9%, a transmittance of not less than 90%, and a thermal conductivity of not less than 750 kgf / mm 2 Vickers hardness of not less than 1.2Mpa•m 1 / 2 The fracture toughness is not less than 125 GPa and the elastic modulus is not less than 125 GPa.

4. The method for preparing an antibacterial UTG glass according to any one of claims 1 to 3, characterized in that: The following steps are involved: Weighing raw materials, melting the raw materials and forming them into UTG glass; The UTG glass is sequentially subjected to pretreatment, preheating, primary strengthening, secondary strengthening and cooling treatment to obtain the antibacterial UTG glass.

5. The method for preparing an antibacterial UTG glass according to claim 4, characterized in that: The forming method is a down-draw method, a slit down-draw method or a melting method.

6. The method for preparing an antibacterial UTG glass according to claim 4, characterized in that: The pretreatment is to ultrasonically clean the UTG glass in sodium hydroxide alkaline solution, citric acid solution and water in sequence; the temperature of the ultrasonic cleaning is 30-60° C. and the frequency is 40-120 kHz.

7. The method for preparing an antibacterial UTG glass according to claim 4, characterized in that: The preheating temperature is 300-420°C.

8. The method for preparing an antibacterial UTG glass according to claim 4, characterized in that: In terms of molar ratio, the salt bath used in the primary strengthening includes 100% NaNO3; the temperature of the primary strengthening is 380-500°C, and the time is 30-420min.

9. The method for preparing an antibacterial UTG glass according to claim 4, characterized in that: In terms of molar ratio, the salt bath used in the secondary strengthening includes 98%-99.9% NaNO3 and 0.1%-2% AgNO3; the temperature of the secondary strengthening is 380-450°C and the time is 2-30 minutes.

10. The method for preparing antibacterial UTG glass according to claim 4, characterized in that: The temperature is lowered to 70-100°C at a rate of 2-10°C / min.

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