CN110357455B - Preparation method of antibacterial glass and antibacterial vacuum glass - Google Patents
Preparation method of antibacterial glass and antibacterial vacuum glass Download PDFInfo
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- CN110357455B CN110357455B CN201910650282.2A CN201910650282A CN110357455B CN 110357455 B CN110357455 B CN 110357455B CN 201910650282 A CN201910650282 A CN 201910650282A CN 110357455 B CN110357455 B CN 110357455B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
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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
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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
- C03C21/005—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 introduce in the glass such metals or metallic ions as Ag, Cu
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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
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/08—Joining glass to glass by processes other than fusing with the aid of intervening metal
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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
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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Abstract
The invention belongs to the technical field of glass preparation, and particularly relates to a preparation method of antibacterial glass and antibacterial vacuum glass. The preparation method of the antibacterial glass comprises the following steps of carrying out one-step ion exchange on the glass and a solution or a melt containing silver and ferrous ions, and introducing antibacterial ions into a glass body to obtain the antibacterial glass. The invention realizes the exchange of the antibacterial ions and the sodium and potassium ions in the glass by a one-step ion exchange method, introduces the antibacterial ions into the glass body, has simple and effective method and saves the cost. By introducing ferrous ions and the like in the ion exchange process, the oxidation of antibacterial ions can be effectively inhibited, the concentration of the antibacterial ions is effectively improved, the reduction of the light transmittance of the glass is avoided, and the performance and the light transmittance of the antibacterial glass are improved.
Description
Technical Field
The invention belongs to the technical field of glass preparation, and particularly relates to a preparation method of antibacterial glass and antibacterial vacuum glass.
Background
Along with the improvement of science and technology and the improvement of the living standard of people, people pay more and more attention to environmental sanitation. Refrigerators and freezers are increasingly common as heat preservation and refrigeration equipment for daily life, the glass for the common freezer door at present is hollow glass, and compared with vacuum glass, the glass has large thickness and poor heat insulation performance, and the vacuum glass is only applied to luxury goods such as high-grade wine cabinets and the like in a small amount at present; the antibacterial vacuum glass has less research, and no related mature product exists at present.
The antibacterial glass is also called green glass, is a novel ecological functional material, and has important significance for improving ecological environment, keeping human health and guiding the research and development of related functional glass materials. The novel inorganic antibacterial agent is added to inhibit and kill bacteria, so that the traditional glass product is added with high and new technology content. The antibacterial glass not only keeps the characteristics of transparency, cleanness, high mechanical strength, good chemical stability and the like of the glass material, but also adds a new function of killing and inhibiting germs, and is a product combining new material science and microbiology.
The antibacterial glass is processed and manufactured by adding an antibacterial agent to a glass carrier so that the glass carrier has contact type antibacterial and bactericidal functions. The contact type antibacterial material is required to have a contact antibacterial function on the surface of the material under an unconditional normal state. Therefore, the coating process technology of the glass surface is the core of the antibacterial glass processing production. At present, the traditional plate glass coating methods mainly comprise three methods, the first method is an online Chemical Vapor Deposition (CVD) method, the second method is an online spraying method, and the two methods for producing the antibacterial glass mainly have the following problems: firstly, the space temperature of the glass is too high in the film coating process, the antibacterial agent is easy to oxidize and lose efficacy, secondly, the method can only carry out film coating on the single surface of the glass, the using effect and the range of the antibacterial glass are limited, the production mode is inflexible, and the third method is a vacuum sputtering film coating method, so that the antibacterial glass is manufactured by the method, and the following problems exist: the antibacterial agent exists on the surface of the glass in an atomic state, and the antibacterial function of the antibacterial agent is difficult to reach the national standard in a normal state; and the antibacterial functional film belongs to a soft film and is not suitable for long-term exposure and contact use.
