CN111620555B - Microcrystalline glass and tempering method and application thereof - Google Patents
Microcrystalline glass and tempering method and application thereof Download PDFInfo
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- CN111620555B CN111620555B CN202010462068.7A CN202010462068A CN111620555B CN 111620555 B CN111620555 B CN 111620555B CN 202010462068 A CN202010462068 A CN 202010462068A CN 111620555 B CN111620555 B CN 111620555B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Abstract
The invention relates to microcrystalline glass and a toughening method and application thereof. The toughening method comprises the following steps: respectively melting glass raw materials and metal salt to prepare a microcrystalline glass precursor and toughened molten salt; immersing the microcrystalline glass precursor into the tempering molten salt, and tempering at 600-950 ℃ to prepare a glass intermediate; cooling the glass intermediate; the microcrystalline glass precursor comprises sodium oxide and/or potassium oxide; the metal salt includes a lithium salt. Changing the surface layer components of the microcrystalline glass precursor by ion exchange to form a thermal expansion coefficient difference; and through crystallization heat treatment, a glass intermediate with inconsistent surface crystal phase and inner crystal phase or inconsistent surface crystal phase ratio and inner crystal phase ratio can be obtained, and a stress layer is formed between the two layers in the cooling shrinkage process, so that the resistance impact strength of the microcrystalline glass is improved. The glass panel can be applied to a glass panel of a display panel or a protective shell of an electronic product.
Description
Technical Field
The invention relates to the technical field of glass, in particular to microcrystalline glass and a toughening method and application thereof.
Background
The glass ceramics is a glass mixed material discovered by accident, and the structure and the performance of the glass ceramics have some special changes compared with the common glass materials, and the glass ceramics mainly show that the structure of the common glass is disordered and partially ordered. That is, the crystallized glass is a composite material composed of crystals and non-crystals.
Compared with common glass, the microcrystalline glass has the following advantages: high mechanical strength, excellent insulating property, less dielectric loss, stable dielectric constant, adjustable thermal expansion coefficient in a large range, good chemical corrosion resistance, good wear resistance, good thermal stability and high service temperature. The microcrystalline glass can be widely applied to structural materials with larger thickness, such as building materials. However, the thickness of the protective glass for display panels or some electronic devices is usually about 1mm, and the microcrystalline glass still shows the brittleness of common glass under the condition of about 1mm of thickness, the impact resistance often does not meet the requirements of products, and the protective glass is easy to break when being impacted by force.
The glass is toughened, so that the impact resistance of the glass can be improved. The existing glass toughening technology comprises physical toughening and chemical toughening, wherein the physical toughening refers to the following steps: the glass is heated to a proper temperature and then rapidly cooled to enable the surface of the glass to shrink rapidly to generate compressive stress, and the middle layer of the glass is cooled slowly to be short of the shrinkage, so that tensile stress is formed, and the glass obtains high strength. And chemical tempering means: the strength of glass is improved by changing the chemical composition of the surface of the glass, usually chemical tempering is carried out by adopting an ion exchange method, silicate glass containing alkali metal ions is immersed into metal salt in a molten state, so that the ions with smaller radius in the surface layer of the glass are exchanged with the ions with larger radius in tempered molten salt, for example, lithium ions in the glass are exchanged with potassium or sodium ions in a solution, sodium ions in the glass are exchanged with potassium ions in the solution, the embedding and extruding stress is formed on the surface layer of the glass by utilizing the difference of the volume of the alkali ions, and after the glass is cooled to normal temperature, the glass is in a state that an inner layer is pulled and an outer layer is pressed, so that the glass obtains higher strength.
However, the existing glass tempering technology is only suitable for common glass and is not suitable for microcrystalline glass. This is mainly due to: (1) the microcrystalline glass contains partial crystals in the structure, the existence of the crystals can prevent ions in the toughened salt from permeating into the glass matrix and hinder the ion exchange treatment, the ion exchange degree is low, and the impact strength of the glass is difficult to improve finally. (2) Quenching and sudden temperature drop in physical tempering are not beneficial to the ordered growth of crystals.
Disclosure of Invention
In view of the above, it is necessary to provide a tempering method suitable for a glass ceramic to improve the impact resistance of the glass ceramic.
The technical scheme is as follows:
a method for toughening microcrystalline glass comprises the following steps:
respectively melting glass raw materials and metal salt to prepare a microcrystalline glass precursor and toughened molten salt;
immersing the microcrystalline glass precursor into the tempering molten salt, and carrying out tempering treatment at the temperature of 600-950 ℃ to prepare a glass intermediate;
cooling the glass intermediate;
the microcrystalline glass precursor comprises sodium oxide and/or potassium oxide;
the metal salt includes a lithium salt.
In one embodiment, the glass intermediate includes a surface layer and an inner layer, and the surface layer of the glass intermediate has a lower coefficient of thermal expansion than the inner layer of the glass intermediate.
In one embodiment, the sodium oxide accounts for 2-6% of the mass of the microcrystalline glass precursor; or the like, or, alternatively,
the potassium oxide accounts for 2-6% of the mass of the microcrystalline glass precursor; or the like, or, alternatively,
the mass percentage of the mixture of sodium oxide and potassium oxide in the microcrystalline glass precursor is 2-6%.
