CN116040959A - Glass with nano silver on surface and preparation method thereof - Google Patents

Glass with nano silver on surface and preparation method thereof Download PDF

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Publication number
CN116040959A
CN116040959A CN202211625648.9A CN202211625648A CN116040959A CN 116040959 A CN116040959 A CN 116040959A CN 202211625648 A CN202211625648 A CN 202211625648A CN 116040959 A CN116040959 A CN 116040959A
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CN
China
Prior art keywords
glass
nano
silver
etching
holes
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Pending
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CN202211625648.9A
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Chinese (zh)
Inventor
彭寿
马立云
刘晓鹏
官敏
王伟
周文彩
王川申
于浩
于静波
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Glass New Material Innovation Center Anhui Co ltd
China Triumph International Engineering Co Ltd
Original Assignee
Glass New Material Innovation Center Anhui Co ltd
China Triumph International Engineering Co Ltd
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Application filed by Glass New Material Innovation Center Anhui Co ltd, China Triumph International Engineering Co Ltd filed Critical Glass New Material Innovation Center Anhui Co ltd
Priority to CN202211625648.9A priority Critical patent/CN116040959A/en
Publication of CN116040959A publication Critical patent/CN116040959A/en
Pending legal-status Critical Current

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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
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • 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
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Abstract

The invention discloses glass with nano silver on the surface and a preparation method thereof, wherein nano holes on the surface of the glass are obtained by etching through a wet chemical method, silver nitrate is introduced into the nano holes, then nano silver generated by in-situ reaction is obtained through heat treatment, the nano scale of silver particles is ensured by the domain-limiting effect of the nano holes, and the nano silver particles are wrapped on the surface of the glass in the collapse process of the nano holes, so that the problem of nano silver oxidation failure is solved, the long-acting glass is obtained, and meanwhile, the low-cost manufacture is realized.

