CN107056046B - Toughened sheet glass and preparation method thereof - Google Patents

Toughened sheet glass and preparation method thereof Download PDF

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Publication number
CN107056046B
CN107056046B CN201710381330.3A CN201710381330A CN107056046B CN 107056046 B CN107056046 B CN 107056046B CN 201710381330 A CN201710381330 A CN 201710381330A CN 107056046 B CN107056046 B CN 107056046B
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glass
mixture
sheet
temperature
carbonate
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CN107056046A (en
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杨国洪
刘仲军
王答成
郭萍莉
王志强
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Caihong Group Shaoyang Special Glass Co ltd
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Rainbow Group (shaoyang) Special Glass Co Ltd
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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/02—Tempering or quenching glass products using liquid
    • C03B27/03—Tempering or quenching glass products using liquid the liquid being a molten metal or a molten salt
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the glass
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • 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
    • 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 relates to toughened sheet glass and a preparation method thereof, wherein the method comprises the following steps of 1, accurately weighing and mixing the mixture according to the mass fraction of the mixture to form a mixture; step 2, adding cullet with the mass fraction of 30-55% of the mixture, and uniformly mixing to obtain a batch mixture; step 3, melting the batch to prepare a formed glass sheet; step 4, annealing the formed glass sheet at the temperature of 700-750 ℃ for 30-60 min, and cooling to 450 ℃ to obtain sheet glass; step 5, weighing the toughened raw materials according to mass fraction for later use; step 6, preserving the temperature of the toughened raw material at 410-450 ℃ for 1-2 h to form uniformly mixed molten salt; step 7, putting the sheet glass at 450 ℃ into the uniformly mixed molten salt, preserving the heat at 410-450 ℃ for 1-6 h, and taking out; and 8, drying the sheet glass taken out of the molten salt, naturally cooling to room temperature, cleaning and drying to obtain the toughened sheet glass.

Description

Toughened sheet glass and preparation method thereof
Technical Field
The invention relates to a preparation method of sheet glass, in particular to tempered sheet glass and a preparation method thereof.
Background
Cover glasses are commonly used in electronic and mobile electronic devices, such as personal data assistants, mobile or cellular phones, watches, laptops, notebooks, digital cameras, and PDAs, or as substrate glasses for touch screens, televisions. In recent years, with the rapid development of flat panel Display technology, the conventional CRT (Cathode Ray Tube) Display product has been gradually replaced, and TFT-LCD (Thin Film Transistor Liquid Crystal Display) is the mainstream flat panel Display product in the market at present, wherein TFT-LCD substrate glass (hereinafter referred to as substrate glass) is an important component of TFT-LCD and has become one of the key raw materials that restrict the development of TFT-LCD. For these applications, frequent contact with the cover glass or substrate glass is required in use and production, and the glass may cause problems such as surface damage, scratching, and deformation due to the touch of the user. These defects will affect the proper operation of the device. Due to the frequent contact, these thin glass sheets must have high strength and be scratch-resistant and deformation-resistant.
The strength of glass is essentially determined by the system and composition of the glass. Therefore, glass with higher strength, higher hardness, low brittleness, scratch resistance and deformation resistance is sought, and the elastic modulus, hardness and brittleness of the glass can be improved by adjusting the components and the composition of the glass starting from the glass system and components, so as to obtain glass with high impact resistance, high scratch resistance and high deformation resistance; in order to improve the actual strength of the glass, a compressive stress layer is generally generated on the surface of the glass by a tempering method so as to improve the surface strength of the glass.
At present, there are a physical strengthening method and a chemical strengthening method for forming a compressive stress layer on a glass surface, in which a glass surface heated to a temperature near a softening point is rapidly cooled by air cooling or the like to rapidly contract the glass surface to generate a compressive stress, and a tensile stress is formed in a glass intermediate layer since the glass intermediate layer is cooled slowly and does not contract in time, thereby obtaining a high strength of the glass. However, since the protective glass has a small thickness and a temperature difference is not easily formed between the surface and the inside thereof, it is difficult to form a compressive stress layer on the surface of the glass by a physical strengthening method, and the desired high strength performance cannot be obtained.
The chemical strengthening method is to immerse the heated glass in a molten salt bath to change the chemical composition of the glass surface by ion exchange between the glass and the molten salt, so that the glass surface is strengthenedForming a compressive stress layer to achieve the purpose of improving the glass strength. At present, there are two types of ion exchange strengthening methods, the first is a high temperature type treatment process, ions with small radius in the molten salt replace ions with large radius in the glass above the glass transition temperature, a thin layer with smaller thermal expansion coefficient than that of the main glass is formed on the surface of the glass, a compressive stress layer is formed on the surface of the glass when cooling, and the stress depends on the difference between the thermal expansion coefficients of the glass and the molten salt; the second is a low-temperature treatment process, mainly treating below the glass transition temperature to use ions (K) with large radius in molten salt+) Replacement of small radius ions (Na) in glass+) The surface of the glass is pressed to generate a compressive stress layer, and the stress magnitude of the compressive stress layer depends on the volume effect of the exchanged ions.
China is a large country of production and consumption of household appliances. At present, China has entered the peak period of the updating and upgrading of televisions and computers, and the annual elimination quantity reaches over 600 thousands of television sets. Liquid crystal displays are attracting attention and being used because of their advantages, such as easy colorization, no electromagnetic radiation, long lifetime, and passive display. And the picture color reduction effect is better than that of a CRT; the electromagnetic radiation is very small, the safety and the harmlessness to the human body are realized, and the confidentiality is good; no glare, and no tiredness and dryness of eyes; large amount of display information, etc. Therefore, the replacement of CRT by lcd is the future development trend, and the lcd business is an important place in the business of each display manufacturer. However, the liquid crystal display is updated rapidly, about millions of liquid crystal displays are eliminated every year, and how to correctly, reasonably and efficiently process the waste liquid crystal displays is a problem to be solved at present. The european union directive (WEEE) formally implemented on 1 st 1 of 2008 provides that all electronic devices sold to european union member countries in the future need to have their producers take responsibility for recycling. Including liquid crystal displays.
