CN110357455A - A kind of preparation method and antibacterial vacuum glass of antibiotic glass - Google Patents

A kind of preparation method and antibacterial vacuum glass of antibiotic glass Download PDF

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Publication number
CN110357455A
CN110357455A CN201910650282.2A CN201910650282A CN110357455A CN 110357455 A CN110357455 A CN 110357455A CN 201910650282 A CN201910650282 A CN 201910650282A CN 110357455 A CN110357455 A CN 110357455A
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Prior art keywords
glass
ion
antibiotic
preparation
antibacterial
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CN201910650282.2A
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CN110357455B (en
Inventor
张凡
陈玮
李要辉
王晋珍
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China Building Materials Academy CBMA
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China Building Materials Academy CBMA
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00Tempering or quenching glass products
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001Treatment 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001Treatment 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
    • C03C21/005Treatment 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C27/00Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06Joining glass to glass by processes other than fusing
    • C03C27/08Joining glass to glass by processes other than fusing with the aid of intervening metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C27/00Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06Joining glass to glass by processes other than fusing
    • C03C27/10Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose

Abstract

The invention belongs to glass making techniques fields, and in particular to a kind of preparation method and antibacterial vacuum glass of antibiotic glass.The preparation method of the antibiotic glass, includes the following steps, the solution or fusant of glass and the salt containing silver, ferrous ion are carried out a step ion exchange, antibacterial ion is introduced in glass body, obtains the antibiotic glass.The present invention realizes antibacterial ion and inside glass sodium, potassium ion is exchanged by a step ion-exchange, antibacterial ion is introduced in glass body, method is simple and effective, has saved cost.By introducing ferrous ion etc. in ion exchange process, it can effectively inhibit the oxidation of antibacterial ion, effectively improve the concentration of antibacterial ion, avoid the decline of glass transmission rate, conducive to the promotion of antibiotic glass performance and light transmission.

Description

A kind of preparation method and antibacterial vacuum glass of antibiotic glass
Technical field
The invention belongs to glass making techniques fields, and in particular to a kind of preparation method and antibacterial vacuum glass of antibiotic glass Glass.
Background technique
With the raising of scientific and technological progress and living standards of the people, people are to environmental sanitation pay attention to day by day.Refrigerator, refrigerator-freezer conduct The heat preservation refrigeration equipment of people's daily life is more and more common, and common freezer door glass is using hollow glass, phase now For vacuum glass, thickness is big, and heat-proof quality is poor, and vacuum glass only has in the luxury goods such as high-grade wine cabinet a small amount of at present Using;And antibacterial vacuum glass, research is less, and there has been no related matured products at present.
Antibiotic glass is also known as green glass, is a kind of novel ecological functional material, for improving the ecological environment, keeping the mankind Health instructs the research and development of correlation function glass material to be of great significance.Inhibit and kill using addition New Inorganic Antibacterial Agents Bacterium, so that traditional glass product be made to increase new and high technology content.Antibiotic glass both maintained glass material itself have it is saturating The features such as bright, clean, high mechanical strength, chemical stability are good, and increase killing and inhibit the new function of germ, it is new material The product that science is combined with microbiology.
The processing and fabricating of antibiotic glass is that antibacterial agent is added on glass carrier, make it have contact-type it is antibacterial, sterilization Function.Contact-type anti-biotic material, the surface of material is under unconditional normality, it is necessary to have contact antibacterial functions.Therefore, glass The coating process technology on glass surface is the technological core in antibiotic glass processing.Currently, traditional plate glass plated film side There are mainly three types of methods, the first is online chemical vapor deposition (CVD) method, and second is on-line spray method, uses both methods Antibiotic glass is produced, following problems is primarily present: first is that glass space temperature in coating process is excessively high, easily aoxidizing antibacterial agent Failure limits the using effect and range of antibiotic glass, produces second is that the above method can only carry out plated film in the single side of glass Mode is not flexible, the third is vacuum sputtering coating method, makes antibiotic glass with the method, have the following problems: antibacterial agent is most It on the surface of glass is existed with state of atom afterwards, antibacterial functions are extremely difficult to national standard under normal conditions;And antibacterial functions Film belongs to " mantle ", is not suitable for long-term exposure and contact uses.
