阅读说明：本技术 高透光、高强度抗菌玻璃的制备方法 (Preparation method of high-light-transmission and high-strength antibacterial glass ) 是由 吴贲华 蒋晨巍 高国忠 袁厚呈 赵乐 张祥 吴伟 张�浩 赵鹏 何伟 丁洋 卢 于 2020-07-24 设计创作，主要内容包括：本申请涉及一种高透光、高强度抗菌玻璃的制备方法,包括以下步骤：形成盐溶液,其中盐溶液中硝酸钾的质量比为40％-80％,亚硝酸钾的质量比为10％-20％,硝酸钠的质量比为15％-20％,亚硝酸钠的质量比为5％-10％,硝酸银的质量比为0.005％-0.08％,氧化铝的质量比为1％-7％,氢氧化钾的质量比为1％-3％,氧化硅的质量比为1％-5％,其余物质的质量比为0.15％-1.5％；将待强化的玻璃浸入盐溶液,对玻璃进行化学强化；取出化学强化后的玻璃,并将其逐步冷却至室温。本申请通过重新配制盐溶液中KNO<Sub>3</Sub>、KNO<Sub>2</Sub>、NaNO<Sub>3</Sub>、NaNO<Sub>2</Sub>、AgNO<Sub>3</Sub>的比例,保证了K+、Na+、Ag+可充分和玻璃中碱金属Na+和Li+进行交换,保证了玻璃的抗菌和高强度性能。(The application relates to a preparation method of high-light-transmission and high-strength antibacterial glass, which comprises the following steps: forming a salt solution, wherein the mass ratio of potassium nitrate in the salt solution is 40-80%, the mass ratio of potassium nitrite is 10-20%, the mass ratio of sodium nitrate is 15-20%, the mass ratio of sodium nitrite is 5-10%, the mass ratio of silver nitrate is 0.005-0.08%, the mass ratio of aluminum oxide is 1-7%, the mass ratio of potassium hydroxide is 1-3%, the mass ratio of silicon oxide is 1-5%, and the mass ratio of the rest substances is 0.15-1.5%; immersing glass to be strengthened into a salt solution, and chemically strengthening the glass; the chemically strengthened glass is taken out and gradually cooled to room temperature. This application is achieved by reformulating KNO in salt solution 3 、KNO 2 、NaNO 3 、NaNO 2 、AgNO 3 The proportion of (A) ensures that K +, Na + and Ag + can be fully exchanged with alkali metals Na + and Li + in the glass, and ensures thatAntibacterial and high strength properties of glass.)

1. A preparation method of high-light-transmission and high-strength antibacterial glass is characterized by comprising the following steps:

forming a salt solution, wherein the mass ratio of potassium nitrate in the salt solution is 40-80%, the mass ratio of potassium nitrite is 10-20%, the mass ratio of sodium nitrate is 15-20%, the mass ratio of sodium nitrite is 5-10%, the mass ratio of silver nitrate is 0.005-0.08%, the mass ratio of aluminum oxide is 1-7%, the mass ratio of potassium hydroxide is 1-3%, the mass ratio of silicon oxide is 1-5%, and the mass ratio of the rest substances is 0.15-1.5%;

immersing the glass to be strengthened into the salt solution, and chemically strengthening the glass;

and taking out the chemically strengthened glass, and gradually cooling the glass to room temperature.

2. The method of claim 1, wherein the step of forming the salt solution comprises the steps of:

weighing raw materials according to the mass ratio of each component in the salt solution, and adding the raw materials into a salt tank of a chemical furnace;

setting the heating temperature of the salt tank to 380-480 ℃, and heating the raw materials;

and after all the components in the raw materials are liquefied, waiting for at least more than 20 hours, and uniformly mixing to form the salt solution.

