CN112266185A - Curved surface antibacterial glass and preparation method thereof - Google Patents
Curved surface antibacterial glass and preparation method thereof Download PDFInfo
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- CN112266185A CN112266185A CN202011185669.4A CN202011185669A CN112266185A CN 112266185 A CN112266185 A CN 112266185A CN 202011185669 A CN202011185669 A CN 202011185669A CN 112266185 A CN112266185 A CN 112266185A
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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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3494—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising other salts, e.g. sulfate, phosphate
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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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
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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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
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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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
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Abstract
The invention provides curved surface antibacterial glass and a preparation method thereof, and the curved surface antibacterial glass comprises the following steps of: more than 2 different antibacterial metal ions are sequentially deposited on the surface of the base glass in a layered manner to form a laminated antibacterial coating; preheating: preheating glass forming the antibacterial coating at a temperature of T1; ion exchange for the first time: carrying out primary ion exchange on the preheated glass at the temperature of T2; hot bending ion exchange: carrying out the first ion exchange on the glass at the temperature of T3, and simultaneously carrying out the second ion exchange; and annealing and cooling to obtain the curved surface antibacterial glass. Through setting up the range upon range of antibacterial coating that contains different antibiotic metal ion, 2 steps ion exchange process, the hot bending also carries out ion exchange simultaneously for the production technology time and the flow of curved surface antibacterial glass shorten. Meanwhile, most of the antibacterial metal ions entering the glass are remained on the superficial layer, so that the effect of improving the antibacterial activity is achieved. The curved surface antibacterial glass has an antibacterial activity R which is more than 5 before the photo-aging test and more than 2.9 after the photo-aging test.
Description
Technical Field
The invention relates to the field of curved surface antibacterial glass, in particular to curved surface antibacterial glass and a preparation method thereof.
Background
Manufacturers of electronic products and devices competitively push curved smart wristbands, watches, mobile phones, tablet computers, curved televisions and the like in order to realize more advanced design ideas and product differentiation, and more devices with small-size or medium-size or large-size display screens are becoming popular trends in the design world. At present, 3D curved glass becomes the standard of high-grade fashion mobile phones, and with the continuous release of new models of more manufacturers, the trend of the 'curved surface' of the mobile phone cover plate is also more and more intensified. The hot bending forming of glass is a mature technology in the glass industry, the addition of an antibacterial function to mobile phone glass also becomes a new research and development direction for manufacturers, and most of traditional antibacterial glass has a silver antibacterial layer on the surface of the glass. There are several methods for forming this layer, such as adding an antibacterial component to the raw materials for forming the glass and attaching an antibacterial film material by means of a film-attaching method, for example, chinese patent application CN201821475107.1 discloses a 3D curved surface tempered glass protective film in which an antibacterial layer is provided by means of adhesion. Among these methods, the addition of silver to the surface by ion exchange is the most common and most likely technique used for mass production of glass having antibacterial 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. Chinese patent application 202010623835.8 discloses a technical solution for implanting antibacterial ions on glass by ion exchange method.
The existing curved glass needs an antibacterial function, and the process flow of an antibacterial part must be added, if an antibacterial layer is formed in a film covering mode, long-acting antibacterial can not be realized, and meanwhile, due to the radian of the curved surface, the process of uniformly covering the film on the curved surface is difficult. The antibacterial property is increased by the ion exchange process, the glass is firstly subjected to hot bending forming and then subjected to one-step or multi-step ion exchange, so that the time and the process flow are increased invisibly, the performance strength of the glass is reduced due to multiple times of thermal strengthening, or the shallow surface form of the glass is possibly distorted in the ion exchange process, so that the radian of the curved surface of the glass is changed.
Disclosure of Invention
Therefore, it is necessary to provide curved surface antibacterial glass which can ensure antibacterial performance and curved surface strength and does not affect the curved surface configuration of the glass, and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing curved antibacterial glass, which sequentially comprises the following steps:
deposition: more than 2 different antibacterial metal ions are sequentially deposited on the surface of the base glass in a layered manner to form a laminated antibacterial coating;
preheating: preheating glass forming the antibacterial coating at a temperature of T1;
ion exchange for the first time: carrying out primary ion exchange on the preheated glass at the temperature of T2;
hot bending ion exchange: performing secondary ion exchange on the glass subjected to the primary ion exchange while performing pressure hot bending at the temperature of T3; and annealing and cooling to obtain the curved surface antibacterial glass.