With the development of technology, it is used to by ion exchange bath addition silver hair exhibition for a kind of novel and most probable Volume production has the technology of the glass of antibacterial properties.Traditional ion-exchange process is related to chemically reinforced glass substrate, and generally And glass is placed in the fuse salt containing the ionic radius ion bigger than the ion in glass, so that being present in glass Relatively small ion can be melted the larger ion exchange in salting liquid.Such method in the prior art, different ions are adopted more With substep exchange, complex process is at high cost, and there is a problem of antibacterial ion be easily oxidized, glass transmission rate decline it is more.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that antibiotic glass preparation process in the prior art is overcome to mostly use The defects of substep exchanges, and complex process is at high cost, and there are antibacterial ions to be easily oxidized, glass transmission rate decline is more, thus The preparation method and antibacterial vacuum glass of a kind of antibiotic glass are provided.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of preparation method of antibiotic glass, includes the following steps, by glass and the salt containing silver ion, ferrous ion Solution or fusant carry out a step ion exchange, and antibacterial ion is introduced in glass body, obtains the antibiotic glass.
Further, in the solution of the salt or the cation in fusant also containing copper ion, zinc ion, cobalt from At least one of son, nickel ion.
Further, the step of ion exchange includes:
By the solution spraying of the salt in at least one side of glass, after dry, spraying 1-2 times is repeated, is carried out physical toughened Processing, obtains the antibiotic glass.
Further, the concentration of silver ion is 0.01-3wt% in the salting liquid;
Copper ion in the salting liquid, zinc ion concentration be 0.01-2wt%;
The concentration of the salting liquid ferrous ions is 0.01-2wt%;
The concentration of cobalt ions, nickel ion is in 0.1wt% or less in the salting liquid.
Salt used in the process of this is the soluble-salt of silver, zinc, copper, cobalt, nickel, ferrous plasma, such as silver nitrate, nitric acid Zinc, zinc chloride, zinc sulfate, copper nitrate, copper chloride, copper sulphate, cobalt nitrate, nickel chloride, frerrous chloride, ferrous nitrate, sulfuric acid are sub- The soluble-salts such as iron.
Further, the physical toughened treatment temperature is 650-750 DEG C, and the processing time is 150-280 seconds.
Further, the step of ion exchange includes:
Salt containing silver ion and ferrous ion is mixed with potassium nitrate, 420-500 DEG C of heat preservation is heated to, is melted Glass after preheating is immersed in above-mentioned fuse salt and carries out ion exchange by salt, is then taken out cooling, cleaning, is obtained the antibacterial Glass.
Further, the concentration of silver ion is 0.01-1wt% in the fuse salt;
Copper ion in the fuse salt, zinc ion, ferrous ion concentration be 0.01-0.5wt%;
The mass concentration of cobalt ions, nickel ion is in 0.1wt% or less in the fuse salt.
It is above-mentioned to contain silver, copper, zinc, ferrous iron, nickel, the nitrate of cobalt, sulfate, phosphate, borate, oxide, halogenation One of object or different kinds of ions compound.
Further, the temperature of the ion exchange is 420-500 DEG C, and the time is 1-10 minutes.
The present invention also provides a kind of application of antibiotic glass that the above method is prepared in preparation antibacterial vacuum glass.
Further, the antibacterial vacuum glass is made of two sheet glass of fluctuating plate, and cloth is placed with support between two sheet glass Object, surrounding are seal, sealing materials, and closed vacuum chamber is formed between two sheet glass by vacuumize process.
