CN110577355A - Method for strengthening nanocrystalline glass ceramic - Google Patents

Method for strengthening nanocrystalline glass ceramic Download PDF

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Publication number
CN110577355A
CN110577355A CN201910848530.4A CN201910848530A CN110577355A CN 110577355 A CN110577355 A CN 110577355A CN 201910848530 A CN201910848530 A CN 201910848530A CN 110577355 A CN110577355 A CN 110577355A
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China
Prior art keywords
nanocrystalline glass
glass ceramic
nanocrystalline
strengthening
ceramic
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CN201910848530.4A
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Chinese (zh)
Inventor
姚全星
张月皎
罗恺
袁晓波
刘庆
李军旗
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Shenzhen Jingshi Yun Chuang Technology Co Ltd
Shenzhen Jingjiang Yunchuang Technology Co Ltd
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Shenzhen Jingshi Yun Chuang Technology Co Ltd
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Priority to CN201910848530.4A priority Critical patent/CN110577355A/en
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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
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container 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
    • 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
    • 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
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Abstract

a method for strengthening nanocrystalline glass-ceramics comprises the following steps: providing a nanocrystalline glass-ceramic; placing the nanocrystalline glass ceramic in a preheating furnace for preheating treatment; taking the nanocrystalline glass ceramic subjected to preheating treatment out of the preheating furnace, placing the nanocrystalline glass ceramic in a reaction furnace for strengthening treatment, and placing the nanocrystalline glass ceramic in a first molten salt for first strengthening, wherein the first molten salt is a molten salt at least containing one of potassium nitrate and sodium nitrate, an ion exchange reaction exists between the nanocrystalline glass ceramic and the first molten salt, and the first strengthening time is first strengthening time; and taking out the nanocrystalline glass ceramic from the reaction furnace after the first strengthening is completed, and cooling.

Description

Method for strengthening nanocrystalline glass ceramic
Technical Field
The invention relates to the field of chemical industry, in particular to a method for strengthening nanocrystalline glass ceramic.
background
Nanocrystalline glass-ceramics are a multiphase composite material that combines a dense nanocrystalline phase (crystalline phase) with a glassy phase. After the base glass with specific composition is heat treated, the glass liquid phase generates nucleus and grows crystal, and the composite material with homogeneous nanometer crystal phase and glass phase is further produced. The nano-crystalline glass ceramic has excellent performance, on one hand, the nano-crystalline glass ceramic has the characteristics of high strength, high hardness and the like of the ceramic, and the nano-crystalline glass ceramic has good wear resistance and corrosion resistance, strong impact resistance and stable chemical performance; on the other hand, the nanocrystalline glass ceramic has high permeability of glass, and can realize curved surface molding by using a thermal molding process. The nanocrystalline glass ceramic can be widely applied to screen cover plates and back plates of intelligent products such as smart phones, smart watches, tablet computers, automobile central control protection screens and the like, and can also be widely applied to microscopes, digital cameras, projectors and various optical lenses.
Nanocrystalline glass ceramic materials can have unique advantages in terms of mechanical strength, surface hardness, thermal expansion properties, thermal stability, and the like, but nanocrystalline glass ceramic materials still have surface defects, and may crack when a sufficiently large tensile stress is applied to the surface defects. It is considered by those skilled in the art how to provide a composition distribution ratio of a nanocrystalline glass ceramic and a corresponding strengthening method thereof to further effectively improve the performance of the nanocrystalline glass ceramic.
disclosure of Invention
In view of the above, the present invention provides a method for strengthening a nanocrystalline glass ceramic.
The invention provides a method for strengthening nanocrystalline glass ceramics, which is characterized by comprising the following steps:
Providing a nanocrystalline glass-ceramic;
Placing the nanocrystalline glass ceramic in a preheating furnace for preheating treatment;
Taking the nanocrystalline glass ceramic subjected to preheating treatment out of the preheating furnace, placing the nanocrystalline glass ceramic in a reaction furnace for strengthening treatment, and placing the nanocrystalline glass ceramic in a first molten salt for first strengthening, wherein the first molten salt is a molten salt at least containing one of potassium ions and sodium ions, an ion exchange reaction exists between the nanocrystalline glass ceramic and the first molten salt, and the first strengthening time is first strengthening time; and
And taking out the nanocrystalline glass ceramic from the reaction furnace after the first strengthening is completed, and cooling.
Further, the method also comprises the following steps:
Placing the cooled nanocrystalline glass ceramic in a preheating furnace for preheating treatment;
Taking the nanocrystalline glass ceramic subjected to preheating treatment out of the preheating furnace, placing the nanocrystalline glass ceramic in a reaction furnace for strengthening treatment, and placing the nanocrystalline glass ceramic in a second molten salt for strengthening for the second time, wherein the second molten salt is a molten salt at least containing one of potassium ions or sodium ions, an ion exchange reaction exists between the nanocrystalline glass ceramic and the second molten salt, and the time of strengthening for the second time is the second strengthening time; and
and taking out the nanocrystalline glass ceramic from the reaction furnace after the second strengthening is completed, and cooling.
Further, the first reinforcement time is greater than the second reinforcement time.
Further, the first molten salt and the second molten salt both contain potassium ions, and the concentration of the potassium ions in the first molten salt is smaller than that of the potassium ions in the second molten salt.
Further, the first molten salt is a mixture containing potassium ions and sodium ions, and the second molten salt is a mixture containing potassium ions and sodium ions.
Further, the temperature range of the ion exchange between the nanocrystalline glass ceramic and the first molten salt is 350 ℃ to 600 ℃, and the temperature range of the ion exchange between the nanocrystalline glass ceramic and the second molten salt is 350 ℃ to 600 ℃.
Further, the step of cooling the nanocrystalline ceramic material comprises: and directly taking out the nanocrystalline glass ceramic from the reaction furnace and physically cooling the nanocrystalline glass ceramic sheet to cool the nanocrystalline glass ceramic to room temperature.
Further, the step of cooling the nanocrystalline ceramic material comprises: and taking the nanocrystalline glass ceramic out of the reaction furnace, placing the nanocrystalline glass ceramic above the reaction furnace in a hanging manner for 2-10 minutes to enable molten salt on the surface of the nanocrystalline glass ceramic to drip back into the reaction furnace, placing the nanocrystalline glass ceramic in the preheating furnace to be cooled to a temperature not higher than 100 ℃, and taking the nanocrystalline glass ceramic out of the preheating furnace and cooling to room temperature.