With the development of technology, the addition of silver by means of ion exchange baths has evolved into a novel technology that is also most likely to be used for the mass production of glasses with antimicrobial properties. Conventional ion exchange processes are used to chemically strengthen glass substrates and generally involve placing the glass in a molten salt containing ions with a larger ionic radius than the ions in the glass so that the smaller ions present in the glass can be replaced by the larger ions in the molten salt solution. In the method in the prior art, different ions are exchanged step by step, the process is complex, the cost is high, and the problems that antibacterial ions are easy to oxidize and the light transmittance of glass is reduced greatly exist.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the preparation process of the antibacterial glass in the prior art mostly adopts step-by-step exchange, the process is complex, the cost is high, bacteriostatic ions are easy to oxidize, the light transmittance of the glass is reduced more and the like, and thus the invention provides the preparation method of the antibacterial glass and the antibacterial vacuum glass.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the antibacterial glass comprises the following steps of carrying out one-step ion exchange on the glass and a solution or a melt containing silver ions and ferrous ions, and introducing antibacterial ions into a glass body to obtain the antibacterial glass.
Further, the cation in the salt solution or melt further contains at least one of copper ion, zinc ion, cobalt ion, and nickel ion.
Further, the step of ion exchanging comprises:
and spraying the salt solution on at least one surface of the glass, drying, repeatedly spraying for 1-2 times, and performing physical toughening treatment to obtain the antibacterial glass.
Further, the concentration of silver ions in the salt solution is 0.01-3 wt%;
the concentrations of copper ions and zinc ions in the salt solution are both 0.01-2 wt%;
the concentration of ferrous ions in the salt solution is 0.01-2 wt%;
the concentrations of cobalt ions and nickel ions in the salt solution are both below 0.1 wt%.
The salt used in the process is soluble salt of silver, zinc, copper, cobalt, nickel, ferrous ions, etc., such as silver nitrate, zinc chloride, zinc sulfate, copper nitrate, copper chloride, copper sulfate, cobalt nitrate, nickel chloride, ferrous nitrate, ferrous sulfate, etc.
Further, the processing temperature of the physical tempering is 650-750 ℃, and the processing time is 150-280 seconds.
Further, the step of ion exchanging comprises:
mixing a salt containing silver ions and ferrous ions with potassium nitrate, heating to 420-.
Further, the concentration of silver ions in the molten salt is 0.01-1 wt%;
the concentrations of copper ions, zinc ions and ferrous ions in the molten salt are all 0.01-0.5 wt%;
the mass concentration of cobalt ions and nickel ions in the molten salt is below 0.1 wt%.
The ionic compound contains one or more of nitrate, sulfate, phosphate, borate, oxide and halide of silver, copper, zinc, ferrous iron, nickel and cobalt.
Further, the temperature of the ion exchange is 420-500 ℃, and the time is 1-10 minutes.
The invention also provides application of the antibacterial glass prepared by the method in preparation of antibacterial vacuum glass.
Furthermore, the antibacterial vacuum glass consists of an upper glass sheet and a lower glass sheet, a support is arranged between the two glass sheets, sealing materials are arranged on the periphery of the two glass sheets, and a sealed vacuum cavity is formed between the two glass sheets through vacuumizing treatment.
Wherein the sealing material is glass powder or metal sealing material.
Further, the preparation method of the antibacterial vacuum glass comprises the following steps:
the antibacterial glass prepared by the method is used as upper-layer glass and/or lower-layer glass, supports are uniformly distributed on the lower-layer glass, sealing materials are coated on the periphery of the lower-layer glass, then the lower-layer glass and the upper-layer glass are laminated and sintered to complete edge sealing, finally, vacuumizing treatment is performed through an air exhaust hole, sealing is performed, or one-step air exhaust sintering is directly completed under a vacuum condition, and the antibacterial vacuum glass is obtained.