Description

Glass with nano silver on surface and preparation method thereof
Technical Field
The invention relates to the technical field of functional glass, in particular to glass with nano silver on the surface and a preparation method thereof.
Background
The nano silver as a functional nano particle is widely applied to the fields of medical antibiosis, chemical catalysis, optical display and the like in recent years. However, when nano-sized silver particles are exposed to air, they are oxidized in a short time, thereby losing the properties of metallic silver nanoparticles. Therefore, how to effectively protect the nano silver in the application process and realize the long-acting and stable function of the nano silver is a problem to be solved urgently.
Glass is a transparent material with stable physicochemical properties, and glass-based nano silver is also considered as a representative of long-acting stable functional materials. The invention patent publication No. CN110128858A and CN109502988A adopts a glass surface coating mode to obtain SiO-coated film 2 And covering the protected nano silver coating with resin, thereby obtaining the nano silver glass with antibacterial property. Said invention can be used for preparing silver nano particle dispersion liquor in advance, then can be matched with the following film layer material, and its technological process is complex, cost is high, and the prepared film layer and glass matrix have the problem of poor binding force. The invention patent publication numbers CN111499220a and CN113480195A adopts ion exchange to obtain silver-rich layer on the glass surface, but the silver ion exchange affects the transmittance and strength of the glass, so that the transmittance of the finally produced glass is reduced, the strength is reduced, and the glass is only stored on the glass surface in the form of silver ion, and the antibacterial time or other performance life of the glass is limited. While the glass curtain wall with the nano silver wire coated on the surface, disclosed in the patent of the publication No. CN109853794A, needs double-layer glass to form a hollow,the functional layer is protected inside.
Therefore, in order to solve the problem of oxidation failure of nano silver, a long-acting functional glass is obtained, and meanwhile, low-cost manufacture is realized, and a new preparation method of the glass with nano silver on the surface is urgently needed.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides glass with nano silver on the surface and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides glass with nano silver on the surface, which comprises a glass substrate and a nano silver layer positioned on at least one side of the glass substrate, wherein the nano silver layer comprises silver nano particles uniformly distributed in the surface of the glass substrate, and the silver nano particles are wrapped by the glass and are not in direct contact with the outside.
Further, the glass matrix is common soda-lime-silica glass, aluminosilicate glass or borosilicate glass.
Further, the glass substrate is subjected to wet chemical etching to obtain a surface nano-pore structure, wherein the nano-pore comprises one or more of slit pores, hollowed-out pores and particle stacking pores, and the pore diameter range is 2-100 nm.
The second aspect of the present invention provides a method for preparing glass having nano silver on a surface thereof, for preparing the glass having nano silver on a surface thereof, comprising the steps of:
step one, carrying out wet chemical etching on a glass substrate to obtain glass with nano holes on the surface;
immersing the glass with the nano holes on the surface into a silver nitrate solution, taking out and drying the glass to obtain glass with the surface holes filled with silver nitrate;
and thirdly, carrying out heat treatment on the glass with the silver nitrate filled in the surface holes to obtain the glass with the nano silver on the surface.
Further, the wet chemical etching comprises one or more of acid etching, alkali etching and salt etching.
Further, the methodThe etching liquid used in the wet chemical etching contains 0.005wt.% to 1.0wt.% of HFand H 2 SO 4 0.01wt.％～0.8wt.％、HNO 3 0.01wt.％～0.8wt.％、HCl0.01wt.％～1.0wt.％、H 3 PO 4 0.01wt.％～0.5wt.％、H 2 SiO 3 0.01wt.％～1.0wt.％、Na 2 SiO 3 0.0001wt.％～0.01wt.％，LiOH0.001wt.％～1.0wt.％、NaOH0.001wt.％～1.0wt.％、KOH0.001wt.％～1.0wt.％、NH 3 .H 2 O0.001wt.％～1.0wt.％，Na 3 PO 4 0.001wt.％～0.1wt.％、Na 2 HPO 4 0.001wt.％～0.1wt.％、NaH 2 PO 4 0.001wt.％～0.1wt.％、NaCl0.0001wt.％～0.01wt.％、MgCl 2 0.0001wt.％～0.01wt.％、AlCl 3 0.0001wt.% to 0.01wt.% of one or more.
Further, the wet chemical etching temperature is 20-100 ℃, the etching time is 2-48 h, and the etching is performed at normal pressure.
Further, the acid etching temperature is 20-80 ℃ and the time is 0.5-24 hours; the alkali etching temperature is 40-100 ℃ and the time is 2-48 hours; the salt etching temperature is 30-100 ℃ and the time is 2-48 hours.
Further, the heat treatment comprises one or more of glass tempering treatment, strengthening treatment and annealing treatment, and the heat treatment temperature is 600-650 ℃.
Further, the concentration of the silver nitrate solution is 0.1 to 1 mol.L -1 。
Compared with the prior art, the invention has the following technical effects:
according to the invention, the nano holes on the surface of the glass are obtained by wet chemical etching, silver nitrate is introduced into the nano holes, then nano silver generated by in-situ reaction is obtained by heat treatment, the nano scale of silver particles is ensured by the domain limiting effect of the nano holes, and the nano silver particles are wrapped on the surface of the glass in the collapse process of the nano holes, so that the problem of oxidation failure of the nano silver is solved, and the glass with long-acting function is obtained. Meanwhile, silver nitrate is introduced into the nano holes in a normal pressure impregnation mode, the process is simple, the waste of noble metal silver is greatly reduced, and low-cost manufacture is realized.
Drawings
Fig. 1 is an absorption spectrum of the nano silver glass having a surface of example 1.
Fig. 2 is a transmission and reflection spectrum of the glass having nano silver on the surface of example 1.
FIG. 3 shows XPS high-resolution spectrum of example 2 with nano silver glass on the surface.
FIG. 4 shows the cross-sectional morphology and EDS spectrum analysis results of the glass with nano silver on the surface of example 2.
Detailed Description
The invention provides glass with nano silver on the surface, which comprises a glass substrate and a nano silver layer positioned on at least one side of the glass substrate, wherein the nano silver layer comprises silver nano particles uniformly distributed in the surface of the glass substrate, and the silver nano particles are wrapped by the glass and are not in direct contact with the outside.
The glass with the nano silver on the surface has obvious absorption effect in blue-violet light and ultraviolet band, can be used in the fields of blue-light prevention lenses, displays and the like, and meanwhile, the nano silver distributed in the surface slowly releases silver ions and has antibacterial performance.
In the invention, the surface nano-pore structure is formed by etching on the surface of the glass substrate by acid etching and/or alkali etching and/or salt etching, and can be etched on one side or both sides of the glass, the nano-pore structure is in an irregular pore shape and comprises one or more of slit holes, hollow holes and particle stacking holes, and the pore size is 2-100 nm. The sizes of the nano silver brought by different sizes of the holes are different, and a better size range can be obtained by controlling experimental conditions.