Further, the step of cooling the nanocrystalline ceramic material comprises: and taking the nanocrystalline glass ceramic out of the reaction furnace, placing the nanocrystalline glass ceramic above the reaction furnace in a hanging manner for 2-10 minutes to enable molten salt on the surface of the nanocrystalline glass ceramic to drop back into the reaction furnace, placing the nanocrystalline glass ceramic in the preheating furnace to be cooled to 250-300 ℃, taking the nanocrystalline glass ceramic out of the preheating furnace and physically cooling the nanocrystalline glass ceramic to enable the nanocrystalline glass ceramic to be cooled to room temperature.
Further, the step of cooling the nanocrystalline ceramic material comprises: taking the nanocrystalline glass ceramic out of the reaction furnace, placing the nanocrystalline glass ceramic above the reaction furnace in a hanging manner for 10-30 minutes to enable molten salt on the surface of the nanocrystalline glass ceramic to drop back into the reaction furnace, placing the nanocrystalline glass ceramic in the preheating furnace to be cooled at a constant temperature of 300-400 ℃, naturally cooling the nanocrystalline glass ceramic to be not more than 100 ℃, and taking the nanocrystalline glass ceramic out of the preheating furnace to be cooled to room temperature.
Further, the nanocrystalline glass ceramic comprises the following components in percentage by weight: 40 to 80 percent of silicon dioxide, 5 to 35 percent of aluminum oxide, 0 to 10 percent of magnesium oxide, 0 to 10 percent of zinc oxide, 0.5 to 20 percent of potassium oxide, 0.5 to 20 percent of sodium oxide, 0 to 10 percent of calcium oxide, 0 to 8 percent of ferric oxide, 0 to 8 percent of phosphorus oxide, 0 to 8 percent of titanium dioxide, 0 to 8 percent of zirconium dioxide, 0 to 5 percent of tin dioxide, 0 to 5 percent of antimony oxide, 0 to 5 percent of boron oxide and 0 to 5 percent of arsenic trioxide.
The strengthening method of the nanocrystalline glass ceramic comprises a primary strengthening method and a secondary strengthening method. The primary strengthening method can enable the nanocrystalline glass ceramic to form larger surface compressive stress CS and deeper stress layer DOL; the first strengthening in the two strengthening methods can increase the depth DOL of the ion exchange layer, and the second strengthening can increase the surface compressive stress CS, thereby effectively reducing the central tensile stress CT value of the nanocrystalline glass ceramic. After the nano-crystalline glass ceramic material sheet is subjected to strengthening treatment, the surface chemical components of the nano-crystalline glass ceramic material sheet are changed, the potassium ion content of the surface of the nano-crystalline glass ceramic is increased, the potassium ion content and the sodium ion content in the stress layer are in gradient change, and the strength of the strengthened nano-crystalline glass ceramic is obviously improved.
Drawings
fig. 1 is a schematic flow chart of a primary strengthening method of a nanocrystalline glass ceramic according to an embodiment of the present invention.
FIG. 2 is a schematic flow chart of a secondary strengthening method for a nano-crystalline glass-ceramic according to an embodiment of the present invention.
Description of the main elements
Step (ii) of S101～S107、S201～S212
the following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention and the scope of the present invention is therefore not limited to the specific embodiments disclosed below.
the nanocrystalline glass ceramic of the invention comprises the following raw materials in percentage by weight:
Silicon dioxide (SiO)2) 40-80% of aluminum oxide (Al)2O3) 5-35 percent of magnesium oxide (MgO), 0-10 percent of zinc oxide (ZnO), and potassium oxide (K)20.5% -20% of O), and sodium oxide (Na)20.5 to 20 percent of O), 0 to 10 percent of calcium oxide (CaO), and ferric oxide (Fe)2O3) 0% -8% of phosphorus oxide (P)2O5) 0% -8% of titanium dioxide (TiO)2) 0% -8% of zirconium dioxide (ZrO)2) 0% -8% of tin dioxide (SnO)2) 0% -5%, antimony oxide (Sb)2O3) 0% -5%, boron oxide (B)2O3) 0% -5% of arsenic trioxide (As)2O3)0％-5％。
wherein, SiO2SiO, a basic skeleton for forming nanocrystalline glass-ceramics2An excessively low content may destabilize or coarsen the crystalline phase generated in the nanocrystalline glass ceramic and may cause the nanocrystalline glass ceramic to lack gloss or even to lose transparency, while SiO2Too high a content makes the raw material difficult to melt, so that the nanocrystalline glass-ceramic preparation process requires a higher melting temperature, and therefore, SiO2The weight percentage of the components is controlled to be between 40 and 80 percent.
Wherein, Al2O3Can be used for increasing the nanometerMechanical strength and stability of the crystallized glass-ceramic, however, when Al is used2O3when the content is too high, difficulty may occur in the melting process of the nanocrystalline glass-ceramic or the devitrification resistance thereof may be lowered, and therefore, Al2O3The weight percentage of the components is controlled to be between 5 and 35 percent.
Wherein, MgO can be used to make the nanocrystalline glass ceramic form a high-strength stable crystal phase, and proper amount of MgO can enhance the mechanical strength and chemical stability of the nanocrystalline glass ceramic, therefore, the weight percentage of MgO can be between 0% and 10%.
wherein, ZnO can be used for improving the chemical stability of the nanocrystalline glass ceramic, and can be used for reducing the softening point temperature of the nanocrystalline glass ceramic, which is beneficial to the melting preparation process of the nanocrystalline glass ceramic, but the content of ZnO is too high, which causes great change of the crystal phase type, further leads to the incapability of forming stable crystal grains, therefore, the weight percentage of ZnO is controlled between 0 percent and 10 percent.
Wherein, K2O、Na2O can be used as a good cosolvent, can be an oxide outside a nano-crystalline glass ceramic structure network, and can effectively reduce the viscosity of the nano-crystalline glass ceramic so as to reduce the melting temperature. However, excessive Na2O causes the thermal expansion coefficient of the nanocrystalline glass ceramic to be increased, thereby causing the mechanical strength and the chemical stability of the nanocrystalline glass ceramic to be reduced; k2O can increase the transparency and gloss of the nanocrystalline glass-ceramic, but the content of K is too high2O reduces the devitrification ability of the nanocrystalline glass-ceramic, and thus, K2O or Na2the weight percentage of O should be controlled between 0.5% -20%.