The laminated antibacterial coating layer may be formed by sequentially depositing different antibacterial metal ions on the base glass layer by layer through a physical deposition method, a chemical deposition method, or a spray method, but is not limited thereto. The physical or chemical deposition method comprises one or more of a vacuum coating method, a metal thermal evaporation coating method, a magnetron sputtering method, a laser pulse deposition method, an atomic layer deposition method, a chemical plating method and an electrochemical method. The spraying may be performed by, but is not limited to, spraying the glass surface with an antimicrobial metal melt or an antimicrobial metal-containing solution.
The deposition sequence can be set according to the speed of implanting the antibacterial metal ions into the glass, and in order to ensure that most of the antibacterial metal ions are gathered on the shallow surface layer of the glass, the implantation speed of the antibacterial metal ions can be set to be in direct proportion to the distance between the deposition layer and the surface of the glass. The deposition sequence can also be set according to the set concentration of the antibacterial metal ions implanted into the shallow surface layer, and the closer the antibacterial metal ions are to the surface of the glass, the more the antibacterial metal ions exchange with the ions in the glass, and the implantation concentration is relatively higher.
The preheating step is to preheat the basic glass which is obtained in the deposition step and is provided with the antibacterial coating of the antibacterial metal ions, so that the basic glass is close to the primary ion exchange temperature, the production period of the primary ion exchange process can be greatly shortened, the heat consumption of glass production is reduced, and the production efficiency is improved.
The primary ion exchange step is to perform primary ion exchange on the preheated glass through antibacterial metal ions. In the first ion exchange step, the molten antibacterial metal ions start to perform replacement reaction on lithium ions and/or sodium ions in the glass components and enter the shallow surface layer of the glass.
Meanwhile, the density of the glass shallow surface layer is increased in the first ion exchange step, the difficulty of antibacterial ion penetration in the hot bending ion exchange step is increased, most of antibacterial ions stay on the glass shallow surface layer (including the surface), the implantation depth is controlled, and the strengthening and antibacterial properties of the glass surface are guaranteed.
The step of hot bending ion exchange is to carry out secondary ion exchange and bending on the glass after the primary ion exchange, and carry out pressure forming in the bending process. Pressurization also promotes the exchange efficiency of the secondary ion exchange, allowing more antimicrobial ions, particularly silver ions, to enter the shallow surface layer of the glass.
Furthermore, the preheating temperature T1 is less than or equal to the first ion exchange temperature T2 is less than or equal to the hot-bending ion exchange temperature T3.
The T3 temperature is the temperature at which the heated glass object can be safely bent and shaped, and the T3 temperature is between the glass transition temperature (Tg) and the softening temperature (Ts) of the shaped glass.
Further, in the deposition step, the implantation speed of different antibacterial metal ions in the base glass is proportional to the distance between the deposition layer and the surface of the glass. The antibacterial metal ions with relatively high implantation speed are relatively far away from the surface of the glass to be implanted, so that the antibacterial metal with relatively low implantation speed can be firstly implanted into the glass for ion exchange, and the ion exchange time is relatively sufficient; due to its slow implantation rate, most of it still exists in the shallow surface layer of the glass, although the ion exchange time is long. The antibacterial ions with the higher implantation speed are far away from the surface of the glass, so that the time for entering the glass for ion exchange is shorter, and although the implantation speed is high, the implantation depth is controlled by shortening the implantation time, most of the antibacterial ions also exist in the shallow surface layer of the glass, and less antibacterial ions enter the glass, so that waste is caused.
Further, in the deposition step, the concentration of different antibacterial metal ions on the surface layer of the base glass is inversely proportional to the distance between the deposited layer and the surface of the glass. The closer the antimicrobial metal ions are to the glass surface, the greater the chance of exchanging ions with the glass interior, and the higher the implant concentration.