Wherein, the seal, sealing materials are glass powder or metal sealing material.
Further, the antibacterial vacuum glass preparation method the following steps are included:
The antibiotic glass that the above method is prepared is as upper layer glass and/or lower layer's glass, on lower layer's glass It is even to lay supporter, and seal, sealing materials are coated in lower layer's glass surrounding, it is then sintered with upper layer glass conjunction piece and completes edge Sealing carries out vacuumize process, sealing finally by aspirating hole, or directly completes step pumping sintering under vacuum conditions, Obtain the antibacterial vacuum glass.
The preparation method of vacuum glass is mainly divided to two big kinds at present, and one is wherein a piece of glass surfaces to make a call to an aspirating hole, Then small supporter, glass surrounding glass powder or metal sealed edges are laid between two sheet glass, are finally connect from punch position Vacuum pump pumping, then seals the hole beaten, and inside cavity forms vacuum, to obtain vacuum glass.Another kind is in two panels Glass directly lays supporter, and surrounding lays glass powder or metal material, is directly evacuated in vacuum cavity, and one step of edge sealing is complete At glass surface does not need to punch.
Further, the antibiotic glass with a thickness of 2-6mm;
And/or above support distance between two points are 30-50mm, the diameter of supporter is 0.5-2mm, supporter Height is 0.1-0.2mm;
And/or the sintering temperature is 380-460 DEG C, vacuum degree 10-4Pa。
Technical solution of the present invention has the advantages that
1. the preparation method of antibiotic glass provided by the invention, includes the following steps, by glass and contain silver ion, ferrous iron The solution or fusant of the salt of ion carry out a step ion exchange, and antibacterial ion is introduced in glass body, obtain described anti- Bacterium glass.The present invention realizes antibacterial ion and inside glass sodium, potassium ion is exchanged by a step ion-exchange, in glass Antibacterial ion is introduced in glass ontology, method is simple and effective, has saved cost.By introduced in ion exchange process it is ferrous from Son etc. can effectively inhibit the oxidation of antibacterial ion, effectively improve the concentration of antibacterial ion, avoid under glass transmission rate Drop, conducive to the promotion of antibiotic glass performance and light transmission.
2. the preparation method of antibiotic glass provided by the invention, in the solution or fusant of the salt also containing copper from Son, zinc ion, cobalt ions, nickel ion cooperate between each ion, can further increase the bacteriostasis property of antibiotic glass.
3. the preparation method of antibiotic glass provided by the invention, the specific steps of the ion exchange are as follows: by the salt Solution spraying after dry, repeat spraying 1-2 times, carries out physical toughened processing, obtain the antibacterial glass in at least one side of glass Glass.The antibiotic glass produced using the method, on the basis of not influencing strength of glass, granularity, while has glass Anti-microbial property.In addition, the especially suitable preparation low-e all steel antibacterial vacuum glass of the method, because low-e glass is without forensic chemistry Tempering carries out chemical tempering film layer with regard to being all broken, low-e is without forensic chemistry steel this is because low-e glass is the film of plating on one side Change, and solution spraying and physical toughened method match, and can introduce antibacterial ion in the non-membrane surface of low-e glass, make it have Anti-microbial property.The present invention is by the control to concentration in salting liquid, on the basis of utmostly improving antibacterial ionic availability, The bacteriostasis property that ensure that antibacterial glass has been saved the dosage of antibacterial ion, has been reduced costs, and it is too low anti-to avoid ion concentration Bacterium performance is poor or without anti-microbial property, and different degrees of oxidation can all occur for the antibacterial ion of the excessively high introducing of ion concentration, introduces It is too many, oxidation it is more, glass will appear yellowing phenomenon, influence glass transmission.