3. The method for preparing high-transmittance, high-strength antimicrobial glass according to claim 1, wherein the glass composition to be strengthened comprises: 50-70% of silicon oxide, 1-18% of aluminum oxide, 8-15% of sodium oxide, 5-7% of magnesium oxide, 2-5% of potassium oxide, 1-8% of calcium oxide, 0.002% or less of iron oxide, 1.5% or less of boron oxide, zinc oxide, cerium oxide and zirconium oxide.

4. The method for preparing high-transparency high-strength antibacterial glass according to claim 1, wherein the step of preheating the glass to be strengthened is further included before the step of immersing the glass to be strengthened in the salt solution.

5. The method as claimed in claim 4, wherein the preheating temperature is 230-300 ℃ and the preheating time is at least 2 hours.

6. The method for manufacturing a high-transmittance, high-strength antimicrobial glass according to claim 2, wherein the method for immersing the glass to be strengthened in the salt solution comprises the steps of placing the glass to be strengthened in a basket of the chemical furnace, lowering the glass to be strengthened into the salt bath through the basket, and immersing the glass in the salt solution.

7. The method as claimed in claim 1, wherein the glass to be strengthened is immersed in the salt solution at 380-480 ℃ for 10-36 hours.

8. The method for preparing high-transparency high-strength antibacterial glass according to claim 1, wherein the method for gradually cooling the chemically strengthened glass comprises the following steps:

firstly, placing the chemically strengthened glass at the temperature of 230-300 ℃, and preserving heat for at least 2 hours;

then placing the glass subjected to chemical strengthening at the temperature of 100-150 ℃, and preserving the heat for at least 1 hour;

and finally, placing the chemically strengthened glass at room temperature until the glass is cooled to room temperature.

9. The method for preparing high-transparency high-strength antibacterial glass according to claim 1, further comprising the following steps: and cleaning the cooled glass.

10. The method for preparing high-transmittance high-strength antibacterial glass according to claim 9, wherein the glass is washed with citric acid solution, detergent and deionized water in sequence when the glass is washed and cooled.

Technical Field

The application relates to a preparation method of glass, in particular to a preparation method of high-light-transmission and high-strength antibacterial glass.

Background

Glass is an amorphous inorganic nonmetallic material, and is generally prepared by taking a plurality of organic minerals as main raw materials and adding a small amount of auxiliary raw materials. With the development of glass industrialization and scale, glass with various purposes and various properties comes out in succession, the glass has the characteristics of high light transmittance, high temperature resistance, chemical corrosion resistance and the like, and the properties of radiation resistance, display, shielding, electric heating, strength, scratch resistance, antibiosis and the like can be integrated on the glass after deep processing. Nowadays, glass has become an important material in the fields of daily life, production and science, and is widely applied to the fields of buildings, daily use, art, medical treatment, chemistry, electronic components, instruments, automobiles, rail transit and the like.

Along with the improvement of life quality and protection consciousness, a large amount of bacteria can be generated in glass articles contacted with human beings in daily work and life, the body health is influenced, and even the safety of the human beings is seriously involved. Therefore, the application of the antibacterial glass in the fields of medical and sanitary environments, personal communication, public transportation means, special occasions with high requirements on sterile conditions and the like becomes a trend. The first method is to prepare hydroxyl (-OH) by adopting an organic Coating (CVD) gel method technology, and the antibacterial effect is achieved on the surface of the glass; the second is to adopt the technology of the magnetron sputtering method of the inorganic coating (PVD) to plate TiO2, and the catalytic reaction is carried out under the illumination condition, thus realizing the antibiosis on the glass surface; and thirdly, the ion exchange technology is adopted, and ions with antibacterial property and alkali metal ions on the surface of the glass are used for replacement, so that the antibacterial property is realized on the surface of the glass.

In the process of implementing the present application, the applicant finds that the antibacterial glass prepared by the third preparation method has at least the following technical problems:

referring to fig. 3, which is a schematic structural diagram of a glass surface structure before and after ion exchange when the glass is strengthened by the conventional ion exchange technology, as shown in the figure, it is difficult to control the ratio and strengthening parameters of each component in the whole preparation process, so that more silver ions (Ag +) are used in the preparation process, but the transmittance and strength of the finally prepared antibacterial glass are reduced due to the influence of the silver ion (Ag +) exchange, and the glass surface is prone to crack due to the fact that the transmittance and strength of the finally prepared antibacterial glass are reduced and the requirements for temperature rise and temperature drop of the glass are high in the whole preparation process.