In the invention, the surface nano silver glass is prepared by immersing glass with nano holes after surface etching into a silver nitrate aqueous solution with a certain concentration, wherein the concentration of the solution is related to the size of the finally obtained silver nano particles.
The invention also provides a preparation method of the glass with the nano silver on the surface, which comprises the following steps:
pretreatment, namely cleaning the surface of the glass matrix to remove floating dust and greasy dirt on the surface of the glass matrix;
step one, carrying out wet chemical etching on a glass substrate to obtain glass with nano holes on the surface;
immersing the glass with the nano holes on the surface into a silver nitrate solution, taking out and drying the glass to obtain glass with the surface holes filled with silver nitrate;
and thirdly, carrying out heat treatment on the glass with the silver nitrate filled in the surface holes to obtain the glass with the nano silver on the surface.
In the invention, the nano silver layer on the surface is obtained by immersing the glass with nano holes on the surface into silver nitrate solution, and immersing the silver nitrate solution into the nano holes; the size of the nano-hole controls the volume of the silver nitrate solution and finally influences the size of the silver nano-particle; in the process of etching the nano holes, a large amount of hydroxyl groups are exposed on the surface of the glass, so that the surface of the glass presents a super-hydrophilic state, and after the glass contacts with the silver nitrate solution, the silver nitrate solution is easy to dip into the nano holes.
In the invention, the heat treatment temperature is 600-650 ℃, and the heat treatment mode comprises one or more of glass tempering treatment, strengthening treatment and annealing treatment; in the heat treatment process, optionally, the temperature is raised to 440 ℃ firstly, silver nitrate is decomposed to generate elemental silver, the size of the elemental silver is controlled to be in a nanoscale due to the limiting effect of the nanopores, then the temperature is raised to 600-650 ℃ to reach the softening temperature of the glass, the nanopores collapse in the process, and the elemental silver is wrapped in the holes to obtain the glass with the surface self-encapsulated with the elemental silver.
The invention is further described below with reference to the drawings and specific examples, which are not intended to be limiting. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. In the examples described below, the reagents, glass raw materials and instruments used are commercially available unless otherwise specified.
Example 1
Float process ultra-white Na with thickness of 1.1mm 2 O-CaO-SiO 2 Etching the glass system with acid etching solution at 70deg.C for 16 hr, taking out the clear water and flushingWashing to obtain nano-pore structure glass; the acid etching liquid comprises HF0.04wt.% and H 2 SO 4 0.05wt.％、HNO 3 0.05wt.％、HCl0.05wt.％、H 2 SiO 3 0.5wt.% with the balance being deionized water.
Further drying the glass with nano holes on the surface, immersing the glass into 0.1 mol.L -1 And (3) carrying out ultrasonic treatment for 20 minutes, taking out and drying.
And (3) annealing the glass, wherein the final treatment temperature is 640 ℃, the glass is kept at the temperature for 5 minutes and then is cooled along with a furnace, the glass with nano silver on the surface is yellowish, the spectral transmittance and the absorptivity are shown in the attached drawings 1 and 2, and a strong absorption peak appears near a 405nm wave band, which indicates that the nano silver is formed on the surface of the glass and has smaller particle size.
Example 2
Etching 0.9mm thick float ultrawhite aluminosilicate glass with alkali etching solution at 100deg.C for 40 hr, and cleaning with clear water to obtain nano-pore structure glass; the alkaline etching solution comprises LiOH0.05wt.%, naOH0.05wt.%, KOH0.05wt.% and NH 3 .H 2 0.05wt.% o, the balance deionized water.
Further drying the glass with nano holes on the surface, immersing the glass into 0.5 mol.L -1 And (3) carrying out ultrasonic treatment for 20 minutes, taking out and drying.
The glass is annealed, the final treatment temperature is 620 ℃, the temperature is kept for 8 minutes, then the glass is cooled along with a furnace, the glass with nano silver on the surface is obtained, the silver element distribution from the surface to the inside is increased and then reduced through scanning electron microscopy and EDS (electronic data storage) energy spectrum analysis, wherein the Ag element contained in the glass surface is shown in the figure 3 by measuring XPS high-resolution spectrum at the position about 400nm below the glass surface by ion beam etching.
Example 3
Etching float borosilicate glass with the thickness of 2mm for 30 hours at the temperature of 90 ℃ by using salt etching liquid, and taking out clear water to clean to obtain nano-pore structure glass; the salt etching liquid comprises Na 3 PO 4 0.001wt.％、Na 2 HPO 4 0.1wt.％、NaH 2 PO 4 0.1wt.％、NaCl0.01wt.％、MgCl 2 0.001wt.％、AlCl 3 0.05wt.% with the balance being deionized water.
Further drying the glass with the nano holes on the surface, immersing the glass into 1 mol.L -1 And (3) carrying out ultrasonic treatment for 30 minutes, taking out and drying.
And (3) annealing the glass, wherein the final treatment temperature is 650 ℃, and after the heat preservation is carried out for 3 minutes, cooling along with a furnace to obtain the glass with nano silver on the surface.
Example 4
Float process ultra-white Na with thickness of 1.1mm 2 O-CaO-SiO 2 Etching the glass system by an alkali etching solution at 90 ℃ for 48 hours, taking out clear water, and washing cleanly to obtain nano-pore structure glass; the alkaline etching solution comprises NaOH0.01wt.% and KOH0.01wt.% and NH 3 .H 2 0.05wt.% o, the balance deionized water.
Further drying the glass with nano holes on the surface, immersing the glass into 0.2 mol.L -1 And (3) carrying out ultrasonic treatment for 10 minutes, taking out and drying.
And (3) strengthening the glass, wherein the final treatment temperature is 630 ℃, preserving the heat for 5 minutes, and taking out for air cooling to obtain the glass with nano silver on the surface.
Example 5
Float process ultra-white Na with thickness of 2mm 2 O-CaO-SiO 2 Etching the glass system by using a salt etching solution at 90 ℃ for 40 hours, and taking out clean water to clean the glass system to obtain nano-pore structure glass; the salt etching liquid comprises Na 3 PO 4 0.05wt.％、Na 2 HPO 4 0.01wt.％、NaH 2 PO 4 0.01wt.％、MgCl 2 0.1wt.％、AlCl 3 0.05wt.% with the balance being deionized water.
Further drying the glass with nano holes on the surface, immersing the glass into 0.5 mol.L -1 And (3) carrying out ultrasonic treatment for 15 minutes, taking out and drying.
And (3) tempering the glass, wherein the final treatment temperature is 650 ℃, and after the heat preservation is carried out for 3 minutes, quenching tempering is carried out by compressed air, so that the glass with nano silver on the surface is obtained.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings and illustrations of the present invention, and that such variations are intended to be included within the scope of the present invention.

