CN116177902A - Preparation method of flexible glass - Google Patents
Preparation method of flexible glass Download PDFInfo
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- CN116177902A CN116177902A CN202310459799.XA CN202310459799A CN116177902A CN 116177902 A CN116177902 A CN 116177902A CN 202310459799 A CN202310459799 A CN 202310459799A CN 116177902 A CN116177902 A CN 116177902A
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- glass
- flexible glass
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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
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- 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
- C03C21/008—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in solid phase, e.g. using pastes, powders
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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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
-
- 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
-
- 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
- C03C2218/119—Deposition methods from solutions or suspensions by printing
Abstract
The invention relates to the technical field of glass surface treatment, and provides a preparation method of flexible glass, wherein after the glass is subjected to surface treatment by using a flexible treating agent, the temperature is raised to 320-370 ℃ to obtain the flexible glass; the flexible treatment agent comprises KOH, inorganic salt, solvent and binder. By the technical scheme, the problems that the production method of the flexible glass in the prior art is complex in process, incapable of locally processing, good in flexibility and high in strength and difficult to coexist are solved.
Description
Technical Field
The invention relates to the technical field of glass surface treatment, in particular to a preparation method of flexible glass.
Background
With rapid development of aviation and aerospace science and technology, the energy requirements of spacecrafts are increasing, and it is well known that energy required by spacecrafts such as spacecrafts, satellites and space stations in the space operation process is mainly provided by solar cell sailboards, and after entering space, solar cells arranged on the sailboards can provide electric energy for the operation of the spacecrafts along with the unfolding of the sailboards. Therefore, the solar cell sailboard is an indispensable component for maintaining normal operation of spacecrafts such as high-power communication satellites, space stations and the like.
The flexible solar cell sailboard not only can enable the primary energy system of satellites, space stations, lunar space and fire space vehicles to be better adapted to space environment, but also can reduce the influence on the solar cells, so that the adoption of the flexible solar cell sailboard is a future development direction. The flexible solar cell sailboard has the smallest size and the lowest weight, so the solar cell substrates and cover plates in satellites, spaceships and spacecraft are all made of ultrathin glass, and the purposes of saving energy consumption in launching and running, reducing the take-off weight and the launching cost when the spacecraft launches, enabling the flexible solar cell sailboard to perform functions of folding, bending and the like in space and increasing the variability of the spacecraft are achieved.
In recent years, the flexibility of glass materials is mainly increased by preparing flexible glass through adjusting a composition formula of the glass, but the whole composition of the glass needs to be redesigned when the glass formula is adjusted, so that the glass flexibility requirement, the irradiation resistance performance requirement and other physical and chemical performance requirements of the glass are met, the adjustment space is very limited, the requirements of good flexibility and high strength are difficult to achieve, the whole glass can be changed into the flexibility, the local part of the glass cannot be changed into the flexibility, and the application effect cannot meet the requirements of future spacecrafts.
Therefore, there is a need to provide a glass production method which is simple in process, can be locally processed, and has good flexibility and high strength.
Disclosure of Invention
The invention provides a preparation method of flexible glass, which solves the problems that the production method of flexible glass in the related art is complex in process, incapable of being treated locally, good in flexibility and high in strength and difficult to coexist.
The technical scheme of the invention is as follows:
the preparation method of the flexible glass comprises the steps of carrying out surface treatment on the glass by using a flexible treating agent, and then heating to 320-370 ℃ to obtain the flexible glass;
the flexible treatment agent comprises KOH, inorganic salt, solvent and binder.
As a further technical scheme, the flexible treating agent comprises the following components in parts by mass: 0.5-6 parts of KOH, 35-120 parts of inorganic salt, 4-8 parts of solvent and 1.5-4 parts of binder.
As a further technical scheme, the inorganic salt comprises potassium salt and metal chloride;
the metal chloride packageInclude SnCl 4 、ZnCl 2 、ZrCl 4 One or more of the following;
the potassium salt comprises KCl and K 2 SO 4 、K 3 PO 4 、KH 2 PO 4 、KClO 4 、K 2 H 2 Sb 2 O 7 ·4H 2 One or more of O.
The flexible treating agent of the invention has different K content + 、Zn 2+ 、Zr 4+ 、Sn 4+ After the surface treatment of the glass, forming a film on the surface of the glass, wherein K is in the film + 、Zn 2+ 、Zr 4+ 、Sn 4+ With Na in glass + Ion-exchanged to make Na on the surface of glass + Into the film layer, K in the film layer + 、Zn 2+ 、Zr 4+ 、Sn 4+ Enters the surface of the glass, and ions on the surface of the glass change after the exchange, so that the flexibility and the strength of the glass are improved.