Disclosure of Invention

The embodiment of the application provides a preparation method of high-light-transmission and high-strength antibacterial glass, and solves the problems that the transmittance and the strength of the finally prepared antibacterial glass are easily reduced due to the fact that the proportion and the strengthening parameters of all components are difficult to control in the process of preparing the antibacterial glass by adopting an ion exchange technology.

In order to solve the above technical problem, the present application is implemented as follows:

in a first aspect, a method for preparing high-transmittance and high-strength antibacterial glass is provided, which comprises the following steps: forming a salt solution, wherein the mass ratio of potassium nitrate in the salt solution is 40-80%, the mass ratio of potassium nitrite is 10-20%, the mass ratio of sodium nitrate is 15-20%, the mass ratio of sodium nitrite is 5-10%, the mass ratio of silver nitrate is 0.005-0.08%, the mass ratio of aluminum oxide is 1-7%, the mass ratio of potassium hydroxide is 1-3%, the mass ratio of silicon oxide is 1-5%, and the mass ratio of the rest substances is 0.15-1.5%; immersing glass to be strengthened into a salt solution, and chemically strengthening the glass; the chemically strengthened glass is taken out and gradually cooled to room temperature.

In a first possible implementation of the first aspect, the method of forming a salt solution comprises the steps of: weighing raw materials according to the mass ratio of each component in the salt solution, and adding the raw materials into a salt tank of a chemical furnace; setting the heating temperature of the salt tank to 380-; after all the components in the raw materials are liquefied, waiting for at least more than 20 hours, and uniformly mixing to form a salt solution.

In a second possible implementation form of the first aspect, the glass composition to be strengthened comprises: 50-70% of silicon oxide, 1-18% of aluminum oxide, 8-15% of sodium oxide, 5-7% of magnesium oxide, 2-5% of potassium oxide, 1-8% of calcium oxide, 0.002% or less of iron oxide, 1.5% or less of boron oxide, zinc oxide, cerium oxide and zirconium oxide.

In a third possible implementation manner of the first aspect, the step of preheating the glass to be strengthened is further included before immersing the glass to be strengthened in the salt solution.

With reference to the third possible implementation manner of the first aspect, in a fourth possible implementation manner of the first aspect, when the glass to be strengthened is preheated, the preheating temperature is 230-300 ℃, and the preheating time is at least 2 hours.

With reference to the first possible implementation manner of the first aspect, in a fifth possible implementation manner of the first aspect, the method for immersing the glass to be strengthened in the salt solution includes the steps of placing the glass to be strengthened in a basket of a chemical furnace, and lowering the glass to be strengthened into a salt bath through the basket so as to immerse the glass in the salt solution.

In a sixth possible implementation manner of the first aspect, when the glass to be strengthened is immersed in the salt solution, the temperature of the salt solution is 380-480 ℃, and the heat preservation time is 10-36 hours.

In a seventh possible implementation manner of the first aspect, the method for gradually cooling the chemically strengthened glass comprises the following steps: firstly, placing the chemically strengthened glass at the temperature of 230 ℃ and 300 ℃ and preserving heat for at least 2 hours; then placing the chemically strengthened glass at the temperature of 100-150 ℃, and preserving the heat for at least 1 hour; and finally, placing the chemically strengthened glass at room temperature until the glass is cooled to room temperature.

In an eighth possible implementation manner of the first aspect, the method further includes the following steps: and cleaning the cooled glass.

With reference to the eighth possible implementation manner of the first aspect, in a ninth possible implementation manner of the first aspect, when the glass is cleaned after cooling, the surface of the glass is cleaned sequentially with a citric acid solution, a cleaning agent, and deionized water.