Further, the antibacterial metal ions include silver ions, copper ions, zinc ions, cobalt ions, and nickel ions.
Further, in the step of hot bending ion exchange, a hot bending machine is adopted for hot bending, and the hot bending pressure is 0.3MPa-0.8 MPa.
Further, in the deposition step, the antibacterial coating is obtained by sequentially spraying nitrate solutions of different antibacterial metal ions on the surface of the glass.
Preferably, the nitrate solution has a concentration of silver ions, copper ions and zinc ions of 0.5 to 3 wt%; the concentration of cobalt ion and nickel ion is 0.01-0.05 wt%. But is not limited thereto.
Preferably, the nitrate solution further comprises potassium ions. KNO3Is a molten salt matrix, has the characteristic of low melting point, and is a good choice for ion exchange molten salt.
Further, the method comprises the following steps:
deposition:
spraying nitrate solution containing copper ions and potassium ions on the surface of the base glass, and drying to form a first coating;
spraying nitrate solution containing zinc ions and potassium ions on the surface of the first coating, and drying to form a second coating;
spraying nitrate solution containing silver ions and potassium ions on the surface of the substrate, and drying to form a third coating; the first coating, the second coating and the third coating form a laminated antibacterial coating;
preheating: preheating glass forming the antibacterial coating at a temperature of T1;
ion exchange for the first time: carrying out primary ion exchange on the preheated glass at the temperature of T2;
hot bending ion exchange: carrying out secondary ion exchange on the glass subjected to the primary ion exchange while carrying out hot bending by external pressure at the temperature of T3; annealing and cooling to obtain the curved surface antibacterial glass;
the preheating temperature T1 is not less than the first ion exchange temperature T2 is not less than the hot bending ion exchange temperature T3;
further, the preheating temperature T1 is 300-450 ℃; the primary ion exchange temperature T2 is 400-500 ℃; the hot-bending ion exchange temperature T3 is 500-600 ℃.
Further, the preheating time is 100S-130S; the first ion exchange time is 120S-210S; the hot bending ion exchange time is 140S-210S.
The deposition sequence of the antibacterial metal ions on the glass surface is as follows: copper ions, zinc ions, silver ions. Speed of implanting antibacterial metal ions into glass: silver ions are most easily implanted, secondly copper and finally zinc. The silver ions are arranged on the outermost layer, so that the distance between the silver ions and the surface of the glass is increased, and the phenomenon that a large amount of silver ions enter the glass to cause waste in the ion exchange process is avoided. This layering setting for in the same ion exchange time, there are the antibiotic metal ion of different translation rates in glass, most all stay in shallow top layer, reach the effect that improves antibacterial power.
And the deposition order has an effect on the metal ion concentration at the glass surface. And the set concentration of zinc ions in the antibacterial glass is greatly lower than that of copper ions. Thus, although the implantation rate is slightly lower than that of copper ions, the deposition sequence is still set after the copper ions.
Furthermore, the surface metal element concentration Cu of the curved surface antibacterial glass is more than Ag and more than Zn.
The invention also provides curved surface antibacterial glass, which is prepared by the preparation method of the curved surface antibacterial glass of the first aspect of the invention.
Different from the prior art, the technical scheme at least comprises the following beneficial effects: through setting up the range upon range of antibacterial coating that contains different antibiotic metal ion, 2 steps ion exchange process, the hot bending also carries out ion exchange simultaneously for the production technology time and the flow of curved surface antibacterial glass shorten. Meanwhile, most of the antibacterial metal ions entering the curved glass stay on the shallow surface of the glass, so that the effect of improving the antibacterial activity of the glass is achieved. The curved surface antibacterial glass has an antibacterial activity R which is more than 5 before the photo-aging test and more than 2.9 after the photo-aging test.
Drawings
FIG. 1 is a table of process parameters of examples 1-4 in the production process and performance test data of the curved antibacterial glass obtained in examples 1-4. .