In one embodiment, the microcrystalline glass precursor further comprises 45% -60% of silicon dioxide, 15% -30% of aluminum oxide, 1% -17% of calcium oxide, 5% -10% of magnesium oxide, 6% -10% of zinc oxide, 2% -6% of zirconium oxide, 1% -4% of titanium dioxide, 2% -4% of phosphorus pentoxide, 0% -3% of boron oxide, 0% -2% of tin oxide and 1% -2% of antimony trioxide.
In one preferable embodiment, the microcrystalline glass precursor further comprises 45% -60% of silicon dioxide, 15% -30% of aluminum oxide, 1% -2% of calcium oxide, 5% -10% of magnesium oxide, 6% -10% of zinc oxide, 2% -6% of zirconium oxide, 1% -4% of titanium dioxide, 2% -4% of phosphorus pentoxide, 0% -3% of boron oxide, 0% -2% of tin oxide and 1% -2% of antimony trioxide.
In one embodiment, the lithium salt is selected from at least one of lithium nitrate, lithium carbonate, lithium chloride, and lithium hydroxide.
In one embodiment, the metal salt further comprises a potassium salt selected from at least one of potassium nitrate, potassium carbonate, potassium chloride and potassium hydroxide.
In a more preferred embodiment, the metal salt is formed by mixing lithium carbonate and potassium nitrate according to a molar ratio of 1: 1-3: 1.
In one embodiment, the temperature at which the metal salt is melted is 600 ℃ to 950 ℃.
In one embodiment, the toughening treatment time is 5 min-10 h.
In one preferable embodiment, the temperature of the toughening treatment is 700-850 ℃, and the time is 1-4 h.
In one embodiment, the glass raw material is melted at 1400-1600 ℃ for 2-10 h.
In one embodiment, the step of melting the glass raw material in preparing the glass-ceramic precursor further comprises the steps of cooling, cutting and polishing.
In one embodiment, when the glass intermediate is subjected to cooling treatment, the cooling rate of the cooling treatment is 60 ℃/min to 80 ℃/min.
The invention also provides the microcrystalline glass prepared by the method for toughening the microcrystalline glass.
The invention also provides application of the microcrystalline glass. The technical scheme is as follows:
a shell of an electronic product, which is prepared from the microcrystalline glass prepared by the method for tempering the microcrystalline glass described in any one of the above embodiments, or the microcrystalline glass described above;
the electronic product is selected from a mobile phone, a flat panel, a watch or a vehicle-mounted product.
The glass cover plate of the display panel is prepared from the microcrystalline glass prepared by the microcrystalline glass toughening method in any embodiment, or the microcrystalline glass;
the display panel is selected from a display panel of a mobile phone, a display panel of a flat plate, a display panel of a watch or a display panel of a vehicle.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for toughening microcrystalline glass, which comprises the steps of respectively melting glass raw materials and molten metal salt to prepare a microcrystalline glass precursor and toughened molten salt; and immersing the microcrystalline glass precursor into the toughened molten salt, and carrying out toughening treatment at the temperature of 600-950 ℃, wherein the process comprises ion exchange treatment and crystallization heat treatment which are carried out synchronously, preparing a glass intermediate and cooling the glass intermediate.
Sodium ions (and/or potassium ions) on the surface of the microcrystalline glass precursor are exchanged with lithium ions in the tempering salt through ion exchange, and the glass is crystallized to generate crystals. Specifically, a microcrystalline glass precursor is immersed into tempered molten salt for ion exchange treatment, namely the surface of the microcrystalline glass precursor is modified, so that sodium ions (and/or potassium ions) on the surface of the microcrystalline glass precursor are exchanged with metal ions (including lithium ions) in the tempered salt, the surface layer component of the microcrystalline glass precursor is changed, the surface of the glass contains lithium ions through ion permeation, the inner layer does not contain lithium ions through lithium ion permeation, and the glass with inconsistent inner layer components and outer layer components is prepared. And performing crystallization heat treatment to enable the inner layer and the surface layer of the microcrystalline glass precursor to respectively form a crystal structure with partial ordered arrangement, and preparing the glass intermediate with inconsistent surface crystal phase and inner crystal phase or inconsistent surface crystal phase ratio and inner crystal phase ratio. And then cooling the glass intermediate, wherein the surface layer crystalline phase and the inner layer crystalline phase are not consistent or the surface layer crystalline phase ratio and the inner layer crystalline phase ratio are not consistent, so that a thermal expansion coefficient difference exists, the shrinkage rates of the glass surface layer and the glass inner layer are not consistent during cooling, and a tempering stress is formed between the glass surface layer and the glass inner layer, so that the impact strength of the glass ceramic is improved, and the impact action of an external force can be resisted. The method for toughening the microcrystalline glass provided by the invention is simple to operate, high in toughening efficiency and easy to realize mass production.
Furthermore, by controlling the types of glass raw materials or the process conditions of ion exchange treatment, the toughened glass ceramics with high transparency, semitransparent glass ceramics or opaque glass ceramics can be prepared.
The impact strength of the microcrystalline glass prepared by the invention is represented by a falling ball crushing property test, the crushing height can reach 65cm, and the microcrystalline glass has excellent impact resistance; simultaneously, the Vickers hardness of the alloy can reach 750kgf/mm 2 . The method can be applied to a display panel cover plate or an electronic product protective shell.
Drawings
Fig. 1 is a schematic view of the structure of a crystallized glass produced in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Interpretation of terms:
(1) crystallization heat treatment: the method refers to a process that a glass matrix (or called glass master batch and mother glass) formed by melting a microcrystalline glass raw material undergoes nucleation and crystal growth (crystallization) under the condition of heating, and is a key process for generating a preset crystalline phase and a glass phase of the microcrystalline glass.