The preparation method of the vacuum glass mainly comprises two major methods at present, wherein one method is to drill an extraction hole on the surface of one glass, then arrange a micro support between the two glasses, seal the periphery of the glass by using glass powder or metal, finally connect a vacuum pump to extract air from the drilling position, seal the drilled hole, and form vacuum inside a cavity, thereby obtaining the vacuum glass. The other method is that the supports are directly distributed on two pieces of glass, glass powder or metal materials are distributed on the periphery of the two pieces of glass, air is directly exhausted from the vacuum cavity, edge sealing is finished in one step, and holes do not need to be punched on the surfaces of the glass.
Further, the thickness of the antibacterial glass is 2-6 mm;
and/or the distance between two points of the support is 30-50mm, the diameter of the support is 0.5-2mm, and the height of the support is 0.1-0.2 mm;
and/or the sintering temperature is 380-460 ℃, and the vacuum degree is 10-4Pa。
The technical scheme of the invention has the following advantages:
1. the preparation method of the antibacterial glass comprises the following steps of carrying out one-step ion exchange on the glass and a solution or a melt containing silver ions and ferrous ions, and introducing antibacterial ions into a glass body to obtain the antibacterial glass. The invention realizes the exchange of the antibacterial ions and the sodium and potassium ions in the glass by a one-step ion exchange method, introduces the antibacterial ions into the glass body, has simple and effective method and saves the cost. By introducing ferrous ions and the like in the ion exchange process, the oxidation of antibacterial ions can be effectively inhibited, the concentration of the antibacterial ions is effectively improved, the reduction of the light transmittance of the glass is avoided, and the performance and the light transmittance of the antibacterial glass are improved.
2. According to the preparation method of the antibacterial glass, the solution or the melt of the salt also contains copper ions, zinc ions, cobalt ions and nickel ions, and the ions are matched with each other, so that the antibacterial performance of the antibacterial glass can be further improved.
3. The preparation method of the antibacterial glass provided by the invention comprises the following specific steps of ion exchange: and spraying the salt solution on at least one surface of the glass, drying, repeatedly spraying for 1-2 times, and performing physical toughening treatment to obtain the antibacterial glass. The antibacterial glass produced by the method has antibacterial performance on the basis of not influencing the strength and granularity of the glass. In addition, the method is particularly suitable for preparing low-e full-tempered antibacterial vacuum glass, because the low-e glass cannot be chemically tempered, because one surface of the low-e glass is a plated film, the chemical tempering film layer is completely damaged, the low-e glass cannot be chemically tempered, and the antibacterial ions can be introduced into the non-film surface of the low-e glass by matching the solution spraying method and the physical tempering method, so that the low-e full-tempered antibacterial vacuum glass has antibacterial performance. According to the invention, by controlling the concentration of the salt solution, on the basis of improving the utilization rate of the antibacterial ions to the maximum extent, the antibacterial performance of the antibacterial glass is ensured, the using amount of the antibacterial ions is saved, the cost is reduced, and the problems that the antibacterial performance is poor or no antibacterial performance is caused due to too low ion concentration, the antibacterial ions introduced by too high ion concentration can be oxidized to different extents, too much is introduced, the glass is yellowed, and the transmittance of the glass is influenced are avoided.
4. The preparation method of the antibacterial glass provided by the invention comprises the following specific steps of ion exchange: mixing a salt containing silver ions and ferrous ions with potassium nitrate, heating to 420-. The method realizes the exchange of the antibacterial ions and the sodium and potassium ions in the glass, introduces the antibacterial ions into the glass body, and is simple and effective. Meanwhile, the antibacterial glass prepared by the method is common antibacterial glass, and can be directly physically tempered to prepare safe antibacterial glass, for example, tempered and semi-tempered antibacterial vacuum glass. According to the invention, by controlling the concentration of the salt solution, on the basis of improving the utilization rate of the antibacterial ions to the maximum extent, the antibacterial performance of the antibacterial glass is ensured, the using amount of the antibacterial ions is saved, and the cost is reduced. The temperature of the ion exchange is 420-500 ℃, and the time is 1-10 minutes. The invention has short exchange time, avoids the coloring of the glass and improves the light transmittance of the antibacterial glass.