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
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 reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
deposition: taking a glass sheet, carrying out early-stage CNC cutting, edging and cleaning, and uniformly spraying a prepared compound solution of copper nitrate and potassium nitrate on one surface of the glass, wherein the mass concentration of copper ions is 3%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; uniformly spraying the prepared zinc nitrate and potassium nitrate compound solution on the glass spraying surface again, wherein the mass concentration of zinc ions is 1%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; uniformly spraying the prepared silver nitrate and potassium nitrate compound solution on the glass spraying surface again, wherein the mass concentration of silver ions is 3%, and the spray gun is used for spraying silver nitrate and potassium nitrate compound solution at the concentration of 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; obtaining a glass sheet with three layers of laminated antibacterial coatings of silver ions, zinc ions and copper ions from outside to inside;
placing the glass sheet with the antibacterial coating into a graphite forming mold, placing the mold into a forming machine for preheating, first ion exchange, hot bending ion exchange, annealing and cooling,
a preheating procedure: 2 stations are divided, the temperature is respectively 300 ℃ plus 300 ℃, and the time is respectively 60s plus 60 s;
a first ion exchange process: the method comprises the following steps of dividing the system into 3 stations, wherein the temperature is 400 ℃, 400 ℃ and 400 ℃, and the time is 70s +70s +70 s;
a hot bending ion exchange procedure: 550 degrees centigrade, +570 degrees centigrade, +600 degrees centigrade, the time is 60s +60s +60s respectively;
annealing and cooling: the method comprises 3 stations, wherein the temperature is respectively 600 degrees centigrade +300 degrees centigrade, and the time is respectively 60s +60s +60s, and finally the curved surface antibacterial glass is obtained.
deposition: taking a glass sheet, carrying out early-stage CNC cutting, edging and cleaning, and uniformly spraying a prepared compound solution of copper nitrate and potassium nitrate on one surface of the glass, wherein the mass concentration of copper ions is 2%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; uniformly spraying the prepared zinc nitrate and potassium nitrate compound solution on the glass spraying surface again, wherein the mass concentration of zinc ions is 1.5%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; uniformly spraying the prepared silver nitrate and potassium nitrate compound solution on the glass spraying surface again, wherein the mass concentration of silver ions is 2%, and the spray gun is used for spraying silver nitrate and potassium nitrate compound solution at the concentration of 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; obtaining a glass sheet with three layers of laminated antibacterial coatings of silver ions, zinc ions and copper ions from outside to inside;
placing the glass sheet with the antibacterial coating into a graphite forming mold, placing the mold into a forming machine for preheating, first ion exchange, hot bending ion exchange, annealing and cooling,
a preheating procedure: 2 stations are divided, the temperature is 350 ℃ plus 400 ℃, and the time is 60s plus 60 s;
a first ion exchange process: the method comprises the following steps of dividing the system into 2 stations, wherein the temperature is 450 ℃ and 500 ℃, and the time is 80s and 80s respectively; a hot bending ion exchange procedure: the method comprises the following steps of dividing the system into 3 stations, wherein the temperature is 500 ℃, 550 ℃ and 600 ℃, and the time is 60s +60s +60 s;
annealing and cooling: the method comprises 3 stations, wherein the temperature is respectively 600 degrees centigrade +300 degrees centigrade, and the time is respectively 60s +60s +60s, and finally the curved surface antibacterial glass is obtained.