At present, home and abroad manufacturers disassemble notebook computers, plastic shells, circuit boards, electric wires, heavy metals and the like are completely recycled, but the related liquid crystal display board part has no relevant technical specification, so that all manufacturers adopt an in-factory storage mode and do not adopt a mode aiming at the notebook computersAnd (4) a sexual treatment method. As the price of liquid crystal displays decreases, the conventional CRT market is gradually replaced by liquid crystal displays, and in addition, the number of notebook computers sold increases year by year, so that the number of waste liquid crystal display panels will continue to increase in the future. For notebook computers, the LCD panel accounts for 20-30% of the total weight, and the recycled parts of the LCD panel include glass, circuit board, wires, outer frame, etc. according to the literature data, the recycled parts of the LCD panel are the current problems, and the two glass panels contain liquid crystal material and some films or sealing materials. In particular, in the field of liquid crystal displays, consumers often consider that if a product is damaged during use, the liquid crystal material will overflow, so that the safety of the liquid crystal material is concerned. However, the liquid crystal material used in the liquid crystal display panel has a unit area of only 0.6mg/cm per screen2For example: 15 inches, its content is only 400 mg; further, as described by those skilled in the art, even if the glass is broken, the liquid crystal material on the back surface does not flow out in a large amount due to the surface tension between the glass substrates. Therefore, in terms of safety, a person does not directly touch the liquid crystal material, and even if the person touches the liquid crystal material, the person does not affect the human body. How to separate these substances from the substrate efficiently and rapidly will be a technical key. Meanwhile, the technologies also need to consider factors such as equipment cost, energy consumption, difficulty and easiness in operation, load prevention of later pollution and the like, and the equipment cost, the energy consumption and the simplicity in operation need to be found. In addition, the most important is a treatment technique which does not cause secondary pollution.
In addition, in the current domestic substrate glass production process, a large amount of substrate glass waste residues are generated due to glass defects in the production. Meanwhile, due to the particularity of the substrate glass production process, waste glass produced in a production line cannot be recycled for reproduction, mostly adopts yard stacking, and is not treated by a reasonable and effective method at present.
CN1712376 discloses a method for using cullet in the production of ultrathin glass. The method for using cullet in ultrathin glass production is to use the same batch of raw materialsThe amount of the cullet produced in a batch is 20-30% of the total amount of the glass to be produced. The ultra-thin glass with stable quality is produced. But the adding amount of the cullet is less, the bending strength of the prepared ultrathin glass is 85-100, the Vickers hardness is 580-600, and the strength of the glass is to be improved; CN102408193A discloses a high-aluminum high-alkali silicate glass composition, and the surface strength of the prepared ultra-thin glass after tempering is obviously higher than that of common lithium-calcium-silicon glass, and the ultra-thin glass has excellent mechanical properties. The composition comprises the following components in percentage by mass: SiO 2258.0-62.0% of Al2O3Not less than 16.0 percent, 0.15 to 0.6 percent of CaO, 3.0 to 4.0 percent of MgO and K2O+Na2O content not less than 15%, Sb2O30.3-0.5% and ZrO 0.5-1.0%, wherein Na2O content higher than K2O content, high-strength ultrathin glass with the thickness of 0.3-1.3mm prepared from the O content, and a preparation method and application of the high-strength ultrathin glass. The problems that the glass frit is all oxides, the melting atmosphere is strong reducing atmosphere, and platinum and rhodium in a platinum crucible are possibly seriously corroded; CN101508524 provides a glass suitable for chemical tempering and a preparation method of the chemically tempered glass, and proposes a silica-alumina-lithium oxide glass which is suitable for low temperature type ion exchange process and is easy to melt, the glass is suitable for chemical tempering, and the glass comprises the following components by weight percent: SiO 22：55-60％、B2O3：0.1-2.5％、Al2O3：11-16％、Na2O：14-17％、K2O：1-8％、ZrO2：0-8％、CaO：0-5％、MgO：0-5％、Sb2O3: 0 to 1 percent. According to the scheme, the components are reasonably set, the glass manufacturing difficulty is reduced, the glass melting temperature is obviously reduced, and the reduction of energy consumption and the improvement of the yield of products are facilitated. The obtained glass has surface compressive stress of 610-1100MPa and stress layer depth of 31-80 μm, and the scheme only adopts K2Ion exchange of O, a molten salt containing potassium ions, for chemical tempering may result in incomplete chemical tempering due to insufficient potassium ions.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides tempered sheet glass with large addition of clinker broken glass, low melting temperature, high melting speed, good tempering quality and high efficiency and a preparation method thereof.
The invention is realized by the following technical scheme:
a method for preparing toughened sheet glass comprises the following steps,
step 1, accurately weighing 48.5-52.1% of quartz sand, 1.35-1.55% of boric acid, 1.1-1.5% of borax, 8.5-10.5% of alumina, 16.5-18.1% of lithium carbonate, 3.5-4.5% of lithium nitrate, 3.5-5.0% of sodium carbonate, 1.0-2.5% of tripotassium phosphate, 0.2-0.5% of calcium carbonate, 1.5-3.5% of calcium phosphate, 6.5-7.5% of basic magnesium carbonate, 1.0-1.5% of strontium carbonate, 0.15-0.25% of stannous oxide and 0.001-0.01% of selenium powder according to the mass fraction of the mixture; 0.02-0.05% of cobalt oxide, and mixing to form a mixture;
step 2, adding cleaned cullet with the mass fraction of 30-55% of the mixture, and then mixing all the raw materials until the uniformity is more than 98% to form a uniformly mixed batch;
step 3, melting the uniformly mixed batch materials to prepare a formed glass sheet;
step 4, annealing the formed glass sheet at the temperature of 700-750 ℃ for 30-60 min, and cooling to 450 ℃ according to the cooling speed of 10-30 ℃/min to obtain sheet glass;
step 5, weighing 65-75% of potassium nitrate, 15-25% of tripotassium phosphate, 4.9-10% of potassium sulfate and 0.1-5% of silver nitrate according to mass fractions of toughening raw materials;
step 6, preserving the heat of the weighed tempering raw materials for 1-2 hours at the temperature of 410-450 ℃, and stirring for 3-5 min to form uniformly mixed molten salt;
step 7, putting the sheet glass at 450 ℃ into the uniformly mixed molten salt, preserving the heat at 410-450 ℃ for 1-6 h, and taking out;
and 8, drying the sheet glass taken out of the molten salt at the temperature of 150-250 ℃ for 10-60 min, naturally cooling to room temperature, cleaning and drying to obtain the tempered sheet glass.