4. the preparation method of antibiotic glass provided by the invention, the specific steps of the ion exchange are as follows: will containing silver from The salt of son and ferrous ion is mixed with potassium nitrate, is heated to 420-500 DEG C of heat preservation, is obtained fuse salt, the glass after preheating is soaked Enter and carry out ion exchange in above-mentioned fuse salt, then takes out cooling, cleaning, obtain the antibiotic glass.The method achieve anti- Bacterium ion and inside glass sodium, potassium ion exchange, and antibacterial ion are introduced in glass body, method is simple and effective.Simultaneously Using this method preparation antibiotic glass be common antibiotic glass, can carry out directly it is physical toughened prepare safe antibiotic glass, For example, the antibacterial vacuum glass of tempering and half tempered can be prepared.The present invention is by the control to concentration in salting liquid, in maximum On the basis of degree improves antibacterial ionic availability, it ensure that the bacteriostasis property of antibacterial glass, saved the dosage of antibacterial ion, It reduces costs.The temperature of the ion exchange is 420-500 DEG C, and the time is 1-10 minutes.Swap time is shorter in the present invention, Glass coloration is avoided, the light transmittance of antibacterial glass is improved.
5. application of the antibiotic glass provided by the invention in preparation antibacterial vacuum glass, gained antibacterial vacuum glass have both Antibacterial and heat-insulated, sound insulation property, especially have broad application prospects in terms of refrigerator, freezer door.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition Conventional reagent product.
Embodiment 1 (embodiment 1-6 is chemical method)
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
The potassium nitrate, silver nitrate, ferrous sulfate fused salt mixt of melting will be put into a thickness of 4mm original sheet glass by cutting In, wherein silver ion mass fraction is 0.1%, and the mass concentration of ferrous ion is 0.2%, under the conditions of 500 DEG C, ion exchange 2 minutes, then glass is taken out, cooling, cleaning obtains the antibiotic glass.
Embodiment 2
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
The potassium nitrate, silver nitrate, ferrous sulfate fused salt mixt of melting will be put into a thickness of 4mm original sheet glass by cutting In, wherein the mass fraction of silver ion is 3%, and the mass concentration of ferrous ion is 1.5%, under the conditions of 480 DEG C, ion exchange 1 minute, then glass is taken out, cooling, cleaning obtains the antibiotic glass.
Embodiment 3
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
The potassium nitrate, silver nitrate, ferrous sulfate fused salt mixt of melting will be put into a thickness of 4mm original sheet glass by cutting In, wherein silver ion mass fraction is 0.01%, and the mass concentration of ferrous ion is 0.01%, and under the conditions of 420 DEG C, ion is handed over It changes 10 minutes, then takes out glass, cooling, cleaning obtains the antibiotic glass.
Embodiment 4
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
Will be with a thickness of 5mm original sheet glass by cutting, potassium nitrate, silver nitrate, zinc nitrate, the ferrous sulfate for being put into melting are mixed It closes in fused salt, wherein silver ion mass fraction is 0.1%, and the mass concentration of ferrous ion is 0.2%, the mass fraction of zinc ion It is 0.1%, under the conditions of 500 DEG C, ion exchange 2 minutes, then takes out glass, cooling, cleaning obtains the antibacterial glass Glass.
Embodiment 5
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
Potassium nitrate, silver nitrate, zinc nitrate, nickel nitrate, the nitre of melting will be put into a thickness of 3mm original sheet glass by cutting In sour cobalt, ferrous sulfate fused salt mixt, wherein silver ion mass fraction is 0.1%, and the mass concentration of ferrous ion is 0.2%, The mass fraction of zinc ion is 0.1%, and the mass fraction of nickel ion is 0.02%, and the mass fraction of cobalt ions is 0.03%, Under the conditions of 500 DEG C, ion exchange 3 minutes, then glass is taken out, cooling, cleaning obtains the antibiotic glass.