Wherein, CaO can be used as a good cosolvent, can be an oxide outside a nanocrystalline glass ceramic structure network, and can effectively reduce the viscosity of the nanocrystalline glass ceramic so as to reduce the melting temperature. However, excessive CaO may cause the glass to have a short glass batch, an increased brittleness, and an increased tendency to crystallize in the nanocrystalline glass-ceramic, and therefore, the weight percentage of CaO should be controlled between 0% and 10%.
Wherein, B2O3Can be used as a good cosolvent, can be an oxide outside a nanocrystalline glass ceramic structure network, and has important influence on forming a stable network structure, so that B2O3May be between 0% and 5% by weight.
Wherein, Fe2O3Can be used as a crystal nucleus agent, Fe2O3precipitation and formation of nanocrystalline phases may be promoted, however, Fe2O3Too high a content may result in a deterioration of the compactness of the material and a decrease in the chemical stability of the material, and therefore, Fe2O3The weight percentage of the components is controlled to be between 0 and 8 percent.
Wherein, P2O5Can be used as a crystal nucleus agent, P2O5Can promote the precipitation and formation of nanocrystalline phase and prevent excessive grain growth, and can improve the dispersion coefficient and transmittance of nanocrystalline glass-ceramics, but the content of P is too high2O5The thermal expansion coefficient of the material is increased, so that the nanocrystalline glass ceramic generates a white turbidity phenomenon and is devitrified, and therefore, P2O5the weight percentage of the components is controlled to be between 0 and 8 percent.
Wherein, TiO2Can be used as a crystal nucleus agent, TiO2Can promote the precipitation and formation of nanocrystalline phases and increase the uniformity of nanocrystalline glass-ceramics, but contains too much TiO2May cause devitrification of the nanocrystalline glass-ceramic, and thus, TiO2The weight percentage of the components is controlled to be between 0 and 8 percent.
wherein, ZrO2Can be used as a nucleating agent, ZrO2Can promote the precipitation and formation of nanocrystalline phase and make the crystal grain fine, further can increase the mechanical strength and chemical stability of nanocrystalline glass ceramic, but the content of TiO is too high2May cause difficulty in melting the raw material, and thus, ZrO2The weight percentage of the components is controlled to be between 0 and 8 percent.
Wherein Sb2O3、As2O3、SnO2Can be used as clarifier, Sb2O3、As2O3、SnO2Is favorable for promoting the melting process of the raw materialsDischarge of bubbles to further improve the compactness of the nanocrystalline glass-ceramic, Sb2O3、As2O3、SnO2May be between 0% and 5% by weight.
The raw materials can be mixed according to the proportion to prepare the nanocrystalline glass ceramic, and the prepared nanocrystalline glass ceramic can be strengthened by a strengthening method to enhance the performance of the nanocrystalline glass ceramic.
As shown in FIG. 1, the present invention provides a primary strengthening method of nanocrystalline glass-ceramics:
Step S101: and cutting, polishing and cleaning the nanocrystalline glass ceramic.
Specifically, after polishing and grinding, cutting the nanocrystalline glass ceramic into nanocrystalline glass ceramic sheets with the thickness ranging from 0.2mm to 5mm, polishing the nanocrystalline glass ceramic sheets, then placing the nanocrystalline glass ceramic sheets in a cleaning clamping groove and placing the nanocrystalline glass ceramic sheets in a cleaning machine for cleaning for 30-60 minutes, and taking out the nanocrystalline glass ceramic sheets after cleaning.
Step S102: transferring the nanocrystalline glass ceramic to a fixing frame, and placing the fixing frame provided with the nanocrystalline glass ceramic in a bearing basket.
specifically, the cleaned nanocrystalline glass ceramic sheet is moved to a tempering fixing frame from a cleaning clamping groove, the tempering fixing frame provided with the nanocrystalline glass ceramic sheet is placed into a bearing hanging basket of the strengthening equipment, and the bearing hanging basket can bear materials and enter a strengthening preheating furnace and a reaction furnace.
Step S103: and placing the nanocrystalline glass ceramic in a preheating furnace for preheating treatment.
Specifically, the nanocrystalline glass-ceramic sheet is placed in a preheating furnace and subjected to a preheating treatment at a temperature in the range of 320 ℃ to 400 ℃ for 40 to 120 minutes.
Step S104: and placing the nanocrystalline glass ceramic in first molten salt of the reaction furnace for first strengthening.
Specifically, the preheated nanocrystalline glass ceramic sheet is placed in a reaction furnace, and the nanocrystalline glass ceramic sheet is immersed in a first molten salt for ion exchange, wherein the first strengthening temperature (temperature range of the ion exchange process) is 350 ℃ to 600 ℃, and the first strengthening time (ion exchange holding time) is 120 to 600 minutes.
the first molten salt is a molten salt, and the salt ratio can be as follows:
The first proportioning: pure potassium nitrate (KNO)3)，KNO3The purity of (A) is more than 99.9%;
the second proportioning: pure sodium nitrate (NaNO)3)，NaNO3The purity of (A) is more than 99.9%;
and a third ratio: 50% -99.9% potassium nitrate (KNO)3) 0.1-50% of sodium nitrate (NaNO)3) And 0-5% of additives and catalysts;
And a fourth ratio: 0.1-50% potassium nitrate (KNO)3) 50 to 99.9 percent of sodium nitrate (NaNO)3) And 0-5% of additive and catalyst.
The nanocrystalline glass ceramic sheet can be placed in a first molten salt with any ratio from the first ratio to the fourth ratio for ion exchange, wherein potassium nitrate in the ratio can be replaced by other salts containing potassium ions, such as potassium sulfate, potassium chloride and the like, sodium nitrate can be replaced by other salts containing sodium ions, such as sodium sulfate, sodium chloride and the like, and lithium nitrate can be replaced by other salts containing lithium ions, such as lithium sulfate, lithium chloride and the like.