Preferably, the granularity of the quartz sand is larger than 150 meshes of standard sieve.
Preferably, the content of ferric oxide in quartz sand, boric acid, borax, alumina, lithium carbonate, lithium nitrate, sodium carbonate, tripotassium phosphate, calcium carbonate, calcium phosphate, basic magnesium carbonate, strontium carbonate, stannous oxide, selenium powder, cobalt oxide, potassium nitrate, potassium sulfate and silver nitrate is less than 50 ppm.
Preferably, the mixture in step 1 is obtained by mixing,
1.1, uniformly mixing weighed aluminum oxide and lithium nitrate to form a mixture A;
1.2, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
1.3 sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 1-2 min to form a mixture.
Preferably, in step 2, the cleaned cullet is obtained by the following steps;
2.1, removing organic elements from the collected various types of sheet glass cullets, and crushing the sheet glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2.2, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
2.3 putting the iron-removed broken glass particles into a cleaning machine for cleaning;
2.4 drying the cleaned cullet at 110-150 ℃ to obtain a clean cullet raw material.
Preferably, in step 3, the specific steps for preparing the shaped glass sheet are as follows,
3.1 adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1570-1600 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1570-1600 ℃ in 10 minutes, and preserving heat for 360-600 min;
3.2, reducing the furnace temperature from 1570-1600 ℃ to 1450-1480 ℃ within 30 minutes, and stirring the molten glass for 1-2 hours by using a stirring paddle, wherein the temperature is kept at 1450-1480 ℃ during the stirring process;
3.2, reducing the temperature of the furnace from 1450-1480 ℃ to 1400 ℃ in 30 minutes, and preserving the temperature for 30 minutes;
3.3 pouring the glass liquid at 1400 ℃ into a mold at 650 ℃ to form a glass sheet with the thickness of 0.5-1 mm.
Preferably, in step 7, the thin glass plate with the temperature of 450 ℃ is placed into a frame made of stainless steel, and the frame and the thin glass plate are placed into the uniformly mixed molten salt for treatment.
Preferably, in the step 8, after naturally cooling to room temperature, ultrasonic cleaning is performed on the surface of the toughened sheet glass for 10-30 min by using ultrasonic waves, and the toughened sheet glass is taken out and dried to obtain the toughened sheet glass.
The invention relates to tempered thin glass prepared by the method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention prepares the toughened thin glass sheet by adding a large amount of waste cullet into the glass batch, and the process has the following outstanding advantages.
(1) The addition amount of clinker broken glass is large, the glass melting clarification temperature is 40-100 ℃ lower than that of other methods, the melting speed is high, the efficiency is high, and the cost is 10-20% lower than that of other methods.
(2) The REDOX of the batch is weak oxidizing atmosphere in the high-temperature melting process, the platinum is less corroded in the production process than other methods, and particularly the corrosion amount of rhodium in the platinum crucible is smaller. The generation of devitrification defects in the glass forming process is avoided. Meanwhile, the requirements of anions and cations in the components can be met through one raw material, volatilization is reduced, and the quality stability of the glass is ensured.
(3) The tempering quality is good, and the efficiency is high. The process of combining the annealing furnace and the toughening furnace is adopted, the toughening time and the heat consumption are shortened, and the toughening process is simplified. Meanwhile, the formula process of mixing several molten salts with different solubilities is adopted, so that the K ion concentration of the molten salts is enhanced, the tempering stress layer is deep, and the glass strength is high.
The toughened thin plate glass prepared by the invention has the advantages of deep stress layer, high toughening strength, good glass flatness and uniformity. The glass melting temperature is low, the energy consumption is low, the energy is saved, the environment is protected, the production efficiency is high, the glass melting furnace is suitable for mass production, and the added value of products is high.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention relates to a preparation method of toughened sheet glass, which comprises the following whole process.
The first step, the treatment of cullet.
1) Firstly, removing organic elements from various collected sheet glass cullets, and crushing the glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2) then, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
3) then, putting the iron-removed broken glass particles into a cleaning machine for cleaning;
4) and finally, drying the cleaned cullet at 110-150 ℃ to obtain the cullet raw material.
And secondly, preparing the sheet glass.
1) Firstly, accurately weighing 48.5-52.1% of quartz sand, 1.35-1.55% of boric acid, 1.1-1.5% of borax, 8.5-10.5% of alumina, 16.5-18.1% of lithium carbonate, 3.5-4.5% of lithium nitrate, 3.5-5.0% of sodium carbonate, 1.0-2.5% of tripotassium phosphate, 0.2-0.5% of calcium carbonate, 1.5-3.5% of calcium phosphate, 6.5-7.5% of basic magnesium carbonate, 1.0-1.5% of strontium carbonate, 0.15-0.25% of stannous oxide and 0.001-0.01% of selenium powder according to the mass fraction of a mixture; 0.02-0.05% of cobalt oxide;
2) then, uniformly mixing the weighed aluminum oxide and lithium nitrate to form a mixture A;
3) then, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
4) then, sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 1-2 min to form a mixture;
5) then, adding the cleaned cullet with the mass fraction of 30-55% of the mixture into a mixer,
6) then, mixing all the raw materials until the uniformity is more than 98 percent to form a uniformly mixed batch;
7) then, adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1570-1600 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1570-1600 ℃ in 10 minutes, preserving heat for 360-600 minutes, then cooling the furnace temperature from 1570-1600 ℃ to 1450-1480 ℃ in 30 minutes, stirring the molten glass for 1-2 hours by adopting a stirring paddle, and keeping the temperature at 1450-1480 ℃ in the stirring process;
8) then, cooling the furnace temperature from 1450-1480 ℃ to 1400 ℃ in 30 minutes, and preserving the temperature for 30 minutes;
9) then pouring the glass liquid into a mold at 650 ℃ to form a glass sheet with the thickness of 0.5-1 mm;
10) then, putting the formed glass sheet sample into an annealing furnace at 700-750 ℃, and preserving heat for 30-60 min;
11) and finally, cooling to 450 ℃ according to a cooling speed of 10-30 ℃/min to obtain the sheet glass.