Compared with the prior art, the application has the advantages that:

the preparation method of the high-light-transmission and high-strength antibacterial glass comprises the step of preparing KNO in salt solution again₃、KNO₂、NaNO₃、NaNO₂、AgNO₃The ratio of (A) to (B) ensures that K +, Na + and Ag + can be fully exchanged with alkali metal Na + and Li + in the glass, ensures the antibacterial and high-strength performances of the glass, reduces the mass ratio of Ag + influencing the transmittance by preparing a salt solution again, and then adds Al₂O₃KOH and SiO₂The catalyst and the adsorbent can realize rapid ion exchange, and avoid the problem of light transmittance reduction caused by the interference of impurity ions (Ag +). Meanwhile, the surface of the strengthened glass forms Ag + with positive charge, the charge balance of bacteria can be destroyed, the aim of sterilization is achieved, and in addition, the problems that the glass is poor in adhesion with a base material, and is easy to wear and age can be solved as the Ag + exists on the surface of the glass in an ionic state.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:

fig. 1 is a schematic flow chart illustrating steps of a method for manufacturing a high-transmittance, high-strength antimicrobial glass according to an embodiment of the present application.

FIG. 2 is a schematic structural view of the surface structure of a glass before and after ion exchange according to an embodiment of the present invention.

FIG. 3 is a schematic structural view of the glass surface structure before and after ion exchange in the case of strengthening glass by the conventional ion exchange technique.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

In an embodiment of the present application, please refer to fig. 1, which is a schematic flow chart illustrating steps of a method for manufacturing high-transmittance high-strength antimicrobial glass according to an embodiment of the present application, as shown in the figure, the method 1 for manufacturing high-transmittance high-strength antimicrobial glass includes the following steps 101 to 103, wherein:

step 101, preparing a salt solution. Forming a salt solution, wherein potassium nitrate (KNO) in the salt solution₃) 40-80% of potassium nitrite (KNO)₂) 10-20% of sodium nitrate (NaNO)₃) 15-20% of sodium nitrite (NaNO)₂) 5-10% of silver nitrate (AgNO)₃) 0.005-0.08% of aluminum oxide (Al)₂O₃) 1-7% of potassium hydroxide (KOH) and 1-3% of silicon oxide (SiO)₂) The mass ratio of the components is 1 to 5 percent, and the mass ratio of the rest components is 0.15 to 1.5 percent.

Specifically, the raw materials are weighed according to the mass ratio of each component in the salt solution, and the raw materials are mixedMiddle KNO₃40-80% by mass of KNO₂10 to 20 percent of NaNO, and₃15-20% by mass of NaNO₂5-10% of AgNO₃0.005-0.08% of Al₂O₃1-7% of KOH, 1-3% of SiO₂The mass ratio of the components is 1 to 5 percent, and the mass ratio of the rest components is 0.15 to 1.5 percent.

Then, the raw materials are added into a salt tank of a chemical furnace, the heating temperature of the salt tank is set to 380-.

After all the components in the raw materials are liquefied, waiting for at least 20 hours to uniformly mix the components to form a salt solution, reducing the mass ratio of Ag + in the salt solution prepared in the way, and adding Al₂O₃KOH and SiO₂And the catalyst and the adsorbent can realize rapid ion exchange in the subsequent step, and avoid the problem of light transmittance reduction caused by the interference of impurity ions (Ag +). In the present embodiment, the waiting time is preferably 20-40h, for example, the waiting time may be 20h, 30h or 40h, but is not limited thereto, and the specific waiting time may be selected according to the actual production requirement (total amount of salt solution).

And 102, chemically strengthening. And immersing the glass to be strengthened into a salt solution to chemically strengthen the glass.