Claims (9)

1. The glass with the nano silver on the surface is characterized by comprising a glass substrate and a nano silver layer positioned on at least one side of the glass substrate, wherein the nano silver layer comprises silver nano particles uniformly distributed in the surface of the glass substrate, and the silver nano particles are wrapped by the glass and are not in direct contact with the outside.
2. The glass with nano-silver on the surface according to claim 1, wherein the glass substrate is common soda-lime-silica glass, aluminosilicate glass or borosilicate glass.
3. The glass with nano silver on the surface according to claim 1, wherein the glass substrate is etched by wet chemical method to obtain a surface nano pore structure, the nano pore comprises one or more of slit pores, hollow pores and particle stacking pores, and the pore diameter ranges from 2nm to 100nm.
4. The preparation method of the glass with the nano silver on the surface is characterized by comprising the following steps of:
step one, carrying out wet chemical etching on a glass substrate to obtain glass with nano holes on the surface;
immersing the glass with the nano holes on the surface into a silver nitrate solution, taking out and drying the glass to obtain glass with the surface holes filled with silver nitrate;
and thirdly, carrying out heat treatment on the glass with the silver nitrate filled in the surface holes to obtain the glass with the nano silver on the surface.
5. The method of claim 4, wherein the wet chemical etching comprises one or more of acid etching, alkali etching, and salt etching.
6. The method according to claim 5, wherein the etching solution used for wet chemical etching contains 0.005wt.% to 1.0wt.% of HFH 2 SO 4 0.01wt.％～0.8wt.％、HNO 3 0.01wt.％～0.8wt.％、HCl0.01wt.％～1.0wt.％、H 3 PO 4 0.01wt.％～0.5wt.％、H 2 SiO 3 0.01wt.％～1.0wt.％、Na 2 SiO 3 0.0001wt.％～0.01wt.％，LiOH0.001wt.％～1.0wt.％、NaOH0.001wt.％～1.0wt.％、KOH0.001wt.％～1.0wt.％、NH 3 .H 2 O0.001wt.％～1.0wt.％，Na 3 PO 4 0.001wt.％～0.1wt.％、Na 2 HPO 4 0.001wt.％～0.1wt.％、NaH 2 PO 4 0.001wt.％～0.1wt.％、NaCl0.0001wt.％～0.01wt.％、MgCl 2 0.0001wt.％～0.01wt.％、AlCl 3 0.0001wt.% to 0.01wt.% of one or more.
7. The method according to claim 4, wherein the wet chemical etching temperature is 20-100 ℃, the etching time is 2-48 h, and the etching is performed at normal pressure.
8. The method according to claim 4, wherein the heat treatment comprises one or more of tempering, strengthening and annealing, and the heat treatment temperature is 600 to 650 ℃.
9. The method according to claim 4, wherein the concentration of the silver nitrate solution is 0.1 to 1 mol.L -1 。
CN202211625648.9A 2022-12-16 2022-12-16 Glass with nano silver on surface and preparation method thereof Pending CN116040959A (en)

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CN202211625648.9A CN116040959A (en) 2022-12-16 2022-12-16 Glass with nano silver on surface and preparation method thereof

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Application Number Priority Date Filing Date Title
CN202211625648.9A CN116040959A (en) 2022-12-16 2022-12-16 Glass with nano silver on surface and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116040959A true CN116040959A (en) 2023-05-02

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Country Status (1)

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