The nucleation and crystal growth of the glass-ceramic are generally performed at a glass transition temperature (Tg) or higher and a melting point of a main crystal phase or lower.
(2) Precursor of the glass ceramics: a glass matrix without heat treatment and having no crystal phase inside.
The invention provides a toughening method suitable for microcrystalline glass, which improves the shock resistance of the microcrystalline glass.
The technical scheme is as follows:
respectively melting glass raw materials and metal salt to prepare a microcrystalline glass precursor and toughened molten salt;
immersing the microcrystalline glass precursor into the tempering molten salt, and carrying out tempering treatment at the temperature of 600-950 ℃ to prepare a glass intermediate;
cooling the glass intermediate;
the microcrystalline glass precursor comprises sodium oxide and/or potassium oxide;
the metal salt includes a lithium salt.
Sodium ions (and/or potassium ions) on the surface of the microcrystalline glass precursor are exchanged with lithium ions in the tempering salt through ion exchange, and the glass is crystallized to generate crystals. Specifically, a microcrystalline glass precursor is immersed into tempered molten salt to carry out ion exchange treatment, namely, the surface of the microcrystalline glass precursor is modified, so that sodium ions (and/or potassium ions) on the surface of the microcrystalline glass precursor are exchanged with metal ions (including lithium ions) in the tempered salt, the surface layer component of the microcrystalline glass precursor is changed, the surface of the glass contains lithium ions through ion permeation, the inner layer does not contain lithium ions through lithium ion permeation, and the glass with inconsistent inner layer components and outer layer components is prepared. And performing crystallization heat treatment to enable the inner layer and the surface layer of the microcrystalline glass precursor to respectively form partially orderly arranged crystal structures, so as to prepare the glass intermediate with inconsistent surface crystal phase and inner crystal phase or inconsistent surface crystal phase ratio and inner crystal phase ratio. And then cooling the glass intermediate, wherein the difference of thermal expansion coefficients exists because the surface layer crystalline phase is inconsistent with the inner layer crystalline phase or the surface layer crystalline phase ratio is inconsistent with the inner layer crystalline phase ratio, and the shrinkage rates of the glass surface layer and the glass inner layer are inconsistent during cooling, so that tempering stress is formed between the glass surface layer and the glass inner layer, the impact strength of the microcrystalline glass is improved, and the impact effect of external force can be resisted. The method for toughening the microcrystalline glass provided by the invention is simple to operate, high in toughening efficiency and easy to realize mass production.
In one embodiment, the glass intermediate includes a surface layer and an inner layer, and the surface layer of the glass intermediate has a coefficient of thermal expansion that is less than a coefficient of thermal expansion of the inner layer of the glass intermediate.
If the thermal expansion coefficient of the surface layer of the glass is smaller than that of the inner layer of the glass, the shrinkage rate of the surface layer of the glass relative to the inner layer of the glass is smaller in the cooling shrinkage process, and the inner layer of the glass applies compressive stress to the surface layer of the glass, so that the impact strength of the microcrystalline glass can be further improved.
In one embodiment, the step of melting the glass raw material in preparing the glass-ceramic precursor further comprises the steps of cooling, cutting and polishing.
Preferably, the step of preparing the microcrystalline glass precursor is: the method comprises the steps of putting prepared raw materials (comprising glass raw materials and an auxiliary agent, wherein the auxiliary agent is sodium sulfate) into a platinum crucible, melting the raw materials in a high-temperature furnace, pouring molten glass out of the molten glass, pouring the molten glass into a preheated metal mold to obtain a microcrystalline glass precursor with a large volume, cutting glass into sheets with the thickness of 1mm, and grinding and polishing the sheets to obtain microcrystalline glass substrate sheets, wherein the microcrystalline glass precursor is uncrystallized glass.
The microcrystalline glass precursor comprises sodium oxide and/or potassium oxide as the basis of ion exchange. In addition, sodium oxide or potassium oxide can be used as the external structure of the glass network to reduce the melting temperature of the glass and the viscosity of the glass liquid, so that the melting process is easier to carry out.
In one preferable embodiment, the sodium oxide accounts for 2 to 6 percent of the mass of the microcrystalline glass precursor; or the like, or a combination thereof,
the potassium oxide accounts for 2-6% of the mass of the microcrystalline glass precursor; or the like, or, alternatively,
the mass percentage of the mixture of sodium oxide and potassium oxide in the microcrystalline glass precursor is 2-6%.
It is understood that, in the present invention, the mass percentage of the sodium oxide and/or the potassium oxide in the microcrystalline glass precursor may be set to be, but not limited to, 2%, 2.1%, 2.5%, 3%, 3.2%, 3.5%, 4%, 4.5%, 5%, 5.5%, and 6%. More preferably, the sodium oxide and/or potassium oxide accounts for 2 to 4 percent of the glass raw material by mass.
In one embodiment, the microcrystalline glass precursor further comprises 45% -60% of silicon dioxide, 15% -30% of aluminum oxide, 1% -17% of calcium oxide, 5% -10% of magnesium oxide, 6% -10% of zinc oxide, 2% -6% of zirconium oxide, 1% -4% of titanium dioxide, 2% -4% of phosphorus pentoxide, 0% -3% of boron oxide, 0% -2% of tin oxide and 1% -2% of antimony trioxide.