As a further technical scheme, the metal chloride comprises the following components in parts by weight: snCl 4 15-35 parts of ZnCl 2 3-8 parts of ZrCl 4 2-4 parts of a lubricant;
the potassium salt comprises the following components in parts by mass: KCl 5-12 parts, K 2 SO 4 8-16 parts, K 3 PO 4 3-7 parts of KH 2 PO 4 15-30 parts of KClO 4 0.5-4 parts, K 2 H 2 Sb 2 O 7 ·4H 2 0.5-2 parts of O.
As a further technical scheme, the solvent comprises one or more of absolute ethyl alcohol, methanol, isopropanol and n-butanol;
the adhesive comprises one or more of dextrin, cyanoacrylate and polyimide adhesive.
As a further technical solution, the glass includes: the oxide composition is SiO 2 72%、Al 2 O 3 1.0%、MgO 4.5%、CaO 8.5%、K 2 O+Na 2 O14.0% sodium-calcium-silicon glass, oxide composition of Li 2 O+Na 2 O+K 2 O 11%、CaO+MgO 8.0%、Al 2 O 3 20%、SiO 2 61% of high alumina glass and oxide composition of SiO 2 65%、Al 2 O 3 7.0%、MgO 2.0%、CaO2.0%、K 2 O+Na 2 O 14.0%、CeO 2 5.0%、B 2 O 3 5.0% of one of the special glasses.
As a further technical scheme, the surface treatment adopts a screen printing process.
The screen printing process can be used for carrying out surface treatment on glass by adopting different materials for different positions.
As a further technical scheme, the screen printing temperature is 230-270 ℃ and the screen printing time is 25-50 s.
As a further technical scheme, the thickness of the flexible treating agent on the surface of the glass after screen printing is 5-20 mu m.
As a further technical scheme, the temperature is kept for 20-60 s after the temperature is raised.
The working principle and the beneficial effects of the invention are as follows:
the invention provides a preparation method of flexible glass, which is characterized in that KOH, inorganic salt, solvent and binder are used as a flexible treating agent to treat the surface of the glass to obtain the flexible glass.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The oxide composition of the soda lime silica glass of examples 1 to 4 was SiO 2 72%、Al 2 O 3 1.0%、MgO 4.5%、CaO 8.5%、K 2 O+Na 2 O14.0%, available from Shahehong Kong, incA driver;
the oxide composition of the high alumina glass of example 5 is Li 2 O+Na 2 O+K 2 O 11%、CaO+MgO 8.0%、Al 2 O 3 20%、SiO 2 61%, purchased from angyang sunburn electric technologies limited;
the oxide composition of the specialty glass of example 6 was SiO 2 71.9%、Al 2 O 3 0.5%、MgO 3.2%、BaO 0.1%、CaO 8.0%、K 2 O 0.3%、Na 2 O 10%、CeO 2 0.3%、TiO 2 0.7%、Sb 2 O 3 0.5%、B 2 O 3 4.0%、Li 2 O0.5% is self-produced by the company, and the preparation method is recorded in the invention patent of the patent number CN 103833223B.
The method for referencing GB/T37900-2019 to the sodium-calcium-silicon glass, the high-alumina glass and the special glass is respectively tested for Vickers hardness; flexural strength testing was performed with reference to the method of GB 4741-1999; the compressive strength was tested with reference to the method of GB 4740-1999; the results are recorded in table 1.
TABLE 1 Performance parameters of soda lime silica glass, high alumina glass and specialty glass
Example 1
S1, KOH 3.1 parts, snCl 4 After 35 parts of the components are uniformly mixed, 6 parts of absolute ethyl alcohol is added, the components are uniformly mixed again, and 2.6 parts of dextrin is added, so that the flexible treating agent is obtained;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the soda-lime-silica glass respectively by adopting a screen printing mode, and then treating the glass at 350 ℃ for 50S to obtain the flexible glass, wherein the screen printing temperature is 258 ℃, the printing time is 40S, and the thickness of a printing film layer is 13 mu m.
Example 2
S1, KOH 3.1 parts, snCl 4 35 parts, KH 2 PO 4 Adding 6 parts of absolute ethyl alcohol after uniformly mixing 30 parts, uniformly mixing again, adding 2.6 parts of dextrin, and uniformly mixing to obtain a flexible treating agent;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the soda-lime-silica glass respectively by adopting a screen printing mode, and then treating the glass at 350 ℃ for 50S to obtain the flexible glass, wherein the screen printing temperature is 258 ℃, the printing time is 40S, and the thickness of a printing film layer is 13 mu m.