Specifically, the glass to be strengthened is selected, and the glass comprises the following components: 50-70% of silicon oxide, 1-18% of aluminum oxide, 8-15% of sodium oxide, 5-7% of magnesium oxide, 2-5% of potassium oxide, 1-8% of calcium oxide, 0.002% or less of iron oxide, 1.5% or less of boron oxide, zinc oxide, cerium oxide and zirconium oxide, wherein the internal molecular structure of the glass is alundum.

Then, wiping the surface of the glass with absolute alcohol, loading the glass into a hanging basket of a chemical furnace, lifting the hanging basket into a preheating box of the chemical furnace, setting the preheating temperature of the preheating box at 230-.

After preheating, the hanging basket is lowered into the salt bath, so that the glass is immersed in the salt solution, the cover of the bath is closed, and the glass is subjected to heat preservation for 10-36h in the salt solution with 480 ℃ of 380-. In this embodiment, the temperature of the salt solution may be 380 ℃, 420 ℃, 440 ℃ or 480 ℃, and the holding time may be 10h, 20h, 30h or 36h, but is not limited thereto, and the specific temperature and holding time of the salt solution may be selected according to the actual production requirements (the mass ratio of the components of the salt solution, the size and thickness of the glass).

And step 103, gradually cooling. The chemically strengthened glass is taken out and gradually cooled to room temperature.

Specifically, after the chemical strengthening is completed, the cover is opened, the basket is lifted to the preheating box of the chemical furnace, the basket drives the chemically strengthened glass to enter the preheating box, the temperature of the preheating box is set to be 230-.

After the first cooling and heat preservation is completed, the temperature of the preheating box is set to be 150 ℃., the second cooling and heat preservation is performed on the chemically strengthened glass at 150 ℃., the heat preservation time is at least 1 hour, so as to ensure that the temperature of the glass is reduced to 150 ℃.,. in this embodiment, the temperature of the preheating box may be 100 ℃, 120 ℃, 140 ℃ or 150 ℃, but is not limited thereto.

And after the second cooling and heat preservation, stopping heating the preheating box, and when the temperature in the preheating box is reduced to be below 100 ℃, reducing the hanging basket from the preheating box to the normal temperature environment, so that the chemically strengthened glass is placed at the room temperature until the glass is cooled to the room temperature.

In an embodiment, the method 1 for preparing the high-transmittance high-strength antibacterial glass further includes a step 104 of cleaning the glass after cooling. Specifically, the glass surface is washed by citric acid solution, then by detergent, and finally by deionized water.

The beneficial effects of the preparation method of the high-transparency high-strength antibacterial glass are further described below by combining specific experimental data. The specific experimental process is as follows:

experiment process I, preparation of curved glass

The method comprises the following specific steps:

step 1: selecting a piece of plate glass, selecting a part without defects on the surface, and cutting the glass into the size of a product by using a diamond numerical control cutting machine;

step 2: grinding and chamfering the edge of the cut glass by using a numerical control edge grinding machine to form a C-shaped chamfer with uniform upper and lower chamfers;

step 3, corroding the edge area with the ink for glass to form a unique identifier, so as to facilitate tracking and tracing;

and 4, step 4: and (3) placing the glass on a tool according to a certain sequence for hot bending, heating to the softening point of the glass, and utilizing the self-weight forming of the glass to enable the glass to be attached to a mold to obtain the curved glass.

Second experiment Process, strengthened glass

The curved glass prepared in the first experimental process is strengthened according to the preparation method of the high-light-transmittance and high-strength antibacterial glass, the existing organic Coating (CVD) gel method technology, the existing inorganic coating (PVD) magnetron sputtering method technology and the existing ion exchange technology, wherein the step of strengthening the curved glass according to the preparation method of the high-light-transmittance and high-strength antibacterial glass is shown in the above embodiment, and is not described herein again, and the strengthening of the curved glass according to the existing CVD gel method technology, the existing PVD magnetron sputtering method technology and the existing ion exchange technology is known to those skilled in the art, so that the description of the curved glass is also not repeated herein.