And thirdly, preparing the toughened sheet glass.
1) Firstly, weighing 65-75% of potassium nitrate, 15-25% of tripotassium phosphate, 4.9-10% of potassium sulfate and 0.1-5% of silver nitrate according to mass percentage of a toughening raw material;
2) then, adding the weighed toughening raw materials into a stainless steel container at the temperature of 410-450 ℃, preserving heat for 1-2 hours at the temperature of 410-450 ℃, and stirring for 3-5 min to form uniformly mixed molten salt;
3) then, quickly putting the 450 ℃ thin glass plate into a frame made of stainless steel;
4) then, putting the frame and the sheet glass into the uniformly mixed molten salt, and preserving heat for 1-6 h at the temperature of 410-450 ℃;
5) then, taking out the frame, putting the frame into a drying oven at the temperature of 150-250 ℃, preserving heat for 10-60 min, taking out and naturally cooling to room temperature;
6) and finally, ultrasonically cleaning the surface of the toughened sheet glass for 10-30 min by using ultrasonic waves, taking out and drying to obtain the toughened sheet glass.
The granularity of the quartz sand is larger than 150 meshes of standard sieve. Wherein, the content of ferric oxide in quartz sand, boric acid, borax, alumina, lithium carbonate, lithium nitrate, sodium carbonate, tripotassium phosphate, calcium carbonate, calcium phosphate, basic magnesium carbonate, strontium carbonate, stannous oxide, selenium powder, cobalt oxide, potassium nitrate, potassium sulfate and silver nitrate is less than 50 ppm.
The specific operation is shown in the following examples.
Example 1:
the first step, the treatment of cullet.
1) Firstly, removing organic elements from various collected sheet glass cullets, and crushing the glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2) then, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
3) then, putting the iron-removed broken glass particles into a cleaning machine for cleaning;
4) finally, the cleaned cullet is dried at 110 ℃ to become the cullet raw material.
And secondly, preparing the sheet glass.
1) Firstly, accurately weighing 48.5% of quartz sand, 1.55% of boric acid, 1.1% of borax, 9.97% of alumina, 16.5% of lithium carbonate, 4.5% of lithium nitrate, 3.5% of sodium carbonate, 2.5% of tripotassium phosphate, 0.2% of calcium carbonate, 3.5% of calcium phosphate, 6.5% of basic magnesium carbonate, 1.5% of strontium carbonate, 0.15% of stannous oxide and 0.01% of selenium powder according to the mass fraction of the mixture; 0.02% cobalt oxide;
2) then, uniformly mixing the weighed aluminum oxide and lithium nitrate to form a mixture A;
3) then, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
4) then, sequentially putting quartz sand, boric acid, borax, sodium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 1min to form a mixture;
5) then, adding the cleaned cullet with the mass fraction of the mixture being 30% into the mixer,
6) then, mixing all the raw materials until the uniformity is more than 98 percent to form a uniformly mixed batch;
7) then, adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1570 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1570 ℃ in 10 minutes, preserving heat for 360 minutes, cooling the furnace temperature from 1570 ℃ to 1450 ℃ in 30 minutes, and stirring the glass liquid for 1 hour by adopting a stirring paddle, wherein the temperature is kept at 1450 ℃ in the stirring process;
8) then, the furnace temperature is reduced from 1450 ℃ to 1400 ℃ in 30 minutes, and the temperature is kept for 30 min;
9) then, pouring the glass liquid into a mold at 650 ℃ to form a glass sheet with the thickness of 0.5 mm;
10) then, putting the formed glass sheet sample into an annealing furnace at 700 ℃, and preserving heat for 30 min;
11) and finally, cooling to 450 ℃ according to the cooling speed of 10 ℃/min to obtain the sheet glass.
And thirdly, preparing the toughened sheet glass.
1) Firstly, weighing 75% of potassium nitrate, 17% of tripotassium phosphate, 4.9% of potassium sulfate and 3.1% of silver nitrate according to the mass fraction of a toughening raw material;
2) then, adding the weighed toughening raw materials into a stainless steel container at 410 ℃, preserving heat for 1h at 410 ℃, and stirring for 3min to form uniformly mixed molten salt;
3) then, quickly putting the 450 ℃ thin glass plate into a frame made of stainless steel;
4) then, putting the frame and the sheet glass into the uniformly mixed molten salt, and preserving heat for 1h at 410 ℃;
5) then, taking out the frame, putting the frame into a drying oven at 150 ℃, preserving heat for 10min, taking out and naturally cooling to room temperature;
6) and finally, ultrasonically cleaning the surface of the toughened sheet glass for 10min by using ultrasonic waves, taking out and drying to obtain the toughened sheet glass.
Testing the surface compressive stress of the toughened thin plate glass to be 820MPa and the depth of a stress layer after the toughened thin plate glass is toughened to be 40 mu m by using a FSM-6000 surface stress instrument; the Vickers hardness of the toughened thin plate glass is tested to be 610kg/mm according to the GB/T4340.1-1999 standard2(ii) a The strain point temperature of the tempered thin glass is measured to be 525 ℃ by using an ANS-800 type instrument according to the ASTMC-336 standard; the linear expansion of the toughened sheet glass was tested by NETZSCH DIL402PC to 35.5 x 10-7/° c; the density of the tempered thin glass sheet as measured by ASTM C-693 Standard was 2.36g/cm3。
Example 2:
the first step, the treatment of cullet.
1) Firstly, removing organic elements from various collected sheet glass cullets, and crushing the glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2) then, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
3) then, putting the iron-removed broken glass particles into a cleaning machine for cleaning;
4) finally, the cleaned cullet is dried at 120 ℃ to become the cullet raw material.
And secondly, preparing the sheet glass.