Potassium ions in the molten salt can exchange with sodium ions in the nanocrystalline glass ceramic, potassium ions in the nanocrystalline glass ceramic migrate to the surface, sodium ions in the molten salt migrate to the nanocrystalline glass ceramic part, and a surface pressure stress layer is formed on the surface of the nanocrystalline glass ceramic. In the exchange process, more potassium ions are obtained from the surface of the nanocrystalline glass ceramic through exchange, less potassium ions are obtained from the interior of the nanocrystalline glass ceramic through exchange, and the compressive stress of the surface of the nanocrystalline glass ceramic is gradually reduced from the surface to the interior.
Step S105: and taking out the nanocrystalline glass ceramic from the reaction furnace for cooling after the first strengthening is completed.
Specifically, after the first strengthening, the carrying basket carrying the nanocrystalline glass ceramic sheet is taken out of the reaction furnace and cooled, and the cooling process may include the following four cooling methods:
the first cooling method: rapidly cooling, namely directly taking out the bearing hanging basket from the reaction furnace without placing the bearing hanging basket in a preheating furnace, and physically cooling the nanocrystalline glass ceramic sheet by using a fan, wherein the temperature of the nanocrystalline glass ceramic sheet is rapidly reduced to room temperature;
The second cooling method: naturally cooling, namely taking the bearing hanging basket bearing the nanocrystalline glass ceramic sheet out of a reaction furnace, taking the nanocrystalline glass ceramic sheet out of the reaction furnace, suspending and placing the nanocrystalline glass ceramic sheet above the reaction furnace, and allowing molten salt on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, wherein in the process, on one hand, the waste of molten salt can be avoided, and on the other hand, excessive salt can be avoided from being generated on the surface of the cooled nanocrystalline glass ceramic sheet, the salt dropping time is 2-10 minutes, then, the nanocrystalline glass ceramic sheet is placed in a preheating furnace for cooling, then, the temperature is reduced to be below 100 ℃ in a natural cooling mode, then, a preheating furnace door is opened, the bearing hanging basket is taken out, and the nanocrystalline glass ceramic sheet is allowed to stand to room temperature;
The third cooling method: gradient cooling, namely taking out the nanocrystalline glass ceramic sheet from the reaction furnace, suspending the nanocrystalline glass ceramic sheet above the reaction furnace, and enabling molten salt on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, wherein in the process, on one hand, the molten salt can be prevented from being wasted, on the other hand, excessive salt can be prevented from being generated on the surface of the cooled nanocrystalline glass ceramic sheet, the salt dropping time is 2-10 minutes, the temperature is reduced to 250-300 ℃ in a natural cooling mode, then the hanging basket bearing material is taken out from the furnace, a fan is used for physically cooling the nanocrystalline glass ceramic sheet, and the temperature of the nanocrystalline glass ceramic sheet is quickly reduced to room temperature;
The fourth cooling method: annealing, taking the bearing hanging basket bearing the nanocrystalline glass ceramic sheet out of the reaction furnace, taking the nanocrystalline glass ceramic sheet out of the reaction furnace, suspending the nanocrystalline glass ceramic sheet above the reaction furnace, and enabling the salt in the molten state on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, the process can avoid the waste of salts in a molten state on one hand and the excessive salt generated on the surface of the cooled nanocrystalline glass ceramic sheet on the other hand, the salt dripping time is 10 to 30 minutes, then the nanocrystalline glass ceramic sheet is placed in the preheating furnace for cooling, the temperature in the preheating furnace is constant, the temperature range in the preheating furnace is 300-400 ℃, after the molten salt dripping is finished, and cooling to below 100 ℃ in a natural cooling mode, then opening a preheating furnace door, taking out the bearing hanging basket, and standing the nanocrystalline glass ceramic sheet to room temperature.
the strengthening time of the nanocrystalline glass ceramic can be prolonged through the cooling and annealing processes, and the depth of ion exchange is increased.
Step S106: and cleaning the nanocrystalline glass ceramic to remove the molten salt on the surface of the nanocrystalline glass ceramic.
Specifically, the tempered fixing frame bearing the nanocrystalline glass ceramic is placed in a water bath to remove the molten salt on the surface of the nanocrystalline glass ceramic, and the water bath mode for dissolving the molten salt at least comprises the following 3 modes:
The first water bath mode: placing the toughened fixing frame bearing the nanocrystalline glass ceramics in a hot water bath with the temperature range of 50-70 ℃ for soaking or spraying for 20-60 minutes;
the second water bath mode: placing the toughened fixing frame bearing the nanocrystalline glass ceramics in a cold water bath at the temperature of 15-35 ℃ for soaking or spraying for 20-60 minutes;
the third water bath mode: firstly, the toughened fixing frame bearing the nanocrystalline glass ceramics is placed in a hot water bath with the temperature range of 50-70 ℃ for soaking or spraying for 20-60 minutes, and then the toughened fixing frame bearing the nanocrystalline glass ceramics is placed in a cold water bath with the temperature range of 15-35 ℃ for soaking or spraying for 20-60 minutes.
step S107: and drying the nanocrystalline glass ceramic.
Specifically, the tempered fixing frame bearing the nanocrystalline glass ceramic is taken out of the water bath and is kept stand for draining water for 20-30 minutes until the water stain is drained.
As shown in FIG. 2, the present invention provides a secondary strengthening method of a nanocrystalline glass-ceramic:
Step S201: and cutting, polishing and cleaning the nanocrystalline glass ceramic.
specifically, after polishing and grinding, cutting the nanocrystalline glass ceramic into nanocrystalline glass ceramic sheets with the thickness ranging from 0.2mm to 5mm, polishing the nanocrystalline glass ceramic sheets, then placing the nanocrystalline glass ceramic sheets in a cleaning clamping groove and placing the nanocrystalline glass ceramic sheets in a cleaning machine for cleaning for 30-60 minutes, and taking out the nanocrystalline glass ceramic sheets after cleaning.
Step S202: transferring the nanocrystalline glass ceramic to a fixing frame, and placing the fixing frame provided with the nanocrystalline glass ceramic in a bearing basket.
Specifically, the cleaned nanocrystalline glass ceramic sheet is moved to a tempering fixing frame from a cleaning clamping groove, the tempering fixing frame provided with the nanocrystalline glass ceramic sheet is placed into a bearing hanging basket of the strengthening equipment, and the bearing hanging basket can bear materials and enter a strengthening preheating furnace and a reaction furnace.
step S203: and placing the nanocrystalline glass ceramic in a preheating furnace for preheating treatment.