5. The antibacterial vacuum glass provided by the invention has antibacterial, heat-insulating and sound-insulating properties, and has a wide application prospect in the aspects of refrigerator doors and refrigerator doors.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1 (examples 1 to 6 are chemical methods)
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a 4mm thick glass sheet, putting the glass sheet into molten potassium nitrate, silver nitrate and ferrous sulfate mixed molten salt, wherein the mass fraction of silver ions is 0.1%, the mass concentration of ferrous ions is 0.2%, performing ion exchange for 2 minutes at 500 ℃, taking out the glass, cooling and cleaning to obtain the antibacterial glass.
Example 2
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a 4mm thick glass sheet, putting the glass sheet into molten mixed molten salt of potassium nitrate, silver nitrate and ferrous sulfate, wherein the mass fraction of silver ions is 3%, the mass concentration of ferrous ions is 1.5%, performing ion exchange for 1 minute at 480 ℃, taking out the glass, cooling and cleaning to obtain the antibacterial glass.
Example 3
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a 4mm thick glass sheet, putting the glass sheet into molten potassium nitrate, silver nitrate and ferrous sulfate mixed molten salt, wherein the mass fraction of silver ions is 0.01%, the mass concentration of ferrous ions is 0.01%, performing ion exchange for 10 minutes at the temperature of 420 ℃, taking out the glass, cooling and cleaning to obtain the antibacterial glass.
Example 4
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a 5mm thick glass sheet, putting the glass sheet into molten mixed molten salt of potassium nitrate, silver nitrate, zinc nitrate and ferrous sulfate, wherein the mass fraction of silver ions is 0.1%, the mass concentration of ferrous ions is 0.2%, and the mass fraction of zinc ions is 0.1%, performing ion exchange for 2 minutes at 500 ℃, taking out the glass, cooling and cleaning to obtain the antibacterial glass.
Example 5
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a glass original sheet with the thickness of 3mm, putting the glass original sheet into molten mixed molten salt of potassium nitrate, silver nitrate, zinc nitrate, nickel nitrate, cobalt nitrate and ferrous sulfate, wherein the mass fraction of silver ions is 0.1%, the mass concentration of ferrous ions is 0.2%, the mass fraction of zinc ions is 0.1%, the mass fraction of nickel ions is 0.02%, and the mass fraction of cobalt ions is 0.03%, performing ion exchange for 3 minutes at the temperature of 500 ℃, taking out the glass, cooling and cleaning to obtain the antibacterial glass.
Example 6
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a glass original sheet with the thickness of 3mm, putting the glass original sheet into molten mixed molten salt of potassium nitrate, silver nitrate, zinc nitrate, copper nitrate, nickel nitrate, cobalt nitrate and ferrous sulfate, wherein the mass fraction of silver ions is 0.08%, the mass concentration of ferrous ions is 0.2%, the mass fraction of zinc ions is 0.1%, the mass concentration of copper ions is 0.1%, the mass fraction of nickel ions is 0.04%, and the mass fraction of cobalt ions is 0.03%, performing ion exchange for 3 minutes at the temperature of 500 ℃, taking out the glass, cooling and cleaning to obtain the antibacterial glass.
Example 7 (examples 7-9 physical methods)
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a 5mm thick glass sheet, edging, cleaning, uniformly coating prepared compound solutions of silver nitrate, zinc nitrate, copper nitrate and ferrous nitrate on two sides of the glass, wherein the mass concentration of silver ions is 1%, the mass concentration of zinc ions is 0.5%, the mass concentration of copper ions is 0.4%, and the mass concentration of ferrous ions is 2%, the coating amount is determined on the basis that liquid drops cannot be formed into drops and left, drying at normal temperature, repeatedly coating for 1 time, taking out the glass, then physically toughening at 750 ℃ for 150s, and cooling to obtain the antibacterial glass.