Wherein, the magnesium oxide, the zinc oxide, the aluminum oxide and the silicon dioxide are main components of the glass to form a glass network structure or a crystal structure. The boron oxide and the calcium oxide can reduce the high-temperature viscosity of the glass liquid. Titanium dioxide, zirconium oxide and phosphorus pentoxide are used as crystal nucleus agent components to make the glass more easily devitrified. Antimony trioxide and tin oxide are used as clarifying agents to eliminate bubbles in the molten glass.
The microcrystalline glass precursor has an oxide composition. In the actual melting process, the raw materials may be oxides or inorganic salts of oxides.
Specifically, the source of magnesium oxide may be magnesium-containing raw materials such as magnesium oxide and magnesium carbonate. The raw material of the zinc oxide can be zinc oxide, the raw material of the aluminum oxide is aluminum oxide, the raw material of the silicon dioxide is silicon dioxide, the raw material source of the sodium oxide is sodium carbonate or sodium nitrate, the raw material source of the calcium oxide is calcium carbonate, the raw material source of the tin oxide is tin oxide, the raw material source of the titanium dioxide is titanium dioxide, the raw material source of the zirconium oxide is zirconium oxide, the raw material source of the phosphorus pentoxide is ammonium dihydrogen phosphate, the raw material source of the antimony oxide is antimony oxide or sodium antimonate, and the raw material source of the boron oxide is boric acid.
And (3) carrying out equimolar conversion on the raw materials and oxides, weighing, fully and uniformly mixing, and melting to obtain glass liquid for preparing the microcrystalline glass precursor subsequently.
In one embodiment, the glass raw material is melted at 1400-1600 ℃ for 2-10 h.
Preferably, the step of preparing the tempered molten salt is: and (3) putting the metal salt into a tempering furnace, heating to melt the salt into a liquid state, and using the salt as a salt bath for ion exchange of the microcrystalline glass substrate.
In one embodiment, the temperature at which the metal salt is melted is 600 ℃ to 950 ℃.
In one embodiment, the lithium salt is selected from at least one of lithium nitrate, lithium carbonate, lithium chloride, and lithium hydroxide.
In a preferred embodiment, the metal salt further includes a potassium salt, and the potassium salt is at least one selected from potassium nitrate, potassium carbonate, potassium chloride and potassium hydroxide. By adding potassium salt, on one hand, the eutectic point formed by the salts with lower melting points such as potassium nitrate can be used to prepare the mixed salt with adjustable melting point, on the other hand, the concentration of lithium ions can be adjusted, the problem that the stability of the glass is reduced due to the overlarge concentration of the lithium ions in the glass is solved, and the purpose of adjusting the tempering degree is achieved.
In a more preferable embodiment, the metal salt is formed by mixing lithium carbonate and potassium nitrate according to a molar ratio of 1: 1-3: 1.
Preferably, the microcrystalline glass precursor is immersed in the toughened molten salt for ion exchange treatment and crystallization heat treatment, and the step of preparing the glass intermediate is as follows: preheating a microcrystalline glass precursor, then immersing the preheated microcrystalline glass precursor into tempering bath salt, so that molten tempering salt is enabled to be submerged in the microcrystalline glass precursor, and carrying out ion exchange treatment, namely modifying the surface of the microcrystalline glass precursor, so that sodium ions (and/or potassium ions) on the surface of the microcrystalline glass precursor are exchanged with metal ions (including lithium ions) in the tempering salt, so that the surface layer component of the microcrystalline glass precursor is changed, the surface of the glass contains the lithium ions through ion permeation, and the inner layer does not contain the lithium ions through the lithium ion permeation, thereby preparing the glass with inconsistent inner layer components and outer layer components. And when the microcrystalline glass precursor is subjected to ion exchange with toughened salt, the interior of the glass can generate atomic rearrangement due to heating so that the glass is nucleated and crystallized to form crystals, so that the inner layer and the surface layer of the microcrystalline glass precursor respectively form partially-arranged and orderly-arranged crystal structures, and the glass intermediate with inconsistent surface layer crystal phase and inner layer crystal phase or inconsistent surface layer crystal phase ratio and inner layer crystal phase ratio is prepared.
In the invention, the temperature of the toughening treatment is 600-950 ℃.
In one embodiment, the toughening treatment time is 5 min-10 h. The tempering time is short, and the tempering effect is good.
It is understood that, in the present invention, the temperature of the ion exchange treatment may be set to, but not limited to, 600 ℃, 620 ℃, 640 ℃, 650 ℃, 655 ℃, 670 ℃, 680 ℃, 700 ℃, 720 ℃, 750 ℃, 780 ℃, 800 ℃, 830 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 900 ℃ and 950 ℃. The time of the ion exchange treatment may be set to, but not limited to, 5min, 10min, 15min, 20min, 25min, 30min, 45min, 60min, 1.5h, 2h, 2.5h, 3h, 3.5h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, and 10 h.
In one preferable embodiment, the temperature of the ion exchange treatment and the crystallization heat treatment is 700-850 ℃, and the time is 1-4 h.
Preferably, the step of cooling the glass intermediate is: and slowly cooling the glass intermediate after the ion exchange treatment and crystallization are finished to prepare the glass ceramics. Because the surface crystal phase is inconsistent with the inner crystal phase or the surface crystal phase proportion is inconsistent with the inner crystal phase proportion, the thermal expansion coefficient difference exists, the shrinkage rates of the glass surface layer and the glass inner layer are inconsistent during cooling, the tempering stress is formed between the glass surface layer and the glass inner layer, the impact strength of the microcrystalline glass is improved, and the impact action of external force can be resisted.