Embodiment 6
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
Potassium nitrate, silver nitrate, zinc nitrate, copper nitrate, the nitre of melting will be put into a thickness of 3mm original sheet glass by cutting Sour nickel, cobalt nitrate, in ferrous sulfate fused salt mixt, wherein silver ion mass fraction is 0.08%, the mass concentration of ferrous ion It is 0.2%, the mass fraction of zinc ion is 0.1%, and the mass concentration of copper ion is 0.1%, and the mass fraction of nickel ion is 0.04%, the mass fraction of cobalt ions is 0.03%, under the conditions of 500 DEG C, ion exchange 3 minutes, is then taken out glass, cold But, clean, obtain the antibiotic glass.
Embodiment 7 (embodiment 7-9 physical method)
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
It takes with a thickness of 5mm original sheet glass by cutting, configured nitric acid is uniformly brushed in glass two sides by edging cleaning Silver, zinc nitrate, copper nitrate, ferrous nitrate compound solution, wherein the mass concentration of silver ion be 1%, the quality of zinc ion Concentration is 0.5%, and the mass concentration of copper ion is 0.4%, and the mass concentration of ferrous ion is 2%, and brushing amount will not with drop It is dry under room temperature subject to leaving at drop, it repeats to brush 1 time, takes out glass, then physical toughened 150s is carried out for 750 DEG C, after cooling Obtain the antibiotic glass.
Embodiment 8
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
It takes with a thickness of 5mm original sheet glass by cutting, edging cleaning, glass one side is uniformly brushed into configured nitric acid Silver, zinc nitrate, copper nitrate, ferrous nitrate compound solution, brushing amount, which is subject to drop, to be left at drop, wherein silver from The mass concentration of son is 1.5%, and the mass concentration of zinc ion is 0.5%, and the mass concentration of copper ion is 0.4%, ferrous ion Mass concentration be 1.8%, it is dry under room temperature, repeat to brush 1 time, take out glass, then carry out physical toughened 200s for 720 DEG C, The antibiotic glass is obtained after cooling.
Embodiment 9
The present embodiment provides a kind of preparation method of antibiotic glass, specific steps are as follows:
It takes with a thickness of 5mm original sheet glass by cutting, configured nitric acid is uniformly brushed in glass two sides by edging cleaning Silver, zinc nitrate, copper nitrate, ferrous nitrate, cobalt nitrate, nickel nitrate compound solution, brushing amount will not leave with drop at drop Subject to, wherein the mass concentration of silver ion is 2.5%, and the mass concentration of zinc ion is 0.4%, and the mass concentration of copper ion is 0.2%, the mass concentration of ferrous ion is 1.5%, and the mass concentration of cobalt ions is 0.01%, and the mass concentration of nickel ion is 0.03%, it is dry under room temperature, repeat to brush 2 times, take out glass, then carry out physical toughened 280s for 650 DEG C, it is cooling after it is described Antibiotic glass.
Embodiment 10
The present embodiment provides a kind of antibiotic glass antibacterial vacuum glass preparation in application, the antibacterial vacuum glass The preparation method comprises the following steps:
Two panels 4mm original sheet glass is by cutting, edging cleaning a, wherein sheet glass makes a call to an aspirating hole again, in another glass The slot for placing getter is beaten on glass, then two sheet glass are put into the potassium nitrate, silver nitrate, ferrous nitrate fused salt mixt of melting In, wherein silver ion mass fraction is 0.1%, and the mass fraction of ferrous ion is 0.2%, under the conditions of 500 DEG C, ion exchange 2 minutes, then two sheet glass are taken out, cooling cleaning.It takes with reeded glass, between glass surface uniformly lays supporter Away from 40mm, the low temperature glass slurry that glass surrounding is coated in another side, then two surface glasses close piece, carry out 460 DEG C of sintering, finally It is evacuated from pumping hole site with vacuum pump, is sealed with sheet glass, obtain conventional vacuum antibiotic glass.