Example 8
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a 5mm thick glass sheet, edging and cleaning, uniformly coating a prepared compound solution of silver nitrate, zinc nitrate, copper nitrate and ferrous nitrate on one surface of the glass, wherein the coating amount is based on that liquid drops cannot be formed into drops, the mass concentration of silver ions is 1.5%, the mass concentration of zinc ions is 0.5%, the mass concentration of copper ions is 0.4%, the mass concentration of ferrous ions is 1.8%, drying at normal temperature, repeatedly coating for 1 time, taking out the glass, then physically toughening at 720 ℃ for 200s, and cooling to obtain the antibacterial glass.
Example 9
The embodiment provides a preparation method of antibacterial glass, which comprises the following specific steps:
cutting a 5mm thick glass sheet, edging and cleaning, uniformly coating prepared compound solutions of silver nitrate, zinc nitrate, copper nitrate, ferrous nitrate, cobalt nitrate and nickel nitrate on two sides of the glass, wherein the coating amount is based on that liquid drops cannot be formed into drops, the mass concentration of silver ions is 2.5%, the mass concentration of zinc ions is 0.4%, the mass concentration of copper ions is 0.2%, the mass concentration of ferrous ions is 1.5%, the mass concentration of cobalt ions is 0.01%, the mass concentration of nickel ions is 0.03%, drying at normal temperature, repeatedly coating for 2 times, taking out the glass, then physically toughening at 650 ℃ for 280s, and cooling to obtain the antibacterial glass.
Example 10
The embodiment provides an application of antibacterial glass in preparation of antibacterial vacuum glass, and the preparation method of the antibacterial vacuum glass comprises the following steps:
cutting two 4mm glass original sheets, edging and cleaning, drilling an air suction hole on one glass sheet, drilling a groove for placing an air suction agent on the other glass sheet, putting the two glass sheets into molten potassium nitrate, silver nitrate and ferrous nitrate mixed molten salt, wherein the mass fraction of silver ions is 0.1%, the mass fraction of ferrous ions is 0.2%, carrying out ion exchange for 2 minutes at 500 ℃, taking out the two glass sheets, cooling and cleaning. Taking glass with grooves, uniformly distributing supports on the surface of the glass at an interval of 40mm, coating low-temperature glass slurry on the periphery of the glass on the other side, then laminating the two sides of the glass, sintering at 460 ℃, finally exhausting air from the positions of the exhaust holes by using a vacuum pump, and sealing by using glass sheets to obtain the common vacuum antibacterial glass.
Example 11
The embodiment provides an application of antibacterial glass in preparation of antibacterial vacuum glass, and the preparation method of the antibacterial vacuum glass comprises the following steps:
cutting two 5mm glass sheets, edging and cleaning, wherein one glass sheet is provided with an air exhaust hole, the other glass sheet is provided with a groove for placing a getter, the surfaces of the two glass sheets are uniformly coated with prepared compound solution of silver nitrate, zinc sulfate, copper chloride and ferrous nitrate, the coating amount is based on that liquid drops can not be formed into drops and left, the mass concentration of silver ions is 2 percent, the mass concentration of zinc ions is 0.8 percent, the mass concentration of copper ions is 0.9 percent, the mass concentration of ferrous ions is 1.7 percent, drying is carried out at the temperature of below 60 ℃, after drying, spraying is carried out for 2 times repeatedly, glass with grooves is taken, support slurry is distributed on the surface of the glass by an automatic dispenser at the distance of 40mm, then carrying out physical tempering at the temperature of 720 ℃, the other glass sheet is directly physically tempered, low-temperature glass slurry is coated on the periphery of the tempered glass, then two glass sheets are combined and sintered at the temperature of 420 ℃, and finally, exhausting air from the position of the air exhaust hole by using a vacuum pump, and sintering and sealing by using sealing equipment to obtain the toughened vacuum antibacterial glass.