deposition: taking a glass sheet, carrying out early-stage CNC cutting, edging and cleaning, and uniformly spraying a prepared compound solution of copper nitrate and potassium nitrate on one surface of the glass, wherein the mass concentration of copper ions is 0.5%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; uniformly spraying the prepared zinc nitrate and potassium nitrate compound solution on the glass spraying surface again, wherein the mass concentration of zinc ions is 1%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; spraying the prepared silver nitrate and potassium nitrate compound solution with silver ion mass concentration of 0.5% onto the glass surface, and spraying with spray gun at a rate of 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; obtaining a glass sheet with three layers of laminated antibacterial coatings of silver ions, zinc ions and copper ions from outside to inside;
placing the glass sheet with the antibacterial coating into a graphite forming mold, placing the mold into a forming machine for preheating, first ion exchange, hot bending ion exchange, annealing and cooling,
a preheating procedure: 2 stations are divided, the temperature is 350 ℃ plus 450 ℃ respectively, and the time is 60s plus 60s respectively;
a first ion exchange process: the method comprises the following steps of 1 station, wherein the temperature is 500 ℃, and the time is 120s respectively;
a hot bending ion exchange procedure: the method comprises the following steps of dividing the system into 2 stations, wherein the temperature is 550 ℃ plus 600 ℃, and the time is 60s plus 80 s; annealing and cooling: the method comprises 3 stations, wherein the temperature is respectively 600 degrees centigrade +300 degrees centigrade, and the time is respectively 60s +60s +60s, and finally the curved surface antibacterial glass is obtained.
Embodiment 4 provides a method for preparing curved surface antibacterial glass, which comprises the following steps:
deposition: taking a glass sheet, carrying out early-stage CNC cutting, edging and cleaning, and uniformly spraying a prepared compound solution of copper nitrate and potassium nitrate on one surface of the glass, wherein the mass concentration of copper ions is 2.5%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; spraying the glassUniformly spraying the prepared zinc nitrate and potassium nitrate compound solution on the coating surface again, wherein the mass concentration of zinc ions is 1.5%, and the spray gun is used for spraying 1.2kg/cm2The atomization pressure and the flow rate of 10mL/min are sprayed on the surface of the glass, and the glass is dried at normal temperature; uniformly spraying the prepared silver nitrate and potassium nitrate compound solution on the glass spraying surface again, wherein the mass concentration of silver ions is 1%, and the spray gun is used for spraying silver nitrate and potassium nitrate compound solution at the concentration of 1.2kg/cm2The glass sheet is sprayed on the surface of glass under the atomizing pressure and the flow rate of 10mL/min, and is dried at normal temperature to obtain the glass sheet with the three-layer laminated antibacterial coating of silver ions, zinc ions and copper ions from outside to inside;
placing the glass sheet with the antibacterial coating into a graphite forming mold, placing the mold into a forming machine for preheating, first ion exchange, hot bending ion exchange, annealing and cooling,
a preheating procedure: 2 stations are divided, the temperature is 350 ℃ plus 450 ℃ respectively, and the time is 60s plus 60s respectively;
a first ion exchange process: the method comprises the following steps of dividing the system into 2 stations, wherein the temperature is 470 ℃ and 490 ℃, and the time is 70s and 70s respectively; a hot bending ion exchange procedure: the method comprises the following steps of dividing the system into 2 stations, wherein the temperature is 580 ℃ plus 600 ℃, and the time is 70s plus 70 s; a cooling annealing process: the method comprises 3 stations, wherein the temperature is respectively 600 degrees centigrade +300 degrees centigrade, and the time is respectively 60s +60s +60s, and finally the curved surface antibacterial glass is obtained.
FIG. 1 is a table of process parameters of examples 1-4 in the production process and performance test data of the curved antibacterial glass obtained in examples 1-4. As can be seen from FIG. 1, the surface metal element concentration Cu of the curved antibacterial glass is more than Ag and more than Zn; the curved antimicrobial glass samples had an antimicrobial activity R of greater than 5 before the light aging test and greater than 2.9 after the light aging test.
The curved antibacterial glass obtained in the examples 1 to 4 has smooth curved surface and no distortion, and the shallow surface layer and the surface containing antibacterial metal ions have antibacterial property, and the curved surface also has better strength.
Wherein, the antibacterial activity R value of the curved surface antibacterial glass sample is calculated by the following formula:
N＝(C×D×V)/A
wherein N is the number of viable bacteria (per 1cm2 test piece); c is bacterial colonyCounts (average count of colonies from both dishes used); d is a dilution factor; v is the volume of Soy Casein Digested Lecithin Polysorbate (SCDLP) broth (ml) used for washing out; and A is the surface area of the cover film (cm 2). When the count of bacterial colonies is less than 1, the viable cell number N is calculated by setting C to 1. For example, when V is 10ml, A is 16cm2When D is 1, the count of colonies is expressed as "0.63".