Embodiment 11
The present embodiment provides a kind of antibiotic glass antibacterial vacuum glass preparation in application, the antibacterial vacuum glass The preparation method comprises the following steps:
Two panels 5mm original sheet glass is by cutting, edging cleaning a, wherein sheet glass is making a call to an aspirating hole, in another glass Beaten on glass place getter slot, then by two panels glass surface uniformly brush configured silver nitrate, zinc sulfate, copper chloride, The compound solution of ferrous nitrate, brushing amount, which is subject to drop, to be left at drop, and wherein the mass concentration of silver ion is 2%, The mass concentration of zinc ion is 0.8%, and the mass concentration of copper ion is 0.9%, and the mass concentration of ferrous ion is 1.7%, 60 DEG C or less it is dry, after dry, repeat spraying 2 times, take with reeded glass, lay support in glass surface with automatic dispensing machine Object slurry, spacing 40mm, then 720 DEG C of progress are physical toughened, and another sheet glass is directly physical toughened, glass four after tempering The low temperature glass slurry of week coating, then two surface glasses close piece, carry out 420 DEG C of sintering, finally from pumping hole site vacuum pump Pumping is sintered with sealing device and is sealed, obtains toughened vacuum antibiotic glass.
Embodiment 12
The present embodiment provides a kind of antibiotic glass antibacterial vacuum glass preparation in application, the antibacterial vacuum glass The preparation method comprises the following steps:
Two panels 5mm original sheet glass is by cutting, edging cleaning a, wherein sheet glass is low-e glass, on lowe glass One aspirating hole beats the slot for placing getter on another sheet glass, two panels glass surface is uniformly then brushed configured nitre Sour silver, zinc sulfate, copper chloride, ferrous sulfate compound solution, brushing amount, which is subject to drop, to be left at drop, wherein silver-colored The mass concentration of ion is 1.5%, and the mass concentration of zinc ion is 0.3%, and copper ion mass concentration is 1%, ferrous ion Mass concentration is 1.2%, wherein low-e glass only sprays non-low-e film surface, and drying under room temperature repeats to brush 2 times, takes and have The glass of groove lays supporter slurry in glass surface with automatic dispensing machine, spacing 30mm, then 720 DEG C of progress physics steel Change, another low-e glass is directly physical toughened, the low temperature glass slurry of glass surrounding coating after tempering, then two sides Glass closes piece, carries out 380 DEG C of sintering, is finally evacuated from pumping hole site with vacuum pump, is sintered and is sealed with sealing device, obtained Low-e toughened vacuum antibiotic glass.
Comparative example 1
The antibiotic glass that this comparative example provides is similar to Example 6, and difference is, ferrous sulfate is not included in fuse salt.
Comparative example 2
The antibiotic glass that this comparative example provides is similar to Example 8, and difference is, does not include nitric acid Asia in compound solution Iron.
Test case
The antibiotic glass that 1-9 of the embodiment of the present invention and comparative example 1-2 are provided carries out biocidal property and light transmittance test, In, numerous bacteriums existing for nature can classify according to certain rule, can be divided into leather according to Gram's stain Lan Shi negative bacterium and gram-positive bacteria.Wherein the representative bacterium of Gram-negative bacteria is Escherichia coli, and Gram-positive The representative bacterium of bacterium is then staphylococcus aureus.Staphylococcus aureus is according to national standard " plated film antibiotic glass JC/T 1054-2007 " it measures, Escherichia coli measure according to " HG3950-2007 antibiotic paint ".
The test method of light transmittance is tested according to method as defined in GB/T2680.It is specific that test result is as follows shown in table:
Table 1
It can be seen from the data in the table that antibiotic glass generally all reaches the anti-microbial property of Escherichia coli and staphylococcus aureus 95% or more, while requirement of the visible transmission of glass than still conforming to plate glass national standard itself.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or It changes still within the protection scope of the invention.

Claims (12)

1. a kind of preparation method of antibiotic glass, which is characterized in that include the following steps, by glass and contain silver ion, ferrous iron The solution or fusant of the salt of ion carry out a step ion exchange, and antibacterial ion is introduced in glass body, obtain described anti- Bacterium glass.