Specifically, the nanocrystalline glass-ceramic sheet is placed in a preheating furnace and subjected to a preheating treatment at a temperature in the range of 320 ℃ to 400 ℃ for 40 to 120 minutes.
Step S204: and placing the nanocrystalline glass ceramic in first molten salt of the reaction furnace for first strengthening.
specifically, the preheated nanocrystalline glass ceramic sheet is placed in a reaction furnace, and the nanocrystalline glass ceramic sheet is immersed in a first molten salt for ion exchange, wherein the first strengthening temperature (temperature range of the ion exchange process) is 350 ℃ to 600 ℃, and the first strengthening time (ion exchange holding time) is 120 to 600 minutes.
The first molten salt is a molten salt, and the salt ratio can be as follows:
The first proportioning: pure potassium nitrate (KNO3)，KNO3The purity of (A) is more than 99.9%;
The second proportioning: pure sodium nitrate (NaNO)3)，NaNO3The purity of (A) is more than 99.9%;
And a third ratio: 50% -99.9% potassium nitrate (KNO)3) 0.1-50% of sodium nitrate (NaNO)3) And 0-5% of additives and catalysts;
And a fourth ratio: 0.1-50% potassium nitrate (KNO)3) 50 to 99.9 percent of sodium nitrate (NaNO)3) And 0-5% of additive and catalyst.
the nanocrystalline glass ceramic sheet can be placed in a first molten salt with any ratio from the first ratio to the fourth ratio for ion exchange, wherein potassium nitrate in the ratio can be replaced by other salts containing potassium ions, such as potassium sulfate, potassium chloride and the like, sodium nitrate can be replaced by other salts containing sodium ions, such as sodium sulfate, sodium chloride and the like, and lithium nitrate can be replaced by other salts containing lithium ions, such as lithium sulfate, lithium chloride and the like.
Potassium ions in the molten salt can exchange with sodium ions in the nanocrystalline glass ceramic, potassium ions in the nanocrystalline glass ceramic migrate to the surface, sodium ions in the molten salt migrate to the nanocrystalline glass ceramic part, and a surface pressure stress layer is formed on the surface of the nanocrystalline glass ceramic. In the exchange process, more potassium ions are obtained from the surface of the nanocrystalline glass ceramic through exchange, less potassium ions are obtained from the interior of the nanocrystalline glass ceramic through exchange, and the compressive stress of the surface of the nanocrystalline glass ceramic is gradually reduced from the surface to the interior.
Step S205: and taking out the nanocrystalline glass ceramic from the reaction furnace for cooling after the first strengthening is completed.
Specifically, after the first strengthening, the carrying basket carrying the nanocrystalline glass ceramic sheet is taken out of the reaction furnace and cooled, and the cooling process may include the following four cooling methods:
The first cooling method: rapidly cooling, namely directly taking out the bearing hanging basket from the reaction furnace without placing the bearing hanging basket in a preheating furnace, and physically cooling the nanocrystalline glass ceramic sheet by using a fan, wherein the temperature of the nanocrystalline glass ceramic sheet is rapidly reduced to room temperature;
The second cooling method: naturally cooling, namely taking the bearing hanging basket bearing the nanocrystalline glass ceramic sheet out of a reaction furnace, taking the nanocrystalline glass ceramic sheet out of the reaction furnace, suspending and placing the nanocrystalline glass ceramic sheet above the reaction furnace, and allowing molten salt on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, wherein in the process, on one hand, the waste of molten salt can be avoided, and on the other hand, excessive salt can be avoided from being generated on the surface of the cooled nanocrystalline glass ceramic sheet, the salt dropping time is 2-10 minutes, then, the nanocrystalline glass ceramic sheet is placed in a preheating furnace for cooling, then, the temperature is reduced to be below 100 ℃ in a natural cooling mode, then, a preheating furnace door is opened, the bearing hanging basket is taken out, and the nanocrystalline glass ceramic sheet is allowed to stand to room temperature;
The third cooling method: gradient cooling, namely taking out the nanocrystalline glass ceramic sheet from the reaction furnace, suspending the nanocrystalline glass ceramic sheet above the reaction furnace, and enabling molten salt on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, wherein in the process, on one hand, the molten salt can be prevented from being wasted, on the other hand, excessive salt can be prevented from being generated on the surface of the cooled nanocrystalline glass ceramic sheet, the salt dropping time is 2-10 minutes, the temperature is reduced to 250-300 ℃ in a natural cooling mode, then the hanging basket bearing material is taken out from the furnace, a fan is used for physically cooling the nanocrystalline glass ceramic sheet, and the temperature of the nanocrystalline glass ceramic sheet is quickly reduced to room temperature;
The fourth cooling method: annealing, taking the bearing hanging basket bearing the nanocrystalline glass ceramic sheet out of the reaction furnace, taking the nanocrystalline glass ceramic sheet out of the reaction furnace, suspending the nanocrystalline glass ceramic sheet above the reaction furnace, and enabling the salt in the molten state on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, the process can avoid the waste of salts in a molten state on one hand and the excessive salt generated on the surface of the cooled nanocrystalline glass ceramic sheet on the other hand, the salt dripping time is 10 to 30 minutes, then the nanocrystalline glass ceramic sheet is placed in the preheating furnace for cooling, the temperature in the preheating furnace is constant, the temperature range in the preheating furnace is 300-400 ℃, after the molten salt dripping is finished, and cooling to below 100 ℃ in a natural cooling mode, then opening a preheating furnace door, taking out the bearing hanging basket, and standing the nanocrystalline glass ceramic sheet to room temperature.
Step S206: and cleaning the nanocrystalline glass ceramic to remove the molten salt on the surface of the nanocrystalline glass ceramic.
Specifically, the tempered fixing frame bearing the nanocrystalline glass ceramic is placed in a water bath to remove the molten salt on the surface of the nanocrystalline glass ceramic, and the water bath mode for dissolving the molten salt at least comprises the following 3 modes:
The first water bath mode: placing the toughened fixing frame bearing the nanocrystalline glass ceramics in a hot water bath with the temperature range of 50-70 ℃ for soaking or spraying for 20-60 minutes;
The second water bath mode: placing the toughened fixing frame bearing the nanocrystalline glass ceramics in a cold water bath at the temperature of 15-35 ℃ for soaking or spraying for 20-60 minutes;
The third water bath mode: firstly, the toughened fixing frame bearing the nanocrystalline glass ceramics is placed in a hot water bath with the temperature range of 50-70 ℃ for soaking or spraying for 20-60 minutes, and then the toughened fixing frame bearing the nanocrystalline glass ceramics is placed in a cold water bath with the temperature range of 15-35 ℃ for soaking or spraying for 20-60 minutes.