1) Firstly, accurately weighing 48.7% of quartz sand, 1.52% of boric acid, 1.22% of borax, 10.5% of alumina, 17.1% of lithium carbonate, 4.31% of lithium nitrate, 3.25% of sodium carbonate, 2.25% of tripotassium phosphate, 0.25% of calcium carbonate, 3.1% of calcium phosphate, 6.2% of basic magnesium carbonate, 1.4% of strontium carbonate, 0.17% of stannous oxide and 0.004% of selenium powder according to the mass fraction of the mixture; 0.026% cobalt oxide;
2) then, uniformly mixing the weighed aluminum oxide and lithium nitrate to form a mixture A;
3) then, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
4) then, sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 1min to form a mixture;
5) then, adding clean cullet with the mass fraction of the mixture being 35% into the mixer,
6) then, mixing all the raw materials until the uniformity is more than 98 percent to form a uniformly mixed batch;
7) then, adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1575 ℃ within 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1575 ℃ within 10 minutes, preserving heat for 400 minutes, cooling the furnace temperature from 1575 ℃ to 1455 ℃ within 30 minutes, stirring the molten glass for 1 hour by adopting a stirring paddle, and keeping the temperature at 1455 ℃ during the stirring process;
8) then, the furnace temperature is reduced from 1455 ℃ to 1400 ℃ in 30 minutes, and the temperature is kept for 30 min;
9) then, pouring the glass liquid into a mold at 650 ℃ to form a glass sheet with the thickness of 0.6 mm;
10) then, putting the formed glass sheet sample into an annealing furnace at 710 ℃, and preserving heat for 35 min;
11) and finally, cooling to 450 ℃ according to the cooling speed of 14 ℃/min to obtain the sheet glass.
And thirdly, preparing the toughened sheet glass.
1) Firstly, 73% of potassium nitrate, 15% of tripotassium phosphate, 7% of potassium sulfate and 5% of silver nitrate are weighed according to the mass fraction of a toughening raw material;
2) then, adding the weighed tempering raw materials into a 420 ℃ stainless steel container, preserving heat for 1h at 420 ℃, and stirring for 3min to form uniformly mixed molten salt;
3) then, quickly putting the 450 ℃ thin glass plate into a frame made of stainless steel;
4) then, putting the frame and the sheet glass into the uniformly mixed molten salt, and preserving heat for 2 hours at 420 ℃;
5) then, taking out the frame, putting the frame into an oven at 170 ℃, preserving heat for 20min, taking out and naturally cooling to room temperature;
6) and finally, ultrasonically cleaning the surface of the toughened sheet glass for 14min by using ultrasonic waves, taking out and drying to obtain the toughened sheet glass.
Testing the surface compressive stress of the toughened thin plate glass to be 867MPa and the depth of a strengthened stress layer to be 47 mu m by using an FSM-6000 surface stress instrument; the Vickers hardness of the toughened thin plate glass is 645kg/mm according to the GB/T4340.1-1999 standard2(ii) a The strain point temperature of the toughened thin plate glass is measured to be 531 ℃ by using an ANS-800 type instrument according to the ASTMC-336 standard; the linear expansion of the toughened sheet glass was tested by NETZSCH DIL402PC to 35.8 x 10-7/° c; the density of the tempered sheet glass measured by ASTM C-693 Standard was 2.381g/cm3。
Example 3:
the first step, the treatment of cullet.
1) Firstly, removing organic elements from various collected sheet glass cullets, and crushing the glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2) then, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
3) then, putting the iron-removed broken glass particles into a cleaning machine for cleaning;
4) finally, the cleaned cullet is dried at 130 ℃ to become a cullet raw material.
And secondly, preparing the sheet glass.
1) Firstly, accurately weighing 49.2% of quartz sand, 1.41% of boric acid, 1.3% of borax, 9.5% of alumina, 17.3% of lithium carbonate, 4.2% of lithium nitrate, 4% of sodium carbonate, 2% of tripotassium phosphate, 0.3% of calcium carbonate, 2.5% of calcium phosphate, 6.7% of basic magnesium carbonate, 1.3% of strontium carbonate, 0.2% of stannous oxide and 0.055% of selenium powder according to the mass fraction of the mixture; 0.035% cobalt oxide;
2) then, uniformly mixing the weighed aluminum oxide and lithium nitrate to form a mixture A;
3) then, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
4) then, sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 1min to form a mixture;
5) then, adding clean cullet with the mass fraction of the mixture being 40% into the mixer,
6) then, mixing all the raw materials until the uniformity is more than 98 percent to form a uniformly mixed batch;
7) then, adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1580 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1580 ℃ in 10 minutes, preserving heat for 450 minutes, cooling the furnace temperature from 1580 ℃ to 1460 ℃ in 30 minutes, stirring the glass liquid for 1 hour by adopting a stirring paddle, and keeping the temperature at 1460 ℃ in the stirring process;
8) then, the furnace temperature is reduced from 1460 ℃ to 1400 ℃ in 30 minutes, and the temperature is kept for 30 minutes;
9) then, pouring the glass liquid into a mold at 650 ℃ to form a glass sheet with the thickness of 0.7 mm;
10) then, putting the formed glass sheet sample into a 720 ℃ annealing furnace, and preserving heat for 40 min;
11) and finally, cooling to 450 ℃ according to a cooling speed of 18 ℃/min to obtain the sheet glass.
And thirdly, preparing the toughened sheet glass.
1) Firstly, weighing 70% of potassium nitrate, 19% of tripotassium phosphate, 10% of potassium sulfate and 1% of silver nitrate according to mass fractions of toughening raw materials;
2) then, adding the weighed tempering raw materials into a 425 ℃ stainless steel container, preserving heat for 1h at 425 ℃, and stirring for 4min to form uniformly mixed molten salt;
3) then, quickly putting the 450 ℃ thin glass plate into a frame made of stainless steel;
4) then, putting the frame and the sheet glass into the uniformly mixed molten salt, and preserving heat for 3 hours at 425 ℃;
5) then, taking out the frame, putting the frame into a baking oven at 190 ℃, preserving heat for 30min, taking out and naturally cooling to room temperature;
6) and finally, ultrasonically cleaning the surface of the toughened sheet glass for 18min by using ultrasonic waves, taking out and drying to obtain the toughened sheet glass.