In one embodiment, when the glass intermediate is subjected to cooling treatment, the cooling rate of the cooling treatment is 60-80 ℃/min.
Furthermore, according to the method for toughening the glass ceramics, the toughened glass ceramics with high transparency, and the semitransparent or opaque glass ceramics can be prepared by controlling the types of glass raw materials or the process conditions of ion exchange treatment.
In one preferable embodiment, the sodium oxide and/or potassium oxide accounts for 2 to 6 percent of the mass of the microcrystalline glass precursor; the microcrystalline glass precursor also comprises 45-60% of silicon dioxide, 15-30% of aluminum oxide, 1-2% of calcium oxide, 5-10% of magnesium oxide, 6-10% of zinc oxide, 2-6% of zirconium oxide, 1-4% of titanium dioxide, 2-4% of phosphorus pentoxide, 0-3% of boron oxide, 0-2% of tin oxide and 1-2% of antimony trioxide; the metal salt is prepared from lithium carbonate and potassium nitrate according to the molar ratio of 1: 1-3: 1.
Sodium ions (and/or potassium ions) on the surface of the microcrystalline glass precursor are exchanged with lithium ions in the tempering salt through ion exchange, and the glass is crystallized to generate crystals. The glass surface contains lithium ions by ion permeation, and the inner layer does not contain lithium ions by lithium ion permeation. Because the surface lithium ion is enriched, beta-eucryptite crystals with negative expansion coefficient characteristics or spodumene crystals with low expansion coefficients are precipitated on the surface layer of the glass, and the glass also contains a partially disordered structure. And the glass inner layer forms spinel or cordierite crystals having a positive expansion coefficient characteristic due to the lack of lithium ions. The two can form shrinkage value difference in the process of cooling from high temperature to room temperature, thereby forming surface stress, the surface stress intensity is high, and higher external impact force can be absorbed.
Preferably, the method for tempering glass ceramics further comprises a step of cleaning the cooled glass ceramics, specifically: placing the glass ceramics in an acid solution, and removing toughened salt on the surface of the glass ceramics; and then the surface of the glass is fully cleaned by clear water.
In one embodiment, the acid solution is dilute hydrochloric acid or dilute sulfuric acid.
The invention also provides the microcrystalline glass prepared by the method for toughening the microcrystalline glass.
The impact strength of the microcrystalline glass prepared by the invention is represented by a falling ball crushing property test, the crushing height can reach 65cm, and the microcrystalline glass has excellent impact resistance; simultaneously, the Vickers hardness of the alloy can reach 750kgf/mm 2 。
The invention also provides application of the microcrystalline glass. The technical scheme is as follows:
the glass cover plate of the electronic product comprises microcrystalline glass prepared by the method for toughening the microcrystalline glass;
the electronic product is selected from a mobile phone, a flat panel, a watch or a vehicle.
The glass cover plate of the display panel is prepared from the raw materials including the microcrystalline glass prepared by the microcrystalline glass toughening method;
the display panel is selected from a display panel of a mobile phone, a display panel of a flat plate, a display panel of a watch or a display panel of a vehicle.
The present invention is further illustrated by the following specific examples.
The acid solution used in the following examples and comparative examples was dilute hydrochloric acid and the auxiliary agent was sodium sulfate.
Example 1
The embodiment provides a method for toughening microcrystalline glass and microcrystalline glass prepared by the toughening method.
(1) The microcrystalline glass precursor in this example had the following composition:
MgO 6％；ZnO 7％；Al 2 O 3 20％；SiO 2 50％；Na 2 O 4％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, sodium carbonate, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance to form a microcrystalline glass precursor with large volume.
(2) The microcrystalline glass precursor is cut and polished to be made into a thin glass sheet 1 with the thickness of 1mm, and the thin glass sheet is preheated at 500 ℃ to be subjected to ion exchange treatment.
(3) Lithium carbonate and potassium nitrate salt are prepared into mixed molten salt according to the molar ratio of 3:1, and the mixed molten salt is put into a toughening container and is melted into a liquid toughening salt bath at the temperature of 750 ℃.
(4) And immersing the preheated thin glass sheet 1 into a tempering salt bath at 750 ℃ for ion exchange treatment and crystallization heat treatment for 1 hour to prepare a glass intermediate.
(5) And taking out the glass intermediate, and cooling at the speed of 70 ℃/min to obtain the microcrystalline glass 1.
(6) And (3) cleaning the toughened salt on the surface of the microcrystalline glass 1 in an acid solution, and then fully cleaning the surface of the microcrystalline glass with clear water.
Fig. 1 is a schematic view of the structure of the glass-ceramic of the present example, in which the surface layer of the glass-ceramic has spodumene and its solid solution or eucryptite and its solid solution as the main crystal phase (001), and the inner layer of the glass-ceramic has spinel or cordierite as the main crystal phase (002).
Example 2
The embodiment provides a method for toughening microcrystalline glass and microcrystalline glass prepared by the toughening method.
(1) The microcrystalline glass precursor in this example had the following composition:
MgO 6％；ZnO 7％；Al 2 O 3 20％；SiO 2 50％；Na 2 O 4％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, sodium carbonate, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance to form a microcrystalline glass precursor with large volume.
(2) The microcrystalline glass precursor is cut and polished to be made into a thin glass sheet 2 with the thickness of 1mm, and the thin glass sheet is preheated at 500 ℃ to be subjected to ion exchange treatment.