Step S207: and drying the nanocrystalline glass ceramic.
Specifically, the tempered fixing frame bearing the nanocrystalline glass ceramic is taken out of the water bath and is kept stand for draining water for 20-30 minutes until the water stain is drained.
Step S208: and placing the nanocrystalline glass ceramic in the preheating furnace for preheating treatment.
specifically, the nanocrystalline glass-ceramic sheet is placed in a preheating furnace and subjected to a preheating treatment at a temperature in the range of 320 ℃ to 400 ℃ for 40 to 120 minutes.
Step S209: and placing the nanocrystalline glass ceramic in second molten salt of the reaction furnace for second strengthening.
Specifically, the preheated nanocrystalline glass ceramic sheet is placed in a reaction furnace, and the nanocrystalline glass ceramic sheet is immersed in a second molten salt for ion exchange, wherein the second strengthening temperature (temperature range of the ion exchange process) is 350 ℃ to 600 ℃, and the second strengthening time (ion exchange holding time) is 10 to 200 minutes.
the second molten salt is a molten salt, and the salt ratio can be as follows:
The first proportioning: pure potassium nitrate (KNO)3)，KNO3The purity of (A) is more than 99.9%;
The second proportioning: pure sodium nitrate (NaNO)3)，NaNO3The purity of (A) is more than 99.9%;
And a third ratio: 50% -99.9% potassium nitrate (KNO)3) 0.1-50% of sodium nitrate (NaNO)3) And 0-5% of additives and catalysts;
And a fourth ratio: 0.1-50% potassium nitrate (KNO)3) 50 to 99.9 percent of sodium nitrate (NaNO)3) And 0-5% of additive and catalyst.
The nanocrystalline glass ceramic sheet can be placed in a second molten salt with any ratio from the first ratio to the fourth ratio for ion exchange, wherein potassium nitrate in the ratio can be replaced by other salts containing potassium ions, such as potassium sulfate, potassium chloride and the like, sodium nitrate can be replaced by other salts containing sodium ions, such as sodium sulfate, sodium chloride and the like, and lithium nitrate can be replaced by other salts containing lithium ions, such as lithium sulfate, lithium chloride and the like.
The first strengthening process emphasizes the increase of the depth of the ion exchange layer, the first chemically strong strengthening time is longer, and further the depth of the sodium-potassium ion exchange layer, namely DOL1, is prolonged. In the second strengthening process, the concentration of potassium ions in the molten salt is greater than that in the first strengthening process, and when the first molten salt and the second molten salt both contain potassium nitrate, the concentration of potassium ions in the first molten salt is less than that in the second molten salt; the strengthening time of the second strengthening is shorter than that of the first strengthening, i.e., the first strengthening time is longer than the second strengthening time, so that a dense ion exchange region is formed in a short distance on the surface of the nanocrystalline glass ceramic, and a larger compressive stress CS1 is formed in a smaller DOL2 region. Two sections of compressive stress regions with different compressive stresses can be formed on the surface of the nanocrystalline glass ceramic through two times of strengthening, so that the nanocrystalline glass ceramic can obtain smaller central tensile stress CT while keeping larger surface compressive stress CS1 and deeper stress layer DOL 1.
Step S210: and taking out the nanocrystalline glass ceramic from the reaction furnace for cooling after the second strengthening is finished.
Specifically, after the second strengthening is completed, the carrying basket carrying the nanocrystalline glass ceramic sheet is taken out of the reaction furnace and cooled, and the cooling process may include the following four cooling methods:
the first cooling method: rapidly cooling, namely directly taking out the bearing hanging basket from the reaction furnace without placing the bearing hanging basket in a preheating furnace, and physically cooling the nanocrystalline glass ceramic sheet by using a fan, wherein the temperature of the nanocrystalline glass ceramic sheet is rapidly reduced to room temperature;
The second cooling method: naturally cooling, namely taking the bearing hanging basket bearing the nanocrystalline glass ceramic sheet out of a reaction furnace, taking the nanocrystalline glass ceramic sheet out of the reaction furnace, suspending and placing the nanocrystalline glass ceramic sheet above the reaction furnace, and allowing molten salt on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, wherein in the process, on one hand, the waste of molten salt can be avoided, and on the other hand, excessive salt can be avoided from being generated on the surface of the cooled nanocrystalline glass ceramic sheet, the salt dropping time is 2-10 minutes, then, the nanocrystalline glass ceramic sheet is placed in a preheating furnace for cooling, then, the temperature is reduced to be below 100 ℃ in a natural cooling mode, then, a preheating furnace door is opened, the bearing hanging basket is taken out, and the nanocrystalline glass ceramic sheet is allowed to stand to room temperature;
The third cooling method: gradient cooling, namely taking out the nanocrystalline glass ceramic sheet from the reaction furnace, suspending the nanocrystalline glass ceramic sheet above the reaction furnace, and enabling molten salt on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, wherein in the process, on one hand, the molten salt can be prevented from being wasted, on the other hand, excessive salt can be prevented from being generated on the surface of the cooled nanocrystalline glass ceramic sheet, the salt dropping time is 2-10 minutes, the temperature is reduced to 250-300 ℃ in a natural cooling mode, then the hanging basket bearing material is taken out from the furnace, a fan is used for physically cooling the nanocrystalline glass ceramic sheet, and the temperature of the nanocrystalline glass ceramic sheet is quickly reduced to room temperature;
The fourth cooling method: annealing, taking the bearing hanging basket bearing the nanocrystalline glass ceramic sheet out of the reaction furnace, taking the nanocrystalline glass ceramic sheet out of the reaction furnace, suspending the nanocrystalline glass ceramic sheet above the reaction furnace, and enabling the salt in the molten state on the surface of the nanocrystalline glass ceramic sheet to drop back into the reaction furnace, the process can avoid the waste of salts in a molten state on one hand and the excessive salt generated on the surface of the cooled nanocrystalline glass ceramic sheet on the other hand, the salt dripping time is 10 to 30 minutes, then the nanocrystalline glass ceramic sheet is placed in the preheating furnace for cooling, the temperature in the preheating furnace is constant, the temperature range in the preheating furnace is 300-400 ℃, after the molten salt dripping is finished, and cooling to below 100 ℃ in a natural cooling mode, then opening a preheating furnace door, taking out the bearing hanging basket, and standing the nanocrystalline glass ceramic sheet to room temperature.