When the test is valid, the antimicrobial activity value is calculated according to the formula, the first decimal point is retained, and rounded to obtain the second decimal point below the decimal point. When the colony count is "0.63", the "0.63" is calculated as the mean of the logarithms.
R＝(Ut-U0)-(At-U0)＝Ut-At
Wherein R is antibacterial activity; u0 is the log mean of the number of viable cells obtained immediately after inoculation on untreated test pieces; ut is the log mean of the number of viable cells obtained 24 hours after inoculation on untreated test pieces; and At is the log average of the number of viable cells obtained 24 hours after inoculation on the antimicrobial test strip.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal 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 terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (10)
1. The preparation method of the curved surface antibacterial glass is characterized by sequentially comprising the following steps of:
deposition: more than 2 different antibacterial metal ions are sequentially deposited on the surface of the base glass in a layered manner to form a laminated antibacterial coating;
preheating: preheating glass forming the antibacterial coating at a temperature of T1;
ion exchange for the first time: carrying out primary ion exchange on the preheated glass at the temperature of T2;
hot bending ion exchange: carrying out the first ion exchange on the glass at the temperature of T3, and simultaneously carrying out the second ion exchange; and annealing and cooling to obtain the curved surface antibacterial glass.
2. The method for preparing curved antibacterial glass according to claim 1, wherein the preheating temperature T1 is not less than the first ion exchange temperature T2 is not less than the hot bending ion exchange temperature T3.
3. The method of claim 1, wherein in the step of depositing, the implantation speed of different antibacterial metal ions in the base glass is proportional to the distance between the deposited layer and the surface of the glass.
4. The method of claim 1, wherein in the step of depositing, the concentration of different antimicrobial metal ions on the surface of the base glass is inversely proportional to the distance between the deposited layer and the surface of the glass.
5. The method of claim 1, wherein the antimicrobial metal ions comprise silver ions, copper ions, zinc ions, cobalt ions, and nickel ions.
6. The method for preparing curved antibacterial glass according to claim 1, wherein in the step of hot bending ion exchange, a hot bending machine is used for hot bending, and the hot bending pressure is 0.3MPa to 0.8 MPa.
7. The method for preparing the curved antibacterial glass according to claim 1, wherein in the step of depositing, the antibacterial coating is obtained by sequentially spraying nitrate solutions of different antibacterial metal ions on the surface of the glass.
8. The method for preparing curved antibacterial glass according to claim 1, characterized by comprising the following steps:
deposition:
spraying nitrate solution containing copper ions and potassium ions on the surface of the base glass, and drying to form a first coating;
spraying nitrate solution containing zinc ions and potassium ions on the surface of the first coating, and drying to form a second coating;
spraying nitrate solution containing silver ions and potassium ions on the surface of the substrate, and drying to form a third coating; the first coating, the second coating and the third coating form a laminated antibacterial coating;
preheating: preheating glass forming the antibacterial coating at a temperature of T1;
ion exchange for the first time: carrying out primary ion exchange on the preheated glass at the temperature of T2;
hot bending ion exchange: carrying out secondary ion exchange on the glass subjected to the primary ion exchange while carrying out hot bending by external pressure at the temperature of T3; annealing and cooling to obtain the curved surface antibacterial glass;
wherein the content of the first and second substances,
the preheating temperature T1 is not less than the first ion exchange temperature T2 is not less than the hot bending ion exchange temperature T3;
the primary ion exchange temperature T2 is 400-500 ℃; the hot-bending ion exchange temperature T3 is 500-600 ℃.
9. The method for preparing curved surface antibacterial glass according to claim 1, wherein the surface metal element concentration of the curved surface antibacterial glass is Cu > Ag > Zn.
10. Curved antibacterial glass, characterized in that, the curved antibacterial glass, which is prepared by the method for preparing the curved antibacterial glass of any claim 1-9.
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| US20220289624A1 (en) * | 2021-03-12 | 2022-09-15 | Tubitak | Fast and economical glass functionalization in one step |
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