2. the preparation method of antibiotic glass according to claim 1, which is characterized in that the solution or fusant of the salt In cation also contain at least one of copper ion, zinc ion, cobalt ions, nickel ion.
3. the preparation method of antibiotic glass according to claim 1 or 2, which is characterized in that the step of the ion exchange Include:
By the solution spraying of the salt in at least one side of glass, after dry, spraying 1-2 times is repeated, physical toughened processing is carried out, Obtain the antibiotic glass.
4. the preparation method of antibiotic glass according to claim 3, which is characterized in that silver ion is dense in the salting liquid Degree is 0.01-3wt%;
Copper ion in the salting liquid, zinc ion concentration be 0.01-2wt%;
The concentration of the salting liquid ferrous ions is 0.01-2wt%;
The concentration of cobalt ions, nickel ion is in 0.1wt% or less in the salting liquid.
5. the preparation method of antibiotic glass according to claim 3, which is characterized in that the physical toughened treatment temperature It is 650-750 DEG C, the processing time is 150-280 seconds.
6. the preparation method of antibiotic glass according to claim 1 or 2, which is characterized in that the step of the ion exchange Include:
Salt containing silver ion and ferrous ion is mixed with potassium nitrate, 420-500 DEG C of heat preservation is heated to, obtains fuse salt, it will Glass after preheating, which immerses in above-mentioned fuse salt, carries out ion exchange, then takes out cooling, cleaning, obtains the antibiotic glass.
7. the preparation method of antibiotic glass according to claim 6, which is characterized in that silver ion is dense in the fuse salt Degree is 0.01-1wt%;
Copper ion in the fuse salt, zinc ion, ferrous ion concentration be 0.01-0.5wt%;
The mass concentration of cobalt ions, nickel ion is in 0.1wt% or less in the fuse salt.
8. the preparation method of antibiotic glass according to claim 6, which is characterized in that the temperature of the ion exchange is 420-500 DEG C, the time is 1-10 minutes.
9. the antibiotic glass that a kind of any one of claim 1-8 the method is prepared answering in preparation antibacterial vacuum glass With.
10. application according to claim 9, which is characterized in that the antibacterial vacuum glass is by two sheet glass group of fluctuating plate At cloth is placed with supporter between two sheet glass, and surrounding is seal, sealing materials, is formed between two sheet glass by vacuumize process close The vacuum chamber closed.
11. application according to claim 10, which is characterized in that the preparation method of the antibacterial vacuum glass includes following Step:
The antibiotic glass that any one of claim 1-8 the method is prepared as upper layer glass and/or lower layer's glass, Supporter is uniformly laid on lower layer's glass, and is coated with seal, sealing materials in lower layer's glass surrounding, is then closed piece with upper layer glass and is carried out Edge sealing is completed in sintering, carries out vacuumize process, sealing finally by aspirating hole, or directly complete one under vacuum conditions Step pumping sintering, obtains the antibacterial vacuum glass.
12. application described in 0 or 11 according to claim 1, which is characterized in that the antibiotic glass with a thickness of 2-6mm;
And/or above support distance between two points are 30-50mm, the diameter of supporter is 0.5-2mm, the height of supporter For 0.1-0.2mm;
And/or the sintering temperature is 380-460 DEG C, vacuum degree 10-4Pa。
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CN111844965A (en) * 2020-06-15 2020-10-30 珠海市楚威塑胶有限公司 Sterilization and virus killing method based on flexible glass
CN113800780A (en) * 2020-06-17 2021-12-17 菲斯卡斯芬兰有限公司 Method and apparatus for manufacturing glass products
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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
CN115650592A (en) * 2022-10-26 2023-01-31 秦皇岛玻璃工业研究设计院有限公司 Glass flake and preparation method and application 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

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