Step S211: and cleaning the nanocrystalline glass ceramic to remove the molten salt on the surface of the nanocrystalline glass ceramic.
Specifically, the tempered fixing frame bearing the nanocrystalline glass ceramic is placed in a water bath to remove the molten salt on the surface of the nanocrystalline glass ceramic, and the water bath mode for dissolving the molten salt at least comprises the following 3 modes:
The first water bath mode: placing the toughened fixing frame bearing the nanocrystalline glass ceramics in a hot water bath at the temperature of 50-70 ℃ for soaking for 20-60 minutes;
The second water bath mode: placing the toughened fixing frame bearing the nanocrystalline glass ceramics in a cold water bath at the temperature of 15-35 ℃ for soaking for 20-60 minutes;
The third water bath mode: firstly, the toughened fixing frame bearing the nanocrystalline glass ceramics is placed in a hot water bath with the temperature range of 50-70 ℃ for soaking for 20-60 minutes, and then the toughened fixing frame bearing the nanocrystalline glass ceramics is placed in a cold water bath with the temperature range of 15-35 ℃ for soaking for 20-60 minutes.
Step S212: and drying the nanocrystalline glass ceramic.
specifically, the tempered fixing frame bearing the nanocrystalline glass ceramic is taken out of the water bath and is kept stand for draining water for 20-30 minutes until the water stain is drained.
The strengthening method of the nanocrystalline glass ceramic provided by the invention comprises a primary strengthening method and a secondary strengthening method. The primary strengthening method can enable the nanocrystalline glass ceramic to form larger surface compressive stress CS and deeper stress layer DOL; the first strengthening in the two strengthening methods can increase the depth DOL of the ion exchange layer, and the second strengthening can increase the surface compressive stress CS, thereby effectively reducing the central tensile stress CT value of the nanocrystalline glass ceramic.
After the nanocrystalline glass ceramic material sheet with the thickness of about 0.2mm-5mm is subjected to strengthening treatment, the surface chemical composition of the nanocrystalline glass ceramic material sheet is changed, the potassium ion content on the surface of the nanocrystalline glass ceramic material is increased, and the potassium ion content and the sodium ion content in the stress layer are in gradient change. The DOL value of the depth of the ion exchange layer of the nanocrystalline glass ceramic can be 35-160 μm, further can be 35-79 μm, 80-120 μm and 121-160 μm, and the CS value of the surface compressive stress can be 700-1200 MPa.
The shock resistance of the strengthened nanocrystalline glass ceramic can reach 2-3 joules, and the shock resistance of the common glass ceramic strengthened by the prior strengthening technology can only reach 1 joule; the flexural strength of the strengthened nanocrystalline glass ceramic is also obviously enhanced, the flexural strength of the strengthened nanocrystalline glass ceramic can reach more than 900MPa, and the flexural strength of the common glass ceramic strengthened by the prior strengthening technology is about 600 MPa; the Vickers hardness HV of the strengthened nanocrystalline glass ceramic is obviously improved, and the Vickers hardness reaches 850kgf/mm after strengthening2. The strength of the strengthened nanocrystalline glass ceramic is obviously improved.
Example 1
2D (or 2.5D) sheets of the polished nano-crystalline glass ceramic with the size of 155mm x 75mm x 0.6mm are strengthened by adopting a primary strengthening method. In pure KNO3Performing primary strengthening in molten salt, wherein the strengthening temperature is 450 ℃, and the strengthening time is 100 minutes. The surface stress value and the stress layer depth of the strengthened nanocrystalline glass ceramic sheet are as follows:
Serial number CS1/Mpa DOL1/μm CT/Mpa
1 1061 102 24
2 1077 103.5 24
3 1072 104 24
4 1068 102.5 24
5 1066 102.2 24
6 1078 101.6 23
From the above table, it can be seen that after the 2D (or 2.5D) sheet of the nanocrystalline glass ceramic with the size of 155mm x 75mm x 0.6mm is subjected to the primary strengthening method, the surface compressive stress value (CS1 value) can reach 1078MPa, and the depth of stress layer (DOL1 value) can reach 103.5 μm. The Vickers hardness HV after strengthening is up to 831kgf/mm according to various performance tests2The impact resistance is 2.8 joules at most, and the breaking strength is 1130MPa at most.
Example 2
The 3D sheet of the polished nanocrystalline glass ceramic with dimensions of 155mm by 75mm by 0.6mm was strengthened by a double strengthening process. At KNO3：NaNO3Carrying out first strengthening in molten salt with the ratio of 13:7, wherein the strengthening temperature is 480 ℃, and the strengthening time is 480 minutes; in pure KNO3And performing secondary strengthening in molten salt, wherein the strengthening temperature is 480 ℃ and the strengthening time is 20 minutes. The surface stress value and the stress layer depth of the 3D sheet of the strengthened nanocrystalline glass ceramic sheet are as follows:
From the above table, after the 3D sheet of nanocrystalline glass ceramic with a size of 155mm x 75mm x 0.6mm is twice strengthened, the surface compressive stress value (CS1 value) reaches 985MPa, the maximum depth of the stress layer (DOL1 value) reaches 99.2 μm, the compressive stress value at the inflection point (CS2 value) reaches 248.1MPa, and the depth of the stress layer at the inflection point (DOL2 value) reaches 21.85 μm. The Vickers hardness HV of the alloy can be up to 825kgf/mm2impact resistancethe highest force can be 2 joules, and the highest breaking strength can be 925 MPa.