Testing the surface compressive stress of the toughened thin plate glass to be 924MPa and the depth of a stress layer after the toughened thin plate glass is toughened to be 56 microns by using an FSM-6000 surface stress instrument; the Vickers hardness of the toughened thin plate glass is 691kg/mm according to the test of GB/T4340.1-1999 standard2(ii) a The strain point temperature of the toughened thin plate glass is 542 ℃ measured by using an ANS-800 type instrument according to the ASTMC-336 standard; the toughened sheet glass was tested by NETZSCH DIL402PC for linear expansion of 36.8 x 10-7/° c; the density of the tempered thin glass sheet was measured by ASTM C-693 Standard to be 2.420g/cm3。
Example 4:
the first step, the treatment of cullet.
1) Firstly, removing organic elements from various collected sheet glass cullets, and crushing the glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2) then, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
3) then, putting the iron-removed broken glass particles into a cleaning machine for cleaning;
4) finally, the cleaned cullet is dried at 135 ℃ to become the cullet raw material.
And secondly, preparing the sheet glass.
1) Firstly, accurately weighing 49.8% of quartz sand, 1.45% of boric acid, 1.36% of borax, 8.5% of alumina, 18.1% of lithium carbonate, 4% of lithium nitrate, 4.25% of sodium carbonate, 1.75% of tripotassium phosphate, 0.35% of calcium carbonate, 2% of calcium phosphate, 7% of basic magnesium carbonate, 1.25% of strontium carbonate, 0.15% of stannous oxide and 0.002% of selenium powder according to the mass fraction of the mixture; 0.038% cobalt oxide;
2) then, uniformly mixing the weighed aluminum oxide and lithium nitrate to form a mixture A;
3) then, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
4) then, sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 2min to form a mixture;
5) then, adding clean cullet with the mass fraction of the mixture being 45% into the mixer,
6) then, mixing all the raw materials until the uniformity is more than 98 percent to form a uniformly mixed batch;
7) then, adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1590 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1590 ℃ in 10 minutes, preserving heat for 500 minutes, cooling the furnace temperature from 1590 ℃ to 1470 ℃ in 30 minutes, stirring the molten glass for 2 hours by a stirring paddle, and keeping the temperature at 1470 ℃ in the stirring process;
8) then, the furnace temperature is reduced from 1470 ℃ to 1400 ℃ in 30 minutes, and the temperature is kept for 30 minutes;
9) then, pouring the glass liquid into a mold at 650 ℃ to form a glass sheet with the thickness of 0.8 mm;
10) then, putting the formed glass sheet sample into an annealing furnace at 730 ℃, and preserving heat for 50 min;
11) and finally, cooling to 450 ℃ according to the cooling speed of 22 ℃/min to obtain the sheet glass.
And thirdly, preparing the toughened sheet glass.
1) Firstly, weighing 69% of potassium nitrate, 20% of tripotassium phosphate, 8.9% of potassium sulfate and 2.1% of silver nitrate according to the mass fraction of a toughening raw material;
2) then, adding the weighed toughening raw materials into a 435 ℃ stainless steel container, preserving heat for 2 hours at 435 ℃, and stirring for 4 minutes to form uniformly mixed molten salt;
3) then, quickly putting the 450 ℃ thin glass plate into a frame made of stainless steel;
4) then, putting the frame and the sheet glass into the uniformly mixed molten salt, and preserving heat for 4 hours at 435 ℃;
5) then, taking out the frame, putting the frame into a 210 ℃ oven, preserving the heat for 40min, taking out the frame and naturally cooling the frame to room temperature;
6) and finally, ultrasonically cleaning the surface of the toughened sheet glass for 22min by using ultrasonic waves, taking out and drying to obtain the toughened sheet glass.
Testing the surface compressive stress of the toughened thin plate glass after being toughened by an FSM-6000 surface stress instrument to 955MPa, and the depth of a toughened thin plate glass stress layer is 60 mu m; the Vickers hardness of the toughened thin plate glass is 719kg/mm according to the test of GB/T4340.1-1999 standard2(ii) a The strain point temperature of the toughened sheet glass is 557 ℃ measured by using an ANS-800 type instrument according to the ASTMC-336 standard; the toughened sheet glass was tested by NETZSCH DIL402PC for a linear expansion of 37.3 x 10-7/° c; the density of the tempered thin glass sheet as measured by ASTM C-693 Standard was 2.440g/cm3。
Example 5:
the first step, the treatment of cullet.
1) Firstly, removing organic elements from various collected sheet glass cullets, and crushing the glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2) then, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
3) then, putting the iron-removed broken glass particles into a cleaning machine for cleaning;
4) finally, the cleaned cullet is dried at 145 ℃ to become a cullet raw material.
And secondly, preparing the sheet glass.
1) Firstly, accurately weighing 50.3% of quartz sand, 1.43% of boric acid, 1.43% of borax, 9.1% of alumina, 17.76% of lithium carbonate, 3.6% of lithium nitrate, 4% of sodium carbonate, 1.5% of tripotassium phosphate, 0.4% of calcium carbonate, 1.7% of calcium phosphate, 7.5% of basic magnesium carbonate, 1% of strontium carbonate, 0.228% of stannous oxide and 0.002% of selenium powder according to the mass fraction of the mixture; 0.05% cobalt oxide;
2) then, uniformly mixing the weighed aluminum oxide and lithium nitrate to form a mixture A;
3) then, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
4) then, sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 2min to form a mixture;
5) then, adding clean cullet with the mass fraction of 50 percent of the mixture into a mixer,
6) then, mixing all the raw materials until the uniformity is more than 98 percent to form a uniformly mixed batch;
7) then, adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1595 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1595 ℃ in 10 minutes, preserving heat for 550 minutes, cooling the furnace temperature from 1595 ℃ to 1475 ℃ in 30 minutes, stirring the molten glass for 2 hours by adopting a stirring paddle, and keeping the temperature at 1475 ℃ in the stirring process;
8) then, the furnace temperature is reduced from 1475 ℃ to 1400 ℃ in 30 minutes, and the temperature is kept for 30 minutes;
9) then, pouring the glass liquid into a mold at 650 ℃ to form a glass sheet with the thickness of 0.9 mm;
10) then, putting the formed glass sheet sample into an annealing furnace at 740 ℃, and preserving heat for 55 min;
11) and finally, cooling to 450 ℃ according to the cooling speed of 26 ℃/min to obtain the sheet glass.