Example 3
S1, KOH 3.1 parts, snCl 4 32.9 parts of ZnCl 2 5 parts of ZrCl 4 3 parts of KCl 8 parts, K 2 SO 4 12 parts, K 3 PO 4 4.5 parts, KH 2 PO 4 Adding 6 parts of absolute ethyl alcohol after uniformly mixing 28 parts, uniformly mixing again, and adding 2.6 parts of dextrin and uniformly mixing to obtain a flexible treating agent;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the soda-lime-silica glass respectively by adopting a screen printing mode, and then treating the glass at 350 ℃ for 50S to obtain the flexible glass, wherein the screen printing temperature is 258 ℃, the printing time is 40S, and the thickness of a printing film layer is 13 mu m.
Example 4
S1, KOH 3.1 parts, snCl 4 32.9 parts of ZnCl 2 5 parts of ZrCl 4 3 parts of KCl 8 parts, K 2 SO 4 12 parts, K 3 PO 4 4.5 parts, KH 2 PO 4 28 parts, K 2 H 2 Sb 2 O 7 ·4H 2 Mixing evenly O3.5 parts, adding 6 parts of absolute ethyl alcohol, mixing evenly again, adding 2.6 parts of dextrin, and mixing evenly to obtain the flexible treating agent;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the soda-lime-silica glass respectively by adopting a screen printing mode, and then treating the glass at 350 ℃ for 50S to obtain the flexible glass, wherein the screen printing temperature is 258 ℃, the printing time is 40S, and the thickness of a printing film layer is 13 mu m.
Example 5
S1, KOH 3.1 parts, snCl 4 32.9 parts of ZnCl 2 5 parts of ZrCl 4 3 parts of KCl 8 parts, K 2 SO 4 12 parts, K 3 PO 4 4.5 parts, KH 2 PO 4 28 parts of KClO 4 3.5 parts of the mixture are evenly mixed, 6 parts of absolute ethyl alcohol is added, the mixture is evenly mixed again, and 2.6 parts of dextrin is addedAfter being uniformly mixed, the flexible treating agent is obtained;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the soda-lime-silica glass respectively by adopting a screen printing mode, and then treating the glass at 350 ℃ for 50S to obtain the flexible glass, wherein the screen printing temperature is 258 ℃, the printing time is 40S, and the thickness of a printing film layer is 13 mu m.
Example 6
S1, KOH 3.1 parts, snCl 4 32.9 parts of ZnCl 2 5 parts of ZrCl 4 3 parts of KCl 8 parts, K 2 SO 4 12 parts, K 3 PO 4 4.5 parts, KH 2 PO 4 28 parts of KClO 4 2.2 parts, K 2 H 2 Sb 2 O 7 ·4H 2 Mixing uniformly 1.3 parts of O, adding 6 parts of absolute ethyl alcohol, mixing uniformly again, adding 2.6 parts of dextrin, and mixing uniformly to obtain a flexible treating agent;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the soda-lime-silica glass respectively by adopting a screen printing mode, and then treating the glass at 350 ℃ for 50S to obtain the flexible glass, wherein the screen printing temperature is 258 ℃, the printing time is 40S, and the thickness of a printing film layer is 13 mu m.
Example 7
S1, KOH 0.5 part and SnCl 4 15 parts of ZnCl 2 3 parts of ZrCl 4 2 parts of KCl 5 parts, K 2 SO 4 8 parts, K 3 PO 4 3 parts, KH 2 PO 4 15 parts of KClO 4 0.5 part, K 2 H 2 Sb 2 O 7 ·4H 2 Mixing 0.5 part of O uniformly, adding 4 parts of methanol, mixing uniformly again, adding 1.5 parts of polyimide adhesive, and mixing uniformly to obtain a flexible treating agent;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the high-alumina glass respectively in a screen printing mode, and then treating the high-alumina glass at 320 ℃ for 60 seconds to obtain the flexible glass, wherein the screen printing temperature is 230 ℃, the printing time is 50 seconds, and the thickness of a printing film layer is 5 mu m.