(3) Lithium carbonate and potassium nitrate salt are prepared into mixed molten salt according to the molar ratio of 2:1, and the mixed molten salt is put into a toughening container and is melted into liquid toughening salt bath at the temperature of 730 ℃.
(4) And immersing the preheated thin glass sheet 2 into a tempering salt bath at 730 ℃ for ion exchange treatment and crystallization heat treatment for 1 hour to prepare a glass intermediate.
(5) And taking out the glass intermediate, and cooling at the speed of 70 ℃/min to obtain the glass ceramics 2.
(6) And (3) cleaning the toughened salt on the surface of the microcrystalline glass 2 in an acid solution, and then fully cleaning the surface of the microcrystalline glass with clear water.
Example 3
The embodiment provides a method for toughening microcrystalline glass and microcrystalline glass prepared by the toughening method.
(1) The microcrystalline glass precursor in this example had the following composition:
MgO 6％；ZnO 7％；Al 2 O 3 20％；SiO 2 50％；Na 2 O 4％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, sodium carbonate, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance to form a microcrystalline glass precursor with large volume.
(2) The microcrystalline glass precursor is cut and polished to be made into a thin glass sheet 3 with the thickness of 1mm, and the thin glass sheet is preheated at 500 ℃ to be subjected to ion exchange treatment.
(3) Lithium carbonate and potassium nitrate salt are prepared into mixed molten salt according to the molar ratio of 1:2, and the mixed molten salt is put into a toughening container and is melted into a liquid toughening salt bath at the temperature of 700 ℃.
(4) And immersing the preheated thin glass sheet 3 into a 700 ℃ tempering salt bath for ion exchange treatment and crystallization heat treatment, wherein the duration is 1 hour, and preparing the glass intermediate.
(5) And taking out the glass intermediate, and cooling at the speed of 70 ℃/min to obtain the glass ceramics 3.
(6) And (4) cleaning the toughened salt on the surface of the microcrystalline glass 3 in an acid solution, and then fully cleaning the surface of the microcrystalline glass with clear water.
Example 4
The embodiment provides a method for toughening microcrystalline glass and microcrystalline glass prepared by the toughening method.
(1) The microcrystalline glass precursor in this example had the following composition:
MgO 6％；ZnO 7％；Al 2 O 3 20％；SiO 2 50％；Na 2 O 4％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, sodium carbonate, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance to form a microcrystalline glass precursor with large volume.
(2) The microcrystalline glass precursor is cut and polished to be made into a thin glass sheet 4 with the thickness of 1mm, and the thin glass sheet is preheated at 500 ℃ to be subjected to ion exchange treatment.
(3) And putting the lithium carbonate into a toughening container, and melting the lithium carbonate into a liquid toughening salt bath at the temperature of 750 ℃.
(4) And immersing the preheated thin glass sheet 4 into a tempering salt bath at 750 ℃ for ion exchange treatment and crystallization heat treatment for 1 hour to prepare a glass intermediate.
(5) And taking out the glass intermediate, and cooling at the speed of 70 ℃/min to obtain the glass ceramics 4.
(6) And (4) cleaning the toughened salt on the surface of the microcrystalline glass 4 in an acid solution, and then fully cleaning the surface of the microcrystalline glass with clear water.
Comparative example 1
The comparative example provides a method for tempering microcrystalline glass and microcrystalline glass prepared by the tempering method.
(1) The composition of the microcrystalline glass precursor in this comparative example was as follows:
MgO 6％；ZnO 7％；Al 2 O 3 22％；SiO 2 52％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance to form a microcrystalline glass precursor with large volume.
(2) Cutting and polishing the microcrystalline glass precursor to prepare a thin glass sheet 5 with the thickness of 1mm, preheating at 500 ℃ and waiting for ion exchange treatment.
(3) Lithium carbonate and potassium nitrate salt are prepared into mixed molten salt according to the molar ratio of 1:2, and the mixed molten salt is put into a toughening container and is melted into a liquid toughening salt bath at the temperature of 700 ℃.
(4) And immersing the preheated thin glass sheet 5 into a 700 ℃ tempering salt bath for ion exchange treatment and crystallization heat treatment, wherein the duration is 1 hour, and preparing the glass intermediate.
(5) And taking out the glass intermediate, and cooling at the speed of 70 ℃/min to obtain the microcrystalline glass 5.
(6) And (3) cleaning the toughened salt on the surface of the microcrystalline glass 5 in an acid solution, and then fully cleaning the surface of the microcrystalline glass with clear water.
Comparative example 2
The comparative example provides a method for tempering microcrystalline glass and microcrystalline glass prepared by the tempering method.
(1) The composition of the microcrystalline glass precursor in this comparative example was as follows:
MgO 6％；ZnO 7％；Al 2 O 3 20％；SiO 2 50％；Na 2 O 4％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, sodium carbonate, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance to form a microcrystalline glass precursor with large volume.
(2) Cutting and polishing the microcrystalline glass precursor to prepare a thin glass sheet 6 with the thickness of 1mm, preheating at 380 ℃, and waiting for ion exchange treatment.
(3) Putting potassium nitrate salt into a toughening container, and melting into a liquid toughening salt bath at the temperature of 400 ℃.
(4) And (3) tempering the preheated thin glass sheet 6 in tempering salt at 400 ℃ for 10 hours to obtain a glass intermediate.