Example 3
Two times of strengthening is adopted for the nano-crystalline glass ceramic sheet with the size of 155mm by 75mm by 0.8mm after grinding and polishing. At KNO3：NaNO3Carrying out first strengthening in molten salt with the ratio of 13:7, wherein the strengthening temperature is 500 ℃, and the strengthening time is 500 minutes; in pure KNO3And performing secondary strengthening in the molten salt, wherein the strengthening temperature is 500 ℃, and the strengthening time is 20 minutes. The surface stress value and the stress layer depth of the strengthened nanocrystalline glass ceramic sheet are as follows:
From the above table, after the nanocrystalline glass ceramic sheet with the size of 155mm 75mm 0.8mm is subjected to two times of strengthening methods, the surface compressive stress value (CS1 value) reaches 1087MPa, the maximum depth (DOL1 value) of the stress layer reaches 95.1 μm, the compressive stress value (CS2 value) at the inflection point reaches 255.5MPa, and the depth (DOL2 value) of the stress layer at the inflection point reaches 20.95 μm. The impact resistance can be 3 joules at maximum, and the Vickers hardness HV can be 850kgf/mm at maximum2the maximum breaking strength can be 970 MPa.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (11)

1. A method for strengthening nanocrystalline glass-ceramics is characterized by comprising the following steps:
providing a nanocrystalline glass-ceramic;
Placing the nanocrystalline glass ceramic in a preheating furnace for preheating treatment;
Taking the nanocrystalline glass ceramic subjected to preheating treatment out of the preheating furnace, placing the nanocrystalline glass ceramic in a reaction furnace for strengthening treatment, and placing the nanocrystalline glass ceramic in a first molten salt for first strengthening, wherein the first molten salt is a molten salt at least containing one of potassium ions and sodium ions, an ion exchange reaction exists between the nanocrystalline glass ceramic and the first molten salt, and the first strengthening time is first strengthening time; and
and taking out the nanocrystalline glass ceramic from the reaction furnace after the first strengthening is completed, and cooling.
2. The method for strengthening a nanocrystalline glass-ceramic of claim 1, further comprising the steps of:
Placing the cooled nanocrystalline glass ceramic in a preheating furnace for preheating treatment;
taking the nanocrystalline glass ceramic subjected to preheating treatment out of the preheating furnace, placing the nanocrystalline glass ceramic in a reaction furnace for strengthening treatment, and placing the nanocrystalline glass ceramic in a second molten salt for strengthening for the second time, wherein the second molten salt is a molten salt at least containing one of potassium ions or sodium ions, an ion exchange reaction exists between the nanocrystalline glass ceramic and the second molten salt, and the time of strengthening for the second time is the second strengthening time; and
And taking out the nanocrystalline glass ceramic from the reaction furnace after the second strengthening is completed, and cooling.
3. The method for strengthening a nanocrystalline glass-ceramic of claim 2, wherein the first strengthening time is greater than the second strengthening time.
4. the method for strengthening a nanocrystalline glass-ceramic according to claim 2, wherein the first molten salt and the second molten salt both contain potassium ions, and a concentration of potassium ions in the first molten salt is smaller than a concentration of potassium ions in the second molten salt.
5. the method for strengthening a nanocrystalline glass-ceramic according to claim 2, wherein the first molten salt is a mixture containing potassium ions and sodium ions, and the second molten salt is a mixture containing potassium ions and sodium ions.
6. The method for strengthening a nanocrystalline glass-ceramic according to any one of claims 2 to 5, wherein the nanocrystalline glass-ceramic is ion-exchanged with the first molten salt at a temperature in a range of 350 ℃ to 600 ℃ and the nanocrystalline glass-ceramic is ion-exchanged with the second molten salt at a temperature in a range of 350 ℃ to 600 ℃.
7. the method for strengthening a nanocrystalline glass-ceramic of claim 6, wherein the step of cooling the nanocrystalline ceramic material comprises: and directly taking out the nanocrystalline glass ceramic from the reaction furnace and physically cooling the nanocrystalline glass ceramic to cool the nanocrystalline glass ceramic to room temperature.
8. The method for strengthening a nanocrystalline glass-ceramic of claim 6, wherein the step of cooling the nanocrystalline ceramic material comprises: and taking the nanocrystalline glass ceramic out of the reaction furnace, placing the nanocrystalline glass ceramic above the reaction furnace in a hanging manner for 2-10 minutes to enable molten salt on the surface of the nanocrystalline glass ceramic to drip back into the reaction furnace, placing the nanocrystalline glass ceramic in the preheating furnace to be cooled to a temperature not higher than 100 ℃, and taking the nanocrystalline glass ceramic out of the preheating furnace and cooling to room temperature.
9. the method for strengthening a nanocrystalline glass-ceramic of claim 6, wherein the step of cooling the nanocrystalline ceramic material comprises: and taking the nanocrystalline glass ceramic out of the reaction furnace, placing the nanocrystalline glass ceramic above the reaction furnace in a hanging manner for 2-10 minutes to enable molten salt on the surface of the nanocrystalline glass ceramic to drop back into the reaction furnace, placing the nanocrystalline glass ceramic in the preheating furnace to be cooled to 250-300 ℃, taking the nanocrystalline glass ceramic out of the preheating furnace and physically cooling the nanocrystalline glass ceramic to enable the nanocrystalline glass ceramic to be cooled to room temperature.
10. The method for strengthening a nanocrystalline glass-ceramic of claim 6, wherein the step of cooling the nanocrystalline ceramic material comprises: taking the nanocrystalline glass ceramic out of the reaction furnace, placing the nanocrystalline glass ceramic above the reaction furnace in a hanging manner for 10-30 minutes to enable molten salt on the surface of the nanocrystalline glass ceramic to drop back into the reaction furnace, placing the nanocrystalline glass ceramic in the preheating furnace to be cooled at a constant temperature of 300-400 ℃, naturally cooling the nanocrystalline glass ceramic to be not more than 100 ℃, and taking the nanocrystalline glass ceramic out of the preheating furnace to be cooled to room temperature.
11. The method for strengthening a nanocrystalline glass-ceramic according to claim 6, wherein the nanocrystalline glass-ceramic comprises the following components in weight percent: 40 to 80 percent of silicon dioxide, 5 to 35 percent of aluminum oxide, 0 to 10 percent of magnesium oxide, 0 to 10 percent of zinc oxide, 0.5 to 20 percent of potassium oxide, 0.5 to 20 percent of sodium oxide, 0 to 10 percent of calcium oxide, 0 to 8 percent of ferric oxide, 0 to 8 percent of phosphorus oxide, 0 to 8 percent of titanium dioxide, 0 to 8 percent of zirconium dioxide, 0 to 5 percent of tin dioxide, 0 to 5 percent of antimony oxide, 0 to 5 percent of boron oxide and 0 to 5 percent of arsenic trioxide.
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