And thirdly, preparing the toughened sheet glass.
1) Firstly, weighing 67% of potassium nitrate, 23% of tripotassium phosphate, 7.5% of potassium sulfate and 2.5% of silver nitrate according to the mass fraction of a toughening raw material;
2) then, adding the weighed toughening raw materials into a stainless steel container with the temperature of 450 ℃, preserving heat for 2 hours at the temperature of 440 ℃, and stirring for 5 minutes to form uniformly mixed molten salt;
3) then, quickly putting the 450 ℃ thin glass plate into a frame made of stainless steel;
4) then, putting the frame and the sheet glass into the uniformly mixed molten salt, and preserving heat for 5 hours at 440 ℃;
5) then, taking out the frame, putting the frame into a 230 ℃ oven, preserving the heat for 50min, taking out the frame and naturally cooling the frame to room temperature;
6) and finally, ultrasonically cleaning the surface of the toughened sheet glass for 26min by using ultrasonic waves, taking out and drying to obtain the toughened sheet glass.
Testing the surface compressive stress of the toughened thin plate glass after being toughened by an FSM-6000 surface stress meter to be 1004MPa, wherein the depth of a toughened stress layer is 75 mu m; the Vickers hardness of the toughened thin plate glass is 769kg/mm according to the test of GB/T4340.1-1999 standard2(ii) a The strain point temperature of the tempered thin glass is 564 ℃ measured by using an ANS-800 type instrument according to the ASTMC-336 standard; the toughened sheet glass was tested by NETZSCH DIL402PC for linear expansion of 38.2 x 10-7/° c; the density of the tempered thin glass sheet measured by ASTM C-693 Standard was 2.465g/cm3。
Example 6:
the first step, the treatment of cullet.
1) Firstly, removing organic elements from various collected sheet glass cullets, and crushing the glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2) then, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
3) then, putting the iron-removed broken glass particles into a cleaning machine for cleaning;
4) finally, the cleaned cullet is dried at 150 ℃ to become the cullet raw material.
And secondly, preparing the sheet glass.
1) Firstly, accurately weighing 52.1% of quartz sand, 1.35% of boric acid, 1.5% of borax, 8.5% of alumina, 17.16% of lithium carbonate, 3.5% of lithium nitrate, 5% of sodium carbonate, 1% of tripotassium phosphate, 0.5% of calcium carbonate, 1.5% of calcium phosphate, 6.6% of basic magnesium carbonate, 1% of strontium carbonate, 0.25% of stannous oxide and 0.001% of selenium powder according to the mass fraction of a mixture; 0.039% cobalt oxide;
2) then, uniformly mixing the weighed aluminum oxide and lithium nitrate to form a mixture A;
3) then, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
4) then, sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 2min to form a mixture;
5) then, adding clean cullet with the mass fraction of 55% of the mixture into a mixer,
6) then, mixing all the raw materials until the uniformity is more than 98 percent to form a uniformly mixed batch;
7) then, adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1600 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1600 ℃ in 10 minutes, preserving heat for 600 minutes, cooling the furnace temperature from 1600 ℃ to 1480 ℃ in 30 minutes, and stirring the molten glass for 2 hours by adopting a stirring paddle, wherein the temperature is kept at 1480 ℃ in the stirring process;
8) then, the furnace temperature is reduced from 1480 ℃ to 1400 ℃ in 30 minutes, and the temperature is kept for 30 min;
9) then, pouring the glass liquid into a mold at 650 ℃ to form a glass sheet with the thickness of 1 mm;
10) then, putting the formed glass sheet sample into an annealing furnace at 750 ℃, and preserving heat for 60 min; 11) and finally, cooling to 450 ℃ according to the cooling speed of 30 ℃/min to obtain the sheet glass. Thirdly, preparing the tempered sheet glass
And thirdly, preparing the toughened sheet glass.
1) Firstly, weighing 65% of potassium nitrate, 25% of tripotassium phosphate, 9.9% of potassium sulfate and 0.1% of silver nitrate according to the mass fraction of a toughening raw material;
2) then, adding the weighed raw materials into a stainless steel container with the temperature of 450 ℃, preserving heat for 2 hours at the temperature of 450 ℃, and stirring for 5 minutes to form uniformly mixed molten salt;
3) then, quickly putting the 450 ℃ thin glass plate into a frame made of stainless steel;
4) then, putting the frame and the sheet glass into the uniformly mixed molten salt, and preserving heat for 6 hours at 450 ℃;
5) then, taking out the frame, putting the frame into a drying oven at 250 ℃, preserving heat for 60min, taking out and naturally cooling to room temperature;
6) and finally, ultrasonically cleaning the surface of the toughened sheet glass for 30min by using ultrasonic waves, taking out and drying to obtain the toughened sheet glass.
Testing the surface compressive stress of the toughened thin plate glass to 1050MPa and the depth of a strengthened stress layer to 80 microns by using an FSM-6000 surface stress meter; the Vickers hardness of the toughened thin plate glass is 800kg/mm according to the test of GB/T4340.1-1999 standard2(ii) a The strain point temperature of the toughened thin plate glass is measured to be 575 ℃ by using an ANS-800 type instrument according to the ASTMC-336 standard; the toughened sheet glass was tested by NETZSCH DIL402PC for linear expansion of 38.5 x 10-7/° c; the density of the tempered thin glass sheet as measured by ASTM C-693 Standard was 2.49g/cm3。
According to the invention, a large amount of waste cullet is added into the glass batch to prepare the toughened thin glass, the glass melting clarification temperature is 40-100 ℃ lower than that of other methods, the melting speed is high, and the efficiency is high. The toughened thin plate glass prepared by the method has the advantages of deep stress layer, high toughening strength, good glass flatness and uniformity. The glass melting temperature is low, the energy consumption is low, the energy is saved, the environment is protected, the production efficiency is high, the glass melting furnace is suitable for mass production, and the added value of products is high. The prepared toughened thin plate glass has high strength, high hardness, high chemical stability, low linear expansion coefficient and high impact resistance, is suitable for protective glass of devices such as mobile phones, smart phones, tablet computers, notebook computers, televisions, MTA equipment, watches, industrial displays and the like, protective windows, automobile windows, train windows, aviation machinery windows and hard disk substrates, and can also be used for white household appliances such as refrigerators, kitchen ware and the like. Therefore, the toughened sheet glass prepared by the method has considerable economic and social benefits and very wide application prospect.