(5) And taking out the glass intermediate, and cooling at the speed of 70 ℃/min to obtain the glass ceramics 6.
(6) And (4) cleaning the toughened salt on the surface of the microcrystalline glass 6 in an aqueous solution.
Comparative example 3
The comparative example provides a method for tempering microcrystalline glass and microcrystalline glass prepared by the tempering method.
(1) The composition of the microcrystalline glass precursor in this comparative example was as follows:
MgO 6％；ZnO 7％；Al 2 O 3 20％；SiO 2 50％；Na 2 O 4％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, sodium carbonate, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance to form a microcrystalline glass precursor with large volume.
(2) Crystallizing the microcrystalline glass precursor at 700 ℃ to prepare a glass intermediate I.
(3) And cutting and polishing the glass intermediate I to prepare a thin glass sheet 7 with the thickness of 1mm, preheating at 380 ℃, and waiting for ion exchange treatment.
(4) Lithium carbonate and potassium nitrate salt are prepared into mixed molten salt according to the molar ratio of 1:2, and the mixed molten salt is put into a toughening container and is melted into a liquid toughening salt bath at the temperature of 500 ℃.
(4) And (3) immersing the preheated thin glass sheet 7 into a 500-DEG C tempering salt bath for ion exchange treatment, wherein the duration is 1 hour, and preparing a glass intermediate II.
(5) And taking out the glass intermediate II, and cooling at the speed of 70 ℃/min to obtain the glass ceramics 7.
(6) And (3) cleaning the toughened salt on the surface of the microcrystalline glass 7 in an acid solution, and then fully cleaning the surface of the microcrystalline glass with clear water.
Comparative example 4
The comparative example provides a method for tempering microcrystalline glass and microcrystalline glass prepared by the tempering method.
(1) The composition of the microcrystalline glass precursor in this comparative example was as follows:
MgO 6％；ZnO 7％；Al 2 O 3 20％；SiO 2 50％；Na 2 O 4％；CaO 1％；SnO 2 1％；TiO 2 2％；ZrO 4％；P 2 O 5 2％；Sb 2 O 3 1％；B 2 O 3 2％。
the glass raw materials are as follows: magnesium carbonate, zinc oxide, alumina, silica, sodium carbonate, calcium carbonate, tin oxide, titanium dioxide, zirconium oxide, ammonium dihydrogen phosphate, sodium antimonate and boric acid.
After the ingredients are converted, the glass raw materials and the auxiliary agents are fully and uniformly mixed and put into a glass melting furnace to be melted at the temperature of 1550 ℃ for 3 hours. Pouring the molten glass into a mold preheated to 500 ℃ in advance after the melting is finished, and forming a microcrystalline glass precursor with larger volume.
(2) The microcrystalline glass precursor is cut and polished to be made into a thin glass sheet 8 with the thickness of 1mm, and the thin glass sheet is preheated at 500 ℃ to be subjected to ion exchange treatment.
(3) Putting potassium nitrate salt into a toughening container, and melting into a liquid toughening salt bath at 700 ℃.
(4) And immersing the preheated thin glass sheet 8 into a 700 ℃ tempering salt bath for ion exchange treatment and crystallization heat treatment, wherein the duration is 1 hour, and preparing the glass intermediate.
(5) And taking out the glass intermediate, and cooling at the speed of 70 ℃/min to obtain the glass ceramics 8.
(6) And (3) washing the toughened salt on the surface of the microcrystalline glass 8 in water, and fully washing the surface of the microcrystalline glass with clear water.
The microcrystalline glasses obtained in examples 1 to 4 and comparative examples 1 to 4 were subjected to appearance test, stress depth test, impact resistance and micro vickers hardness test.
The evaluation method is as follows:
appearance: through a light transmittance test, the glass is transparent when the lowest transmittance of the glass is more than 80 percent in the visible light wavelength range, is semitransparent when the lowest transmittance is between 60 and 80 percent, and is opaque when the lowest transmittance is less than 60 percent.
Stress depth: and (3) carrying out element content test on the surface of the glass by using an XPS test method, and testing the relative content of lithium elements or sodium elements at different depths to judge the depth of ion exchange.
Fixing the glass ceramics, dropping a steel ball with the mass of 60g from the height of 30cm by free-fall motion, pounding the steel ball to the center position of the overhead glass surface, increasing the height of the dropped ball gradually by 5cm in sequence without breaking until the glass is broken, and recording the dropping height of the steel ball when the glass is broken.
And performing a micro Vickers hardness test on the glass before and after tempering, wherein the test loading load is 200 g.
The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the microcrystalline glasses obtained in examples 1 to 4 had normal appearance, and were classified into 3 types, i.e., transparent, opaque and translucent; the stress depth is 21-38 μm; the breaking height is more than or equal to 60cm, which shows that the toughened glass has good impact resistance, and the Vickers hardness after toughening is increased by 12-20% compared with the Vickers hardness before toughening.
In comparison with comparative example 1, it can be seen that if the addition of sodium oxide is omitted in the formula of the glass raw material, no exchangeable alkali metal ions are present in the glass, so that the surface component cannot be modified, and after crystallization, a microcrystalline glass phase with a difference between the surface layer and the inner layer cannot be formed, so that the surface layer cannot form a tempering stress, and the impact resistance result is poor.