Third experiment procedure, test glass performance

And testing the transmittance, the bending strength (four-point bending test method), the bonding force and the antibacterial capability of the glass strengthened in the second experimental process according to the test methods of standard GJB 503-88 general test method for laminated glass of airplanes, JC 977-2005 chemical toughened glass, GB/T9286-1998G lattice test for paint films of colored paint and varnish, B/T21866-2008 method for antibacterial property test method and antibacterial effect of antibacterial paint (paint film). The test data are as follows:

a first group: the preparation method of the high-light-transmittance and high-strength antibacterial glass strengthens the curved glass: the light transmittance is about 88 percent, the bending strength is about 450Mpa, the bonding force is 0 grade, and the antibacterial property is 99.9 percent;

second group: curved glass strengthened by the existing organic Coating (CVD) gel method technology: the light transmittance is about 75%, the bending strength is about 350Mpa, the bonding force is 2-level, and the antibacterial property is 90%;

third group: the curved glass reinforced by the existing inorganic coating (PVD) magnetron sputtering method technology comprises the following steps: the light transmittance is about 75%, the bending strength is about 350Mpa, the bonding force is 3 grades, and the antibacterial property is 90%;

and a fourth group: the prior art is that the curved glass after being strengthened by ion exchange technology: the light transmittance is about 80%, the bending strength is about 200Mpa, the bonding force is 0 grade, and the antibacterial property is 99%.

As shown in the first set of test data, the curved glass strengthened by the preparation method of the high-light-transmittance and high-strength antibacterial glass has been subjected to test verificationAccurate, and compare in fourth group's test data, curved surface glass's high strength performance has been guaranteed to the saline solution of this application reformulation, makes its bending strength promote greatly, and curved surface glass's luminousness also has the promotion of certain degree simultaneously, thereby can reach, KNO among the saline solution of this application reformulation₃、KNO₂、NaNO₃、NaNO₂、AgNO₃The proportion ensures that K + and Na + can be fully exchanged with alkali metal Na + and Li + in the glass, reduces the mass ratio of Ag + influencing the transmittance, and avoids the problem of reducing the transmittance due to the interference of impurity ions (Ag +).

First group's test data compares again in second group and third group's test data, and the glass surface antibacterial property after this application is reinforceed is better, and the luminousness is higher to can obtain, the glass surface after this application is reinforceed forms the Ag +, that positive charges are taken to it can destroy bacterium charge balance, reaches the purpose of disinfecting. In addition, the strengthening process combining the existing CVD gel method technology and the existing PVD magnetron sputtering method technology is known, and the strengthened curved glass surface is plated with TiO₂Film due to TiO₂The film has poor adhesion performance and is easy to fall off when in contact, so that the problems that the curved glass reinforced by the existing CVD gel method technology and the existing PVD magnetron sputtering method technology has poor wear resistance, the antibacterial performance is easy to lose after long-term use and the like are caused.

In summary, the present application provides a method for preparing a high-transmittance, high-strength antimicrobial glass by reformulating KNO in a salt solution₃、KNO₂、NaNO₃、NaNO₂、AgNO₃The ratio of (A) to (B) ensures that K +, Na + and Ag + can be fully exchanged with alkali metal Na + and Li + in the glass, ensures the antibacterial and high-strength performances of the glass, reduces the mass ratio of Ag + influencing the transmittance by preparing a salt solution again, and then adds Al₂O₃KOH and SiO₂The catalyst and the adsorbent can realize the rapid exchange of ions,and the problem of light transmittance reduction caused by the interference of impurity ions (Ag +) is avoided. Meanwhile, the surface of the strengthened glass forms Ag + with positive charge, the charge balance of bacteria can be destroyed, the aim of sterilization is achieved, and in addition, the problems that the glass is poor in adhesion with a base material, and is easy to wear and age can be solved as the Ag + exists on the surface of the glass in an ionic state.

It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.

While the present embodiments have been described with reference to the accompanying drawings, it is to be understood that the invention is not limited to the precise embodiments described above, which are meant to be illustrative and not restrictive, and that various changes may be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.