Claims (9)

1. A method for preparing toughened sheet glass is characterized by comprising the following steps,
step 1, accurately weighing 48.5-52.1% of quartz sand, 1.35-1.55% of boric acid, 1.1-1.5% of borax, 8.5-10.5% of alumina, 16.5-18.1% of lithium carbonate, 3.5-4.5% of lithium nitrate, 3.5-5.0% of sodium carbonate, 1.0-2.5% of tripotassium phosphate, 0.2-0.5% of calcium carbonate, 1.5-3.5% of calcium phosphate, 6.5-7.5% of basic magnesium carbonate, 1.0-1.5% of strontium carbonate, 0.15-0.25% of stannous oxide and 0.001-0.01% of selenium powder according to the mass fraction of the mixture; 0.02-0.05% of cobalt oxide, and mixing to form a mixture;
step 2, adding cleaned cullet with the mass fraction of 30-55% of the mixture, and then mixing all the raw materials until the uniformity is more than 98% to form a uniformly mixed batch;
step 3, melting the uniformly mixed batch materials to prepare a formed glass sheet;
step 4, annealing the formed glass sheet at the temperature of 700-750 ℃ for 30-60 min, and cooling to 450 ℃ according to the cooling speed of 10-30 ℃/min to obtain sheet glass;
step 5, weighing 65-75% of potassium nitrate, 15-25% of tripotassium phosphate, 4.9-10% of potassium sulfate and 0.1-5% of silver nitrate according to the mass fraction of the toughening raw materials;
step 6, preserving the heat of the weighed tempering raw materials for 1-2 hours at the temperature of 410-450 ℃, and stirring for 3-5 min to form uniformly mixed molten salt;
step 7, putting the sheet glass at 450 ℃ into the uniformly mixed molten salt, preserving the heat at 410-450 ℃ for 1-6 h, and taking out;
and 8, drying the sheet glass taken out of the molten salt at the temperature of 150-250 ℃ for 10-60 min, naturally cooling to room temperature, cleaning and drying to obtain the tempered sheet glass.
2. The method of claim 1, wherein the quartz sand has a particle size of more than 150 mesh standard sieve.
3. The method of claim 1, wherein the amount of ferric oxide in the sand, boric acid, borax, alumina, lithium carbonate, lithium nitrate, sodium carbonate, tripotassium phosphate, calcium carbonate, calcium phosphate, basic magnesium carbonate, strontium carbonate, stannous oxide, selenium powder, cobalt oxide, potassium nitrate, potassium sulfate and silver nitrate is less than 50 ppm.
4. The method for manufacturing a tempered thin glass as recited in claim 1, wherein the mixture in the step 1 is obtained by mixing,
1.1, uniformly mixing weighed aluminum oxide and lithium nitrate to form a mixture A;
1.2, uniformly mixing the weighed calcium carbonate, sodium carbonate, strontium carbonate, stannous oxide, selenium powder and cobalt oxide to form a mixture B;
1.3 sequentially putting quartz sand, boric acid, borax, lithium carbonate, tripotassium phosphate, calcium phosphate and basic magnesium carbonate into a mixer, putting the mixture A and the mixture B, and mixing for 1-2 min to form a mixture.
5. A method for manufacturing a tempered thin glass as recited in claim 1, wherein in the step 2, the cleaned cullet is obtained by the steps of;
2.1, removing organic elements from the collected various types of sheet glass cullets, and crushing the sheet glass cullets into particles with the particle size of less than 10mm by using a wheel mill;
2.2, the crushed particles are processed by an electromagnetic iron removal device to remove iron;
2.3 putting the iron-removed broken glass particles into a cleaning machine for cleaning;
2.4 drying the cleaned cullet at 110-150 ℃ to obtain a clean cullet raw material.
6. A method for manufacturing a tempered thin glass as recited in claim 1, wherein the step 3 of manufacturing the shaped glass sheet comprises the following steps,
3.1 adding half of the batch into a platinum crucible which is heated to 1500 ℃; then, heating to 1570-1600 ℃ in 10 minutes, preserving heat for 30 minutes, adding the rest batch materials into a platinum crucible, heating to 1570-1600 ℃ in 10 minutes, and preserving heat for 360-600 min;
3.2, reducing the furnace temperature from 1570-1600 ℃ to 1450-1480 ℃ within 30 minutes, and stirring the molten glass for 1-2 hours by using a stirring paddle, wherein the temperature is kept at 1450-1480 ℃ during the stirring process;
3.2, reducing the temperature of the furnace from 1450-1480 ℃ to 1400 ℃ in 30 minutes, and preserving the temperature for 30 minutes;
3.3 pouring the glass liquid at 1400 ℃ into a mold at 650 ℃ to form a glass sheet with the thickness of 0.5-1 mm.
7. The method according to claim 1, wherein in step 7, the thin glass sheet with a temperature of 450 ℃ is placed in a frame made of stainless steel, and the frame and the thin glass sheet are placed in the molten salt which is uniformly mixed for treatment.
8. The method for preparing tempered thin glass as claimed in claim 1, wherein in the step 8, after naturally cooling to room temperature, the surface of the tempered thin glass is ultrasonically cleaned for 10-30 min by using ultrasonic waves, and then the tempered thin glass is taken out and dried to obtain the tempered thin glass.
9. A tempered thin glass sheet produced by the method of any one of claims 1-8.
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