Example 12
The embodiment provides an application of antibacterial glass in preparation of antibacterial vacuum glass, and the preparation method of the antibacterial vacuum glass comprises the following steps:
cutting two 5mm glass original sheets, edging and cleaning, wherein one glass is low-e glass, an extraction hole is formed in the low-e glass, a groove for placing a getter is formed in the other glass, then uniformly painting prepared compound solutions of silver nitrate, zinc sulfate, copper chloride and ferrous sulfate on the surfaces of the two glasses, the painting amount is based on that liquid drops can not be left as drops, wherein the mass concentration of silver ions is 1.5%, the mass concentration of zinc ions is 0.3%, the mass concentration of copper ions is 1%, and the mass concentration of ferrous ions is 1.2%, wherein the low-e glass is only sprayed with a non-low-e film surface, drying is carried out at normal temperature for 2 times, the glass with the groove is taken, support slurry is distributed on the surface of the glass by an automatic dispenser, the distance is 30mm, then carrying out physical tempering at 720 ℃, and the other piece of low-e glass is directly physically tempered, coating low-temperature glass slurry on the periphery of the toughened glass, then laminating two pieces of glass, sintering at 380 ℃, finally exhausting air from the position of an exhaust hole by using a vacuum pump, and sintering and sealing by using sealing equipment to obtain the low-e toughened vacuum antibacterial glass.
Comparative example 1
This comparative example provides an antibacterial glass similar to that of example 6 except that the molten salt does not contain ferrous sulfate.
Comparative example 2
This comparative example provides an antimicrobial glass similar to that of example 8, except that ferrous nitrate was not included in the compound solution.
Test example
The antibacterial glass provided in examples 1 to 9 and comparative examples 1 to 2 of the present invention was subjected to bacteriostasis and transmittance tests, in which a number of bacteria existing in the nature can be classified according to a certain rule and classified into gram-negative bacteria and gram-positive bacteria according to the gram staining method. Representative of gram-negative bacteria is Escherichia coli, and representative of gram-positive bacteria is Staphylococcus aureus. Staphylococcus aureus was measured according to the national standard JC/T1054-Buck 2007 for coated antibacterial glass, and Escherichia coli was measured according to HG3950-2007 for antibacterial coatings.
The light transmittance was measured according to the method specified in GB/T2680. The specific test results are shown in the following table:
TABLE 1
As can be seen from the data in the table, the antibacterial performance of the antibacterial glass to escherichia coli and staphylococcus aureus can reach more than 95% generally, and meanwhile, the visible light transmittance of the glass still meets the national standard requirements of flat glass.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (12)
1. The preparation method of the antibacterial glass is characterized by comprising the following steps of carrying out one-step ion exchange on the glass and a solution or a melt containing silver ions and ferrous ions, and introducing antibacterial ions into a glass body to obtain the antibacterial glass;
wherein the concentration of ferrous ions in the salt solution is 0.01-2 wt%;
the concentration of ferrous ions in the molten salt is 0.01-0.5 wt%.
2. The method according to claim 1, wherein the cations in the salt solution or melt further contain at least one of copper ions, zinc ions, cobalt ions, and nickel ions.
3. The method of producing an antibacterial glass according to claim 1 or 2, wherein the step of ion exchange comprises:
and spraying the salt solution on at least one surface of the glass, drying, repeatedly spraying for 1-2 times, and performing physical toughening treatment to obtain the antibacterial glass.
4. The method for preparing antibacterial glass according to claim 3, wherein the concentration of silver ions in the salt solution is 0.01-3 wt%;
the concentrations of copper ions and zinc ions in the salt solution are both 0.01-2 wt%;
the concentrations of cobalt ions and nickel ions in the salt solution are both below 0.1 wt%.
5. The method for preparing antibacterial glass according to claim 3, wherein the treatment temperature of the physical tempering is 650-750 ℃, and the treatment time is 150-280 seconds.
6. The method of producing an antibacterial glass according to claim 1 or 2, wherein the step of ion exchange comprises:
mixing a salt containing silver ions and ferrous ions with potassium nitrate, heating to 420-.