In comparison with comparative example 2, it can be seen that if the glass ceramics are tempered by using a common tempering method, potassium ions in the tempered salt exchange with sodium ions in the glass and then the surface expands to form compressive stress, but the ball drop effect is inferior to that of the method of the present invention, and the glass has poor surface hardness because no crystal is formed by the glass which is not crystallized.
As can be seen from comparison example 3, if the crystallized glass precursor is subjected to the crystallization heat treatment and then the ion exchange treatment, the inner layer and the surface layer of the glass form partially ordered crystal structures after the crystallization heat treatment, and thus ion exchange is difficult to perform, even if the glass intermediate obtained after the crystallization heat treatment is immersed in the tempered molten salt, the ion exchange efficiency is low, and the ion exchange temperature is higher than the glass transition point, and the surface compressive stress is not formed. The difference of thermal expansion coefficients between the inner layer microcrystalline glass and the surface layer microcrystalline glass is not obvious, the pressure stress is difficult to form in the cooling process, and the shock resistance is poor.
In comparison with comparative example 4, it is known that if the addition of lithium salt is omitted in the tempered molten salt, the surface layer cannot form a high concentration lithium ion content, and therefore, the surface layer cannot form spodumene or eucryptite glass ceramics having a lower coefficient of thermal expansion, the surface layer and the inner layer cannot form glass ceramics having a difference in coefficient of expansion, the surface layer cannot form compressive stress, and the impact resistance result is poor.
The above data fully show that according to the method for tempering microcrystalline glass of the present invention, the surface layer components of the microcrystalline glass precursor are changed by ion exchange, i.e. the surface of the glass is modified, and then the glass intermediate is subjected to crystallization heat treatment to obtain microcrystalline glass with a surface crystal phase inconsistent with an inner crystal phase. The thermal expansion coefficient of the surface layer microcrystalline glass is greatly different from that of the inner layer microcrystalline glass, and the surface layer microcrystalline glass is subjected to the compressive stress applied by the inner layer microcrystalline glass in the cooling shrinkage process, so that the aim of toughening the microcrystalline glass is fulfilled, the resistance impact strength of the microcrystalline glass is improved, and the problem that the traditional chemical toughening method of the aluminosilicate glass is not suitable for the microcrystalline glass is solved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The method for toughening the microcrystalline glass is characterized by comprising the following steps of:
respectively melting glass raw materials and metal salt to prepare a microcrystalline glass precursor and toughened molten salt;
immersing the microcrystalline glass precursor into the tempering molten salt, and carrying out tempering treatment for 1-4 h at the temperature of 700-850 ℃ to prepare a glass intermediate;
cooling the glass intermediate;
the metal salt is lithium salt, or the metal salt is formed by mixing lithium carbonate and potassium nitrate according to the molar ratio of (1:1) - (3: 1);
the glass intermediate comprises a surface layer and an inner layer, and the thermal expansion coefficient of the surface layer of the glass intermediate is smaller than that of the inner layer of the glass intermediate;
the microcrystalline glass precursor comprises the following components in percentage by mass:
2 to 6 percent of sodium oxide, 45 to 60 percent of silicon dioxide, 15 to 30 percent of aluminum oxide, 1 to 17 percent of calcium oxide, 5 to 10 percent of magnesium oxide, 6 to 10 percent of zinc oxide, 2 to 6 percent of zirconium oxide, 1 to 4 percent of titanium dioxide, 2 to 4 percent of phosphorus pentoxide, 0 to 3 percent of boron oxide, 0 to 2 percent of tin oxide and 1 to 2 percent of antimony trioxide.
2. The method for tempering glass ceramic according to claim 1, wherein said lithium salt is selected from at least one of lithium nitrate, lithium carbonate, lithium chloride and lithium hydroxide.
3. The method for tempering glass ceramic according to claim 2, wherein said metal salt further comprises a potassium salt selected from at least one of potassium nitrate, potassium carbonate, potassium chloride and potassium hydroxide.
4. A method for tempering glass ceramics according to claim 3, wherein said metal salt is formed by mixing lithium carbonate and potassium nitrate in a molar ratio of (2:1) - (3: 1).
5. The method for tempering glass ceramic according to claim 4, wherein said metal salt is formed by mixing lithium carbonate and potassium nitrate in a molar ratio of 2:1 or 3: 1.
6. The method for tempering glass ceramic according to any one of claims 1 to 5, wherein a temperature for melting said metal salt is 600 ℃ to 950 ℃; the temperature for melting the glass raw materials is 1400-1600 ℃, and the time is 2-10 h.
7. The method for tempering glass ceramics according to any one of claims 1 to 5, wherein in the preparation of the glass ceramics precursor, after the step of melting the glass raw material, the method further comprises the steps of cooling, cutting and polishing;
and when the glass intermediate is cooled, the cooling rate of the cooling treatment is 60-80 ℃/min.
8. The microcrystalline glass prepared by the method for tempering microcrystalline glass recited in any one of claims 1 to 7.
9. A shell of an electronic product is characterized in that the preparation raw material comprises microcrystalline glass prepared by the toughening method of any one of claims 1 to 7 or microcrystalline glass of claim 8;
the electronic product is selected from a mobile phone, a flat panel, a watch or a vehicle-mounted product.
10. The glass cover plate of the display panel is characterized in that raw materials for preparing the glass cover plate comprise microcrystalline glass prepared by the microcrystalline glass toughening method according to any one of claims 1 to 7 or microcrystalline glass according to claim 8;
the display panel is selected from a display panel of a mobile phone, a display panel of a flat plate, a display panel of a watch or a display panel of a vehicle.
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