Example 8
S1, KOH 6 parts and SnCl 4 35 parts of ZnCl 2 8 parts of ZrCl 4 4 parts of KCl 12 parts, K 2 SO 4 16 parts, K 3 PO 4 7 parts, KH 2 PO 4 30 parts of KClO 4 4 parts, K 2 H 2 Sb 2 O 7 ·4H 2 After mixing evenly O2 parts, adding 8 parts of n-butanol, mixing evenly again, adding 4 parts of cyanoacrylate, and mixing evenly to obtain the flexible treating agent;
s2, printing the obtained flexible treating agent on the upper surface and the lower surface of the special glass respectively in a screen printing mode, and then treating the special glass at 370 ℃ for 20S to obtain the flexible glass, wherein the screen printing temperature is 270 ℃, the printing time is 25S, and the thickness of a printing film layer is 20 mu m.
Performance test:
respectively testing the Vickers hardness of the flexible glass obtained in the examples 1-8 by referring to the method of GB/T37900-2019; testing the surface compressive stress and the depth of a stress layer by using an FSM-6000 surface stress meter; flexural strength testing was performed with reference to the method of GB/T4741-1999; the compressive strength was tested with reference to the method of GB/T4740-1999; the critical bending radius of 0.1mm thick flexible glass was tested by reference to the method of T/CSTM 00409-2021; the results are recorded in table 2.
TABLE 2 Performance parameters of Flexible glass
As can be seen from tables 1 and 2, the present invention uses KOH, inorganic salt, solvent and binder as a flexibility treating agent, and improves the vickers hardness, bending strength and compressive strength of glass while improving the flexibility of glass after the glass is surface treated.
Examples 3 to 5 compared with example 6, no KClO was added in example 3 4 And K 2 H 2 Sb 2 O 7 ·4H 2 O, example 4 where K was added 2 H 2 Sb 2 O 7 ·4H 2 O, example 5 wherein KClO was added 4 KClO is added in example 6 4 And K 2 H 2 Sb 2 O 7 ·4H 2 O, vickers glass provided in examples 4 to 5The hardness, flexural strength and compressive strength are higher than those of example 3. Description of the addition of K to Flexible treatment 2 H 2 Sb 2 O 7 ·4H 2 O or KClO 4 The Vickers hardness, the bending strength and the compressive strength of the glass can be improved. The glass provided in example 6 has higher vickers hardness, flexural strength and compressive strength than examples 3-5. Description of the addition of K to Flexible treatment 2 H 2 Sb 2 O 7 ·4H 2 O and KClO 4 Than adding single K 2 H 2 Sb 2 O 7 ·4H 2 O or KClO 4 The obtained glass has good Vickers hardness, bending strength and compressive strength.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The preparation method of the flexible glass is characterized in that after the surface treatment of the glass is carried out by using a flexible treating agent, the temperature is raised to 320-370 ℃ to obtain the flexible glass;
the flexible treatment agent comprises KOH, inorganic salt, solvent and binder.
2. The preparation method of the flexible glass according to claim 1, wherein the flexible treating agent comprises the following components in parts by mass: 0.5-6 parts of KOH, 35-120 parts of inorganic salt, 4-8 parts of solvent and 1.5-4 parts of binder.
3. The method of producing a flexible glass according to claim 2, wherein the inorganic salt comprises a potassium salt and a metal chloride;
the metal chloride comprises SnCl 4 、ZnCl 2 、ZrCl 4 One or more of the following;
the potassium salt comprises KCl and K 2 SO 4 、K 3 PO 4 、KH 2 PO 4 、KClO 4 、K 2 H 2 Sb 2 O 7 ·4H 2 One or more of O.
4. A method of producing a flexible glass according to claim 3, wherein the metal chloride comprises the following components in parts by mass: snCl 4 15-35 parts of ZnCl 2 3-8 parts of ZrCl 4 2-4 parts of a lubricant;
the potassium salt comprises the following components in parts by mass: KCl 5-12 parts, K 2 SO 4 8-16 parts, K 3 PO 4 3-7 parts of KH 2 PO 4 15-30 parts of KClO 4 0.5-4 parts, K 2 H 2 Sb 2 O 7 ·4H 2 0.5-2 parts of O.
5. The method for producing a flexible glass according to claim 4, wherein the solvent comprises one or more of absolute ethanol, methanol, isopropanol, and n-butanol;
the adhesive comprises one or more of dextrin, cyanoacrylate and polyimide adhesive.
6. The method of claim 1, wherein the surface treatment is performed by a screen printing process.
7. The method for preparing flexible glass according to claim 6, wherein the screen printing temperature is 230-270 ℃ and the time is 25-50 s.
8. The method for preparing flexible glass according to claim 6, wherein the thickness of the flexible treating agent on the surface of the glass after screen printing is 5-20 μm.
9. The method for preparing the flexible glass according to any one of claims 1 to 8, wherein the temperature is maintained for 20 to 60 seconds after the temperature is raised.
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