7. The method for producing an antibacterial glass according to claim 6, wherein the concentration of silver ions in the molten salt is 0.01 to 1 wt%;
the concentrations of copper ions and zinc ions in the molten salt are both 0.01-0.5 wt%;
the mass concentration of cobalt ions and nickel ions in the molten salt is below 0.1 wt%.
8. The method as claimed in claim 6, wherein the temperature of the ion exchange is 420-500 ℃ and the time is 1-10 minutes.
9. Use of the antibacterial glass prepared by the method according to any one of claims 1 to 8 in the preparation of antibacterial vacuum glass.
10. The use according to claim 9, wherein the antibacterial vacuum glass consists of an upper glass sheet and a lower glass sheet, a support is arranged between the two glass sheets, sealing materials are arranged on the periphery of the two glass sheets, and a closed vacuum cavity is formed between the two glass sheets through vacuumizing treatment.
11. The use according to claim 10, wherein the method for preparing the antibacterial vacuum glass comprises the following steps:
the antibacterial glass prepared by the method of any one of claims 1 to 8 is used as upper glass and/or lower glass, supports are uniformly distributed on the lower glass, sealing materials are coated on the periphery of the lower glass, then the lower glass and the upper glass are laminated and sintered to complete edge sealing, and finally, vacuumizing treatment and sealing are performed through a vacuumizing hole, or one-step vacuumizing sintering is directly completed under a vacuum condition, so that the antibacterial vacuum glass is obtained.
12. Use according to claim 10 or 11, wherein the antimicrobial glass has a thickness of 2-6 mm;
and/or the distance between two points of the support is 30-50mm, the diameter of the support is 0.5-2mm, and the height of the support is 0.1-0.2 mm;
and/or the sintering temperature is 380-460 ℃, and the vacuum degree is 10-4Pa。
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| EP3925939A1 (en) * | 2020-06-17 | 2021-12-22 | Fiskars Finland Oy Ab | Method of manufacturing glass products and arrangement |
| CN112266185B (en) * | 2020-10-30 | 2022-08-09 | 科立视材料科技有限公司 | Curved surface antibacterial glass and preparation method thereof |
| CN115650592B (en) * | 2022-10-26 | 2024-02-06 | 秦皇岛玻璃工业研究设计院有限公司 | Glass flake and preparation method and application thereof |
| CN116143421A (en) * | 2022-11-10 | 2023-05-23 | 西部金属材料股份有限公司 | Reaction device for antibacterial and antiviral glass and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565683A (en) * | 2015-12-15 | 2016-05-11 | 洛阳兰迪玻璃机器股份有限公司 | Preparation method and production line of tempered vacuum glass |
| CN106061914A (en) * | 2015-02-12 | 2016-10-26 | 科立视材料科技有限公司 | Antimicrobial chemically strengthened glass and method for making antimicrobial glass article |
| CN106348622A (en) * | 2016-08-24 | 2017-01-25 | 中国建筑材料科学研究总院 | High-strength antibacterial glass and preparation method thereof |
-
2019
- 2019-07-18 CN CN201910650282.2A patent/CN110357455B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106061914A (en) * | 2015-02-12 | 2016-10-26 | 科立视材料科技有限公司 | Antimicrobial chemically strengthened glass and method for making antimicrobial glass article |
| CN105565683A (en) * | 2015-12-15 | 2016-05-11 | 洛阳兰迪玻璃机器股份有限公司 | Preparation method and production line of tempered vacuum glass |
| CN106348622A (en) * | 2016-08-24 | 2017-01-25 | 中国建筑材料科学研究总院 | High-strength antibacterial glass and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 载银高强度抗菌玻璃的制备及性能研究;陆勇祺等;《硅酸盐通报》;20151130;第34卷;12-16 * |
| 陆勇祺等.载银高强度抗菌玻璃的制备及性能研究.《硅酸盐通报》.2015,第34卷12-16. * |
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